Está en la página 1de 311

Particle Size Distribution

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
In Particle Size Distribution; Provder, T.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
ACS SYMPOSIUM SERIES 332

Particle Size Distribution


Assessment and Characterization

Theodore Provder, EDITOR


The Glidden Company

Developed from a symposium sponsored by


the Division of Polymeric Materials: Science and Engineering
at the 190th Meeting
of the American Chemical Society,
Chicago, Illinois,
September 8-13, 1985

American Chemical Society, Washington, DC 1987

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Library of Congress Cataloging-in-Publication Data
Particle size distribution.
(ACS symposium series, ISSN 0097-6156; 332)
"Developed from a symposium sponsored by the
Division of Polymeric Materials: Science and
Engineering at the 190th meeting of the American
Chemical Society, Chicago, Illinois, September 8-13,
1985."
Includes bibliographies and index
1. Particle size determinationCongresses
I. Provder, Theodore, 1939- . II. American
Chemical Society. Division of Polymeric Materials:
Science and Engineering. III. American Chemical
Society. Meeting (190th: 1985: Chicago, Ill.) IV. Series.
TA418.8.P33 1987 620.1'1299 86-32185
ISBN 0-8412-1016-0

Copyright 1987
American Chemical Society
All Rights Reserved. The appearance of the code at the bottom of the first page of each
chapter in this volume indicates the copyright owner's consent that reprographic copies of the
chapter may be made for personal or internal use or for the personal or internal use of
specific clients. This consent is given on the condition, however, that the copier pay the stated
per copy fee through the Copyright Clearance Center, Inc., 27 Congress Street, Salem, MA
01970, for copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright L a w .
This consent does not extend to copying or transmission by any meansgraphic or
electronicfor any other purpose, such as for general distribution, for advertising or
promotional purposes, for creating a new collective work, for resale, or for information
storage and retrieval systems. The copying fee for each chapter is indicated in the code at
the bottom of the first page of the chapter.
The citation of trade names and/or names of manufacturers in this publication is not to be
construed as an endorsement or as approval by A C S of the commercial products or services
referenced herein; nor should the mere reference herein to any drawing, specification,
chemical process, or other data be regarded as a license or as a conveyance of any right or
permission, to the holder, reader, or any other person or corporation, to manufacture,
reproduce, use, or sell any patented invention or copyrighted work that may in any way be
related thereto. Registered names, trademarks, etc., used in this publication, even without
specific indication thereof, are not to be considered unprotected by law.
PRINTED IN THE UNITED STATES OF AMERICA

American Chemical Society


Library
In Particle1155 16th St., Provder,
Size Distribution; N.W., T.;
ACS Symposium Series;Washington,
American ChemicalD.C. 20036
Society: Washington, DC, 1987.
ACS Symposium Series
M. Joan Comstock, Series Editor

1987 Advisory Board


Harvey W. Blanch
University of CaliforniaBerkeley Battelle Columbus Laboratories

Alan Elzerman W. H . Norton


Clemson University J. T. Baker Chemical Company

John W. Finley James C . Randall


Nabisco Brands, Inc. Exxon Chemical Company

Marye Anne Fox E . Reichmanis


The University of TexasAustin AT&T Bell Laboratories

Martin L . Gorbaty C . M . Roland


Exxon Research and Engineering Co. U.S. Naval Research Laboratory

Roland F. Hirsch W. D. Shults


U.S. Department of Energy Oak Ridge National Laboratory

G . Wayne Ivie Geoffrey K . Smith


USDA, Agricultural Research Service Rohm & Haas Co.

Rudolph J. Marcus Douglas B. Walters


Consultant, Computers & National Institute of
Chemistry Research Environmental Health

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Foreword
The ACS SYMPOSIUM SERIES was founded in 1974 to provide a
medium for publishing symposia quickly in book form. The
format of the Series parallels that of the continuing ADVANCES
IN CHEMISTRY SERIES except that, in order to save time, the
papers are not typese
by the authors in camera-ready form. Papers are reviewed under
the supervision of the Editors with the assistance of the Series
Advisory Board and are selected to maintain the integrity of the
symposia; however, verbatim reproductions of previously pub-
lished papers are not accepted. Both reviews and reports of
research are acceptable, because symposia may embrace both
types of presentation.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Preface

THE FIELD OF PARTICLE SIZE DISTRIBUTION ANALYSIS has experienced a


renaissance over the past five years and is now a rapidly growing and lively
area of scientific and technological activity. This revitalization has been
driven by advances in electronics and computer technology in conjunction
with the market pull for particle size distribution analysis methods that
cover a wide dynamic particle size range and have improved resolution.
These technological advances are embodied in computer-aided, user-
friendly, reliable, and
characterize this renaissance
The first activity is the commercial use of instrumental methods used
previously in a few academic and industrial laboratories by individuals with
a high level of skill and expertise. Examples of such methods are
hydrodynamic chromatography (HDC) and sedimentation field-flow
7
fractionation (SFFF). HDC, first reported in 1976 , was invented in an
industrial laboratory by Hamish Small to fulfill an analysis need. It has
taken about 10 years for HDC to be transformed from a laboratory method
requiring a high degree of skill into a commercial instrument requiring a
moderate degree of skill. SFFF, a more extreme case, was invented by
2i
J. Calvin Giddings and co-workers and reported in 1967 . The technology
transfer of SFFF from academic laboratory method to viable commercial
instrument has taken almost 20 years to occur.
The second activity is characterized by the revitalization of older
instrumental methods such as gravitational and centrifugal sedimentation
methods. Redesign, modernization with advanced electronics, and user-
friendly, computer-aided analysis have extended the instrument product
life cycle. A good example is disc centrifuge photosedimentometry (DCP),
the subject of three chapters in this volume.
The third activity is the evolution of a research instrument into a low-
cost instrument that requires a minimum degree of skill to use. An excellent
example of this process is the transformation of research-grade photon
correlation spectrometers into low-cost, easy-to-use, limited-function
instruments for routine analysis applications.
The activity in the field of particle size analysis has produced an
explosion of papers. A useful review of recent literature is provided by H. G.
4
Barth and S.-T. Sun in Analytical Chemistry . This survey covers papers,
books, and reviews from late 1981 to late 1984. A monograph published in
5
1984 and edited by H. G. Barth gives excellent overviews of most new

ix

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
methods, emphasizing those that provide distribution information. Barth's
monograph is an excellent companion text to this volume.
The papers in this book reflect current activity in the field and
emphasize measurement techniques, methodology, and application to a
variety of particulate systems. The topics are divided into four sections. The
first section deals with image analysis methodology and application, an area
in which technology is in a state of flux. This area benefits significantly
from advances in computer technology. The second section examines
photon correlation spectroscopy and light-scattering methods. It presents
refinements in classical light-scattering data analysis methodologies that
involve angular light scattering and turbidity. Advances in and limitations
of photon correlation spectroscopy with respect to data analysis and its
application to emulsion and latex systems also are discussed. The third
section deals with sedimentation techniques Recent improvements in DC
instrumentation, experimenta
are reported. It presents the applicability of SFFF, a hybrid technique that
combines centrifugal sedimentation with liquid chromatography, to colloid
systems. Of special interest is a particle size analysis study that compares
the results of SFFF, DCP, HDC, microscopy, and light-scattering methods
for a common latex system. The fourth section emphasizes the use of
column chromatography methods, HDC, and size-exclusion chromatogra
phy for latex systems.
Because of the commercial availability of new, revitalized, and low-
cost routine instrumental methods, the field of particle size distribution
analysis will continue to grow. I hope that this book will spur further
activity.
I thank the authors for their effective oral and written communications
and the reviewers for their critiques and constructive comments. I also
acknowledge the book jacket design concepts provided by Ann F. Kah.

T H E O D O R E PROVDER
The Glidden Company
Dwight P. Joyce Research Center
Strongsville, OH 44136

November 5, 1986

1
Small, . J. Colloid InterfaceSci.1976, 57, 337.
2
Thompson, G. H.; Meyers, M . N.; Giddings, J. C. Sep. Sci. 1967, 2, 797.
3
Giddings, J. C. J. Chem. Phys. 1968, 49, 81.
4
Barth, H. G.; Sun, S.-T. Anal. Chem. 1985, 57, 151R.
5
Modern Methods of Particle Size Analysis; Barth, H. G., Ed.; Wiley: New
York, 1984.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 1

Size, Shape, and Texture Analysis


J. K. Beddow
Center for Particulate Material Processing Sciences, Department of Chemical and
Materials Engineering, The University of Iowa, Iowa City, IA 52242

This paper is a brief review of original basic


engineering research in morphological analysis applied to
particle characterizatio
the last 20 years a
Particulate Material Processing Sciences. The topics
discussed include definitions, theory, instrumental and
experimental aspects of size, shape and texture
measurements of particulate material.

Morphological Analysis
Morphological analysis is concerned with particle characterization in
the case of particle size, particle shape and particle texture.
Particle texture may deal with the particle surface characteristics
and also with the particle microstructure. Particle size and shape
influence physical and chemical properties of particulate
materials. Morphological analysis is being developed in order to
facilitate a more accurate description of the properties and behavior
of particulate systems from a fundamental knowledge of the
characteristics of the particles of the system [1,2].
Shape is defined as the pattern of relationships among a l l of
the points of the surface or profile of the particle. The
development of this operational definition has in turn led to the
development of morphological analysis.
Experimental
An image of the particle is obtained, the profile of that image is
converted to a set of x,y pairs, a process known as d i g i t i z i n g . The
x,y set is then converted to polar coordinates, (R,6). The curve in
the R,6 space is converted to a Fourier equation, the coefficients of
which are extracted, and then mathematically transformed to morphic
terms which themselves constitute the shape features of the
particle. A sample usually consists of 100 particles, upwards of 150
profile points are extracted from each particle, giving a total of
15,000 x,y points per analysis. Once the morphic terms are obtained,
the data analysis can be carried out in order to facilitate the

0097-6156/87/0332-0002$08.25/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
1. BEDDOW Size, Shape, and Texture Analysis 3

s o l u t i o n of the problem a t hand. M o r p h o l o g i c a l a n a l y s i s i s c a r r i e d


o u t u s i n g an i n s t r u m e n t known a s a Shape A n a l y z e r [ 3 ] , w h i c h c o n s i s t s
e s s e n t i a l l y o f a h i g h q u a l i t y g r a p h i c s y s t e m and computer p l u s
s o p h i s t i c a t e d s o f t w a r e and p e r i p h e r a l s [ 2 ] .
The S h a p e A n a l y z e r i s a s c i e n t i f i c i n s t r u m e n t w h i c h i s u s e d t o
a n a l y z e t h e s h a p e , s i z e , a n d t e x t u r e o f o b j e c t s . The i t e m f o r
a n a l y s i s may be t h e o b j e c t i t s e l f , i t s p h o t o g r a p h , o p t i c a l o r
e l e c t r o n m i c r o g r a p h , e t c . The s h a p e - s i z e a n a l y s i s i s a c h i e v e d b y
c o n v e r t i n g t h e p r o f i l e t o a s e t o f shape and s i z e d e s c r i p t o r s w h i c h
a r e c o m p l e t e , u n e q u i v o c a l and i n v a r i a n t . The t e x t u r e a n a l y s i s
c o n v e r t s t h e f u l l image o f t h e o b j e c t i n t o a s e t o f t e x t u r a l
d e s c r i p t o r s w h i c h a r e u n e q u i v o c a l , c o m p l e t e and i n v a r i a n t . These
s h a p e , s i z e a n d t e x t u r e d e s c r i p t o r s c a n be u s e d i n r e s e a r c h , i n
q u a l i t y c o n t r o l , i n p r o c e s s c o n t r o l and s p e c i f i c a t i o n s . A d d i t i o n a l
d e t a i l s a r e g i v e n i n Table 1 and t h e A p p e n d i x .
The m o r p h o l o g i c a l f e a t u r e d i t h Shap Analyze
include the f o l l o w i n g :

Table 1. Morphological Analysis

Topic Feature Application

Size Equivalent radius Hydraulic radius


Mean r a d i u s / d i a m e t e r Sedimentation
Correlations with other particle
s i z e a n a l y s i s methods

Shape Not-roundness Wear a n a l y s i s


L2(2) Dust e x p l o s i o n s
L2(3) Particle characterization
L2(4) Settling
Roughness Bulk p r o p e r t i e s
Symmetry Slurry flow
F l u i d i z e d beds

Texture Mean t e x t u r e Microstructure analysis


Standard d e v i a t i o n Cancer c e l l i d e n t i f i c a t i o n and
Symmetry differentiation

Mixtures Cross-over points P a r t i c l e mixture and b l e n d a n a l y s i s

Strategy

The s h a p e a n d t e x t u r e f e a t u r e s a r e i n v a r i a n t , u n i q u e a n d
unequivocal. They a r e a s s o c i a t e d w i t h i n d i c a t i o n s o f p h y s i c a l
meaning. The u s e d f o r m o f t h e F o u r i e r e q u a t i o n i s

R(9) = a + f a s i n + b c o s ) J

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
4 PARTICLE SIZE DISTRIBUTION

the raw F o u r i e r c o e f f i c i e n t s n o t u s e f u l t o d e s c r i b e t h e p r o f i l e
because they change i n v a l u e as t h e p r o f i l e i s r o t a t e d * F o r t h i s
r e a s o n t h e y a r e t r a n s f o r m e d i n t o i n v a r i a n t m o r p h o l o g i c a l s i z e and
shape d e s c r i p t o r i n t h e f o l l o w i n g way:

Theory o f M o r p h o l o g i c a l A n a l y s i s [4]

S i z e a n d S h a p e D e s c r i p t o r s * The f o l l o w i n g s i z e a n d s h a p e t e r m s a r e
defined* These a r e r o t a t i o n a l l y i n v a r i a n t and r e l a t e d t o t h e
amplitudes, and b , as f o l l o w s *
n

The s i z e t e r m i s d e f i n e d a s

/ a 2
+ I L
I (a 2
+ b )
2
(1)
o 2 , ^ n'
n=l

i n w h i c h R i s termed " e q u i v a l e n t r a d i u s and i s t h e r a d i u s o f a


Q

c i r c l e h a v i n g t h e same a r e a a s t h a t o f t h e p a r t i c l e p r o f i l e , a n d i s
the order of the c o e f f i c i e n t .
The s h a p e t e r m s a r e d e f i n e d a s

a /R (2)

L, =0 for a l l
,

L
1
( a

+ b
(3)
2 , n ~ ^ 2 ( n n)

r 2
(a a 0
b a + 2a b b J 0 0 ;
(4)
J
3,n J
v
2n 2n 2n
4R

a Q i s t h e mean r a d i u s .
E q u a t i o n ( 2 ) d e f i n e s t h e v a l u e o f t h e s i z e n o r m a l i z e d mean
radius of the p a r t i c l e . E q u a t i o n ( 3 ) d e f i n e s t h e s i z e n o r m a l i z e d sum
of the squares of the F o u r i e r c o e f f i c i e n t s . Equation (4) defines the
sum a n d d i f f e r e n c e s o f t h e m u l t i p l e s . I t h a s b e e n s h o w n t h a t t h e s e
s i z e a n d s h a p e d e s c r i p t o r s c a n be u s e d t o r e g e n e r a t e t h e o r i g i n a l
particle profile. This i n d i c a t e s that the d e s c r i p t o r s together
c o n t a i n a l l o f t h e s i z e and shape i n f o r m a t i o n c o n t a i n e d i n t h e
original profile.
The m o r p h o l o g i c a l d e s c r i p t o r s d e s c r i b e d a b o v e w i l l be e x a m i n e d
later f o rtheir physical interpretation. But f i r s t t h e i r very
i n t e r e s t i n g relationship to the s t a t i s t i c a l properties of the
p a r t i c l e p r o f i l e r a d i a l d i s t r i b u t i o n w i l l be c o n s i d e r e d *

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
1. BEDDOW Size, Shape, and Texture Analysis 5

Statistical P r o p e r t i e s of Descriptors*

L R (mean radius)
U

w h e r e i s t h e r a d i a l s t a n d a r d d e v i a t i o n ( t h e NR
2 not-roundness)
a n d ^ i s t h e r a d i a l s k e w n e s s ( S K E ) .

Symmetry Operations [5]

I n c r y s t a l l o g r a p h y one i s a c c u s t o m e d t o t h e i d e a t h a t a s t r u c t u r e
e i t h e r h a s a p a r t i c u l a r s y m m e t r y e l e m e n t o r i t d o e s n o t . The
membership i s thus e i t h e r 1 o r z e r o . In morphological a n a l y s i s the
s y m m e t r y h a s a v a l u e o f z e r o t h r o u g h 1 d e p e n d i n g u p o n how c l o s e l y t h e
p r o f i l e a p p r o a c h e s t h e symmetry b e i n g c o n s i d e r e d * The d e f i n i t i o n s o f
t h e s y m m e t r y o p e r a t i o n s a r e shown b e l o w :

Rotation

C
m = ^ f c - (-1.2.3. (8)

Reflection

2
IL (n)cos ( -3-2)
P A T ( 9 )
- < >

if

ZL (j-n)
2 (10)
rj=m
u
j>i ZL (n>
2 Lj=2mJ

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
6 PARTICLE SIZE DISTRIBUTION

Inversion

ZL (2n)
?

I = ( 1 1
-L7) >

Rotation-Reflection

(2n)
S
2 -5^(n7
=
1 0 ( 1 2 )

Texture [6]

Texture i s d e f i n e d as th
l e v e l s o f the d e f i n e d image
a n a l y s i s i s d e v e l o p a n a n a l y t i c a l m e t h o d w h e r e b y t h e i m a g e c a n be
regenerated.
I n o r d e r t o do t h i s t h e p o i n t s o f t h e i m a g e h a v e t o be
incorporated i n t o the a n a l y s i s i n the form of i n v a r i a n t
descriptors. The i n t e r p r e t a t i o n o f t h e t e x t u r a l m o r p h o l o g y f e a t u r e s
depends upon t h e p h y s i c s o f t h e s i t u a t i o n ( f o r e x a m p l e , t h e g r a y
l e v e l may be r e l a t e d t o a l t i t u d e o r i n a n o t h e r c a s e t o t h e c h e m i c a l
a n a l y s i s from point t o p o i n t . The i n t e r p r e t a t i o n a l s o d e p e n d s u p o n
the m a t h e m a t i c a l r e l a t i o n s h i p s between t h e v a r i o u s m o r p h o l o g i c a l
d e s c r i p t o r s used. There a r e t h r e e major types o f m o r p h o l o g i c a l
texture descriptors. These a r e : s t a t i s t i c a l t e r m s , symmetry
o p e r a t i o n s , and i n v a r i a n t t e x t u r e m o r p h o l o g y d e s c r i p t o r s ( I T M D ' s ) .

_ L
G T = I i Pi (13)
i=l

4- J (1 - G j 2
Pi (14)
i=l

in which:

G T i s t h e mean g r a y l e v e l o f t h e image

i s the standard deviation o f t h e image g r a y level

L i s t h e maximum g r a y level

Pi i s the p r o b a b i l i t y d i s t r i b u t i o n at gray l e v e l i .

I f t h e i m a g e i s r o t a t e d b y 2/ a n d t h e o r i g i n a l c o n f i g u r a t i o n i s
r e p r o d u c e d , t h e i m a g e i s s a i d t o p o s s e s s a n -fold r o t a t i o n a l
symmetry.
The t e x t u r a l s y m m e t r y i s

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
1. BEDDOW Size, Shape, and Texture Analysis 7

Cn - 1 - if[Gix. ) TGfx> y')]


y ;
2
dxdy
JJG(xy) dxdy
(TDs)

in which:

G(xy) i s the gray level at (x,y)

x'y' are locations corresponding G(x.y)

The i n v a r i a n t ITMD's h a v e b e e n d e v e l o p e d u s i n g a c o m b i n e d
F o u r i e r - B e s s e l e q u a t i o n i n which the F o u r i e r terms account f o r the
r e p e t a t i v e n a t u r e o f t h e image d e s c r i b e d by a r a d i u s v e c t o r s w e e p i n g
r o u n d on a c e n t r a l o r i g i n . The B e s s e l t e r m s d e a l w i t h t h e f e a t u r e s
o f the image i n the d i r e c t i o n o u t w a r d s a l o n g t h e r a d i i f r o m the
origin. The g e n e r a l f o r
l a t e r date.

Indications of P h y s i c a l Meanings of S h a p e and Textural Descriptors

Particle Size. The e q u i v a l e n t r a d i u s R may a l s o be r e p o r t e d o u t a s


Q

the e q u i v a l e n t p a r t i c l e d i a m e t e r 2R .Q The s i z e may be r e p o r t e d o u t


a s mean a n d s t a n d a r d d e v i a t i o n a s s h o w n i n T a b l e I I o r a s a h i s t o g r a m
as shown i n F i g u r e l a , b . The s i z e t e m p l a t e i n F i g u r e 2 i l l u s t r a t e s t h e
p r i n c i p l e u n d e r l y i n g the R Q term.

Shape C l a s s i f i e r . I t h a s l o n g b e e n known t h a t d i f f e r e n t m e t h o d s o f
p a r t i c l e p r o d u c t i o n w h i c h i n v o l v e d i f f e r e n t modes o f p a r t i c l e
f o r m a t i o n w i l l produce p a r t i c l e s of d i f f e r e n t morphology. To
d e m o n s t r a t e t h i s f a c t , t h r e e s a m p l e s o f a d i p i c a c i d p o w d e r w e r e made
by t h r e e methods: a t o m i z a t i o n , c o m m i n u t i o n and c r y s t a l l i z a t i o n . The
NR and SKE v a l u e s w e r e p l o t t e d a g a i n s t e a c h o t h e r f o r t h e t h r e e
particulate materials. The d a t a s h o w n i n F i g u r e 3a,b c l e a r l y s h o w s t h a t
i t i s p o s s i b l e t o c l a s s i f y t h e t h r e e p r o d u c t s on t h e b a s i s o f t h e i r
morphology. The m e t h o d o f d a t a p l o t t i n g u s e d , s t r e t c h e s t h e p o i n t s
o u t i n a d i a g o n a l f a s h i o n and t h i s p e r m i t s t h e c l a s s i f i c a t i o n l i n e s
t o be d r a w n i n a s s h o w n . The ATM, RED and E L E C T d a t a c o r r e s p o n d to
c o m m e r c i a l i r o n p o w d e r s made b y a t o m i z a t i o n , r e d u c t i o n and
e l e c t r o l y t i c d e p o s i t i o n , r e s p e c t i v e l y . These c o m m e r c i a l m a t e r i a l
d a t a do n o t c o r r e s p o n d t o t h e a d i p i c a c i d d a t a b e c a u s e t h e c o m m e r c i a l
p r o c e s s e s a r e c o m p r i s e d o f many s t e p s i n c l u d i n g : c r u s h i n g and
g r i n d i n g , s i n t e r i n g , hammer m i l l i n g , m i x i n g and b l e n d i n g . For
e x a m p l e , c o n s i d e r t h e a t o m i z e d i r o n p o w d e r , e a c h one o f t h e t h e s e
s t e p s i n f l u e n c e s t h e p a r t i c l e m o r p h o l o g y t o s u c h an e x t e n t t h a t t h e
d a t a i s s h i f t e d i n t o the r e g i o n c o r r e s p o n d i n g t o the comminuted
adipic acid.

Not-Roundness. The s i z e n o r m a l i z e d r a d i a l s t a n d a r d d e v i a t i o n i s
i l l u s t r a t e d i n t h e NR t e m p l a t e shown i n F i g u r e 4. T h u s , no m a t t e r
how t h e p r o f i l e d e v i a t e s f r o m a c i r c l e t h e NR v a l u e w i l l o n l y
i n d i c a t e the s t a t i s t i c a l p r o p e r t y of the r a d i a l d i s t r i b u t i o n . There
i s no i n f o r m a t i o n i n t h i s t e r m c o n c e r n i n g t h e s e q u e n c e o f r a d i a l
terms.

L2(2) Indicator. The e f f e c t o f s h a p e c h a n g e on the size of the


L2(2) t e r m i s i l l u s t r a t e d i n F i g u r e 5.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
8 PARTICLE SIZE DISTRIBUTION

T a b l e I I . S i z e R e p o r t e d a s Means and S t a n d a r d D e v i a t i o n s f o r
S p h e r o i d a l Carbides i n F e r r i t e M a t r i x ( l e f t ) and f o r Atomized
and Sponge I r o n Powders ( r i g h t ) .

R R

Mean S t d . Dev. Mean S t d . Dev.

0.432 0.036 Atom (10) 0.076 0.013

(CIF 40) S p o n g e ( 1 0 ) 0.090 0.031

25

20

1
15-

S

J-l
Pu

51

10 15 20 25 30 35 40
Diameter (microns)

F i g u r e l a . S i z e d i s t r i b u t i o n f o r Rey 511. Reproduced w i t h


p e r m i s s i o n f r o m R e f . 8. C o p y r i g h t 1985 O x f o r d & IBH P u b l i s h i n g ,

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
1. BEDDOW Size, Shape, and Texture Analysis 9

22 -

20 -

1 -

16 -

14 -

12 -

10 -

4 -

2 -


3.3 3.7 3. 4.1 4.3 4.5 4.7 4.9 3.1 3.3 3.5 3.7 5.9 4.1 4.3
Ro(/*m) 10*

F i g u r e l b . Histogram r e p r e s e n t a t i o n of a p a r t i c l e s i z e d i s t r i
bution. R e p r o d u c e d w i t h p e r m i s s i o n f r o m R e f . 8. Copyright 1985
O x f o r d & IBH P u b l i s h i n g .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Size (Equivalent Radius)

In Particle Size Distribution; Provder, T.;


0 15 30 45 60

ACS Symposium Series; American Chemical Society: Washington, DC, 1987.


F i g u r e 2. Size template i l l u s t r a t i n g the p r i n c i p l e underlying the
R term. The a c t u a l s i z e d e p e n d s o n t h e m a g n i f i c a t i o n u s e d . The
2
a r e a o f t h e p r o f i l e i s IT R . q
1. BEDDOW Size, Shape, and Texture Analysis 11

ADIPIC ACID
ATOMIZED COMMINUTED

CRYSTALLIZED

F i g u r e 3a. Morphologie
f r o m R e f . 2. Copyright

10*5
1 1 1-

io* e
\o 7

io 5
1er 1er
4 5
10** 10
RADIAL SKEWNESS
F i g u r e 3b. M o r p h o l o g y p l o t f o r a d i p i c a c i d ; ATM - a t o m i z e d i r o n ,
RED - r e d u c e d i r o n , E L E C T - e l e c t r o l y t i c i r o n . Reproduced w i t h
p e r m i s s i o n f r o m R e f . 2. C o p y r i g h t 1984 CRC P r e s s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Not Roundness

f LU*)
fl-t

Sphere Arizona California Crushed Phosphate


Sand Sand Quartz Rock

0.000 0.012 0.026 0.063 0.137


* A

In Particle Size Distribution; Provder, T.;


8
I 1 $
0.05 0.10 0.15 0.20 &

F i g u r e 4. NR t e m p l a t e i l l u s t r a t i n g t h e s i z e n o r m a l i z e d r a d i a l

ACS Symposium Series; American Chemical Society: Washington, DC, 1987.


s t a n d a r d d e v i a t i o n . R e p r o d u c e d w i t h p e r m i s s i o n f r o m R e f . 8. ^
C o p y r i g h t 1985 Oxford & IBH P u b l i s h i n g . 2
c

1
L2(2)
en

D

Vitrain Limestone Titanium Fusain Coal

In Particle Size Distribution; Provder, T.;


f> H* 1 1 +
0 0.05 0.10 0.15 0.20

F i g u r e 5. Effect o f s h a p e change on the s i z e of the L2(2) term.

ACS Symposium Series; American Chemical Society: Washington, DC, 1987.


14 PARTICLE SIZE DISTRIBUTION

L2(3) Indicator. The e f f e c t o f s h a p e c h a n g e o n t h e v a l u e o f t h e


L2(3) t e r m s i n shown i n F i g u r e 6.

Roughness I n d i c a t o r . T h i s t e r m i s d e f i n e d a s t h e sum o f t h e h i g h e r
o r d e r L2(n) terms. I t r e p r e s e n t s t h e m i n o r d e v i a t i o n s and
i r r e g u l a r i t i e s i n t h e p a r t i c l e p r o f i l e and i s i l l u s t r a t e d i n t h e
t e m p l a t e o f F i g u r e 7.

Shape D i s t r i b u t i o n . One o f t e n h e a r s o f " n a r r o w s i z e d i s t r i b u t i o n " o r


"broad s i z e d i s t r i b u t i o n " . I t i s also meaningful to consider a
n a r r o w shape d i s t r i b u t i o n and a broad shape d i s t r i b u t i o n . Examples
o f t h e s e a r e g i v e n i n F i g u r e 8. The n a r r o w s h a p e d i s t r i b u t i o n s h o w s
a plot of not-roundness of c r y s t a l s of NaCl. After m i l l i n g , the
broad shape d i s t r i b u t i o n r e s u l t s .

Shape C o m p o s i t i o n . Th NR i d f th othe term described


above. Specifically:

NR = L 2 ( 2 ) + L2(3) + L2(4) L2(n)

An a c c o u n t i n g o f t h e p r o p o r t i o n o f NR f o r e a c h c o m p o n e n t t e r m s i s
c a l l e d t h e Shape C o m p o s i t i o n . I t i s i l l u s t r a t e d i n Table 3 f o r the
two s a m p l e s o f N a C l . The f i r s t c o l u m n c o r r e s p o n d s t o t h e r e c e i v e d
c r y s t a l s , t h e second column c o r r e s p o n d s t o t h e m i l l e d s a l t m a t e r i a l .

Residual Porosity. T h i s c a n be d e t e r m i n e d on a n a r e a b a s i s b y
examination of s u i t a b l y prepared microstructures. F o r example, as
shown i n T a b l e I V a , b , t h e r e a r e s u b s t a n t i a l d i f f e r e n c e s b e t w e e n t h e
r e s i d u a l p o r o s i t y i n an a t o m i z e d s i n t e r e d i r o n compact and a s i m i l a r
sponge i r o n compact.

Shape Symmetry. The m e a n i n g o f t h e r o t a t i o n a l s y m m e t r y , f o r e x a m p l e ,


i s demonstrated i n F i g u r e 9. I n t h i s f i g u r e t h e v a l u e s o f C 2 , C3 a n d
are compared between an e q u i l a t e r a l t r i a n g l e and an i s o s c o l e s
triangle. The p r e c i s e d e f i n i t i o n s o f t h e s y m m e t r i e s a r e g i v e n b e l o w .
F i g u r e 10 s h o w s a n i n t e r e s t i n g a p p l i c a t i o n o f p a r t i c l e s h a p e
symmetry i n t h e case o f seven t y p e s o f i n s t a n t c o f f e e p r o d u c t s . I t
w i l l be s e e n t h a t t h e s y m m e t r y a n a l y s i s shows t h a t c o f f e e #3 i s
f u n d a m e n t a l l y d i f f e r e n t f r o m e a c h one o f t h e o t h e r c o f f e e p r o d u c t s .
T e x t u r e a n a l y s i s i s i l l u s t r a t e d i n F i g u r e 11 w h i c h shows t h e
g r a y l e v e l d i s t r i b u t i o n f o r a p o l i s h e d and e t c h e d sample o f t u n g s t e n
carbide material. F r o m t h i s d i s t r i b u t i o n o n e c a n o b t a i n t h e mean a n d
standard deviation of the texture. I n a d d i t i o n , t h e * v a l u e
i n d i c a t e s t h e sharpness o f t h e image.
Some a p p l i c a t i o n s o f t h e mean g r a y l e v e l a r e s h o w n i n F i g u r e s 1 2 a , b
and 1 3 . I n t h e m e a s u r e m e n t o f g r a i n s i z e i t i s n e c e s s a r y t o u t i l i z e
t h e s e r v i c e s o f a s k i l l e d human o p e r a t o r i n o r d e r t o i n t e r p r e t t h e
s i z e measurement. U s i n g t h e mean t e x t u r a l i n d i c a t o r t h e d e c i s i o n
m i g h t be made b y t h e S h a p e A n a l y z e r . Thus, i n F i g u r e 12, a
c o r r e l a t i o n i s d e p i c t e d showing that gray l e v e l can correspond t o
g r a i n s i z e i n c a r e f u l l y prepared samples.
F i g u r e 13 s h o w s f o u r s t a g e s d u r i n g t h e s i n t e r i n g o f F e - C
compacts a t s u c c e s s i v e l y higher temperatures. A g a i n , t h e mean
t e x t u r e v a l u e c a n be u s e d a s a n i n d i c a t o r o f t h e s i n t e r i n g
temperature used i n t h e sample p r e p a r a t i o n .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
ex.
I
DO

5
m

a
D

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
16 PARTICLE SIZE DISTRIBUTION

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
1. BEDDOW Size, Shape, and Texture Analysis 17

material : sodium chloride


two-step processing. BM

60

50

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
18 PARTICLE SIZE DISTRIBUTION

T a b l e I I I . Shape C o m p o s i t i o n Changes f o r
Sodium C h l o r i d e

a
morphic g BM^
descriptor

L2(2) 49.80 65.94

L2(3) 6.92 14.08

L2(4) 31.53 8.16

Ruff 11.75 11.82

S indicates starting material.


'BM i n d i a t e s b a l l - m i l l i n g m a t e r i a l .

Table IVa. Morphic Features of Residual P o r o s i t y i n I r o n Compacts

Elongation Not- - R o u n d n e s s

Mean Std. Dev. Mean Std. Dev.

Atomized Iron 0.049 0.063 0.065 0.085

Sponge Iron 0.008 0.042 0.119 0.057

Table IVb. Morphic Properties of Speroidal Carbide P a r t i c l e s (n=


40) i n a F e r r i t e M a t r i x

Elongation Not-Roundness
2 2
(- ) (" )

Mean Std. Dev. Mean Std. Dev.

3.3 3.5 4.1 4.6

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
1. BEDDOW Size, Shape, and Texture Analysis 19

Includes r o t a t i o n , r e f l e c t i o n . Inversion 4 r o t a t i o n - r e f l e c t i o n

2^ ^ (m I , 2, 3, )
L (n)
2

2-fold r o t a t i o n a l symmetry 0 c 2 < 1


" 3-fold r o t a t i o n a l symmetry <c 3 S 1
- 4 - f o l d r o t a t i o n a l symmetry 0i c A i 1

REGULAR ELONGATED T R I A N G L E
TRIANGLE

C 2 - 013 C 2 - 055
C 3 - 0-99 - 02
c - 001
A C 4 - 0-2A
Inversion - 0*1A Inversion - 0*55
F i g u r e 9. Demonstration of the ing of the rotational symmetry.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
20 PARTICLE SIZE DISTRIBUTION

0.30-1

(24 56)

0.25-

CO

0.20

0.15

0.10 I 1 1
0.5 0.6 0.7 0.8 0.9
C2

F i g u r e 1 0 . S y m m e t r y C2 v s . s y m m e t r y C 3 . I l l u s t r a t i o n o f t h e u s e
o f r o t a t i o n a l shape symmetry i n d i f f e r e n t i a t i n g c o f f e e samples.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
In Particle Size Distribution; Provder, T.;
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 2 0 0 210 220 230 240 250

Gray level

ACS Symposium Series; American Chemical Society: Washington, DC, 1987.


F i g u r e 11. Tungsten carbide gray l e v e l d i s t r i b u t i o n , * i n d i c a t e s
t h e s h a r p n e s s o f t h e i m a g e ; K l a n d K2 a r e l i m i t s , t w o standard
thresholds apart.

to
22 PARTICLE SIZE DISTRIBUTION

NIUI 100X
too*
g Homlnil A ST M g Nominal ASTM
train tttt Ko. I rain altt Ho. f taln tltt
tapteimen h a t a calcu
l a t e d t r a i n t u t of f.Otl
t [men
men haa a ctlcu* w f
- . . m e n hi aajs > c a k u -
l a U d g r a i n a l s o of 10
l a l e d t r a i n sUt of t . t l )

F i g u r e 1 2 a . N o r m a l ASTM g r a i n s i z e m i c r o s t r u c t u r e . Reproduced
w i t h p e r m i s s i o n f r o m R e f . 7. C o p y r i g h t 1 9 7 2 A m e r i c a n S o c i e t y f o r
Metals.
100-

MEAN TEXTURE CRAY LEVEL

111

CO
10H
<
ce

" 1
120 14" r~ 200
100 160
180
GRAY LEVEL
F i g u r e 1 2 b . G r a i n s i z e v s . g r a y l e v e l f o r ASTM m i c r o s t r u c t u r e .
R e p r o d u c e d w i t h p e r m i s s i o n f r o m R e f . 7. C o p y r i g h t 1 9 7 2 A m e r i c a n
Society f o r Metals.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
1. BEDDOW Size, Shape, and Texture Analysis 23

i% *! f v 9 9 % H N O
1 powde
25% graphite, p r r w
1 ff per cu cm. sintered 30 m l n t t Increased to 1*00 1103 C l ,
1150 11010 C I . e i l f h t pea r i l l * m h le h rem) ted In combined carbon
formation t 0 1 0 % combined c a r - content of 0 7 5 % . an essentially e l l *
bon, remaining cur bo It graphite pcerllte structure, and a n Increase
Hi porea M a r k t. T r a n s verse-rupture In transverse-rupture s t r t n g t l i to
strength to 20.000 pel (DO M P f t l . 11,000 put I3S3 M P a ) .

ft

* ew 0 5% HNO, iOOX s % aUrti tu o s H H N O , aoox


m t ftt , M e e n d | W | 1AA1 Same M I60 to 1662 es-
1662 ** *** IUUO J | | . temperature
fept sintering temperature c f e n i e r

was Increased to 3150 (1177 C i .


n

wet Increased to 2050 (1131 C ) , This further Increased pari trie


which resulted In Increases In b o n d i n g , pore s p h e r o l d l r a l l n n :
t i d e bonding and pore spherol<Ir/l! t r a n s v e r s e - r u p t u r e s l r e n g l h In*
tlon. and a transverse-rupture creased to about 09.000 nl (OSS
Strength of 00.000 psl (133 M P a ) .
Combined carbon content* 0 7 3 % . M P a ) . Combined carbon. . ) % .

F i g u r e 13. I r o n powder m i c r o s t r u c t u r e . Reproduced w i t h p e r m i s s i o n


f r o m R e f . 7. C o p y r i g h t 1972 A m e r i c a n S o c i e t y f o r M e t a l s .

C o n t i n u e d on n e x t page

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
PARTICLE SIZE DISTRIBUTION

100H

10 I 1 1 1 1 1
1600 1900 2000 2100 2200 2300
SINTERING TEMPERATURE F
F i g u r e 13. C o n t i n u e d . Sintering temperature v s . gray l e v e l f o r
ASTM m i c r o s t r u c t u r e .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
1. BEDDOW Size, Shape, and Texture Analysis 25

Mixture Analysis* I t has a l w a y s been d i f f i c u l t t o a n a l y z e


p a r t i c u l a t e m a t e r i a l m i x t u r e s f o r a number o f r e a s o n s i n c l u d i n g t h e
l a r g e amount o f d a t a t h a t h a s t o be c o l l e c t e d a n d a n a l y z e d a n d a l s o
i n c l u d i n g t h e p r o p e r c h o i c e o f t h e many " d e g r e e o f m i x i d n e s s "
parameters a v a i l a b l e i n the l i t e r a t u r e . F i g u r e 14 s h o w s t h r e e s t a g e s
in the mixing of a binary mixture at p r o g r e s s i v e l y increasing mixing
t i m e s T^, T 2 , a n d T o . T h e p r o g r e s s o f t h e m i x i n g p r o c e s s i s f o l l o w e d
i n F i g u r e 15a,b, w h i c h shows a p l o t o f r o t a t i o n a l t e x t u r e symmetry
versus time.

Cancer and Normal C e l l s . Although a f a i r l y simple a n a l y s i s , the use


o f t h e mean a n d s t a n d a r d d e v i a t i o n o f t h e m o r p h o l o g i c a l t e x t u r e may
h a v e some s i g n i f i c a n c e . F i g u r e 16 s h o w s a n o r m a l c e l l a n d c a n c e r
c e l l p a t t e r o f a human l i v e r . The c o r r e s p o n d i n g m o r p h i c t e x t u r e
v a l u e s a r e shown i n T a b l e 5. I t i s c l e a r l y p o s s i b l e t o use t e x t u r e
analysis to differentiat betwee health d unhealth cells

Acknowledgments

The a u t h o r s a r e g r a t e f u l t o t h e N a t i o n a l S c i e n c e F o u n d a t i o n
P a r t i c u l a t e M o r p h o l o g y P r o c e s s i n g P r o g r a m , D r . M. O j a l v o , D i r e c t o r
f o r f i n a n c i a l s u p p o r t u n d e r g r a n t CPE 8 0 2 3 8 6 8 .

Appendix

Shape Analyzer

I. Classical Measurements o f P a r t i c l e s

A. Size
E q u i v a l e n t r a d i u s : mean e q u i v a l e n t r a d i u s , s t a n d a r d
deviation,
d i s t r i b u t i o n curve.
B. C l a s s i c a l Measures
P e r i m e t e r , Hausner shape f a c t o r s , M a r t i n s d i a m e t e r , F e r e t
d i a m e t e r , two d i m e n s i o n a l s p h e r i c i t y , r u g o s i t y .
II. Morphological Analysis

A. S h a p e
Not-roundness, L 2 ( 2 ) , L 2 ( 3 ) , L 2 ( 4 ) , roughness.
Mean a n d s t a n d a r d d e v i a t i o n o f t h e s e s h a p e f e a t u r e s ,
d i s t r i b u t i o n curve. Shape c o m p o s i t i o n .
( R , 0 ) ; (,) a n d ( R , S ) m e t h o d s o f a n a l y s i s .
B. I n t e r i o r Measures
P o r o s i t y - t o t a l a r e a , r e l a t i v e a r e a , pore s i z e d i s t r i b u t i o n ,
mean a n d s t a n d a r d d e v i a t i o n o f p o r e s i z e . Pore shape:
mean, s t a n d a r d d e v i a t i o n and d i s t r i b u t i o n o f shape
feature selected.
C. S h a p e S y m m e t r y M e a s u r e s
T w o - f o l d , 3 - f o l d , 4 - f o l d , r o t a t i o n a l symmetry. M i r r o r symmetry
and i n v e r s i o n .
D. T e x t u r e
Mean a n d s t a n d a r d d e v i a t i o n o f g r a y l e v e l o f i m a g e , t e x t u r e
symmetry, c o l o r a n a l y s i s and m i x t u r e a n a l y s i s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
PARTICLE SIZE DISTRIBUTION

T3 > T2 > Tl

Mixing

F i g u r e 14. Mixture of equal p a r t s of b l a c k and w h i t e particles


a f t e r times T^, T2 & T3.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
1. BEDDOW Size, Shape, and Texture Analysis 27

1n
0.8 H

CONTACT NUMBER x100


F i g u r e 1 5 a . The d e g r e e o f m i x i n g : symmetry i n d i c e s v s . c o n t a c t
number. The c o n v e r g e n c e p o i n t i n d i c a t e s c o m p l e t e m i x i n g . The
c o n t a c t number i n d i c a t e s t h e t o t a l number o f b l a c k - w h i t e t r a n s i t i o n s
i n a scan o f t h e f i e l d .

CO 20-

10-

0 i 1 1 1 1 r
0 20 40 60 80 100
CONTACT NUMBER xlOCf 1

F i g u r e 15b. Standard deviation v s . contact number.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Normal C e l l P a t t e r n Tumor C e l l P a t t e r n
F i g u r e 16. A normal c e l l and a cancer cell p a t t e r n o f a human
liver.

T a b l e V. S.D. a n d M.G.L. f o r D i f f e r e n t Cell Patterns

Normal C e l l Tumor Cell N o r m a l + Tumor Cell

S.D. 2 0 . 3 7 30.26 26.48


M.G.L. 123.4 101.60 115.70

S.D. : Standard Deviation


M.G.L.: Mean G r a y L e v e l

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
1. BEDDOW Size, Shape, and Texture Analysis 29

I I I . Fractual Analysis
Measure of the fractual of particles selected.

References
1. Beddow, J.K., Particulate Science and Technology, Chemical
Publishing Company, New York, 1980.
2. Beddow, J.K. (ed.), "Particle Characterization in Technology,"
CRC Press, Boca Raton, Florida, 1984.
3. Shape Technology Limited, "Shape Analyzer Handbook," March 1986.
4. Luerkens, D.W., Beddow, J.K. and Vetter, A . F . , "Invariant Fourier
Descriptors," Powder Technology, 31, 2, 217-220, 1982.
5. Luerkens, D.W., "Symmetr
be submitted to Particulate Science and Technology, an
International Journal.
6. Hsyung, Niey-Bor, MS Thesis, " Particle Texture Analysis,"
University of Iowa, 1984.
7. American Society for Metals, "Metals Handbook," Vol.7, 1972.
8. Beddow, J.K. In Powder Metallurgy and Related High Temperature
Materials; Ramakrishnan, Ed.; Oxford & IBH Publishing, New
Delhi, India, 1985.
RECEIVED July 21, 1986

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 2

Assessment of Particle Size Distribution and Spatial


Dispersion of Rubbery Phase in a Toughened Plastic
. Z. Jang and Y. S. Chang
Materials Science Program, Auburn University, AL 36849

A simplified statistica
has been proposed to describe the spatial
distribution of rubber particles in a plastic
matrix. Based on this scheme, a software package
compatible with a Hewlett-Packard personal computer
has been developed which i s capable of analyzing the
particle size distribution and spatial dispersion of
rubber particles in a toughened plastic. With
slight modification this package may be adapted to
other computer systems for studying the second-phase
morphology of any multiphase composite.
The normalized dispersion index (NDI) calculated
from the TEM micrographs by the image analysis
method appears to be a very sensitive index for
describing the spatial dispersion of rubber
particles in high impact polystyrene (HIPS) samples.
Materials with a small NDI (e.g., NDI < 0.142),
signaling a good dispersion of rubber particles in
the polystyrene matrix, appear to have the
capability of quickly and uniformly developing thick
crazes upon loading and thereby dissipating a great
amount of strain energy. The morphological
parameters obtained were correlated with the
microscopic crazing behavior and the macroscopic
mechanical properties. A stress f i e l d overlap
concept was proposed to explain the effects of
particle dispersion on the mechanical behavior of
HIPS. A general rubber-toughening theory was also
reviewed and discussed.

The technical and commercial success of high impact polystyrene


(HIPS) and (ABS) has led to a
widespread research program on the use of rubbers as toughening
agents for plastics. There is now an impressive l i s t of
rubber-toughened polymers including both amorphous and
0097-6156/87/0332-0030$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
2. JANG AND CHANG Spatial Dispersion of Rubbery Phase 31

s e m i c r y s t a l l i n e t h e r m o p l a s t i c s , and t h e r m o s e t t i n g r e s i n s . In a l l
o f these m a t e r i a l s , the aim i s to i n c r e a s e f r a c t u r e r e s i s t a n c e
w h i l e a t the same time p r e s e r v i n g the d e s i r a b l e p r o p e r t i e s o f the
parent polymer (J.) .
The r e l a t i o n s h i p s between s t r u c t u r e and p r o p e r t i e s o f
r u b b e r - m o d i f i e d polymers are complex because o f the l a r g e number
o f s t r u c t u r a l v a r i a b l e s i n v o l v e d ( 1 - 4 ) . The major s t r u c t u r a l
parameters t h a t are important i n a polymer with a g i v e n chemical
composition and m o l e c u l a r weight c h a r a c t e r i s t i c s are (a) rubber
c o n t e n t , (b) volume f r a c t i o n o f the d i s p e r s e d phase, (c) r u b b e r
p a r t i c l e s i z e d i s t r i b u t i o n , (d) degree o f c r o s s l i n k i n g o f the
r u b b e r , and (e) degree o f i n t e r f a c i a l a d h e s i o n between the
d i s p e r s e d and m a t r i x phases. One p o t e n t i a l l y important f a c t o r
t h a t has been l a r g e l y overlooked i s the s t a t e o f rubber p a r t i c l e
d i s p e r s i o n . P a r t i c l e d i s p e r s i o n w i l l a f f e c t the s t r e s s
d i s t r i b u t i o n i n the p l a s t i c m a t r i x and t h e r e f o r e w i l l determine
the mechanical behavior
y i e l d i n g g e n e r a l l y are b e l i e v e
energy a b s o r p t i o n when a toughened p l a s t i c i s m e c h a n i c a l l y loaded
(1,3-4). The i n i t i a t i o n and growth o f both c r a z e s and shear bands
are c r i t i c a l l y dependent upon the morphology o f the d i s p e r s e d
r u b b e r y phase. T h e r e f o r e , the a b i l i t y t o adequately c h a r a c t e r i z e
the complex morphology o f the rubbery phase i s o f g r e a t
importance. The development o f s u i t a b l e techniques has i n f a c t
p l a y e d an important p a r t i n the study o f s t r u c t u r e - p r o p e r t y
r e l a t i o n s h i p s , and hence i n improving and extending the range o f
toughened p r o d u c t s .
The p r i n c i p a l methods a v a i l a b l e f o r t a c k l i n g the phase
morphology c h a r a c t e r i z a t i o n problems are o p t i c a l and e l e c t r o n
m i c r o s c o p y , l i g h t s c a t t e r i n g , and C o u l t e r Counter (_1). I f the
rubber p a r t i c l e s are l a r g e enough t o be r e s o l v e d , o p t i c a l
m i c r o s c o p y i s the s i m p l e s t and cheapest method f o r s t u d y i n g
morphology. However, the most s u c c e s s f u l method f o r s t u d y i n g
morphology i n rubber-toughened p l a s t i c s has been the
osmium-staining method developed by Kato ( 5 - 7 ) ; the method being
a p p l i c a b l e t o polymers c o n t a i n i n g u n s a t u r a t e d r u b b e r s . For t h o s e
m a t e r i a l s c o n t a i n i n g rubbers t h a t cannot be s t a i n e d s u c c e s s f u l l y
the technique o f l i g h t s c a t t e r i n g might be u s e f u l (8-10). For
polymers t h a t can be d i s s o l v e d i n an e l e c t r o l y t e , C o u l t e r Counter
may be used t o measure p a r t i c l e s i z e s ( i n the range 0.5 t o 400
jum) ( J ! ) . The method i s w e l l s u i t e d t o measuring the r e l a t i v e l y
l a r g e p a r t i c l e s i n HIPS. S m a l l e r p a r t i c l e s tend to escape the
d e t e c t i o n o f C o u l t e r Counter. F u r t h e r , the s p a t i a l d i s p e r s i o n o f
rubber p a r t i c l e s cannot be r e v e a l e d by t h i s method. However, t h i s
method has the advantages o f r e a d i l y p e r m i t t i n g a l a r g e sampling
space as well as i n d i c a t i n g both p a r t i c l e s i z e and d i s p e r s i t y o f
the d i s t r i b u t i o n .
Presented i n t h i s paper are the r e s u l t s o f an i n v e s t i g a t i o n
c o n c e r n i n g the l i n k between s t r u c t u r e and p r o p e r t i e s o f
rubber-toughened p l a s t i c s . An attempt has been made t o a s s e s s the
importance o f the s p a t i a l d i s t r i b u t i o n o f rubber p a r t i c l e s i n
terms o f t h e i r e f f e c t i v e n e s s i n c o n t r o l l i n g c r a z e i n i t i a t i o n and
growth. A l s o s t u d i e d i n p a r t i c u l a r were the e f f e c t s o f rubber
p a r t i c l e s i z e on the mechanical p r o p e r t i e s o f HIPS m a t e r i a l s . A

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
32 PARTICLE SIZE DISTRIBUTION

computerized image a n a l y s i s and TEM t e c h n i q u e s were u t i l i z e d t o


c h a r a c t e r i z e the r u b b e r y phase morphology. A s o f t w a r e package
based on BASIC language has been developed t h a t i s c a p a b l e o f
a n a l y z i n g the average p a r t i c l e s i z e , s i z e d i s t r i b u t i o n , volume
f r a c t i o n o f p a r t i c l e s , and the degree o f p a r t i c l e d i s p e r s i o n i n a
m a t r i x . A l t h o u g h s p e c i f i c a l l y d e s i g n e d f o r the Hewlett Packard
Model 9836 p e r s o n a l computer, t h i s package may be r e a d i l y m o d i f i e d
to be used i n o t h e r computer systems.
Degree o f D i s p e r s i o n o f Rubber P a r t i c l e s
Gurland (12) has developed a q u a n t i t a t i v e m i c r o s c o p y scheme f o r
measuring the degree o f d i s p e r s i o n o f a g g r e g a t e s . The s t a t e o f
a g g r e g a t i o n o f a c o n s t i t u e n t o f a heterogeneous m u l t i p h a s e
m a t e r i a l may be d e s c r i b e d a s b e i n g d i s p e r s e d , agglomerated, o r
c o n t i n u o u s . Such term r e f e t th degre f d i s p e r s i o n which
is quantitatively relate
interface of separation, ,
p a r t i c l e s w i t h i n the m a t r i x (JL2).
S u r f a c e o f s e p a r a t i o n . Where volume f r a c t i o n o f the d i s p e r s e d
phase i s h i g h so t h a t the a r e a o f c o n t a c t between c o n t i g u o u s
p a r t i c l e s o f the second phase i s u n n e g l i g i b l e the e x t e n t o f the
s u r f a c e o f s e p a r a t i o n between the second phase and the m a t r i x has
to be c o n s i d e r e d i n measuring the degree o f d i s p e r s i o n . For a
two-phase composite the degree o f s e p a r a t i o n dp i s d e f i n e d a s :
Sv(ab) Sv(ab)
dp = = (1)
Sv(aa) + Sv(ab) Sv(total)
where Sv(ab) i s the a r e a o f the i n t e r f a c e between p a r t i c l e s o f the
p a r t i c u l a t e phase and the m a t r i x , and Sv(aa) i s the a r e a o f
c o n t a c t between c o n t i g u o u s p a r t i c l e s o f the p a r t i c u l a t e phase i n a
volume. The v a l u e o f dp may be determined from i n t e r c e p t s o f
random l i n e s and i n t e r n a l s u r f a c e s ( 1 2 ) :
NL(ab)
dp = (2)
NL(ab) + 2NL(aa)
where NL(ab) = average number o f i n t e r s e c t i o n w i t h p a r t i c u l a t e -
m a t r i x i n t e r f a c e per u n i t l e n g t h o f a random t e s t l i n e , and NL(aa)
= t h a t w i t h p a r t i c l e - p a r t i c l e i n t e r f a c e . The d e t e r m i n a t i o n o f
c o n t i g u i t y o r degree o f d i s p e r s i o n does not r e q u i r e any
assumptions r e g a r d i n g volume f r a c t i o n , p a r t i c l e s i z e , o r p a r t i c l e
shape. However, due t o the g e n e r a l l y d i s c r e t e n a t u r e o f the
rubbery phase i n a t y p i c a l toughened p l a s t i c such as HIPS t h e r e
e x i s t s e s s e n t i a l l y no c o n t i g u i t y between r u b b e r p a r t i c l e s , i . e . ,
dp ~ 1.
F i n e n e s s . The a r e a o f the i n t e r f a c e between a p a r t i c u l a t e phase
and the m a t r i x i s a f u n c t i o n o f the p a r t i c l e s i z e , s i n c e p a r t i c l e
s i z e and s p e c i f i c s u r f a c e a r e i n v e r s e l y r e l a t e d . The u l t i m a t e

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
2. JANG AND CHANG Spatial Dispersion of Rubbery Phase 33

l e v e l o f d i s p e r s i o n i s determined by the f i n e n e s s which i s u s u a l l y


s p e c i f i e d by the average p a r t i c l e s i z e and the s i z e d i s t r i b u t i o n
f u n c t i o n . The data on f i n e n e s s may, t h e r e f o r e , be o b t a i n e d from
C o u l t e r Counter measurements o r image a n a l y s i s i n the case o f
toughened p l a s t i c s . The computer programs developed i n our l a b
p r o v i d e a c o n v e n i e n t t o o l t o a n a l y z e the p a r t i c l e f i n e n e s s i n
terms o f p a r t i c l e r a d i u s , a r e a , and p e r i m e t e r .
S p a t i a l D i s t r i b u t i o n . As suggested by Gurland ( 2 ) , a q u a n t i t a t i v e
measure o f the degree o f homogeneity o f p a r t i c l e placement i n the
m a t r i x i s the s t a n d a r d d e v i a t i o n o f the d i s t r i b u t i o n o f p a r t i c l e s
i n small volumes o r areas o f the m i x t u r e :

(3)

Where Nvi i s the observe


the i t h sample and Tfv i s the a r i t h m e t i c mean number o f p a r t i c l e s
i n samples. (The index i r e f e r s t o the i t h sample i n a s e t o f
samples, and not t o the p a r t i c l e s i z e c l a s s ) . Maximum homogeneity
i s c h a r a c t e r i z e d by a minimum s t a n d a r d d e v i a t i o n . If on the

o t h e r hand, s p e c i a l s e p a r a t i n g o r a g g l o m e r a t i n g t e n d e n c i e s e x i s t
among the p a r t i c l e s , the v a l u e o f w i l l be l a r g e .

In p r a c t i c e , the s t a n d a r d d e v i a t i o n v a l u e s are determined


from the observed p a r t i c l e d i s t r i b u t i o n i n small areas o f
m e t a l l o g r a p h i c a l l y prepared random s e c t i o n s through the m u l t i p h a s e
sample. In s t u d y i n g HIPS morphology, t h i n s e c t i o n s were
u l t r a m i c r o t o m e d from 0 s 0 - s t a i n e d samples a t random l o c a t i o n s and
4

o r i e n t a t i o n s . A minimum o f 20 t r a n s m i s s i o n e l e c t r o n micrographs
were taken from each sample and a n a l y z e d . Because the
u n d e r s t a n d i n g o f the l i n k between the p a r t i c l e d i s p e r s i o n s t a t e
and c r a z i n g i s i m p o r t a n t , the use o f the rubber p a r t i c l e volume
f r a c t i o n VFi per u n i t volume o f the i t h sample, i n s t e a d o f N v i , as
an index seems t o be more a p p r o p r i a t e . T h e r e f o r e , E q u a t i o n 3 may
be r e p l a c e d by:

(4)
where VF i s the a r i t h m e t i c mean volume f r a c t i o n o f rubber
p a r t i c l e s i n samples. In two dimensions (such as i n TEM
p h o t o g r a p h s ) , a c o n v e n i e n t d i s p e r s i o n index (DI) may be d e f i n e d
as:

(5)
where A F i i s the area f r a c t i o n o f rubber p a r t i c l e s i n the i t h
micrograph and AF i s the average area f r a c t i o n i n micrographs.
A small v a l u e o f 6 w i l l r e p r e s e n t a u n i f o r m d i s p e r s i o n o f rubber
A F

p a r t i c l e s and i s g e n e r a l l y a p r e f e r r e d m o r p h o l o g i c a l f e a t u r e . In
o r d e r t o a l l o w f o r comparison between two m a t e r i a l s t h a t may have
d i f f e r e n t average p a r t i c l e s i z e s and p a r t i c l e volume f r a c t i o n s ,
the experimental s t a n d a r d d e v i a t i o n <5 may be compared w i t h a
AF

t h e o r e t i c a l s t a n d a r d d e v i a t i o n <s* o f some randomly d i s t r i b u t e d

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
34 PARTICLE SIZE DISTRIBUTION

arrangement o f the p a r t i c l e s a s , f o r i n s t a n c e , the binomial and


P o i s s o n ' s d i s t r i b u t i o n . The r a t i o ( f y p - *)/* approaches z e r o
as the mixture approaches a random d i s t r i b u t i o n . S i n c e 6* f o r
each HIPS m a t e r i a l i s not r e a d i l y a v a i l a b l e , a u s e f u l n o r m a l i z e d
d i s p e r s i o n index (NDI) may be used i n s t e a d :
6
NDI = AF/AF (6)
A s m a l l e r v a l u e o f NDI would i n d i c a t e a b e t t e r s p a t i a l
distribution o f particles.
Experimental Methods
M a t e r i a l s . The m a t e r i a l s used i n the p r e s e n t study i n c l u d e both
commercial and experimental grades o f HIPS. A l a r g e number o f
m a t e r i a l s c o v e r i n g a wide range o f rubbery phase morphologies were
investigated.
T e n s i l e Deformation. An ASTM s t a n d a r d t e n s i l e t e s t was conducted
to understand the general t e n s i l e b e h a v i o r o f each sample. The
specimens were s t r e t c h e d up t o f r a c t u r e . The c r a z i n g p a t t e r n o f
each f r a c t u r e d specimen was s t u d i e d f o l l o w i n g the s t a n d a r d
procedure o f OsO* s t a i n i n g , u l t r a m i c r o t o m i n g , and TEM
i n v e s t i g a t i o n . A l l the samples were s u b j e c t e d t o d i f f e r e n t degrees
o f p l a s t i c d e f o r m a t i o n because t h e i r e l o n g a t i o n s a t break fcb) a r e
not i d e n t i c a l . T h e r e f o r e , a s e n s i b l e comparison may not be made
between the c r a z i n g p a t t e r n s o f two d i f f e r e n t samples.
To overcome t h i s d i f f i c u l t y , the s t r a t e g y was v a r i e d
s l i g h t l y . The specimens were each p u l l e d up t o 15% s t r a i n and then
a l l o w e d t o s t r e s s r e l a x a t t h i s f i x e d e l o n g a t i o n i n the I n s t r o n
u n i v e r s a l t e s t i n g machine. T h i s would p e r m i t a more mature
c r a z i n g degree and reduce the e x t e n t o f c r a z e r e c o v e r y upon
r e l e a s e o f the l o a d . S i n c e each specimen has been e l o n g a t e d t o
the same 15% s t r a i n , the d i f f e r e n c e i n c r a z i n g p a t t e r n may be
a s c r i b e d t o a v a r i a t i o n i n s t r u c t u r a l parameter(s) r a t h e r than i n
testing conditions.
Q u a n t i t a t i v e Image A n a l y s i s . A software package compatible w i t h a
HP p e r s o n a l computer (Model 9836) has been developed t o a s s e s s the
morphology o f rubber p a r t i c l e s i n HIPS. The package i s c a p a b l e o f
a n a l y z i n g the f o l l o w i n g i n f o r m a t i o n :

1. Average p a r t i c l e s area ( A ) , i t s s t a n d a r d d e v i a t i o n ( ) , and
p a r t i c l e area histogram ( p a r t i c l e s i z e d i s t r i b u t i o n based on
area); _
6
2. Average p a r t i c l e r a d i u s ( R ) , i t s s t a n d a r d d e v i a t i o n ( R) and 9

p a r t i c l e r a d i u s histogram; and
6
3. Average p a r t i c l e area f r a c t i o n AF, s t a n d a r d d e v i a t i o n ( A F ) ,
and n o r m a l i z e d d i s p e r s i o n index (NDI).
I n f o r m a t i o n d e r i v e d from (1) and (2) would i n d i c a t e i f the
p a r t i c l e s i z e s are uniform_or not. A small <SA ( o r more a c c u r a t e l y
<SA/A) and small 6R ( o r <$R/R) i n g e n e r a l imply a narrower s i z e
d i s t r i b u t i o n o r more u n i f o r m p a r t i c l e s i z e s . The s t a n d a r d
d e v i a t i o n <SAF ( o r 6AF/AF) i s an index o f the "goodness" o f
p a r t i c l e d i s p e r s i o n o r the s p a t i a l d i s t r i b u t i o n o f p a r t i c l e s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
2. JANG AND C H A N G Spatial Dispersion of Rubbery Phase 35

The n o r m a l i z e d d i s p e r s i o n index NDI was c a l c u l a t e d from the data


o f t h e p a r t i c l e a r e a f r a c t i o n i n each TEM micrograph ( a t l e a s t
twenty photographs were taken from d i f f e r e n t s i t e s i n a sample).
A s m a l l e r magnitude o f (SAF/F) i m p l i e s a more homogeneous
d i s p e r s i o n o f rubber p a r t i c l e s .

U l t r a m i c r o t o m y and T r a n s m i s s i o n E l e c t r o n M i c r o s c o p y (TEM). Small


specimens (5 mm 3 mm 3 mm f o r s h o r t ones and 8 mm 3 mm 3
mm f o r l o n g ones) were c u t from both t e n s i l e deformed and
undeformed samples. S h o r t specimens were c u t w i t h the l e n g t h
p e r p e n d i c u l a r and the microtoming d i r e c t i o n p a r a l l e l t o the
t e n s i l e t e s t i n g d i r e c t i o n . S i n c e c r a z e s grow l a t e r a l l y i n a
d i r e c t i o n normal t o the p r i n c i p a l s t r e s s and the a r e a l dimensions
o f c r a z e s a r e r e l a t i v e l y l a r g e , the microtomed l a y e r s s h o u l d
c o n t a i n many c r a z e c r o s s - s e c t i o n s . C o n t r a r i l y , v e r y few c r a z e s
may be seen i n the t h i n s e c t i o n s microtomed from the l o n g
specimens where the s e c t i o n i n
p l a n e s . T h i s i s becaus
f o r the k n i f e t o t r a v e r s e through the c r a z e i f the c r a z e p l a n e s
a r e p e r f e c t l y p a r a l l e l t o the movement d i r e c t i o n o f k n i f e .
A l l the specimens were immersed i n 0 s 0 s o l u t i o n (1 gram i n
4

100 ml water) f o r a t l e a s t one week t o harden the r u b b e r p a r t i c l e s


( t o reduce the microtoming d i s t o r t i o n ) and t o g i v e the n e c e s s a r y
e l e c t r o n c o n t r a s t d u r i n g TEM i n v e s t i g a t i o n . A P h i l l i p s EM-300 TEM
was used throughout t h i s s t u d y .

Results
Rubbery Phase Morphology and Image A n a l y s i s . A t y p i c a l r u b b e r y
phase morphology o f HIPS i s shown i n F i g u r e 1, where the dark
membrane i n the more o r l e s s s p h e r i c a l p a r t i c l e s i s the
osmium-stained p o l y b u t a d i e n e (PB) phase w i t h the p o l y s t y r e n e (PS)
o c c l u s i o n s b e i n g white c o l o r w h i l e the m a j o r i t y , c o n t i n u o u s phase
i s the PS m a t r i x . The r u b b e r y phase morphology o f HIPS has been
s t u d i e d e x t e n s i v e l y (J.). The importance o f rubber p a r t i c l e s i z e
i n c o n t r o l l i n g the toughness o f r u b b e r - m o d i f i e d polymers has been
r e c o g n i z e d f o r some time (13-30). For each type o f m a t e r i a l ,
t h e r e appears t o e x i s t an optimum p a r t i c l e s i z e f o r t o u g h e n i n g .
The p r e f e r r e d average p a r t i c l e s i z e i n HIPS was b e l i e v e d t o be 0.8
jum (JL). However, our c u r r e n t data i n d i c a t e t h a t a number average
p a r t i c l e d i a m e t e r o f 1.05 urn and 0.5 xim appear t o be a p r e f e r r e d
s i z e f o r HIPS and rubber-toughened p o l y p r o p y l e n e ( P P ) ,
r e s p e c t i v e l y . The morphology o f the r u b b e r y phase i n a toughened
PP appears t o be l e s s complex, as e v i d e n c e d i n F i g u r e 2 where the
d a r k , a l s o osmium-stained, phase i s the s t y r e n e - b u t a d i e n e r u b b e r
(SBR) p a r t i c l e s . No PP o c c l u s i o n s were found i n t h i s m a t e r i a l
s i n c e i t i s a p h y s i c a l b l e n d o f SBR and PP.
A t y p i c a l image a n a l y s i s o u t p u t i s p r e s e n t e d i n F i g u r e 3
which not o n l y shows g r a p h i c a l l y the p a r t i c l e s i z e h i s t o g r a m but
a l s o g i v e s the numerical d a t a o f average p a r t i c l e dimensions i n a
photograph; F i g u r e 3a i n d i c a t i n g the i n f o r m a t i o n on p a r t i c l e
r a d i u s w h i l e F i g u r e 3b on a r e a i n two d i m e n s i o n s . Data from
a n a l y z i n g a l a r g e number o f photographs may a l s o be merged
t o g e t h e r t h a t would l e a d t o a more r e l i a b l e s t a t i s t i c a l r e s u l t .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
PARTICLE SIZE DISTRIBUTION

F i g u r e 1. T y p i c a l morphology o f high impact p o l y s t y r e n e ,


(a) HIPS-N, NDI=.161, poor d i s p e r s i o n , (b) HIPS-P, NDI=.079,
better dispersion.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
2. JANG AND C H A N G Spatial Dispersion of Rubbery Phase 37

F i g u r e 2. Rubbery phase morphology o f a toughened


polypropylene.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
38 PARTICLE SIZE DISTRIBUTION

T O T R L P R R T I C L E [ N O . : 103
B V E R R G E OF R R D I U 5 : .2960327 (MICRON)
STRNDRRD D E V I R T I O N : .2004267

8
.8183 .151 .284 .41? .55 .683 .815 .948 1.88 1.21 1.35

RRDIUS (MICRON )

PRRTICLE FRRCTION : 2 0 . 5 6 %
.3 h T O T A L P R R T I C L E N O . : 103
R V E R R G E OF R R E R : . 4 0 1 5 15 1 ( M I C R O N S )
.8 STRNDRRD D E V I R T I O N : .5589488

.7

.6 [-

.5 -

.4 -

.3 -

8
.88106 .571 1.14 1.71 2.28 2.85 3.42 3.99 4.56 5.13

RRER (MICRONS)

F i g u r e 3. A t y p i c a l image a n a l y s i s output, (a) P a r t i c l e


r a d i u s d i s t r i b u t i o n , ( b ) P a r t i c l e area d i s t r i b u t i o n .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
2. JANG AND CHANG Spatial Dispersion of Rubbery Phase 39

The v a l u e s o f NDI p r e s e n t e d are g e n e r a l l y a cumulated r e s u l t o f


20 photographs ( e . g . , i n F i g u r e 4 ) .
The t o t a l rubber p a r t i c l e area f r a c t i o n i n each randomly
s e l e c t e d l o c a t i o n can be measured ( F i g u r e 3b, e . g . ) . P h y s i c a l l y ,
i f the rubber p a r t i c l e s a r e u n i f o r m l y o r randomly d i s p e r s e d i n a
p l a s t i c m a t r i x , then the measured p a r t i c l e a r e a f r a c t i o n would
v a r y v e r y l i t t l e w i t h the l o c a t i o n s e l e c t e d . As a consequence,
the d i s p e r s i o n index c a l c u l a t e d would be r e l a t i v e l y s m a l l . I f , on
the c o n t r a r y , the p a r t i c l e s tend t o aggregate o r c l u s t e r t o g e t h e r ,
then the p a r t i c l e area f r a c t i o n i s expected t o be l a r g e i n the
l o c a t i o n c o n t a i n i n g c l u s t e r s and small i n the r e g i o n c o n t a i n i n g
o n l y i s o l a t e d p a r t i c l e s . A high degree o f l o c a t i o n dependence o f
p a r t i c l e area f r a c t i o n should lead to a r e l a t i v e l y large
d i s p e r s i o n index. As shown i n F i g u r e l a f o r HIPS Sample-N, some
zones a r e crowded w i t h c l o s e l y spaced p a r t i c l e s w h i l e the o t h e r s
e s s e n t i a l l y f r e e o f p a r t i c l e s ; the n o r m a l i z e d d i s p e r s i o n index
(NDI) being 0.161. In c o n t r a s t
morphology o f Sample-P ( F i g u r
The s e n s i t i v i t y o f the NDI t e c h n i q u e has been f a i r l y w e l l
demonstrated i n s e v e r a l o t h e r samples as w e l l . The image a n a l y s i s
data o f 15 HIPS samples c o v e r i n g a wide v a r i e t y o f morphologies
a r e summarized i n T a b l e 1.

R e l a t i o n s h i p Between C r a z i n g and Rubbery Phase Morphology. Two


d i s t i n c t types o f c r a z i n g b e h a v i o r have been i d e n t i f i e d . The
c r a z e s i n HIPS- ( F i g u r e 5) a r e i n g e n e r a l t h i c k e r than those i n
HIPS-B ( F i g u r e 6 ) . In both m a t e r i a l s the c r a z e s are r e l a t i v e l y
t h i c k near the c r a z e - r u b b e r i n t e r f a c e . The t h i c k n e s s d e c r e a s e s
v e r y r a p i d l y i n HIPS-B as the c r a z e grows l a t e r a l l y away from the
p a r t i c l e s u r f a c e . In HIPS-, the c r a z e t h i n s down a t a much
slower r a t e . In both m a t e r i a l s , c r a z e s i n c e r t a i n areas a r e
t h i c k e r than i n o t h e r s . When the i n t e r p a r t i c l e s p a c i n g s are s h o r t
the c r a z e s tend t o d e v e l o p t o a more mature s t a g e . N u c l e a t i o n o f
c r a z e s appears t o s t a r t e a r l i e r i n A than i n B. Image a n a l y s i s
r e s u l t s ( T a b l e 1) i n d i c a t e t h a t A posesses a s m a l l e r average
p a r t i c l e s i z e and a b e t t e r d i s p e r s i o n o f p a r t i c l e s than B.
D e s p i t e having a l a r g e r Young's modulus, l i k e l y due t o a s m a l l e r
volume f r a c t i o n o f rubbery phase, HIPS- i s s u p e r i o r i n impact
r e s i s t a n c e . The l a t t e r p r o p e r t y seems t o be due t o a b e t t e r
rubbery phase morphology t h a t i s c a p a b l e o f r a p i d l y d e v e l o p i n g a
g r e a t number o f t h i c k c r a z e s , thus d i s s i p a t i n g a g r e a t deal o f
s t r a i n energy, b e f o r e a c a t a s t r o p h i c c r a c k i n t e r v e n e s . An
e x t e n s i v e m o r p h o l o g i c a l and c r a z i n g s t u d y i n d i c a t e d t h a t a HIPS
sample w i t h an NDI g r e a t e r than .142 seems t o l o s e i t s a b i l i t y t o
q u i c k l y accomodate a g r e a t c r a z e d volume, r e s u l t i n g i n an i n f e r i o r
impact r e s i s t a n c e . These o b s e r v a t i o n s may be e x p l a i n e d i n l i g h t
o f the s t r e s s c o n c e n t r a t i o n requirements f o r c r a z e i n i t i a t i o n and
the concept o f s t r e s s f i e l d o v e r l a p between nearby p a r t i c l e s . A
poor d i s p e r s i o n o f rubber p a r t i c l e s may l e a d t o p l a s t i c s t r a i n
l o c a l i z a t i o n , unfavorable f o r uniform formation of crazes. Stress
f i e l d o v e r l a p between two nearby small p a r t i c l e s , which
i n d i v i d u a l l y may not p r o v i d e a s u f f i c i e n t volume o f
s t r e s s - e n h a n c e d zone ( 2 8 ) , may form a f a v o r a b l e c r a z e - i n i t i a t i o n
c o n d i t i o n (13,14).

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
40 PARTICLE SIZE DISTRIBUTION

TOTRL P R R T I C L E NO. : 3146


.9
RVERRGE OF R R D I U S : . 2 9 0 3 8 2 (MICRON )
S T R N D R R D D E V I R T I O N OF R R D I U S : .1915939
.8

6 h

m .s h

g .4
Q.
a


8
8 .135 .269 .484 .539 .6?3 .688 1.88
.943 1.21 1.35
RRDIUS (MICRON )

PRR1ICLE FRRCTION : 22.03


S T R N D R R D D E V I R T I O N OF F R A C T I O N : 3 . 3 5 5
( D I S P E R S I O N INDEX )
TOTRL P R R T I C L E NO. : 3146
R V E R R G E O F FiRERz .3802267 (MICRONS)
S T R N D R R D D E V I R T I O N O F BREBi .5406517

CO .5
CL

g .4
CL

.3 |-

.2 -

.1 I-

88 .5? 1.14 l . ? l 2.28 2.85 3.423.99 4.56 5.13 5.?


RRER (MICRONS)

F i g u r e 4. Cumulated image a n a l y s i s r e s u l t s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
2. J A N G AND CHANG Spatial Dispersion of Rubbery Phase 41

Table I. P a r t i a l l i s t o f image a n a l y s i s data

Sample A,um2 A R,um R Af,% NDI

A .4133 .6127 .3014 .2018 24.46 .139


.3802 .5407 .2904 .1916 22.03 .152
C 1.5000 2.6592 .5311 .4420 35.39 .195
D .8342 1.4010 .4010 .3236 26.98 .143
.4931 .6436 .3410 .2017 23.54 .151
F .5510 .7844 .3510 .2285 21.91 .079
G .3802 .5407 .2904 .1916 22.03 .152
H .4296 .6183 .3118 .1988 23.35 .106
I .5161 .7217 .3431 .2158 23.02 .117
J .5304 .770
1.1913 1.764
L .7277 1.1635 .3946 .2756 25.87 .183
M 1.0407 1.9200 .4627 .3423 29.80 .205
1.106 .9534 .5445 .2357 22.70 .161
.306 .6010 .236 .2040 30.53 .079

The p r e v i o u s o b s e r v a t i o n s were drawn on t h e b a s i s o f a l a r g e


number o f HIPS samples i n c l u d i n g small and l a r g e average p a r t i c l e
s i z e , narrow and broad p a r t i c l e d i s t r i b u t i o n , and homogeneous and
heterogeneous d i s p e r s i o n . One group o f samples were s i m p l y
d i l u t e d from t h e o t h e r s by p h y s i c a l l y b l e n d i n g t h e p a r e n t polymers
w i t h PS homopolymers. The m a t e r i a l s c o v e r many d i f f e r e n t grades
from v a r i o u s s o u r c e s as w e l l as a s e r i e s o f experimental grades
prepared i n t h e l a b o r a t o r y . Both impact loaded and t e n s i l e t e s t e d
samples were i n v e s t i g a t e d . They appear t o g i v e c o n s i s t e n t
results.
Discussion
A combination o f mechanical t e s t i n g , e l e c t r o n m i c r o s c o p y , and t h e
computer-aided image a n a l y s i s has been shown t o be a powerful t o o l
f o r t h e study o f s t r u c t u r e - p r o p e r t y r e l a t i o n s h i p s i n toughened
p l a s t i c s . Examples were p r o v i d e d t o h i g h l i g h t t h e importance o f
the s p a t i a l d i s p e r s i o n o f rubber p a r t i c l e s when c o n s i d e r i n g t h e
mechanical b e h a v i o r o f a toughened p l a s t i c . A l s o demonstrated was
the f e a s i b i l i t y o f a p p l y i n g t h e image a n a l y s i s t e c h n i q u e t o a s s e s s
the s t a t e o f p a r t i c l e d i s p e r s i o n i n a m u l t i p h a s e composites.
The b a s i c mechanism o f rubber toughening i n HIPS polymers may
be summarized as f o l l o w s . In t h e e a r l y stage o f a t e n s i l e t e s t
the a p p l i e d l o a d i s borne m a i n l y by t h e m a t r i x and i s c o n c e n t r a t e d
a t t h e equators o f t h e rubber p a r t i c l e s . The rubber p a r t i c l e s a c t
as s t r e s s c o n c e n t r a t i o n s i t e s and cause t h e i n i t i a t i o n o f a l a r g e
number o f c r a z e s which l e a d s t o a y i e l d p o i n t w i t h t h e a s s o c i a t e d
s t r e s s w h i t e n i n g . These c r a z e s propagate i n t o t h e m a t r i x i n a
d i r e c t i o n perpendicular to the applied s t r e s s , thereby engulfing a
number o f rubber p a r t i c l e s o r being r e t a r d e d / t e r m i n a t e d by

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
PARTICLE SIZE DISTRIBUTION

F i g u r e 5. A uniform d i s t r i b u t i o n o f t h i c k c r a z e s n u c l e a t e d
from a good d i s p e r s i o n o f rubber p a r t i c l e s . Large number o f
crazes.

F i g u r e 6. A nonhomogeneous d i s t r i b u t i o n o f t h i n c r a z e s .
S m a l l e r number o f c r a z e s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
2. JANG AND C H A N G Spatial Dispersion of Rubbery Phase 43

n e i g h b o r i n g p a r t i c l e s . During c r a z e p r o p a t a t i o n , t h e
r u b b e r - m a t r i x adhesion i s o f c r i t i c a l importance i n s u s t a i n i n g
t r i a x i a l t e n s i o n and d e l a y i n g t h e breakdown o f c r a z e s t o produce
c r a c k s . Thus, t h e f u n c t i o n o f rubber p a r t i c l e s i s t o i n i t i a t e
c r a z e s and then t o s t a b i l i z e t h e growing c r a z e which a l l o w s
a d d i t i o n a l c r a z e s t o be i n i t i a t e d i n t h e s u r r o u n d i n g m a t e r i a l . In
o r d e r t o toughen t h e b r i t t l e m a t r i x m a t e r i a l s u c c e s s f u l l y , a
uniform d i s p e r s i o n o f t i g h t l y bonded rubber p a r t i c l e s i s r e q u i r e d .
T h i s can be a c h i e v e d i n t h e p o l y m e r i z a t i o n process by making
c e r t a i n t h a t t h e rubber phase i s a d e q u a t e l y g r a f t e d t o t h e m a t r i x
material.
To ensure high impact r e s i s t a n c e t h e rubber p a r t i c l e s must be
capable o f q u i c k l y n u c l e a t i n g and c o n t r o l l i n g c r a z e s t o a c h i e v e a
maximized c r a z e d volume b e f o r e a c a t a s t r o p h i c c r a c k propagates.
T h i s i s because impact t e s t i n g i n v o l v e s v e r y high deformation
r a t e . That HIPS m a t e r i a l s l i k e Sample- tend t o e a s i l y develop
thicker crazes o r the thickenin
stage i n deformation tha
accommodating a g r e a t e r amount o f c r a z e d volume. The good
d i s p e r s i o n o f small rubber p a r t i c l e s may be r e s p o n s i b l e f o r t h i s
e f f i c i e n t use o f rubbery phase. F u r t h e r , t h e i n t e r f a c i a l adhesion
seems t o be adequate t o help t h e rubber p a r t i c l e s s u s t a i n t h e
triaxial stress f i e l d .
In o r d e r t o e x p l a i n t h e p a r t i c l e d i s p e r s i o n dependence o f t h e
mechanical b e h a v i o r o f HIPS, one h y p o t h e s i s i s h e r e i n proposed
which i s based on t h e s t r e s s f i e l d o v e r l a p concept. Matsuo e t
a l . (34) s t u d i e d t h e c r a z i n g b e h a v i o r o f p o l y s t y r e n e samples
c o n t a i n i n g two rubber b a l l s o f t h e same diameter w i t h v a r y i n g
s e p a r a t i o n . The samples were s u b j e c t e d t o simple t e n s i o n , and
t h e i r c r a z i n g b e h a v i o r was observed. When t h e two b a l l s were
p l a c e d c l o s e t o g e t h e r , t h e c r a z e - i n i t i a t i o n s t r e s s was
c o n s i d e r a b l y lower than t h a t o f s i n g l e - b a l l samples. With an
i n c r e a s e i n t h e d i s t a n c e between two b a l l s t h e c r a z e - i n i t i a t i o n
s t r e s s i n c r e a s e s a t f i r s t almost l i n e a r l y and l e v e l s o f f when 1/d
reaches about 1.45, where 1 and d a r e t h e c e n t e r - t o - c e n t e r
d i s t a n c e and t h e diameter o f t h e b a l l s , r e s p e c t i v e l y . When 1 i s
s u f f i c i e n t l y s m a l l , t h e c r a z e s a r e seen t o develop e x t e n s i v e l y a t
the i n n e r s u r f a c e s o f t h e b a l l s and f i n a l l y b r i d g e w i t h each
o t h e r . The c r a z e s b r i d g e d between t h e b a l l s expand l a r g e l y i n t h e
plane p e r p e n d i c u l a r t o t h e a p p l i e d l o a d .
T h i s study (34) i m p l i e s t h a t a r i g h t d i s p e r s i o n o f rubber
p a r t i c l e s may permit optimum s t r e s s f i e l d o v e r l a p t h a t a f f o r d s
lower c r a z e - i n i t i a t i o n s t r e s s e s and t h e r e f o r e can r a p i d l y
d i s s i p a t e t h e s t r a i n energy i n t h e HIPS. A more homogeneous
s p a t i a l d i s t r i b u t i o n o f rubber p a r t i c l e s a l l o w f o r a uniform
development o f c r a z e s . P r e v e n t i o n o f t h e s t r a i n l o c a l i z a t i o n
phenomenon t o a v o i d t h e d e t r i m e n t a l s i t u a t i o n , where c r a z e s p r e f e r
to develop i n c e r t a i n areas and q u i c k l y l e a d t o a c a t a s t r o p h i c
c r a c k , c o u l d r e s u l t i n a l a r g e r t o t a l volume o f c r a z e d m a t e r i a l .
F u r t h e r , Donald and Kramer (22) d i s c o v e r e d no c r a z e s n u c l e a t i n g
from an i s o l a t e d rubber p a r t i c l e with diameter s m a l l e r than 1 urn
because o f an i n s u f f i c i e n t s i z e o f s t r e s s - e n h a n c e d zone. S i n c e
Sample- has a small average p a r t i c l e s i z e i t should c o n t a i n a
l a r g e number o f small rubber p a r t i c l e s . Two small rubber

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
44 PARTICLE SIZE DISTRIBUTION

p a r t i c l e s w i t h a s e p a r a t i o n small enough t o cause s t r e s s f i e l d


s u p e r p o s i t i o n may be c a p a b l e o f i n i t i a t i n g c r a z e s . F o r i n s t a n c e ,
t h i s advantageous arrangement may be d e s t r o y e d due t o t h e d i l u t i o n
e f f e c t o f adding PS homopolymers t o HIPS.
Conclusions
The p r e s e n t study l e a d s t o t h e f o l l o w i n g c o n c l u s i o n s :
(1) A combination o f e l e c t r o n m i c r o s c o p y , computerized image
a n a l y s i s , and mechanical t e s t i n g p r o v i d e s a powerful t o o l f o r
s t u d y i n g morphology-property r e l a t i o n s h i p s i n toughened
plastics.
(2) A s t a t i s t i c a l framework has been e s t a b l i s h e d f o r d e s c r i b i n g
the s p a t i a l d i s p e r s i o n o f second phase p a r t i c l e s i n a
c o n t i n u o u s m a t r i x . Based on t h i s scheme a computerized image
a n a l y s i s method has been developed f o r c h a r a c t e r i z i n g t h e
morphology o f toughene
(3) The proposed n o r m a l i z e
to be a s e n s i t i v e measure o f t h e "goodness" o f p a r t i c l e
d i s p e r s i o n i n space. An NDI v a l u e o f .142 was shown t o be a
c r i t i c a l l e v e l o f d i s p e r s i o n t h a t demarcates two t o t a l l y
d i f f e r e n t types o f c r a z i n g b e h a v i o r i n HIPS.
(4) A good d i s p e r s i o n o f rubber p a r t i c l e s appears t o f a v o r t h e
n u c l e a t i o n and growth o f a l a r g e number o f t h i c k c r a z e s
uniformly distributed i n the polystyrene matrix. This i s
b e l i e v e d t o be an e f f i c i e n t source o f energy a b s o r p t i o n f o r
the m a t e r i a l under mechanical l o a d i n g . The concepts o f s t r e s s
f i e l d o v e r l a p and c r i t i c a l volume o f s t r e s s c o n c e n t r a t i o n
zone f o r c r a z e i n i t i a t i o n were i n t r o d u c e d t o e x p l a i n t h e
observed mechanical b e h a v i o r o f HIPS.
Acknowledgments
F i n a n c i a l s u p p o r t f o r t h i s work i s p r o v i d e d by t h e P l a s t i c s D i v . ,
American Hoechst Corp. We a r e g r a t e f u l f o r t h i s s u p p o r t .
Literature Cited
1. Bucknall, C. B. "Toughened Plastics", Appl. S c i . Pub.,
London, 1977.
2. Newman. S. "Rubber Modification of Plastics", in "Polymer
Blends". 1980 Ch. 13. Vol. 2; Paul, D. R., E d . ; Academic
Press.
3. Kinlock, A. J. and Young, R. J. Fracture Behavior of
Polymers, Appl. S c i . Pub., London, 1983.
4. Bucknall, C. B. in Polymer Blends, Vol. 2; Paul, D. R., et.
a l , Ed.; Academic Press, 1978.
5. Kato, K. J. Electron Micros. 1965, 14, 220.
6. Kato, K. Polym. Eng. Sci. 1967, 7, 38.
7. Kato, K. Koll. . Z. Polym. 1967, 220, 24.
8. Stein, R. S. in "New Methods of Polymer Characterization",
Ke, B., E d . ; Interscience, New York, 1964, p. 155.
9. Moritani, M.; Inoue, T.; Motegi, M.; Kawai, H. and Kato, K.
in "Colloidal and Morphological Behavior of Block and Graft

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
2. JANG AND CHANG Spatial Dispersion of Rubbery Phase 45

Copolymers"; Molau, G. E., Ed.; Plenum Press, New York, 1971,


p. 33.
10. Visconti, S. and Marchessault, R. H. Macromol. 1974, Vol. 7
p. 913.
11. James, D. E. Polym. Eng. Sci. 1968, 8, 241.
12. Gurland, J. In Quantitative Microscopy; DeHoff, R. T. and
Rhines, F. N.; Eds.; McGraw-Hill, 1968, p. 279.
13. Wang, T. T., Matsuo, M. and Kwei, T. K. Am. Chem. Soc., Div.
Polym. Chem. Polym. Prepr. 12 (1971) 671.
14. Wang, T. T., Matsuo, M. and Kwei, T. K. J. Appl. Phys.,
1971, 42, 4188.
15. Rosen, S. L. Polym. Eng. Sci., 1967, 7, 115.
16. Bender, B. W., J. Appl. Polym. Sci., 1965, 9, 2887.
17. Matsuo, M. Polymer, 1966, 7, 421.
18. Bucknall, C. B., Clayton, D. and Keast, W. F. J. Mater.
Sci. 1972, 7, 1443.
19. Grancio, M. R. Polym
20. Dillon, M. and Bevis, M. Plast. Rubber Process.
Applications, 1982, 2, 225.
21. Dillon, M. and Bevis, M. J. Mater. Sci., 1982, 17, 1903.
22. Donald, A. M. and Kramer, E. J. J. Appl. Polym. Sci., 1982,
27, 3729.
23. Silberberg, J. and Han, C. D. J. Appl. Polym. Sci., 1978,
22, 599.
24. Ricco, T., Pavan, A. and F. Danusso. Polym. Eng. Sci., 1978,
19, 774.
25. Durst, R. R., Griffith, R. M., Urbanic, A. J. and van Essen,
W. I. ACS Adv. Chem. Ser., 1976, 154, 239.
26. Parsons, C. F. and Such, E. L. Acs Adv. Chem. Series, 1971,
99, 340.
27. Purcell, T. O. Am. Chem. Soc. Div. Polym. Chem. Polym.
Prepr., 1972, 13, 699.
28. Donald, A. M. and Kramer, E. J. J. Mater. Sci., 1982, 13,
1765.
29. Michler, G. H. Plaste Kaut, 1979, 12, 497 and 680.
30. Jang, B. Z., Uhlmann, D. R. and Vander Sande, J. B. Polym.
Eng. Sci., 1985, 25, 643.
31. Bucknall, C. B. J. Materials, 1969, 4, 214.
32. Goodier, J. . , Trans. ASME. 1933, 55, 39.
33. Matsuo, M . , Wang, T. T. and Kwei, T. K. J. Polym. Sci.
A-2, 1972, 10, 1085.
RECEIVED July 9, 1986

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 3

Uses and Abuses of Photon Correlation Spectroscopy


in Particle Sizing
. B. Weiner and W. W. Tscharnuter
Brookhaven Instruments Corporation, Ronkonkoma, NY 11779

Examples of particle sizing using photon correlation


spectroscopy are presented to demonstrate the straight
forward uses and
amples include NB
-divinylbenzene,a fractionated sample of polyvinyl
chloride, "dusty" samples of reference latex, a bimodal
mixture of reference latices, a bimodal mixture of
rubber particles, and a 2:1 aggregate.
Correlator hardware and linearly-spaced sample
time limitations are discussed. Data transformation
from an intensity-weighted to a mass-weighted size
distribution is demonstrated. The artificial width of
broad distributions is discussed. The use of multi
-angle measurements is considered, and the effect of
baseline error is shown using computer simulated data.

During the past two decades the technique of quasi-elastic light


scattering (QELS) has been used extensively to characterize
colloidal-sized particles in the size range from a few nanometers to
a few microns. In this range the particles exhibit significant
random motion from collisions with the surrounding liquid medium.
The random motion gives rise to fluctuations in the scattered light
intensity which is usually analyzed with a digital correlator. As a
result the name photon correlation spectroscopy (PCS) is often used.
Several monographs that describe the theory and experimental
requirements for good measurements are available (1-5). Hundreds of
literature citations are included in these sources. Every year con
ferences are devoted to the subject of QELS and PCS. Although the
technique is relatively new to particle size analysts, most of the
advantages and disadvantages are well-known.
Advantages include speed, accuracy, versatility, and a large
potential size range. Disadvantages include limited shape
information, intensity-weighted results, and difficult data analysis
for broad distributions.
The purpose of this article is to demonstrate some of the advan
tages and disadvantages of PCS in particle sizing by presenting some
typical examples of uses and abuses of the technique.

0097-6156/87/0332-0048$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
3. WEINER AND TSCHARNUTER Photon Correlation Spectroscopy 49

Experimental

The measurements described here were made with either a Brookhaven


Instruments model BI-90 p a r t i c l e s i z e r (90deg, f i x e d angle) or a
model BI-200SM multiangle laser l i g h t scattering goniometer attached
to a model BI-2030 d i g i t a l correlator. Both instruments were oper-
ated i n m u l t i p l e sample time mode. In t h i s mode the e q u i v a l e n t of
several thousand linearly-spaced c o r r e l a t o r channels i s a v a i l a b l e ,
enabling the acquisition of a correlation function more f u l l y repre-
sentative of a broad size d i s t r i b u t i o n . A 5mW, v e r t i c a l l y polarized,
HeNe laser was used i n both instruments. Further d e t a i l s are given
elsewhere (6-7)*
Typical sample preparation consisted of d i l u t i n g a few drops of
concentrated dispersion i n about 20cc of twice f i l t e r e d (0.22 micron)
d i l u e n t or u n t i l the d i l u t e d sample appeared s l i g h t l y t u r b i d to
clear. Following sonicatio fo about 1 minute preliminar
ments were made to estimat
size, and polydispersity
ers successive dilutions of about 30? were made u n t i l no concentra-
tion dependence was found i n the f i n a l results.
A l l d i l u t i o n bottles, pipette t i p s , and sample c e l l s were rinsed
repeatedly with twice f i l t e r e d diluent prior to use.
Measurement time varied from under 1 minute for narrow d i s t r i b u -
t i o n s to s e v e r a l minutes f o r broad d i s t r i b u t i o n s . Data a n a l y s i s
times varied from seconds for narrow distributions to a few minutes
for broad distributions. A l l measurements were analyzed using the
technique of cumulants (8) and, for broad distributions, a modified
version of exponential sampling theory (EST) (9).

Results

Monodisperse Spheres. The most straight forward use of PCS i s s i z i n g


monodisperse, r i g i d spheres i n the submicron range. Monodisperse
latex p a r t i c l e s (SRM 1691, NBS, Gaithersburg, Maryland) were measured
at 45, 90 and 135deg s c a t t e r i n g angles. The NBS value i s 269 +/-
7nm. The uncertainty includes random and a l l i d e n t i f i a b l e forms of
s y s t e m a t i c e r r o r . Our r e s u l t s are 273 +/- 5nm. The u n c e r t a i n t y
includes random and systematic variations observed between d i f f e r e n t
i n s t r u m e n t s and d i f f e r e n t days. C l e a r l y the PCS r e s u l t s are very
a c c u r a t e and p r e c i s e . No c a l i b r a t i o n was necessary. Additionally,
sample p r e p a r a t i o n , measurement time, and data a n a l y s i s were much
f a s t e r and s i m p l e r than the analogous steps i n v o l v e d when u s i n g an
electron microscope.
In 1972 Lee, Tscharnuter and Chu (10) showed that labelled 91nm
l a t e x (LS-1132-B, Dow Chemical) was S5 +/- 2nm u s i n g PCS and 2
d i f f e r e n t e l e c t r o n microscopes. Many of the s o - c a l l e d r e f e r e n c e
p a r t i c l e s e x h i b i t even g r e a t e r d i s c r e p a n c i e s between l a b e l l e d and
measured values. Many are not even narrowly distributed as evidenced
by p o l y d i s p e r s i t i e s (defined i n PCS as r e l a t i v e v a r i a n c e s of the
intensity-weighted d i f f u s i o n c o e f f i c i e n t distribution) s i g n i f i c a n t l y
l a r g e r than the t y p i c a l minimums (approx. 0.02) found on the few
t r u l y narrow standards. As a result, a properly designed and working
PCS instrument gives results which are t y p i c a l l y more accurate than
those on the labels of many reference standards.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
50 PARTICLE SIZE DISTRIBUTION

Swollen P a r t i c l e s . Another use for PCS i s for s i z i n g i n situations


where sample preparation, such as drying, would destroy the p a r t i c l e
i n t e g r i t y . Table I shows the e f f e c t of sulfonation on p a r t i c l e size
for 3 d i f f e r e n t formulations of monodisperse, polystyrene-divinylben-
zene (PS-DVB) under c o n s i d e r a t i o n f o r use as packing i n chroma-
tography columns (11). Columns 2 & 3 show, r e s p e c t i v e l y , the s i z e
before and a f t e r s u l f o n a t i o n . Upon d i l u t i o n the same r e s u l t s were
obtained indicating no i n t e r p a r t i c l e e f f e c t s were important at the
concentrations used. PS-DVB i s a r i g i d , hydrophobic p a r t i c l e . After
sulfonation i t i s hydrophilic and would dissolve except for the DVB
c r o s s l i n k s . Instead i t s w e l l s . Columns 4 & 5 show, r e s p e c t i v e l y ,
the percent increase as measured and as predicted from analogous ion-
exchange resins several microns i n diameter. The values show c l e a r l y
that extrapolation of results on swelling should be done with caution
i f at a l l . These r e s u l t s could not be obtained with an EM s i n c e
sample preparation and measurement conditions would completely change
the size of these swolle

TABLE I: Swelling of Sulfonated PS-DVB using PCS

Size Size Percent Increase


Formulation Unsulfonated Sulfonated Measured Predicted

6? DVB 74nm I85nm 150? 40?


10* 58 103 78 30
15% 73 124 70 20

PCS measurements y i e l d the hydrodynamic s i z e . T h i s s i z e i n -


cludes any coating, solvation layer, surface attached molecules (sur-
f a c t a n t s ) , entrapped s o l v e n t ( s w e l l i n g ) , or any other matter which
moves with the p a r t i c l e . This size may be quite different than the
"dry" diameter.

Fractionated Distributions. I t w i l l become apparent that the unam-


biguous determination of broad size distributions, be they multimodal
or unimodal, presents the most problems for PCS. Therefore, a combi-
nation of PCS and a technique which fractionates a broad d i s t r i b u t i o n
has the potential for y i e l d i n g the most information with the least
ambiguity. Sedimentation f i e l d - f l o w fractionation (SFFF) i s one such
technique (12).
In SFFF p a r t i c l e s flowing i n a narrow channel are subjected to a
g r a v i t a t i o n a l f i e l d perpendicular to the flow. The larger p a r t i c l e s
are pushed c l o s e r to the channel w a l l than the s m a l l e r ones. The
v e l o c i t y p r o f i l e i n a narrow channel i s such t h a t the l a r g e r par-
t i c l e s flow more slowly than the smaller ones. Thus, small p a r t i c l e s
elute f i r s t .
In the complete theory the measured elution volume i s shown to
be a f u n c t i o n of the product of the p a r t i c l e mass and d e n s i t y d i f f -
erence between p a r t i c l e and c a r r i e r l i q u i d . The p a r t i c l e d e n s i t y
must be a c c u r a t e l y known before a mass and diameter can be c a l c u -
lated. The density of a c o l l o i d a l - s i z e d p a r t i c l e i s not always w e l l -
known or conveniently measured. For example, s i g n i f i c a n t adsorption
of surfactant or entrapment of c a r r i e r within the p a r t i c l e can lead

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
3. WEINER AND TSCHARNUTER Photon Correlation Spectroscopy 51

to density differences between the bulk material and the suspended


particles.
In contrast, a PCS measurement on a narrowly distributed sample
y i e l d s a d i f f u s i o n c o e f f i c i e n t which does not depend on any p a r t i c l e
property other than s i z e . A combination of the techniques can, i n
p r i n c i p l e , be used to fractionate a broad sample and determine both
p a r t i c l e size and density.
Table I I shows the r e s u l t s of combining SFFF and PCS measure-
ments on a broad unimodal d i s t r i b u t i o n of PVC i n water. The manufac-
turer of the PVC (The BFGoodrich Company) reports the density as 1.4
g/cm The results reported here were obtained i n Prof. K. D. Cald-
well's l a b o r a t o r y at the U n i v e r s i t y of Utah. S i x f r a c t i o n s were
c o l l e c t e d near the peak of a broad fractogram obtained i n the SFFF
experiment. Each f r a c t i o n was measured using the BI-90. Given the
reported density, the average diameter of each f r a c t i o n was calcu-
lated using SFFF theory These values are given i n column 2 Column
3 shows the average diamete
column 4 shows the calculate
ter and the raw SFFF result f o r each fraction.

TABLE I I : Size and Density Determination of a Polydisperse


PVC Sample using PCS and SFFF

Ave. Dia. Ave. Dia. Density


Fraction SFFF PCS SFFF/PCS

3
1 212nm 2l6nm 1.38g/cm
2 225 225 1.40
3 239 241 1.39
4 250 257 1.37
5 261 267 1.37
6 271 276 1.38

The results are i n remarkable agreement. Both SFFF and PCS are
f i r s t p r i n c i p l e techniques, and neither needs calibration. The densi-
3
ty of PVC i s expected to be s i m i l a r to the bulk value of 1.4 g/cm
since, under the conditions of the measurement, PVC remains a r i g i d
sphere w i t h n e g l i g i b l e i n c r e a s e i n s i z e due to adsorbed s u r f a c e
molecules. The average density found by combining the SFFF and PCS
3
measurements i s 1.38 +/- 0.01 g/cm .
The p o t e n t i a l of combining these two techniques for analyzing
samples with density as well as size d i s t r i b u t i o n i s quite clear.
1
"Dusty * Samples. Dust i s a problem i n l i g h t scattering, especially
i n a h i g h l y p o l a r l i q u i d l i k e water. Dust i s a name g i v e n to a l l
unwanted scatterers. This includes any o u t l i e r s i n the size d i s t r i -
bution which are not considered to be part of the main d i s t r i b u t i o n .
F i l t e r i n g of l i q u i d s s i g n i f i c a n t l y reduces the problem; however, some
dust usually remains unless extreme precautions are taken with the
sample c e l l , transfer pipette or syringe, and any d i l u t i o n bottles.
Even then the sample i t s e l f may have dust. Such precautions begin to
l i m i t some of the advantages, l i k e speed and s i m p l i c i t y , PCS has
over o t h e r techniques. F i n a l l y , i f PCS i s ever to be used o n - l i n e ,

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
52 PARTICLE SIZE DISTRIBUTION

then the problem o f dust ( i n c l u d i n g bubbles) w i l l have to be over-


come.
At the present time, i n most PCS instruments, dust i s handled i n
two ways: an experimentally measured, delayed baseline and/or a dust
term i n the calculation. The l a t t e r method usually assumes dust to
be i n f i n i t e l y large with a zero d i f f u s i o n c o e f f i c i e n t . This leads to
a constant, which i s another way of saying a baseline. The problem
with adjusting the baseline i s that even a very small baseline uncer-
tainty can lead to rather large errors i n the d i s t r i b u t i o n parameters
as shown i n the Appendix. A better procedure would be to reject dust
before i t contributed to the correlation function.
An electronic dust f i l t e r has been implemented i n the BI-90 as
f o l l o w s . The t o t a l experiment d u r a t i o n i s d i v i d e d i n t o c y c l e s o f
a p p r o x i m a t e l y 100msec. An average and standard d e v i a t i o n o f the
count rate i s established based upon many short measurements of the
i n t e n s i t y p r i o r to i n i t i a t i n g the buildup of a correlation function
T h i s i s a l l automatic an
each c y c l e , the count r a t
l a r g e r than the average plus a u s e r - s e l e c t a b l e i n t e g e r times the
measured standard d e v i a t i o n , the data f o r that c y c l e are r e j e c t e d .
The f r a c t i o n of rejected cycles i s recorded.
I f the integer i s high (rejected cycles zero), a l l the scattered
l i g h t contributes to the results. Any dust w i l l increase the average
diameter and broaden the d i s t r i b u t i o n . As the integer i s decreased
(rejected cycles increased), a trend toward decreasing average diame-
ter and narrower d i s t r i b u t i o n s should be observed. I f r e a l o u t l i e r s
exist, then a plateau should be apparent i n plots of average size and
d i s t r i b u t i o n width versus f r a c t i o n of cycles rejected. I f a d i s t r i -
bution i s continuous, then no plateau i s observed, and the p o s s i b i l i -
ty exists for d i s t o r t i n g the results by c l i p p i n g the upper t a i l
F i g u r e 1 i s a p l o t o f the average PCS diameter versus percent
r e j e c t e d c y c l e s f o r a l a b e l l e d 87nm l a t e x i n o n c e - f i l t e r e d (0.22
micron) and unfiltered, l o c a l tap water. The average diameter con-
t i n u o u s l y decreases w i t h i n c r e a s i n g r e j e c t i o n f o r the u n f i l t e r e d
case, and i t s deviation from the true value i s quite s i g n i f i c a n t . No
p l a t e a u i s observed. T h i s suggests that the dust i n t h i s case i s
broadly and continuously distributed. A plateau i s observed i n the
once-filtered case. The average diameter i s 89nm from 1 to 7 percent
rejection.
More dramatic evidence i s shown i n Figure 2 where the r e l a t i v e
variance of the d i f f u s i o n c o e f f i c i e n t d i s t r i b u t i o n i s plotted against
the percent r e j e c t e d c y c l e s . The u n f i l t e r e d case s t a r t s out very
broad and approaches the c o r r e c t value a f t e r more than 40J o f the
cycles are rejected. However, no plateau i s evident, and without the
o n c e - f i l t e r e d r e s u l t s to guide the i n t e r p r e t a t i o n , i t would not be
clear where the correct answer occurs. The once-filtered case shows
a dramatic decrease i n the r e l a t i v e variance after approximately 3
percent of the cycles are rejected.
This example shows the potential f o r using PCS under less than
i d e a l circumstances.

Broad Distributions

Broad d i s t r i b u t i o n s present the greatest challenge. Among the sever-


a l reasons for t h i s are:

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
WEINER A N D TSCHARNUTER Photon Correlation Spectroscopy


so I 1 1. JL J
1 0 2 0 3 0 4 0 5 0
Percent Rejected Cycles

F i g u r e 1 Average d i a m e t e r versus percent r e j e c t e d cycles


d u e t o d u s t . N o m i n a l 87nm l a t e x i n u n f i l t e r e d , l o c a l t a p
w a t e r ( s o l i d c i r c l e s ) a n d o n c e - f i l t e r e d (0.22 micron) water
(open c i r c l e s ) .

10 20 30 40
Percent Rejected Cycles
F i g u r e 2. Relative variance versus percent rejected cycles
d u e t o d u s t . N o m i n a l 87nm l a t e x i n u n f i l t e r e d , l o c a l t a p
w a t e r ( s o l i d c i r c l e s ) a n d o n c e - f i l t e r e d (0.22 micron) water
(open c i r c l e s ) .
In Particle Size Distribution; Provder, T.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
54 PARTICLE SIZE DISTRIBUTION

1. The s c a t t e r e d i n t e n s i t y i s a s t r o n g f u n c t i o n of s i z e and,
for larger p a r t i c l e s , scattering angle. The measured signal
may be dominated by the s t r o n g s c a t t e r e r s , and i t may be
d i f f i c u l t to d e t e c t the s m a l l p a r t i c l e s i n a d i s t r i b u t i o n
unless they are present i n overwhelming concentration.
2. I t i s d i f f i c u l t to set a l i m i t e d number of linearly-spaced
correlator channels to cover the range of a broad d i s t r i b u -
tion. Compromises often result i n a r t i f a c t s .
3. Very small errors i n the baseline of a correlation function
r e s u l t i n l a r g e anomalous behavior i n the width of the
distribution. (See the Appendix.)
4. With a broad range of sizes i t i s sometimes d i f f i c u l t for a
4-bit correlator to accommodate the range of photopulses per
sample time encountered. D i l u t i o n or prescaling or reducing
the l a s e r ' s i n t e n s i t y o n l y i n c r e a s e s the experiment dura-
tion.
5. The deconvolutio
6. Random noise on
lated d i s t r i b u t i o n , l i m i t i n g resolution.

Nevertheless, PCS can y i e l d valuable information on broad size


distributions. Three examples are given which demonstrate the type
of information available and the l i m i t a t i o n s .

Accuracy. F i g u r e 3 shows the r e s u l t s obtained from a mixture o f


nominal 87nm (Duke S c i e n t i f i c ) and 269nm (SRM 1691) latexes. Peaks
occur at 84nm and 269nm. P r i o r to mixing the sizes were measured as
85nm and 275nm, r e s p e c t i v e l y . Although peak p o s i t i o n s are very
accurate, the widths are a r t i f i c i a l l y broad due to the noise on the
correlation function.
These very a c c u r a t e peaks were obtained i n about 16 minutes.
The u n c e r t a i n t y decreases w i t h i n c r e a s i n g experiment d u r a t i o n .
Roughly, one can expect that the r e l a t i v e e r r o r decreases w i t h the
square root of the experiment duration. I t takes several hours f o r
the measured d i s t r i b u t i o n widths to approach the correct values (13)*
For strong scatterers an average diameter can be obtained within
+/- 5% every 10 or 20 seconds. To get this precision with the poly-
d i s p e r s i t y takes 2 or 3 minutes. To d i s t i n g u i s h between a broad
unimodal and a bimodal d i s t r i b u t i o n may take several minutes. F i n a l -
l y , as already mentioned, i t may take hours to obtain representative
widths.
F i g u r e 4 shows the r e s u l t s obtained from a rubber sample d i s -
persed i n 95:5 water/glycerin. The peaks occur at 270nm and 1010nm.
Peaks of 300nm and 1150nm were obtained on a disc centrifuge, where
the density of these p a r t i c l e s , i n suspension, affects the accuracy
of these centrifuge results. Of interest here i s the a b i l i t y of PCS
to o b t a i n a good value near the high end of i t s s i z e range i n the
presence of a second peak.
There are two aspects of t h i s example which merit further d i s -
c u s s i o n . One concerns c o r r e l a t o r hardware, and the other concerns
data transformation.

C o r r e l a t o r Hardware L i m i t a t i o n . The equivalent, average number of


photopulses per sample time i n t h i s experiment was 16. The t y p i c a l
4 - b i t c i r c u i t r y found i n many c o r r e l a t o r s would s u f f e r o v e r f l o w

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
3. WEINER AND TSCHARNUTER Photon Correlation Spectroscopy 55

100 V

M
a
s
s

F i g u r e 3. M i x t u r e o f 85nm and 275nm l a t e x e s . Peaks occur


at 84nm and 269nm.

100

M
A

C
t
i

A(nm)
5 50 500 "so8
F i g u r e 4. S i z e d i s t r i b u t i o n o f rubber blend. Peaks a t
270nm and 1010nm agree with r e s u l t s from a disc centrifuge.
A f t e r a p p l y i n g Mie s c a t t e r i n g c o r r e c t i o n s the c a l c u l a t e d
mass r a t i o of the peaks agrees well with the blend as mixed
by weight.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
56 PARTICLE SIZE DISTRIBUTION

problems at t h i s l e v e l . P r e s c a l i n g would be necessary. However,


t h i s i n c r e a s e s the data c o l l e c t i o n time. An 8 - b i t design (255
counts/sample time) could e a s i l y handle t h i s case. However, at lower
scattering angles, say 15 deg, where the sample time for a 1 micron
p a r t i c l e using a 128 channel, linearly-spaced correlator i s several
milliseconds, the average number of photopulses per sample time can
quickly exceed 255. The correlator i n the BI-90 operates, e n t i r e l y
i n hardware, up to the e q u i v a l e n t of I 6 b i t s per sample time, and
would be especially suitable for use with low angle measurements.

Data T r a n s f o r m a t i o n . The raw s i z e d i s t r i b u t i o n obtained i n PCS i s


i n t e n s i t y weighted. Most p a r t i c l e s i z i n g results are either mass,
area, or number weighted. T h e r e f o r e , to compare r e s u l t s , the PCS
measurements would have to be transformed. I f the r a t i o of the
concentrations i n each peak i s desired, then a transformation i s also
necessary. The i n t e n s i t y of l i g h t scattered by a sphere i s given by

where i s an o p t i c a l constant, c i s the mass concentration, d i s the


diameter, and i s the scattering form factor calculated from either
Mie theory or an approximation l i k e Rayleigh-Gans-Debeye theory (14).
Mass-weighted data are obtained by d i v i d i n g the i n t e n s i t y -
3
weighted r e s u l t s by d P, and number-weighted data are obtained by
d i v i d i n g the mass-weighted results by d .
approaches 1 as p a r t i c l e size or scattering angle decreases.
For sizes below about 300nm, can be estimated reasonably well using
RGD theory. The r e f r a c t i v e index of the p a r t i c l e i s not required i n
RGD theory. For l a r g e r p a r t i c l e s must be c a l c u l a t e d from Mie
theory, and i t i s an o s c i l l a t i n g function of size and angle. Further
more, i n t h i s s i z e range i t depends on the r a t i o of the r e f r a c t i v e
index of the p a r t i c l e and the suspension medium. The magnitude of
v a r i e s , i n t y p i c a l cases, over 4 orders of magnitude. T h i s great
variation combined with the d-cubed variation makes the transformed
data s u b j e c t to great e r r o r . I t i s not uncommon f o r an a r t i f a c t at
the low s i z e end of the i n t e n s i t y - w e i g h t e d d i s t r i b u t i o n to become
much more s i g n i f i c a n t i n the mass- or number-weighted d i s t r i b u t i o n
3
because of the d i v i s i o n by d or d , r e s p e c t i v e l y . Likewise, a
spurious size i n the intensity-weighted d i s t r i b u t i o n , which happens
to f a l l at a minimum i n P, w i l l be blown up i n t o a s i g n i f i c a n t
contribution i n the mass- and number-weighted distributions.
The r e s u l t s i n F i g u r e 4 y i e l d a 50:50 r a t i o by mass when a
smoothed approximation of i s used where the smoothing i s performed
i n an attempt to remove p a r t i c l e r e f r a c t i v e index as a necessary
parameter. However, a better calculation, using the correct r e f r a c
t i v e index (1.545) of t h i s p a r t i c u l a r rubber and the f u l l Mie theory
f o r spheres, y i e l d s a mass c o n c e n t r a t i o n r a t i o of 69:31 f o r the
1010nm:270nm s i z e s which i s q u i t e c l o s e to the 70:30 r a t i o of t h i s
blended sample.
Not a l l results agree t h i s well. Before corrections are applied
i t i s important to v e r i f y that peak positions and intensity-weighted
r a t i o s are repeatable. Also note that a p a r t i c l e property, index of
refraction, was needed to transform an intensity-weighted size d i s
t r i b u t i o n into a mass- or number-weighted one. For monodisperse and
narrow d i s t r i b u t i o n s t h i s i s not the case. For d i s t r i b u t i o n s where

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
3. WEINER AND TSCHARNUTER Photon Correlation Spectroscopy 57

the s i g n i f i c a n t features are below about 300nm or for measurements at


s m a l l angles, t h i s i s not the case e i t h e r . But f o r broad d i s t r i b u -
tions, where s i g n i f i c a n t features are above about 300nm, and where
the highest accuracy i s sought, then the p a r t i c l e index of r e f r a c t i o n
must be known.
F i g u r e 5 shows the r e s u l t s obtained from a nominal 65nm l a t e x
dispersion (Polyscience). Four separate samples were run, each show-
ing bimodality with peaks at 45 +/- 1nm and 93 +/- 5nm, suggesting
the formation of doublets. The discrepancy between the nominal and
measured v a l u e s , as w e l l as the l a c k o f monodispersity, i s q u i t e
common for several other samples and sizes from the same source.
The "doublet" peak c o n t r i b u t e s about 33% by i n t e n s i t y , 6% by
weight, and only 0.7 by number. Here RGD theory was used to trans-
form the i n t e n s i t y - w e i g h t e d r e s u l t s . Only a f r a c t i o n of a percent
formed aggregates, yet these were q u i t e e a s i l y detected by l i g h t
s c a t t e r i n g . The o p p o s i t e case where a s m a l l number of s m a l l e r
p a r t i c l e s i s i n the presenc
impossible.

Summary

Abuses of PCS usually occur from attempts to ignore, either experi-


m e n t a l l y or t h e o r e t i c a l l y , what has been l e a r n e d i n the past 20
years. A few of the more important considerations are reviewed here
with respect to t h e i r impact on broad size d i s t r i b u t i o n s .

Deconvolution Algorithms. The correlation function for broad d i s t r i -


butions i s a sum of single exponentials. This i l l - c o n d i t i o n e d mathe-
matical problem i s not subject to the usual c r i t e r i a for goodness-of-
fit. S i z e r e s o l u t i o n i s u l t i m a t e l y l i m i t e d by the n o i s e on the
measured c o r r e l a t i o n f u n c t i o n , and measurements f o r s e v e r a l hours
(13) are required to obtain accurate widths. Peaks closer than about
2:1 are u n l i k e l y to be r e s o l v e d u n l e s s a - p r i o r i assumptions are
invoked to constrain the possible solutions. Such constraints should
be s t a t e d e x p l i c i t l y ; o t h e r w i s e , the r e s u l t s are m i s l e a d i n g . Con-
s t r a i n t s that work well with one type of d i s t r i b u t i o n and one set of
data often f a i l with others. Thus, a r t i f a c t s including nonexistent
b i - , t r i - , and quadramodals abound. Many p a r t i c l e size d i s t r i b u t i o n s
are i n h e r e n t l y nonsmooth, and attempts to smooth the data p r i o r to
deconvolution have not been p a r t i c u l a r l y successful.
Given the d i f f i c u l t i e s one should view with suspicion any decon-
v o l u t i o n f e a t u r e s that are not r e p e a t a b l e , that are f u n c t i o n s of a
p a r t i c u l a r c o n s t r a i n t , and those t h a t occur at the extremes of the
range. Often these are a r t i f a c t s . A physical explanation for mul-
t i p l e peaks should be sought. I n i t i a l aggregation should l e a d to
doublets ( F i g u r e 5) and t r i p l e t s , and f u s i o n should l e a d to a con-
tinuum. Invoking aggregation to explain widely spaced peaks i s not
sufficient.
S e v e r a l d e c o n v o l u t i o n a l g o r i t h m s are now a v a i l a b l e i n c l u d i n g
EST, NNLS, and CONTIN (3).

Number o f C o r r e l a t o r Channels. Proper use of the above a l g o r i t h m s


requires a correlation function which spans the time range over which
l a r g e and s m a l l p a r t i c l e s c o n t r i b u t e . Sample time i s u s u a l l y s e t
such t h a t the l a s t data channels ( l a r g e s t s i z e ) are w i t h i n a few

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
58 PARTICLE SIZE DISTRIBUTION

tenths of a percent of the baseline. With linearly-spaced correlator


channels the same sample time must a l s o be used f o r a l l other par-
t i c l e sizes. This constraint leads to the following estimate of the
required number, M, of linearly-spaced correlator channels,

M = 7mR

where R i s the r a t i o of the l a r g e s t to the s m a l l e s t s i z e , m i s the


channel number (m = 1,2,3...M) at which the exponential corresponding
to the smallest s i z e decays to 1/e, and the number 7 assumes the l a s t
data channel i s within 0.1$ of the baseline.
For broad d i s t r i b u t i o n s t h i s equation p r e d i c t s t h a t a t l e a s t
s e v e r a l hundred l i n e a r l y - s p a c e d channels are r e q u i r e d . N o n l i n e a r
sample time spacing i s superior. Both the fixed-angle instrument and
the correlator used i n t h i s work operate with up to the equivalent of
several thousand linearly-spaced dat channels

Multiangle Measurements
from multiangle measurements. Zero-angle extrapolated data are more
amenable to proper data transformation. Separation of t r a n s l a t i o n a l
and r o t a t i o n a l motion of highly a c i c u l a r p a r t i c l e s i s possible. Ver-
i f i c a t i o n of peaks at more than one angle lends credence to t h e i r
existence. Simultaneous deconvolution of angular data may provide a
u s e f u l constraint.
Angular measurements, however, are more d i f f i c u l t and may give
r i s e to t h e i r own special types of a r t i f a c t s . Alignment i s c r i t i c a l ,
and periodic v e r i f i c a t i o n i s necessary. Scattering by dust i s par-
t i c u l a r l y severe at low angles. As l i t t l e as 0.5 f l a r e can a r t i -
f i c i a l l y broaden d i s t r i b u t i o n s s i g n i f i c a n t l y , and a few percent can
lead to a r t i f i c i a l bimodals (15). Back r e f l e c t i o n s may y i e l d peaks
corresponding to scattering at 180-0.
Multiangle instruments are checked by v e r i f y i n g that IsinO for a
pure l i q u i d i s constant. F i g u r e 6 shows d e v i a t i o n s of IsinO u s i n g
toluene i n the m u l t i a n g l e instrument used i n t h i s work. A l l the
errors are less than a h a l f percent.

Data T r a n s f o r m a t i o n s . The d e c o n v o l u t i o n of c o r r e l a t i o n f u n c t i o n s
y i e l d s the i n t e n s i t y - w e i g h t e d d i f f u s i o n c o e f f i c i e n t d i s t r i b u t i o n .
Transformation to a size d i s t r i b u t i o n requires d i v i s i o n by the diame-
ter raised to a high power and by an angular dependent function which
o s c i l l a t e s over several orders of magnitude for p a r t i c l e s larger than
a h a l f a micron. Given the a r t i f a c t s from the primary deconvolution,
extreme caution i s advised when transforming data.

Conclusions

PCS i s a v a l u a b l e technique f o r p a r t i c l e s i z i n g i n the submicron


range. Results are least ambiguous for narrow distributions. I t may
be used with broad d i s t r i b u t i o n s provided i t s l i m i t a t i o n s are under-
stood. Compared to other techniques i n t h i s s i z e range i t i s o f t e n
very useful even with broad d i s t r i b u t i o n s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
WEINER AND TSCHARNUTER Photon Correlation Spectroscopy

00 I-

1 S 50 500 50$

F i g u r e 5. S i z e d i s t r i b u t i o n of aggregated l a t e x sample.
The 2:1 size r a t i o suggests the formation of doublets.

+0.50 r

+0.25

.00

.25

.501
20 40 60 80 100 120 140 160
i n degrees

Figure 6. Deviations of IsinO from 15 to 160 deg scattering


angle using toluene i n the multiangle system.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
60 PARTICLE SIZE DISTRIBUTION

Appendix

The measured autocorrelation function must be normalized before use


f u l parameters can be extracted from i t . The normalization consists
of establishing a baseline. Normally this i s done experimentally by
measuring a delayed and/or i n f i n i t e - t i m e b a s e l i n e . O c c a s i o n a l l y ,
t h i s i s done by f i t t i n g a baseline as one of the parameters. In any
of these cases the baseline must be correctly established within at
least 0.1J or surprisingly large errors occur i n any parameter which
describes the width of the d i s t r i b u t i o n .
To demonstrate the e f f e c t , s i m u l a t e d data w i t h no noise added
was used. The autocorrelation function for a monodisperse sample,

C(t) = B [ l + A e x p ( - 2 P t ) J

was used to generate exact data where i s the baseline A i s a pre


exponential factor, and

= D T q 2

Dm i s the translational d i f f u s i o n c o e f f i c i e n t , which, f o r spheres, i s


given by,

D T = k T/3Tfyd
B

where kg i s Boltzmann's constant, i s temperature i n Kelvin, and


i s the v i s c o s i t y of the medium i n which p a r t i c l e s of diameter d are
moving. The magnitude of the wave vector q i s given by,

q = (4<rrn/)v )sin(9/2) o

where i s the index o f r e f r a c t i o n o f the s o l u t i o n , X^is the wave


length i n vacuum, and Q i s the scattering angle.
These exact data were then f i t using a weighted, least squares
algorithm. The f i r s t moments of the d i s t r i b u t i o n , the cumulants (8),
were obtained as a f u n c t i o n o f BLINE, where BLINE i s the b a s e l i n e
which was stepped through i n 0.1% increments. The results are shown
i n Table I I I .

TABLE I I I : E f f e c t of Baseline Errors on D i s t r i b u t i o n Parameters

BLINE AVE. DIA. POLY PEXP

1.000 272.0 0.000 0.500


0.999 271.2 0.020 0.502
0.998 270.4 0.038 0.506
0.997 269.7 0.056 0.512
0.996 269.1 0.072 0.520
0.995 268.6 0.087 0.531
0.994 268.1 0.100 0.543
0.993 267.7 0.112 0.557
0.992 267.4 0.123 0.574
0.991 267.1 0.132 0.593
0.990 266.8 0.140 0.613

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
3. WEINER AND TSCHARNUTER Photon Correlation Spectroscopy 61

The f i r s t row shows the r e s u l t s u s i n g the exact b a s e l i n e : an


average diameter of 272nm; an i n f i n i t e l y narrow d i s t r i b u t i o n with a
r e l a t i v e variance i n the d i f f u s i o n c o e f f i c i e n t d i s t r i b u t i o n , POLY, of
zero; and a t y p i c a l p r e - e x p o n e n t i a l f a c t o r o f 0.5 . These were the
values used to generate the data.
For experiment durations of a few minutes with strong scatterers
a random error of 0.1$ i n the baseline i s t y p i c a l , and the second row
shows the effects of this. The average diameter i s hardly changed,
and the r e l a t i v e v a r i a n c e i s 0.02. T h i s i s a f a i r l y t y p i c a l value
found f o r narrow standards. However, an e r r o r o f as l i t t l e as 0.3$
i n the b a s e l i n e r e s u l t s i n a r e l a t i v e v a r i a n c e o f 0.056. T h i s i s
equivalent to a r e l a t i v e standard deviation of 0.24, or 24$. An error
of 1$ i n the baseline results i n an error of only 1.9$ i n the average
diameter, but yields a d i s t r i b u t i o n with a r e l a t i v e standard devia
t i o n o f 37.4$. Thus, very s m a l l e r r o r s i n the b a s e l i n e r e s u l t i n
large errors i n the calculate
I f c o r r e l a t i o n dat
used with one o f the s i z e d i s t r i b u t i o n a l g o r i t h m s , then spurious
peaks are generated. Worse yet, allowing t*o baseline to be f i t with
one of these algorithms may result i n the same type of spurious peak.
I t i s preferable to measure the baseline properly rather than use i t
as a f i t t i n g parameter.

Literature Cited
1. Chu, . "Laser Light Scattering"; Academic Press: New York, 1974.
2. Berne, B.J.; Pecora, R. "Dynamic Light Scattering with Appli
cations to Chemistry, Biology and Physics"; Wiley-Interscience:
New York, 1976.
3. Dahneke, B.E.; Ed. "Measurement of Suspended Particles by Quasi-
Elastic Light Scattering"; Wiley-Interscience: New York, 1983.
4. Chen, S-H; Chu, ; Nossal, R.; Eds. "Scattering Techniques
Applied to Supramolecular and Nonequilibium Systems"; Plenum
Press: New York, 1981.
5. Pecora, R.; Ed. "Dynamic Light Scattering, Applications of Photon
Correlation Spectroscopy"; Plenum Press: New York, 1985.
6. Weiner, B.B. In "Modern Methods of Particle Sizing"; Barth, H.,
Ed.; Wiley-Interscience: New York, 1984; Chap. 3.
7. Weiner, B.B.; Thomas, J.C. "Introduction to Particle Sizing Using
Photon Correlation Spectroscopy"; Brookhaven Instruments:
Ronkonkoma, New York, 1984.
8. Koppel, D. E. J. Chem. Phys. 1972, 57, 4814.
9. Ostrowsky, N.; et. al. Opt. Acta 1981, 28, 1059.
10. Lee, S.P.; Tscharnuter, W.W.; Chu, . J. Polym. Sci.: Phys. 1972,
10, 2453.
11. Papanu, S., Dionex Corp., Sunnyvale, California, private
communication.
12. Caldwell, K.D. In "Modern Methods of Particle Size Analysis";
Barth, H., Ed.; Wiley-Interscience:New York, 1984; Chap. 7.
13. Morrison, I.D.; Grabowski, E.F.; Herb, C.A. "Improved Techniques
for Particle Size Determination by QELS", accepted for publica
tion in Langmuir.
14. Kerker, M. "The Scattering of Light and Other Electromagnetic
Radiation", Academic Press: New York, 1969.
15. Chu, B.; Gulari, E.; Gulari, . Physica Scripta 1979, 19, 476.

RECEIVED September 30, 1986


In Particle Size Distribution; Provder, T.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 4

A Comparison of Methods for Determining


Macromolecular Polydispersity from Dynamic Laser
Light Scattering Data
R. A. Vaidya, M. J. Mettille, and R. D. Hester
Department of Polymer Science, University of Southern Mississippi,
Hattiesburg, MS 39406

Several differen
macromolecular polydispersity information from
normalized intensity correlation functions obtained
from dynamic light scattering have been proposed.
However, detailed comparisons of these methods are
lacking. We have proposed a new analysis method
involving the GEX function in conjunction with
function f i t t i n g . Computer simulated data, convoluted
with noise, was used to compare our method with
Constrained Regularization and the Subdistribution
technique. In general our method yielded results at
least as good as those from constrained regularization
and i s more operator independent. The subdistribution
method yielded the poorest results.

Particle size distribution and polymer molecular weight distribution


(MWD) measurements by dynamic light scattering (DLS) have recently
become an active area of research. Dynamic light scattering (also
known as photon correlation spectroscopy, quasielastic light
scattering (QLS), intensity correlation spectroscopy, and self beat
spectroscopy) i s dependent upon the molecular diffusion rate. The
light scattered by various diffusing polymer molecules in solution
is of different phase. It can be shown that i f the response time of
the detector i s sufficiently fast, the intensity should fluctuate
between zero and twice i t s average value. The timescale on which
this intensity domain fluctuation takes place i s approximately equal
to the time required by two molecules to diffuse far enough relative
to each other that the phase difference between the two i s changed
from zero to radians. The intensity domain output can be
transformed into a time domain function by autocorrelation (V).

The autocorrelation (AC) function as measured by the correlator i s


related to the f i r s t order autocorrelation function by Equation 1.

0097-6156/87/0332-0062$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
4. VAIDYA ET AL. Determining Macromolecular Polydispersity 63

G(T) = A(1+B(g(x)) ) 2
(1)
Where: G ( x ) = Measured a u t o c o r r e l a t i o n f u n c t i o n
g(x) = F i r s t order autocorrelation function
A = Baseline value
= Machine c o n s t a n t
= Delay time
The n o r m a l i z e d c o r r e l a t i o n f u n c t i o n can be r e l a t e d t o the
d i s t r i b u t i o n o f decay c o n s t a n t s as shown by E q u a t i o n 2.
g(x) =/F(r)exp(-rT)dr (2)
Where: = Decay c o n s t a n t
F(r) a Decay c o n s t a n t d i s t r i b u t i o n f u n c t i o n
The r e l a t i o n s h i p c a n a l s o be c a s t i n terms o f d i s t r i b u t i o n s o f
m o l e c u l a r weights f o
a c h i e v e d by r e l a t i n g t h
f
d i f f u s i o n c o e f f i c i e n t D which i n t u r n i s r e l a t e d t o m o l e c u l a r
weight through a Mark-Houwink l i k e r e l a t i o n s h i p . E q u a t i o n 3 shows
the fundamental r e l a t i o n s h i p between t h e a u t o c o r e l a t i o n f u n c t i o n
and polymer m o l e c u l a r weight d i s t r i b u t i o n s .
2 2 3
rF(M)M e x p ( - a q M x ) dM (3)
g(T) =
2
/F(M)M dM

Where: F(M) = m o l e c u l a r weight d i s t r i b u t i o n
q = scattering vector
a,3 = parameters r e l a t i n g d i f f u s i o n c o e f f i c i e n t t o M
through D=O<MP
The above r e a l t i o n s h i p assumes t h a t i n t r a m o l e c u l a r motions a r e n o t
measured and t h a t t h e p o l a r i z a b i l i t y p e r u n i t s c a t t e r i n g mass i s
1 1
independent o f t h e t o t a l s c a t t e r i n g mass. The q u a n t i t i e s ' q , '
1 T
and '8 a r e c o n s t a n t s and a DLS experiment measures g ( ) a t s e v e r a l
v a l u e s o f . Thus t h e problem o f c a l c u l a t i n g a MWD from DLS d a t a
reduces t o c a l c u l a t i n g F(M) by i n v e r t i n g E q u a t i o n 3. M a t h e m a t i c a l l y ,
E q u a t i o n 3 i s a Fredholm i n t e g r a l e q u a t i o n . Such e q u a t i o n s a r e
i l l - c o n d i t i o n e d and cannot be s o l v e d a n a l y t i c a l l y . Numerical
s o l u t i o n i s d i f f i c u l t because t h e e x i s t e n c e o r uniqueness o f a
computed s o l u t i o n i s n o t guaranteed and convergence t o a s o l u t i o n i s
nonuniform.
Any proposed method f o r d e t e r m i n i n g MWDs from t h e Fredholm
e q u a t i o n must converge t o t h e c o r r e c t s o l u t i o n and must do s o
r a p i d l y . Convergence t o t h e c o r r e c t s o l u t i o n i s d i f f i c u l t because
s e v e r a l l o c a l s o l u t i o n s can e x i s t a p a r t from t h e g l o b a l s o l u t i o n and
numerical methods o f t e n converge t o a l o c a l s o l u t i o n . T h i s problem
i s most s e r i o u s w i t h broad unimodal o r mulitmodal MWDs.

P a s t Methods Used To S o l v e The Fredholm I n t e g r a l E q u a t i o n


There have been many methods proposed and used t o e x t r a c t MWDs from
QLS d a t a . Some have had a r e a s o n a b l e amount o f s u c c e s s . One o f t h e
f i r s t used a s i m p l e F o u r i e r t r a n s f o r m o f t h e AC d a t a ( 2 ) . A l t h o u g h
t h i s method i s a n a l y t i c a l l y c o r r e c t , i t p l a c e s such s t r i n g e n t

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
64 PARTICLE SIZE DISTRIBUTION

p r e c i s i o n requirements upon t h e data t h a t i t i s , i n p r a c t i c a l terms,


u n s u i t e d f o r u s e w i t h a n y b u t t h e most simple (unimodal
monodisperse) systems.
Another method t h a t has enjoyed a g r e a t d e a l o f success i s t h e
method o f cumulants. In 1972 Koppel (3) showed t h a t the l o g a r i t h m o f
the f i r s t o r d e r AC f u n c t i o n was i d e n t i c a l t o t h e cummulant
g e n e r a t i n g f u n c t i o n f o r t h e d i s t r i b u t i o n o f decay c o n s t a n t s . The
c o e f f i c i e n t s o f the cummulant expansion c a n be r e l a t e d t o t h e
moments o f t h e d i s t r i b u t i o n . From t h e complete s e t o f moments i t i s
t h e o r e t i c a l l y p o s s i b l e t o regenerate t h e exact distribution
f u n c t i o n . In p r a c t i c e however, even small amounts o f n o i s e i n t h e AC
d a t a can cause l a r g e amounts o f e r r o r i n a l l but t h e f i r s t two o r
t h r e e moments. For narrow unimodal d i s t r i b u t i o n s t h e f i r s t two
moments b a s i c a l l y d e f i n e t h e d i s t r i b u t i o n . However, f o r multimodal,
h i g h l y skewed, o r v e r y broad d i s t r i b u t i o n s , the cumulant expansion
i s inadequate.
A t h i r d method t h a t
(4). T h i s method approximate
form c o n t a i n i n g a f i n i t e sum o f e x p o n e n t i a l s . There i s no p r a c t i c a l
method known t o d i r e c t l y r e g r e s s t h i s type o f e q u a t i o n ; t h e r e f o r e , a
set o f approximate decay c o n s t a n t s i s assumed. T h i s c o n v e r t s t h e
e q u a t i o n from a f i n i t e sum o f e x p o n e n t i a l s t o a m u l t i l i n e a r e q u a t i o n
which c a n be e a s i l y r e g r e s s e d . The method r e j e c t s p h y s i c a l l y
meaningless s o l u t i o n s by c o n s t r a i n i n g both t h e d i s t r i b u t i o n
c o e f f i c i e n t s and t h e decay c o n s t a n t s t o be non-negative. The major
f l a w w i t h t h e histogram method i s t h a t i t has g r e a t d i f f i c u l t y i n
d i s c r i m i n a t i n g between unimodal and multimodal d i s t r i b u t i o n s u n l e s s
the peaks a r e s u f f i c i e n t l y s e p a r a t e d .

Recent Methods To s o l v e t h e Fredholm I n t e g r a l E q u a t i o n


Although t h e methods p r e v i o u s l y d i s c u s s e d have shown some promise i n
s o l v i n g t h e Fredholm e q u a t i o n , two r e c e n t methods were chosen f o r
i n t e n s i v e study and comparison w i t h our GEX f u n c t i o n f i t method.
These methods were t h e c o n s t r a i n e d r e g u l a r i z a t i o n method, and t h e
polynomial s u b d i s t r i b u t i o n method.
C o n s t r a i n e d R e g u l a r i z a t i o n Method. The c o n s t r a i n e d r e g u l a r i z a t i o n
t e c h n i q u e has been developed i n t o a computer package (CONTIN) by
Provencher (5) and has been used f o r a v a r i e t y o f purposes o f which
m o l e c u l a r weight d i s t r i b u t i o n d e t e r m i n a t i o n i s o n l y one. T h i s method
f i n d s t h e s i m p l e s t b e s t f i t s o l u t i o n t o t h e MWD by m i n i m i z i n g the
l e a s t squares e r r o r between experimental and f i t t e d v a l u e s o f g ( x )
while concurrently minimizing t h e t h i r d d e r i v a t i v e o f t h e
d i s t r i b u t i o n o f m o l e c u l a r s i z e s . The requirement o f a minimum t h i r d
d e r i v a t i v e i s i n c o r p o r a t e d i n t o t h e a l g o r i t h m by u s i n g a p e n a l t y
f u n c t i o n c o n s i s t i n g o f a user s p e c i f i e d c o n s t a n t times t h e v a l u e o f
the t h i r d d e r i v a t i v e . S e t t i n g t h i s c o n s t a n t t o o l a r g e can l e a d t o
over-smoothing t h e s o l u t i o n . In a d d i t i o n t o m i n i m i z i n g t h e
i r r e g u l a r i t y o f t h e s o l u t i o n , CONTIN c o n s t r a i n s t h e d i s t r i b u t i o n t o
be non-negative.
Polynomial S u b d i s t r i b u t i o n Method. The polynomial s u b d i s t r i b u t i o n
method as d e s c r i b e d by Cha and Min (6) assumes t h a t t h e d i s t r i b u t i o n
can be r e p r e s e n t e d by a sum o f s u b d i s t r i b u t i o n s a s shown by t h e
equation:

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
4. VAIDYA E T A L . Determining Macromolecular Polydispersity 65

F r = C F ( F ) ( 4 )
( > 2^ n n
I
where C i s a w e i g h t i n g f a c t o r and F ( r ) i s t h e n o r m a l i z e d
n

s u b d i s t r i b u t i o n . In o r d e r t o show what fo?m o f d i s t r i b u t i o n F ( )


t a k e s , i t i s n e c e s s a r y t o perform a Laguerre p o l y n o m i a l expansion o f
the decay c o n s t a n t d i s t r i b u t i o n .
Assuming, ^
(5)
F ( r ) = (- )() ( )



+ 1
y \, , {
n
(+1)

Where: ^ } = f ^ L , ^

,, = c o n s t a n t s
the o r t h o g o n a l i t y o f L a g u e r r e p o l y n o m i a l s c a n be used t o r e w r i t e
E q u a t i o n 5 as:

F(r)=y}c 6(-)()
+ Y = 2^c' F (r)
n n
( 6 )

tf N
( + + 1) n=0 n n

Therefore,
F ( r ) = ( ) ( ) - + "

;

( + + 1 ) (')
r u ;
n

From t h i s i t i s immediately obvious t h a t F ( ) i s a gamma


d i s t r i b u t i o n . Each s u b d i s t r i b u t i o n has a mean o f ++1/ and a
2 r
v a r i a n c e o f ++1/ . A l t h o u g h i n t h e above e q u a t i o n t h e v a r i a b l e
can take on any v a l u e s from z e r o t o i n f i n i t y , gamma i s c o n s t r a i n e d
t o be w i t h i n t h r e e s t a n d a r d d e v i a t i o n s o f t h e s u b d i s t r i b u t i o n mean
f o r s i m p l i c i t y . A l s o t h e b a s e l i n e between t h e s e l i m i t s i s s u b t r a c t e d
in order t o provide a d i s t r i b u t i o n with zero frequency a t i t s
l i m i t s , and we can w r i t e t h e AC f u n c t i o n a s :
2
g (r) = ( n n ( ^ exp(-xr) <*r) C F r 2
(8)
n=0
I
The c o e f f i c e n t s C , and t h e c o n s t a n t s and a r e t h e unknown
parameters t o be s o l v e d f o r i n t h e r e g r e s s i o n . The number o f
s u b d i s t r i b u t i o n s ^+1* u s u a l l y range from 5 t o 9 f o r unimodal
d i s t r i b u t i o n s and up t o 13 f o r multimodal d i s t r i b u i o n s . The
s u b d i s t r i b u t i o n method i s e s s e n t i a l l y a c o n t i n u o u s v e r s i o n o f t h e
h i s t o g r a m method i n t h a t i t uses o v e r l a p p i n g gamma d i s t r i b u t i o n s
i n s t e a d o f t h e n o n - o v e r l a p p i n g square d i s t r i b u t i o n s used i n t h e
h i s t o g r a m method.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
66 PARTICLE SIZE DISTRIBUTION

The GEX f u n c t i o n f i t method.


An a l t e r n a t i v e approach t o determine polymer MWDs from DLS d a t a i s
t o assume t h a t the m o l e c u l a r weight d i s t r i b u t i o n c a n be r e p r e s e n t e d
by a mathematical f u n c t i o n and then r e g r e s s i n g E q u a t i o n 3 t o o b t a i n
the b e s t f i t v a l u e s f o r the parameters i n v o l v e d i n t h e chosen model.
T h i s assumption becomes l i m i t i n g i f the f u n c t i o n chosen cannot f i t
the sample m o l e c u l a r weight d i s t r i b u t i o n . In g e n e r a l methods u s i n g
t h i s s t r a t e g y a r e c a l l e d f u n c t i o n f i t methods.
In t h i s paper we propose the use o f the g e n e r a l i z e d e x p o n e n t i a l
1
('GEX ) f u n c t i o n as a peak model i n the f u n c t i o n f i t method. The GEX
f u n c t i o n f o r a s i n g l e peak i s shown i n F i g u r e 1. Each peak has f i v e
parameters t h r e e o f which ( h , > and X ) have d i r e c t p h y s i c a l
meaning ( F i g u r e 1). A' and ' * are shape parameters t h a t determine
f

the skew and k u r t o s i s o f the peak. We have p r e v i o u s l y shown t h a t the


GEX f u n c t i o n f i t s polymer m o l e c u l a r weight d i s t r i b u t i o n s w e l l and i s
very v e r s a t i l e in that i
(Z) ( F i g u r e 2). The v e r s a t i l i t
shape assumption i n h e r e n t i n the GEX method v e r y n o n - l i m i t i n g .
The GEX f u n c t i o n can be i n t e g r a t e d a n a l y t i c a l l y (8) and thus the
denominator i n E q u a t i o n 3 c a n be c a l c u l a t e d i n a c l o s e d form. The
numerator cannot be i n t e g r a t e d and t h e r e f o r e has t o be c a l c u l a t e d
1 1 1 f f
n u m e r i c a l l y . In E q u a t i o n 3, ' and q a r e known c o n s t a n t s
f
1 1
and hence f o r a g i v e n s e t o f GEX parameters a t a g i v e n v a l u e o f
the r i g h t hand s i d e o f t h e e q u a t i o n c a n be c o m p l e t e l y c a l c u l a t e d .
The d a t a from a dynamic l i g h t s c a t t e r i n g experiment i s i n the form
o f ( , g( )) data p o i n t s . For every v a l u e o f " ', E q u a t i o n 3 can
be used t o c a l c u l a t e a f i t t e d v a l u e o f g( ) and t h e sum o f t h e
square o f t h e d i f f e r e n c e between t h e c a l c u l a t e d and e x p e r i m e n t a l
v a l u e s o f g ( ) i s the l e a s t squares e r r o r . The problem o f f i n d i n g a

MWD thus reduces t o f i n d i n g t h e b e s t v a l u e s f o r the GEX parameters


t o f i t the e x p e r i m e n t a l AC f u n c t i o n .

Experimental
In o r d e r t o compare t h e r e s u l t s o f an a n a l y s i s t e c h n i q u e w i t h t h e
1
' t r u e s o l u t i o n i t i s e s s e n t i a l t h a t t h e MWD be known b e f o r e t h e
a n a l y s i s i s s t a r t e d . Consequently, computer s i m u l a t e d data generated
by assuming a m o l e c u l a r weight d i s t r i b u t i o n and s u b s e q u e n t l y u s i n g
1 1
E q u a t i o n 3 t o generate g(-u) f o r a s e r i e s o f v a l u e s , was used
f o r a n a l y s i s . F i v e d i f f e r e n t MWDs were used, f o u r o f which were
generated u s i n g GEX f u n c t i o n s as models (two GEX f u n c t i o n s f o r
bimodal peaks), and T a b l e I shows t h e GEX parameters used f o r each
o f t h e s e MWDs.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
VAIDYA ET AL. Determining Macromolecular Polydispersity

B 1 A
h = h m L ~ expj(l - L )(B-1)/AJ

with: L = (X - )/( -
X)
e

ARGUMENT (X)

F i g u r e 1 : The GEX f u n c t i o n f o r a unimodal d i s t r i b u t i o n .

A
SK - 0.81 KR - 2 SK -0.5 KR - 2.7 SK - -0.6 KR - 3.4

sK - e.6 KR - 2.8 SK - 0.2 KR - 2.8 SK - 0.07 KR - 2.9

sK - 3.8 KR - 30.2 SK - 2.3 KR 12.5 SK



- 1.3 KR 5.7

1.2 2.8 8.5


SHAPE PARAMETER ''

F i g u r e 2 : V a r i a t i o n i n the shape o f the GEX d i s t r i b u t i o n as


1 f f
f u n c t i o n o f the shape parameters 'A and B .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
68 PARTICLE SIZE DISTRIBUTION

T a b l e I. M o l e c u l a r Weight D i s t r i b u t i o n Specifications
Distribution Peak 1 Peak 2
6
A B x
n A X Xm 10
X
mm 0 m

xlO" 4
xlO" 4
x10~ 4
xlO" 4
sec
Normal 2.8 2.8 1 10 5
Skewed 1.1 1.6 1 5 5
Bimodal I 1.1 1.6 1 5 2.8 2.8 25 34 5
(Skewed:Normal = 3:1 mass r a t i o )
Bimodal I I 1.1 1.6 1 5 2.8 2.8 25 34 10
(Skewed:Normal = 1:3 mass r a t i o )
q=1.87 10 cm , =

Each o f t h e bimodal cases r e p r e s e n t e d a mix o f a skewed low


m o l e c u l a r weight peak and a h i g h e r m o l e c u l a r weight normal peak. The
two cases have a t h r e e - t o - o n e and a o n e - t o - t h r e e r a t i o o f peak areas
r e s p e c t i v e l y . The f i f t h d i s t r i b u t i o n corresponds t o a c l a s s i c a l f r e e
r a d i c a l p o l y m e r i z a t i o n w i t h a number average m o l e c u l a r weight o f
50,000 ( 9 ) .
Data f o r the normal, skewed, and f r e e r a d i c a l d i s t r i b u t i o n s was
generated w i t h 50 l i n e a r l y spaced d e l a y times ( c h a n n e l s ) , w h i l e 100
channels were used f o r t h e bimodal c a s e s . To r e a l i s t i c a l l y model
e x p e r i m a n t a l d a t a a p p r o x i m a t e l y 1% random n o i s e was added t o the AC
d a t a . Each o f the AC d a t a s e t s , w i t h 0 and 1% n o i s e l e v e l s , were
then a n a l y z e d f o r a MWD u s i n g c o n s t r a i n e d regularization,
s u b d i s t r i b u t i o n , and GEX f i t t e c h n i q u e s .
For both the s u b d i s t r i b u t i o n and the GEX f i t methods a Marquardt
a l g o r i t h m f o r c o n s t r a i n e d n o n - l i n e a r r e g r e s s i o n was used t o minimize
the sum o f squares e r r o r ( 1 0 ) . The FORTRAN program CONTIN was used
f o r t h e c o n s t r a i n e d r e g u l a r i z a t i o n method. A l l computations were
performed on a H a r r i s H-800 super mini computer.
Results
Comparisons between generated MWDs and the d i s t r i b u t i o n computed by
the t h r e e methods f o r both normal and skewed d i s t r i b u t i o n s w i t h no
n o i s e are shown i n F i g u r e 3. F i g u r e 4 shows the r e s u l t s f o r t h e s e
cases w i t h 1% added n o i s e . In t h e s e and subsequent f i g u r e s , t h e
t h i n n e r l i n e r e p r e s e n t s the computed m o l e c u l a r weight d i s t r i b u t i o n .
T a b l e I I shows a c o m p a r i s i o n between t h e moments o f t h e
d i s t r i b u t i o n s computed by the c o n s t r a i n e d r e g u l a r i z a t i o n and GEX f i t
methods and t h e c o r r e s p o n d i n g v a l u e s f o r t h e t r u e s o l u t i o n . The
r e s u l t s f o r the bimodal MWDs are shown i n F i g u r e 5 and those f o r the
f r e e r a d i c a l case i n F i g u r e 6.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
VAIDYA E T A L . Determining Macromolecular Polydispersity

NORMAL DISTRIBUTION
GEX CONTIN SUBDIS

O 1 1 S 4 9

SKEWED DISTRIBUTION

0 1 X 3 4 9

MOLECULAR WEIGHT 10" 9

F i g u r e 3 : R e s u l t s o f t h e a n a l y s e s f o r normal and skewed


unimodal d i s t r i b u t i o n s w i t h o u t n o i s e i n the AC f u n c t i o n .

NORMAL DISTRIBUTION
GEX CONTIN SUBDIS

0 1 1 3 4 9

MOLECULAR WEIGHT X 10" 9

F i g u r e 4 : R e s u l t s o f t h e a n a l y s e s f o r normal and skewed


unimodal d i s t r i b u t i o n s w i t h 1% n o i s e i n t h e AC f u n c t i o n .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
PARTICLE SIZE DISTRIBUTION

SKEWED : NORMAL 3 : 1
GEX CONTIN SUBDIS
o

>
<

0 1 X 3 4 1 1

S K E W ED : NORMAL - 1 : 3
0.


0.0
0.0T
0.0
> 0.0
0.04
0.03
0.02
Ixl 0.01

MOLECULAR WEIGHT X 10"

F i g u r e 5 : R e s u l t s o f the a n a l y s e s f o r the bimodal


d i s t r i b u t i o n s w i t h o u t n o i s e i n the AC f u n c t i o n .

0 % NOISE
GEX CONTIN SUBDIS

0 1 X 3 4 8 7

1 % NOISE

0 1 X 3 4 8 1 7
MOLECULAR WEIGHT X 10"'

F i g u r e 6 : R e s u l t s o f the a n a l y s e s f o r the c l a s s i c a l f r e e
r a d i c a l d i s t r i b u t i o n w i t h 0 and 1% n o i s e i n the AC f u n c t i o n .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
4. VAIDYA ET AL. Determining Macromolecular Polydispersity 71

T a b l e I I . Comparison o f Methods
3 5 T T
Method Noise L e v e l M n x l O " MwxIO"" Var 1 0 " Skew K u r t o s i s
Normal D i s t r i b u t i o n
True V a l u e s 104 116 1.3 0.24 2.7
GEX F i t 0% 104 116 1.3 0.22 2.7
1% 100 116 1.5 0.28 2.7
CONTIN 0% 103 115 1.3 0.11 2.6
1Z 97 113 1.6 0.35 3.1
Skewed D i s t r i b u t i o n
True Values 105 154 5.2 1.44 6.0
GEX F i t 0% 105 154 5.2 1.45 6.0
1% 105 155 5.2 1.61 6.9
CONTIN 0% 104 152 5.0 0.68 5.2
1% 123 160 4.6 0.48 3.6

Discussion
There a r e two broad c r i t e r i a by which t h e t h r e e methods c a n be
compared. They a r e : t h e c o r r e c t n e s s o f t h e computed s o l u t i o n ; and,
the degree o f o p e r a t o r independence.
C o r r e c t n e s s o f t h e s o l u t i o n . As c a n be seen from F i g u r e s 3 and 4
the s u b d i s t r i b u t i o n method y i e l d s i n f e r i o r s o l u t i o n s as compared t o
the o t h e r two methods f o r t h e unimodal c a s e . Consequently, t h e
r e s u l t s from t h i s method a r e n o t i n c l u d e d i n T a b l e I I . In t h e
absence o f n o i s e CONTIN f i t s t h e normal case w e l l b u t shows an
a r t i f i c i a l s h o u l d e r on t h e skewed MWD. The GEX f i t method reproduces
the i n p u t d i s t r i b u t i o n s w i t h g r e a t a c c u r a c y . The s u b d i s t r i b u t i o n
method had g r e a t d i f f i c u l t y i n h a n d l i n g t h e cases w i t h added n o i s e .
CONTIN and t h e GEX f i t method were n o t s i g n i f i c a n t l y a f f e c t e d by
n o i s y d a t a . However, CONTIN showed broadening o f t h e MWD i n s t e a d o f
the a r t i f i c i a l s h o u l d e r i n t h e skewed c a s e . The v a l u e s i n T a b l e I I
a t t e s t t o t h e q u a l i t y o f t h e f i t s o b t a i n e d w i t h t h e GEX f i t and
CONTIN methods. The GEX method g i v e s s l i g h t l y b e t t e r numbers b u t
t h i s i s t o be expected s i n c e t h e i n p u t d i s t r i b u t i o n s were GEX
functions.
For bimodal MWDs none o f t h e methods s u c c e s s f u l l y r e s o l v e d t h e
two peaks f o r t h e case where a m a j o r i t y o f t h e m o l e c u l e s were o f low
m o l e c u l a r weight ( F i g u r e 5 ) . However, CONTIN p r o v i d e d t h e c l o s e s t
s o l u t i o n . F o r t h e case where t h e skewed low m o l e c u l a r weight peak
c o n s i s t e d o f o n l y one q u a r t e r o f t h e t o t a l mass, t h e GEX f i t method
gave good r e s u l t s . CONTIN showed t h r e e peaks, b u t t h e agreement can
s t i l l be c o n s i d e r e d f a i r because o f t h e d i f f i c u l t y i n d i s c e r n i n g two
w i d e l y s e p a r a t e d peaks o f t h i s t y p e . As i n t h e unimodal c a s e s , t h e
s u b d i s t r i b u t i o n method showed t h e p o o r e s t f i t s .
The GEX f i t t i n g t e c h n i q u e worked w e l l t o f i n d MWDs from AC d a t a
t h a t have been generated by a GEX f u n c t i o n . Determining i f i t would
work on o t h e r types o f d i s t r i b u t i o n s was t h e next l o g i c a l s t e p . As
can be seen from F i g u r e 6, i t a p p a r e n t l y c a n . The GEX f i t method
shows good agreement between t h e i n p u t MWD and t h e computed
d i s t r i b u t i o n i n t h e c l a s s i c a l f r e e r a d i c a l c a s e . CONTIN shows f a i r
agreement, b u t t h e s u b d i s t r i b u t i o n gave a bimodal peak when t h e r e
was no n o i s e i n t h e AC f u n c t i o n .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
72 PARTICLE SIZE DISTRIBUTION

O p e r a t o r independence. The GEX method i s v i r t u a l l y o p e r a t o r


independent. The o n l y i n p u t s r e q u i r e d b e f o r e f i t t i n g a r e parameters
c o n c e r n i n g the p r e c i s i o n o f the numerical i n t e g r a t i o n and e x i t
c r i t e r i a f o r the Marquardt a l g o r i t h m . The same s e t o f i n p u t s was
used f o r a l l f i v e MWDs. C u r r e n t l y the method a l s o r e q u i r e s upper and
lower l i m i t s on the GEX parameters but a simple m o d i f i c a t i o n o f the
code can e l i m i n a t e t h i s need. The CONTIN a l g o r i t h m has s e v e r a l
o p e r a t o r and case dependent parameters t h a t have t o be chosen b e f o r e
a n a l y s i s . However, i t i s f a i r l y s t a b l e w i t h r e s p e c t t o bad c h o i c e s
f o r some o f t h e s e i n p u t s . The GEX f i t method cannot f i t multimodal
MWDs w i t h o u t p r i o r knowledge o f the number o f peaks i n the
d i s t r i b u t i o n . While CONTIN does not impose t h i s l i m i t a t i o n i t i s
recommended t h a t the number o f peaks be s p e c i f i e d b e f o r e a n a l y s i s .
In our e x p e r i e n c e w i t h CONTIN i f t h i s c o n d i t i o n i s not met t h e
a l g o r i t h m tends t o compute unimodal s o l u t i o n s f o r multimodal MWDs
and sometimes v i s a v e r s a
The s u b d i s t r i b u t i o
number o f d i s t r i b u t i o n
extremely s e n s i t i v e t o t h i s i n p u t and a bad c h o i c e can l e a d t o f a l s e
answers o r no convergence. T h i s c h o i c e i s p a r t i c u l a r l y c r i t i c a l i n
the case o f broad unimodal or multimodal MWDs.
Conclusions
The s u b d i s t r i b u t i o n method i s extremely s e n s i t i v e t o o p e r a t o r i n p u t
and c o n s i s t e n t l y y i e l d e d the p o o r e s t r e s u l t s o f the t h r e e methods
compared. In g e n e r a l CONTIN y i e l d s good r e s u l t s but tends t o s h i f t
MWDs t o h i g h e r m o l e c u l a r weights and sometimes produces a r t i f a c t
peaks o r s h o u l d e r s f o r broad unimodal o r multimodal d i s t r i b u t i o n s .
Of the t h r e e methods, the proposed GEX f i t t i n g t e c h n i q u e seems t o
p r o v i d e r e s u l t s t h a t are most c o n s i t e n t w i t h the i n p u t d i s t r i b u t i o n s
and i s the most o p e r a t o r independent. CONTIN and GEX f i t t i n g a r e not
s i g n i f i c a n t l y a f f e c t e d by n o i s y d a t a .
Acknowledgments
We wish t o thank the Department o f Energy and the Department o f
Commerce f o r t h e i r support o f t h i s p r o j e c t .
Literature Cited
1. Ford, N. C. In Dynamic Light Scattering:Applications of Photon
Correlation Spectroscopy; Pecora, R., Ed.; Plenum Press: New
York, 1985; pp. 12-15
2. McWhirter, J. G.; Pike, E. R. J. Phys. A: Math. Gen. 1978, 11,
1729-45.
3. Koppel, D. E. J. Chem. Phys. 1972, 57, 4814-20.
4. Gulari, E.; Gulari, E.; Tsunashima, Y; Chu, . J. Chem. Phys.
1979, 70, 3965-72.
5. Provencher, S. W. Makromol. Chem. 1979, 180, 201-209.
6. Cha, C. Y.; Min K. W. J. Poly. Sci. Poly. Phys. Ed. 1983, 21,
807-20.
7. Vaidya, R. .; Hester, R. D. J. Chromatogr, 1984, 287, 231-44.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
4. VAIDYA E T AL. Determining Macromolecular Polydispersity 73

8. Vaidya, R. .; Hester, R. D. J. Chromatogr. 1985, 333, 152-55.


9. Tanford, C. "Physical Chemistry of Macromolecules"; John Wiley
and Sons:New York, 1961; pp 603-6.
10. Kuester, J. L.; Mize, J. H. "Optimization Techniques with
Fortran"; McGraw-Hill Book Company:New York, 1973; pp 240-50.

RECEIVED June 27, 1986

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 5

Submicrometer Particle Sizing by Photon Correlation


Spectroscopy: Use of Multiple-Angle Detection
S. E. Bott
Coulter Electronics, Inc., 29 Cottage Street, Amherst, MA 01002

Photon correlation spectroscopy (PCS) has become a method


of choice for sizing particles in the 3-3000nm range. Ad-
vances in the analysis of PCS data permit extraction of
the particle siz
An importan g
tensity averaged distributions, which are measured by PCS
but have little direct meaning, to physically meaningful
weight (volume) averaged distributions. For spherical
particles the intensity to weight conversion at each
scattering angle is given by the 'Mie' equations. How-
ever, the 'Mie' conversion is often an oscillatory function
in which particles of certain sizes contribute virtually
no scattered light. It is shown here that weight distri-
butions from single angle PCS measurements can have huge
errors. Complementary information obtained by measure-
ment at an additional angle allow a good measure of the
weight averaged size distribution.

As new techniques to produce material are developed and older


processes are refined, there has been a general trend toward the
use of component materials of smaller and smaller size. Using
smaller size components often results in bulk materials of
greater strength or uniformity or possessing other advantageous
qualities. Some examples of this trend can be found in
coatings, ceramics and latices 1 2 Concomitant with the trend
has been a requirement for measuring size distributions of
smaller particles in order to control or to characterize the
industrial process.
For particles smaller than around .5 to 1 micron, measuring
methods based on single particle detection generally break down
because the signals (e.g. scattered light, electrical
conductivity through a pore, etc.) obtainable from individual
particles below this size are simply too small to detect. A few
years ago, a commercial instrument, based on a new principle,
photon correlation spectroscopy (PCS)3 , became available for
measurement of mean particle sizes in the submicron range. PCS
(also known as dynamic light scattering (DLS) or quasi-elastic

0097-6156/87/0332-0074$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
5. BOTT Submkrometer Particle Sizing 75

l i g h t s c a t t e r i n g (QELS)) o f f e r s s e v e r a l o u t s t a n d i n g advantages
o v e r o t h e r m e a s u r e m e n t m e t h o d s : 1> t h e m e a s u r e m e n t i s a b s o l u t e ,
i . e . i t r e q u i r e s no c a l i b r a t i o n s t a n d a r d s , 2> t h e m e a s u r e m e n t i s
n o n i n v a s i v e - t h e sample c a n be r e c o v e r e d unchanged a f t e r t h e
m e a s u r e m e n t a n d 3> t h e m e a s u r e m e n t i s q u i c k , u s u a l l y r e q u i r i n g
only a few minutes. PCS c i r c u m v e n t s t h e p r o b l e m o f i n a d e q u a t e
s i g n a l l e v e l f o r i n d i v i d u a l p a r t i c l e s by simultaneously
d e t e c t i n g o f t h e o r d e r o f t h o u s a n d s t o many m i l l i o n s o f
particles. I n t h e l a s t f e w y e a r s , PCS h a s b e c o m e a w i d e l y u s e d
p a r t i c l e s i z i n g t o o l f o r mean p a r t i c l e s i z e s i n t h e s u b m i c r o n
range.
The p o s i t i v e a t t r i b u t e s o f p a r t i c l e s i z i n g b y PCS a r e o p p o s e d b y
two n e g a t i v e o n e s : t h e m e t h o d , b e c a u s e i t i s b a s e d o n l i g h t
s c a t t e r i n g , measures angle dependent ( s c a t t e r e d l i g h t ) i n t e n s i t y
w e i g h t e d r a t h e r t h a n t h e more u s e f u l volume w e i g h t e d p a r t i c l e
d i s t r i b u t i o n s ; and, th
resolution. The a n g l
must u s u a l l y be c o n v e r t e average interpretatio
and c o m p a r i s o n w i t h o t h e r p a r t i c l e s i z i n g m e t h o d s . The
r e l a t i v e l y l o w r e s o l u t i o n o f PCS c o m b i n e d w i t h t h e s e v e r i t y o f
the c o n v e r s i o n o f i n t e n s i t y averages t o weight averages and t h e
heavy dependence o f i n t e n s i t y averaged d i s t r i b u t i o n s on t h e
s c a t t e r i n g a n g l e a t w h i c h t h e m e a s u r e m e n t i s p e r f o r m e d , means
t h a t s i n g l e PCS m e a s u r e m e n t s made a t o n e s c a t t e r i n g a n g l e w i l l
often give misleading r e s u l t s . This a r t i c l e presents data which
show t h a t b y m a k i n g m u l t i p l e m e a s u r e m e n t s a t s e v e r a l s c a t t e r i n g
a n g l e s , much m o r e r e l i a b l e r e s u l t s c a n b e o b t a i n e d .

PHOTON CORRELATION SPECTROSCOPY

F i q u r e 1 s h o w s t h e g e o m e t r y o f a PCS m e a s u r e m e n t . L a s e r l i g h t
i s i n c i d e n t on a sample o f p a r t i c l e s suspended o r d i s s o l v e d i n a
transparent liquid. The p a r t i c l e s , u n d e r g o i n g B r o w n i a n m o t i o n ,
d i f f u s e thoughout t h e s o l u t i o n , A t any g i v e n i n s t a n t , t h e l i g h t
i n t e n s i t y sensed a t t h e detector i s p r o p o r t i o n a l t o the square
of the e l e c t r i c f i e l d a t t h e d e t e c t o r . The phase o f t h e l i g h t
s c a t t e r e d from each p a r t i c l e and measured a t t h e f i x e d d e t e c t o r ,
w i l l d e p e n d o n t h e p o s i t i o n o f t h e p a r t i c l e i n t h e beam a n d o n
the d i s t a n c e between t h e p a r t i c l e and t h e d e t e c t o r . Thus t h e
composite l i g h t s c a t t e r e d from t h e group o f p a r t i c l e s i nt h e
s c a t t e r i n g volume w i l l form an i n t e r f e r e n c e p a t t e r n a t t h e
detector. F i g u r e 2 shows a n i n t e r f e r e n c e p a t t e r n r e s u l t i n g f r o m
the l i g h t s c a t t e r i n g f r o m two p a r t i c l e s . The two s e t s o f
c o n c e n t r i c c i r c l e s r e p r e s e n t t h e wave f r o n t s o f t h e s c a t t e r e d
light. The d a r k ' r a y s ' f o r m e d when two s e t s o f c o n c e n t r i c
c i r c l e s a r e superimposed, as i n t h e f i g u r e , a r e r e g i o n s where
t h e l i g h t s c a t t e r e d f r o m t h e two p a r t i c l e s c o n s t r u c t i v e l y
interferes. I f t h e d e t e c t o r i s l o c a t e d i n one o f t h e s e d a r k
r a y s , a h i g h l i g h t i n t e n s i t y w i l l be s e n s e d .

As t h e p a r t i c l e s r a n d o m l y d i f f u s e t h r o u g h t h e s o l u t i o n , t h e
l o c a t i o n o f the dark rays o f constructive interference w i l l
change; t h e r e f o r e the i n t e n s i t y sensed by t h e f i x e d d e t e c t o r
w i l l v a r y , i . e . t h e i n t e r f e r e n c e p a t t e r n produced by t h e
s c a t t e r i n g p a r t i c l e s w i l l be m o d u l a t e d b y t h e p a r t i c l e m o t i o n s .
The i n t e n s i t y f l u c t u a t i o n s a t t h e d e t e c t o r , t h o u g h r a n d o m , w i l l
be m o r e r a p i d f o r s m a l l , r a p i d l y m o v i n g p a r t i c l e s t h a n f o r

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
76 PARTICLE SIZE DISTRIBUTION

Sample

Laser |11111111111|^1111111111

ye
Photo-
Multiplier

F i g u r e 1. G e o m e t r y o f a P C S m e a s u r e m e n t . The s c a t t e r i n g a n g l e , ,
can v a r y between 0 d e g r e e s a n d 180 d e g r e e s .

F i g u r e 2. A n i n t e r f e r e n c e pattern r e s u l t i n g from t h e s c a t t e r i n g
f r o m two p a r t i c l e s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
5. BOTT Submicrometer Particle Sizing

l a r g e r more s l o w l y d i f f u s i n g p a r t i c l e s . The ' n o i s e ' s i g n a l


p r o d u c e d b y t h e l i g h t s c a t t e r e d f r o m d i f f u s i n g p a r t i c l e s c a n be
c h a r a c t e r i z e d by i t s a u t o c o r r e l a t i o n function, g ( t ) , defined
by

!D g(t) = < I(T) Kt+T) >

where I (T) i s t h e i n t e n s i t y a t t h e d e t e c t o r a t t i m e , and


where t h e a n g u l a r b r a c k e t s r e p r e s e n t a t i m e a v e r a g e o v e r . The
autocorrelation f u n c t i o n measures t h e s i m i l a r i t y , o r c o r r e l a t i o n
between t h e c o n f i g u r a t i o n o f p a r t i c l e s c o n t r i b u t i n g t o an
i n t e n s i t y I a t t o t h a t a t i m e *t l a t e r . F o r s y s t e m o f
Brownian p a r t i c l e s o f u n i f o r m s i z e and shape, t h e
autocorrelation f u n c t i o n w i l l be a d e c a y i n g e x p o n e n t i a l :

(2) g(x

where i s a decay c o n s t a n t c h a r a c t e r i s t i c o f p a r t i c l e s o f t h a t
s i z e and A and a r e c o n s t a n t s dependent on t h e sample,
e x p e r i m e n t a l geometry and c o u n t i n g e f f i c i e n c y o f t h e o p t i c s and
electronics. 1/ i s t h e decay time o f t h e Brownian motion;
r o u g h l y speaking, i ti s t h e time r e q u i r e d f o r any p a r t i c u l a r
c o n f i g u r a t i o n o f p a r t i c l e p o s i t i o n s w i t h i n t h e s c a t t e r i n g volume
to ' r e l a x ' . A f t e r s e v e r a l decay t i m e s , t h e p a r t i c l e s w i l l have
d i f f u s e d s u c h t h a t t h e i r new p o s i t i o n s w i l l b e statistically
u n c o r r e l a t e d w i t h t h e i r former p o s i t i o n s .

The d e c a y c o n s t a n t i s r e l a t e d t o t h e d i f f u s i o n c o n s t a n t o f t h e
p a r t i c l e s and t o t h e geometry o f t h e experiment through t h e
equation,

T = q D ; q = 4ir sin (/2) /


2

(3)

where i s t h e r e f r a c t i v e i n d e x o f t h e s o l v e n t , i s t h e
scattering angle, D i s the d i f f u s i o n constant o f the p a r t i c l e s ,
i s t h e w a v e l e n g t h o f t h e l a s e r i n vacuum and q i s t h e
m a g n i t u d e o f t h e so c a l l e d ' s c a t t e r i n g v e c t o r ' . In turn, f o r
spherical p a r t i c l e s , the d i f f u s i o n constant i s related t othe
p a r t i c l e diameter through the Stokes-Einstein equation:

( 4 )
D = kT / 3
where k i s Boltzmann's c o n s t a n t , i s t h e a b s o l u t e t e m p e r a t u r e ,
i s t h e v i s c o s i t y o f t h e s o l u t i o n and d i s t h e p a r t i c l e
diameter. U s i n g (3) a n d (4), t h e measured decay constant c a n
be d i r e c t l y r e l a t e d t o t h e p a r t i c l e d i a m e t e r .

When t h e s a m p l e c o n t a i n s p a r t i c l e s o f d i f f e r e n t s i z e s , t h e
autocorrelation f u n c t i o n w i l l b e a sum o f d e c a y i n g e x p o n t e n t i a l s
weighted by t h e i n t e n s i t y o f l i g h t s c a t t e r e d from p a r t i c l e s o f
each c h a r a c t e r i s t i c s i z e . T h i s c a n be d e s c r i b e d i n g e n e r a l b y
the e q u a t i o n :

g(x) = X(s) e " r ( s )


ds
(5)
In Particle Size Distribution; Provder, T.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
78 PARTICLE SIZE DISTRIBUTION

where the i n d e x , s, l a b e l s the s i z e of the p a r t i c l e s and X ( s ) i s


the p a r t i c l e s i z e d i s t r i b u t i o n , which g i v e s the r e l a t i v e
p r o p o r t i o n of the s c a t t e r i n g from p a r t i c l e s o f s i z e s. The
c o n s t a n t s a and b are the lower and upper l i m i t s of p a r t i c l e
size. T h i s i n t e g r a l e q u a t i o n must be n u m e r i c a l l y i n v e r t e d t o
e x t r a c t the s i z e d i s t r i b u t i o n , X ( s ) , from the measured
autocorrelation function. The i n v e r s i o n p r o c e d u r e i s
non-trivial. A l t h o u g h v a r i o u s a l g o r i t h m s have been d e v e l o p e d
f o r the i n v e r s i o n , by f a r the most w i d e l y used a n a l y s i s program
f o r t h i s type of d a t a a n a l y s i s i s a FORTRAN program c a l l e d
4 5
CONTIN, d e t a i l s o f which are a v a i l a b l e i n the open l i t e r a t u r e ' .

I t might be imagined t h a t w i t h a r e a s o n a b l e measurement of the


a u t o c o r r e l a t i o n f u n c t i o n and an a p p r o p r i a t e i n v e r s i o n a l g o r i t h m ,
that a very accurate s i z distributio t c o u l d b mad
w i t h PCS. However, i
has u s e f u l , but l i m i t e
6
p a r t i c l e s i z e s . To get an i d e a about the p r e c i s i o n o f PCS
measurements on b i m o d a l samples, b i m o d a l m i x t u r e s of
p o l y s t y r e n e l a t e x spheres (PSL) were p r e p a r e d t o g i v e e q u a l
s c a t t e r i n g i n t e n s i t i e s f r o m each p o p u l a t i o n at a 90 degree
s c a t t e r i n g a n g l e . Twenty measurements were made w i t h each

m i x t u r e . The c o e f f i c i e n t of v a r i a t i o n ( c . v . standard
d e v i a t i o n / m e a n ) o f p e r c e n t a g e of s c a t t e r i n g i n t e n s i t y from each
peak o v e r the twenty runs was computed. The r e s u l t s are g i v e n
below.

PSL #1 (nm) PSL #2 (nm) Run Time ( s e c ) c.v. of #1 c.v. of #2

90 310 120 12% 15%


90 822 600 5% 8%
170 1100 600 6% 6%
310 1300 120 16% 32%

As can be seen, the c.v.s v a r y from sample to sample but are of


the o r d e r of 10%. As measurement t i m e s i n c r e a s e , the c.v. of
the measurements w i l l , n a t u r a l l y , d e c r e a s e .

INTENSITY, WEIGHT AND NUMBER AVERAGES

The p a r t i c l e s i z e d i s t r i b u t i o n , X ( s ) , above i s , u n f o r t u n a t e l y ,
not i n a form which i s u s e f u l f o r most a p p l i c a t i o n s . This i s
because i t i s a s c a t t e r e d i n t e n s i t y w e i g h t e d d i s t r i b u t i o n ( f o r
b r e v i t y , ' i n t e n s i t y d i s t r i b u t i o n ' ) r a t h e r than a s i z e
d i s t r i b u t i o n based on the volume ( w e i g h t ) or number of
particles. The d i f f e r e n c e between d i s t r i b u t i o n s w e i g h t e d i n
d i f f e r e n t ways can be most e a s i l y e x p l a i n e d by r e l a t i n g the
v a r i o u s d i s t r i b u t i o n s t o a number d i s t r i b u t i o n .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
5. BOTT Submicrometer Particle Sizing 79

A n u m b e r d i s t r i b u t i o n g i v e s t h e r e l a t i v e n u m b e r , N, o f p a r t i c l e s
o f s i z e s. A volume or weight d i s t r i b u t i o n V(s) i s r e l a t e d to a
number d i s t r i b u t i o n by

(6) V(s) = N(s) C (s)


v

where C y i s a f a c t o r t o c o n v e r t number t o v o l u m e ; C v (s) i s


e q u a l t o t h e v o l u m e o f a p a r t i c l e o f s i z e s. S i m i l a r l y , an
i n t e n s i t y d i s t r i b u t i o n i s r e l a t e d t o a number d i s t r i b u t i o n by

(7 ) X(s,8) = N(s) C|(s,8)

Cj ( s , ) i s the c o n v e r s i o
t h e amount o f s c a t t e r i n
e x p l i c i t d e p e n d e n c e o f X and C j on T h i s dependence i s
i n c l u d e d to emphasize t h a t the i n t e n s i t y d i s t r i b u t i o n measured
by PCS a t one s c a t t e r i n g a n g l e w i l l be d i f f e r e n t t h a n t h a t a t
a n o t h e r s c a t t e r i n g a n g l e . W e i g h t and n u m b e r d i s t r i b u t i o n s are,
of c o u r s e , independent of s c a t t e r i n g a n g l e .

The i m p l i c a t i o n o f e q u a t i o n ( 7 ) a s i t r e l a t e s t o PCS, is that


l a r g e r p a r t i c l e s s c a t t e r c o n s i d e r a b l y more l i g h t per p a r t i c l e
than smaller p a r t i c l e s . Thus the i n t e n s i t y distributions
m e a s u r e d b y PCS h e a v i l y e m p h a s i z e t h e p r e s e n c e o f larger
particles. I f the i n t e n s i t y d i s t r i b u t i o n s measured w i t h PCS
w e r e e x t r e m e l y a c c u r a t e , t h e f a c t t h a t PCS m e a s u r e s i n t e n s i t y
r a t h e r t h a n v o l u m e o r n u m b e r d i s t r i b u t i o n s w o u l d be o f little
consequence, p r o v i d e d t h a t the proper c o n v e r s i o n f a c t o r ,
C j ( s , 8 ) w e r e k n o w . A s w i l l be s e e n i n t h e n e x t s e c t i o n , fairly
good c o n v e r s i o n s are i n f a c t , a v a i l a b l e . H o w e v e r , as was
p o i n t e d o u t i n t h e p r e v i o u s s e c t i o n , PCS i s a l o w resolution
s i z i n g method; t h i s i m p l i e s t h a t the i n t e n s i t y d i s t r i b u t i o n ,
X ( s , 6 ) , i s m e a s u r e d w i t h l o w p r e c i s i o n and a c c u r a c y . Typically,
t h e i n t e n s i t i e s i n t h e two p e a k s i n a b i m o d e l s a m p l e , f o r
e x a m p l e , w i l l be m e a s u r e d t o 10% o f t h e t o t a l scattering
intensity. P e a k s w h i c h c o m p r i s e l e s s t h a n 10% o f t h e total
s c a t t e r i n g i n t e n s i t y , t h e r e f o r e , c a n be a r t i f a c t s . For s m a l l
r e a l p e a k s , s m a l l e r r o r s i n the measurement of the scattering
i n t e n s i t y from a p o p u l a t i o n of s m a l l p a r t i c l e s w i l l o f t e n l e a d
t o huge e r r o r s i n volume d i s t r i b u t i o n s d e r i v e d f r o m the measured
i n t e n s i t y d i s t r i b u t i o n because the c o n v e r s i o n i n v o l v e s a h i g h
a m p l i f i c a t i o n f a c t o r on t h e s m a l l p a r t i c l e s t o compensate f o r
t h e i r low s c a t t e r i n g i n t e n s i t i e s compared t o l a r g e r p a r t i c l e s .

R A Y L E I G H AND R A Y L E I G H DEBYE REGIMES

When p a r t i c l e s a r e s m a l l c o m p a r e d t o t h e m a g n i t u d e o f the
6
s c a t t e r i n g v e c t o r ( q = 4 n n s i n ( e / 2 ) / A ) , C j (,) s ; i.e. the

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
80 PARTICLE SIZE DISTRIBUTION

c o n v e r s i o n o f i n t e n s i t y t o number d i s t r i b u t i o n s i s a n g l e
independent and s c a l e s as t h e square o f t h e volume o f t h e
p a r t i c l e . I n t h i s regime, c a l l e d t h e Rayleigh regime, t h e
s c a t t e r i n g i n t e n s i t y i s independent o f p a r t i c l e shape. F o r
p a r t i c l e s o f a s i z e o f t h e order o f t h e magnitude o f t h e i n v e r s e
of t h e s c a t t e r i n g v e c t o r q, C p c a n be found by c o n c e p t u a l l y
d i v i d i n g t h e p a r t i c l e i n t o many s m a l l s u b s e g m e n t s , a n d s u m m i n g
the s c a t t e r e d l i g h t c o n t r i b u t i o n o f each subsegment, t a k i n g i n t o
a c c o u n t t h e r e l a t i v e p o s i t i o n s o f each subsegment a n d t h e
d i s t a n c e o f each from t h e d e t e c t o r (andi n c l u d i n g , i f n e c e s s a r y ,
n o n - i s o t r o p i c p o l a r i z a b i l i t i e s o f t h e subsegments and
p o l a r i z a t i o n o f incident and detected l i g h t ) . The r e s u l t o f
this process f o r spherical, isotropic p a r t i c l e s i s

C, = {[3/(qr) ][sin qr - qr cos qr]} r


3 2 6

where r = s / 2 . The a n g l
dependence o f q . T h i s i s t h e R a y l e i g h Debye a p p r o x i m a t i o n f o r
i s o t r o p i c s p h e r e s . I t i s commonly u s e d b e c a u s e o f i t s
simplicity. I n t h i s a p p r o x i m a t i o n , C j c o m p r i s e s two f a c t o r s :
6
the volume squared ( r ) f a c t o r and an a t t e n u t i n g f a c t o r ,
3 2 - 6
{3/(qr) ] [ s i nq r - q r cos q r ] } ! , which i s always between 0
and 1, a n d w h i c h q u a n t i f i e s t h e d e g r e e o f i n t r a p a r t i c l e
d e s t r u c t i v e i n t e r f e r e n c e i n t h e s c a t t e r e d l i g h t from such a
spherical particle. A s w i l l be seen below, t h e range o f
a p p l i c a b i l i t y o f t h e R a y l e i g h Debye a p p r o x i m a t i o n i s l i m i t e d .
R a y l e i g h Debye a p p r o x i m a t i o n s c a n be f o u n d f o r n o n - s p h e r i c a l
p a r t i c l e s , e.g. e l l i p s e s o f r e v o l u t i o n , r i g i d rods and Gaussian
3
coils .

MIE EQUATION

For i s o t r o p i c s p h e r i c a l p a r t i c l e s o f given r e f r a c t i v e index i na


medium o f known r e f r a c t i v e i n d e x , t h e e x a c t f o r m o f C c a n be
found by matching t h e i n c i d e n t , i n t e r n a l and s c a t t e r e d
e l e c t r o m a g n e t i c waves a t t h e p a r t i c l e s u r f a c e , s u b j e c t t o
7
c e r t a i n boundary c o n d i t i o n s . T h e s o l u t i o n comes i n t h e f o r m
of an i n f i n i t e s e r i e s :

C,(s,8) = l(2n+1)/(n(n+1))Ka ir (cos ) + b x (cos 8) }(-1) n n n n


n+l

where

ir (cos 8) = P
n n
(1
\cos 8) / sin 8
(cos 8) = d/d8 (P
n
(1)
(cos 8))
a = n { () ()- () ()}/{< () ()- ()< ()}

/

/

/

/

b = { () ()- () ()}/{ () ()- ()< ()}


n
/

/
>
/

/

<x = 2irsA; B = moc;


: Ricatti-Bessel functions ; : Hankel functions.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
5. BOTT Submicrometer Particle Sizing 81

andJ n a r e r e l a t e d t o L e g e n d r e p o l y n o m i a l s and a
n and b n

a r e c o e f f i c i e n t s dependent on t h e p a r t i c l e s i z e s and t h e
r e l a t i v e r e f r a c t i v e i n d e x o f t h e p a r t i c l e s t o t h e medium i n
w h i c h t h e y a r e s u s p e n d e d . As before, i s t h e s c a t t e r i n g a n g l e .

A complete understanding of the equation i s not important f o r


p u r p o s e s h e r e ; t h e i m p o r t a n t p o i n t s a r e t h a t t h e amount o f l i g h t
s c a t t e r e d by a p a r t i c l e o f a c e r t a i n s i z e depends on t h e
s c a t t e r i n g a n g l e and t h e r e f r a c t i v e i n d e x o f t h e p a r t i c l e
compared t o t h a t o f t h e medium i n w h i c h i t i s s u s p e n d e d . I n t h e
p r e v i o u s a p p r o x i m a t i o n s , C j was i n d e p e n d e n t o f t h e r e f r a c t i v e
i n d e x o f t h e p a r t i c l e . I t m i g h t be n o t e d t h a t t h e e x p r e s s i o n
f o r Cj i s r a t h e r c o m p l i c a t e d ; i t i s f o r t h i s r e a s o n t h a t t h e
R a y l e i g h Debye ( o r sometimes o t h e r ) a p p r o x i m a t i o n s a r e
s u b s t i t u t e d f o r the exact Mi expression F i g u r 3 show C j f o
an i s o t r o p i c s p h e r i c a
medium o f r e f r a c t i v e i n d e
d e g r e e s , w i t h a n i n c i d e n t l a s e r w a v e l e n g t h o f 632.8 nm. The
s o l i d l i n e shows t h e e x a c t M i e c o n v e r s i o n ; t h e d o t t e d l i n e shows
t h e R a y l e i g h Debye a p p r o x i m a t i o n . Although the l i n e s are f a i r l y
c l o s e f o r s m a l l p a r t i c l e s , b e y o n d a b o u t 400 nm, t h e two
i n t e n s i t y c o n v e r s i o n s go ' o u t o f p h a s e ' ; h u g e e r r o r s c o u l d
r e s u l t f r o m u s i n g t h e R a y l e i g h Debye a p p r o x i m a t i o n beyond i t s
l i m i t e d r a n g e o f a p p l i c a b i l i t y . F i g u r e 4 shows a b i m o d a l v o l u m e
d i s t r i b u t i o n ( c h a i n e d l i n e ) and t h e c o r r e s p o n d i n g i n t e n s i t y
d i s t r i b u t i o n s a c c o r d i n g t o t h e Mie ( s o l i d l i n e ) and R a y l e i g h
Debye ( d o t t e d l i n e ) e x p r e s s i o n s . N o t i c e t h e d i f f e r e n c e b e t w e e n
t h e r e l a t i v e s i z e s o f t h e two p e a k s i n t h e v o l u m e v e r s u s i n t h e
two i n t e n s i t y g r a p h s . A l s o note the r e l a t i v e height of the
s m a l l e r s i z e d peak and t h e s h i f t i n g o f t h e l a r g e r s i z e peak i n
t h e Mie v e r s u s R a y l e i g h Debye g r a p h s .

F i g u r e 5 shows t h e a n g u l a r d e p e n d e n c e o f t h e s c a t t e r i n g
i n t e n s i t y f o r t h e same s a m p l e a s i n f i g u r e 3. The o s c i l l a t i o n s
of s c a t t e r i n g i n t e n s i t y per p a r t i c l e over a range of p a r t i c l e
s i z e s i s c h a r a c t e r i s t i c of Cj (s,6) f o r d i e l e c t r i c ( t r a n s p a r e n t )
particles. The p o s i t i o n s a n d a m p l i t u d e s o f t h e p e a k s a n d
v a l l e y s i n t h e p l o t s a r e dependent on t h e r e l a t i v e r e f r a c t i v e
indices. For the lower s c a t t e r i n g a n g l e , t h e r e are fewer
o s c i l l a t i o n s i n the graph. T h i s i s a g e n e r a l t r e n d . As t h e
s c a t t e r i n g a n g l e i s l o w e r e d , t h e number o f o s c i l l a t i o n s i n
Cj (s,6) decreases. For s m a l l s i z e d p a r t i c l e s , the l i n e s
c o r r e s p o n d i n g t o t h e 30 a n d 90 d e g r e e s c a t t e r i n g a n g l e s o v e r l a p .
6
T h i s i s the r e g i o n i n which Cj f o l l o w s the s dependence; i n
t h i s r e g i o n t h e c o n v e r s i o n o f r e l a t i v e i n t e n s i t y t o number
d i s t r i b u t i o n s i s independent of the r e f r a c t i v e index of the
particle.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
82 PARTICLE SIZE DISTRIBUTION

20-1 Scattering Intensity


vs Diameter at 90 V

2 10

05

0 1 2 3 4 5 6 7 8 9 10
Particle Diameter (units of lOOnm)
F i g u r e 3. T h e s c a t t e r i n g i n t e n s i t y , C-j-, p e r p a r t i c l e a s a f u n c t i o n
of p a r t i c l e diameter a c c o r d i n g t o t h e exact M i e t h e o r y ( s o l i d l i n e )
and t h e R a y l e i g h Debye a p p r o x i m a t i o n ( d o t t e d l i n e ) .


i
i

I
i
i

I I I I
200 500 800 1100
Particle Diameter (nm)
F i g u r e 4. A b i m o d a l v o l u m e w e i g h t e d d i s t r i b u t i o n ( c h a i n e d l i n e )
and t h e c o r r e s p o n d i n g i n t e n s i t y d i s t r i b u t i o n s a c c o r d i n g t o t h e
M i e t h e o r y ( s o l i d l i n e ) a n d t h e R a y l e i g h Debye a p p r o x i m a t i o n
(clotted l i n e ) .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
BOTT Submicrometer Particle Sizing


0)

P a r t i c l e D i a m e t e r ( u n i t s of 100 nm)

F i g u r e 5. S c a t t e r i n g i n t e n s i t y per p a r t i c l e as a f u n c t i o n of
p a r t i c l e diameter according to the Mie theory. Upper l i n e
c o r r e s p o n d s t o a 30 d e g r e e a n g l e , l o w e r l i n e t o a 90 d e g r e e
scattering angle.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
84 PARTICLE SIZE DISTRIBUTION

In the p a r t s o f the C j (s,90) and C i ( s , 30) t h a t do not


o v e r l a p , the e x t r e m e l y d i f f e r e n t form o f the i n t e n s i t y
c o n v e r s i o n at the two a n g l e s means t h a t the s c a t t e r e d l i g h t
i n t e n s i t i e s at the two a n g l e s w i l l weight p a r t i c l e s e x t r e m e l y
differently. Because o f t h i s , the i n f o r m a t i o n g l e e n e d f r o m
measurements at d i f f e r e n t a n g l e s i s , to a c e r t a i n e x t e n t ,
i n d e p e n d e n t . Thus the low r e s o l u t i o n i n h e r e n t i n PCS
measurements can be enhanced by making measurements at s e v e r a l
a n g l e s . To l o o k a t i t i n a n o t h e r way, a peak c o n t a i n i n g l e s s
t h a n 10% o f the s c a t t e r i n g i n t e n s i t y at one a n g l e might c o n t a i n
a s u b s t a n t i a l l y g r e a t e r p o r t i o n o f the s c a t t e r i n g i n t e n s i t y a t
a n o t h e r a n g l e and t h e r e f o r e be e a s i e r to d e t e c t . Because of the
low p r e c i s i o n o f PCS measurements, r o u t i n e s i z i n g measurements
at s e v e r a l a n g l e s can h e l p t o s e p a r a t e r e a l peaks f r o m
artifact, and, as w i l l be shown below, to i d e n t i f y p o p u l a t i o n s
o f p a r t i c l e s which do not s c a t t e r enough l i g h t t o be d e t e c t e d a t
90 degrees (or any o t h e

The s e c o n d i m p o r t a n t p i e c e o f i n f o r m a t i o n g i v e n b y f i g u r e 5 i s
that the s c a t t e r i n g i n t e n s i t y per p a r t i c l e of large p a r t i c l e s i s
much g r e a t e r a t t h e l o w e r a n g l e . T h i s i s , a g a i n , a g e n e r a l
observation. PCS m e a s u r e m e n t s a t l o w e r a n g l e s e m p h a s i z e t h e
presence of larger p a r t i c l e s .

The M i e e q u a t i o n a l s o h o l d s f o r a b s o r b i n g o r r e f l e c t i n g
p a r t i c l e s , which have complex r e f r a c t i v e i n d i c e s . The g r a p h s o f
C
I (s,e) f o r such p a r t i c l e s are s i m i l a r to those f o r d i e l e c t r i c
p a r t i c l e s except that the amplitudes of the o s c i l l a t i o n s are
generally smaller.

M A T E R I A L S AND METHODS

The p o l y s t y r e n e l a t e x ( P S L ) s p h e r e s w e r e o b t a i n e d f r o m S e r a g e n
Diagnostics. The n o m i n a l s i z e s o f t h e s e s t a n d a r d s w e r e f r o m
e l e c t r o n m i c r o s c o p y m e a s u r e m e n t s . The s a m p l e s w e r e p r e p a r e d b y
d i l u t i n g t h e 10% s o l i d s i n f i l t e r e d , d o u b l y d i s t i l l e d w a t e r ,
a d d i n g a s m a l l amount o f SDS t o h e l p d i s p e r s e t h e s a m p l e s a n d
s o n i c a t i n g w i t h B r a n s o n 60 w a t t b a t h s o n i c a t o r f o r 30 s e c o n d s t o
d i s p e r s e any a g g r e g a t e s . The r e l a t i v e v o l u m e s ( w e i g h t s ) o f t h e
two s i z e s o f P S L i n t h e m i x e d s a m p l e w e r e e s t i m a t e d t o be
a c c u r a t e t o a b o u t 5-10%.

The l i g h t s c a t t e r i n g m e a s u r e m e n t s w e r e made w i t h a C o u l t e r m o d e l
N4MD p a r t i c l e s i z e r , w h i c h m e a s u r e s p a r t i c l e s s i z e s a t s i x
l a b o r a t o r y f i x e d s c a t t e r i n g a n g l e s (90, 63, 30, 22, 15 a n d 11
d e g r e e s ) . The i n s t r u m e n t u s e s a n i n t e r n a l c o m p u t e r r u n n i n g a
v e r s i o n o f CONTIN t o p e r f o r m t h e i n v e r s i o n o f e q u a t i o n ( 5 ) . It
c o n v e r t s i n t e n s i t y t o volume d i s t r i b u t i o n s u s i n g exact Mie
expression (equation 8). The r e s u l t s o f t h e m u l t i p l e r u n s

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
5. BOTT Submicrometer Particle Sizing

t h r o u g h the s i x s c a t t e r i n g a n g l e s were s t o r e d t o f l o p p y d i s k
u s i n g a C o u l t e r N4 Accucomp d a t a h a n d l i n g system which a l s o
a u t o m a t i c a l l y computes the averages o v e r the m u l t i p l e r u n s o v e r
a l l a n g l e s and o v e r the m u l t i p l e runs a t each s e p a r a t e
s c a t t e r i n g angle*

EXPERIMENTAL RESULTS AND DISCUSSION

The r a m i f i c a t i o n s o f the c o n v e r s i o n o f i n t e n s i t y t o weight


d i s t r i b u t i o n s a r e i l l u s t r a t e d by the f o l l o w i n g examples*
F i g u r e 6a shows a p a r t i c l e s i z e h i s t o g r a m o f a sample o f
p o l y s t y r e n e l a t e x (PLS) spheres t a k e n a t a s c a t t e r i n g a n g l e o f
90 d e g r e e s * Only one peak i s d e t e c t e d a t t h i s a n g l e * F i g u r e s
6b and 6c show the same sample measured a t s c a t t e r i n g a n g l e s o f
30 and 11 degrees r e s p e c t i v e l y * Both sho th f tw
peaks; t h e r e l a t i v e p r o p o r t i o n
quite d i f f e r e n t * The d i f f e r e n c
t a k e n a t the t h r e e a n g l e s g r a p h i c a l l y i l l u s t r a t e s the dependence
o f i n t e n s i t y d i s t r i b u t i o n s on a n g l e *

The PSL i n the a c t u a l sample was composed o f 91% by weight o f


170 nm PSL and 9% by weight o f 822 nm PSL. (These weight
amounts PSL were a c c u r a t e t o not b e t t e r t h a n 5%, i . e . 91% ^
4.55% o f the 170 nm PSL and 9% * .45% o f the 822 nm PSL.)
U s i n g t h e Mie e q u a t i o n , t h e s e weight p r o p o r t i o n s c o n v e r t t o
i n t e n s i t y d i s t r i b u t i o n s of
96% 170 nm PSL and 4% 822 nm PSL a t 90 degrees s c a t t e r i n g a n g l e ,
50% o f each a t 30 degrees and 13% of the 170 nm t o 87% o f the
822 nm PSL a t 11 d e g r e e s . Note t h a t the r e l a t i v e p r o p o r t i o n s o f
the two p o p u l a t i o n s o f PSL, as measured by i n t e n s i t y
d i s t r i b u t i o n s , are almost r e v e r s e d f o r the 90 degree
measurements compared t o the 11 degree measurement.

S i n c e the run t i m e s used f o r the measurement were such t h a t the


t h r e s h o l d f o r d e t e c t i o n o f a peak was around 5% o f the t o t a l
s c a t t e r i n g i n t e n s i t y , the 822 nm PSL was not even d e t e c t e d a t
the 90 degree s c a t t e r i n g a n g l e . A c t u a l measured i n t e n s i t i e s
f o r the two peaks compared w e l l t o the v a l u e s e x p e c t e d by the
Mie c o n v e r s i o n *

Actual Measured

I n t e n s i t y a t 90 Peak 1 96% 100%


I n t e n s i t y at 90 Peak 2 4% 0%

I n t e n s i t y a t 30 Peak 1 50% 48%


I n t e n s i t y at 30 Peak 2 50% 52%

I n t e n s i t y at 11 Peak 1 13% 21%


I n t e n s i t y a t 11 Peak 2 87% 79%

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
86 PARTICLE SIZE DISTRIBUTION

40%

30*

20%-

10%

0%4-
30 300 3000

10%

300 3000

40%

30%

20%

10%

3000

PARTICLE DIAMETER (NM)


SDP DIFFERENTIAL INTENSITY

F i g u r e 6a,b, a n d c. Measured i n t e n s i t y w e i g h t e d p a r t i c l e s i z e
d i s t r i b u t i o n o f a b i m o d a l d i s t r i b u t i o n ( 9 1 % b y w e i g h t 1 7 0 nm P S L
a n d 9% b y w e i g h t 8 2 2 nm P S L ) . a , b, and c c o r r e s p o n d t o measure-
m e n t s made a t 90 d e g r e e , 3 0 d e g r e e , a n d 11 d e g r e e scattering
angles, respectively.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
BOTT Submicrometer Particle Sizing

N o t i c e t h a t i f a measurement had been made a t 90 degrees a l o n e ,


the p r e s e n c e o f t h e 822 nm PSL would have been m i s s e d .

While i n t e n s i t y d i s t r i b u t i o n s a r e dependent on t h e a n g l e a t
which t h e y a r e measured, and t h e r e f o r e cannot be compared u n l e s s
measured a t t h e same a n g l e , volume d i s t r i b u t i o n s a r e , o f c o u r s e ,
a n g l e i n d e p e n d e n t . As was mentioned e a r l i e r , PCS measurements
made a t d i f f e r e n t a n g l e s , because o f t h e d i f f e r e n t w e i g h t i n g s a t
the d i f f e r e n t a n g l e s , c o n t a i n a f a i r degree o f independent
i n f o r m a t i o n . To i n t e g r a t e t h i s i n f o r m a t i o n , i s , however,
difficult. The s i m p l e s t approach toward i n t e g r a t i o n i s t o
s i m p l y average t h e volume d i s t r i b u t i o n s made o v e r s e v e r a l a n g l e s
t o get a composite p i c t u r e o f t h e sample.

The PCS i n s t r u m e n t used c o u l d a u t o m a t i c a l l y c o l l e c t d a t a from


any s i x a n g l e s , s t o r e t h
average t h e runs a f t e r w a r d s
f i v e 300 second runs a
and 90 degrees on t h e same b i m o d a l sample (170/822nm PSL) as
above. The i n d i v i d u a l a n g l e and composite r e s u l t s o f t h e f i v e
runs a t each o f t h e t h r e e a n g l e s a r e g i v e n below.

A n g l e Peak l(nm) Peak 2(nm) Peak 1 ( % i n t , % v o l ) Peak 2(%int,%vol)

15 162 1085 20, 89 80, 11


30 183 977 42, 78 58, 22
90 198 100, 100 100, 0
all 181 1031 89 11

I t s h o u l d be mentioned t h a t 300 second rune a r e r a t h e r s h o r t f o r


r e s o l v i n g b i m o d a l s , e s p e c i a l l y a t t h e lower a n g l e s . The s i g n a l
to n o i s e r a t i o i n t h e a u t o c o r r e l a t i o n f u n c t i o n i n c r e a s e s as t h e
i n v e r s e o f t h e s c a t t e r i n g v e c t o r magnitude. Thus t h e s i g n a l t o
n o i s e r a t i o a t 15 degrees and 30 degrees i n c r e a s e , r e s p e c t i v e l y ,
around 5.4 t i m e s and 2.7 times slower t h a n 90 d e g r e e s . The 300
second r u n a t 30 degrees i s r o u g h l y e q u i v a l e n t t o a 100 second
r u n a t 90 d e g r e e .

The m u l t i a n g l e a v e r a g i n g a l l o w s i d e n t i f i c a t i o n o f b o t h peaks;
w i t h a 90 degree measurement a l o n e , t h e peak a t l a r g e r s i z e
would have been m i s s e d . I n a d d i t i o n , t h e s i z e s and volume
p e r c e n t s o f t h e two peaks a r e r e a s o n a b l y w e l l c h a r a c t e r i z e d . I n
t h e t a b l e above, n o t i c e t h e d i f f e r e n c e i n t h e % i n t e n s i t i e s i n
the two peaks a t t h e d i f f e r e n t a n g l e s . To r e p e a t , t h e s e
d i f f e r e n c e s i n i n t e n s i t i e s w i t h d i f f e r e n t s c a t t e r i n g a n g l e s mean
that independent i n f o r m a t i o n i s o b t a i n e d a t d i f f e r e n t a n g l e s .

T h i s independent i n f o r m a t i o n a t d i f f e r e n t a n g l e s w i l l o c c u r
whenever t h e p a r t i c l e s i z e d i s t r i b u t i o n i n a sample i s b r o a d
enough (whethethe d i s t r i b u t i o n be mono, b i o r m u l t i m o d a l ) and
the p a r t i c l e s i z e s l a r g e enough t h a t t h e s c a t t e r e d l i g h t
i n t e n s i t i e s at d i f f e r e n t s c a t t e r i n g angles are d i f f e r e n t .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
88 PARTICLE SIZE DISTRIBUTION

CONCLUSIONS

The d i s c u s s i o n and r e s u l t s above show t h e danger o f r e l y i n g


h e a v i l y on s i z e d i s t r i b u t i o n i n f o r m a t i o n based on PCS
measurements t a k e n a t a s i n g l e s c a t t e r i n g a n g l e , e s p e c i a l l y on
unknown samples. The r e l a t i o n between i n t e n s i t y and weight
d i s t r i b u t i o n s , s t i p u l a t e d by t h e Mie e q u a t i o n s , i s such t h a t i n
many cases two p o p u l a t i o n s o f p a r t i c l e s may each comprise a
s u b s t a n t i a l p r o p o r t i o n o f a sample when measured by weight
p r o p o r t i o n but be v a s t l y d i f f e r e n t when compared by t h e
i n t e n s i t y d i s t r i b u t i o n s measured by PCS. I n t h e s e c a s e s , t h e
p r e s e n c e o f a p o p u l a t i o n o f p a r t i c l e s may be o v e r l o o k e d o r
poorly sized. By r o u t i n e l y making measurements a t two o r more
s c a t t e r i n g a n g l e s , e s p e c i a l l y on p r e v i o u s l y u n c h a r a c t e r i z e d
samples, t h e r e i s a b e t t e
i n f o r m a t i o n . F o r many samples
measurements a t o n l y one s c a t t e r i n g a n g l e must be t r e a t e d w i t h
caution.

Acknowledgment
The a u t h o r g r a t e f u l l y acknowledges K a r i n Evans o f L a n g l e y F o r d i n -
struments f o r h e r e x p e r t a s s i s t a n c e i n p r e p a r i n g and r u n n i n g t h e
p o l y s t y r e n e samples.

REFERENCES
1. B. Flegley and E.A. Barringer, Materials Research Soc.
Symposium, 32, 187 (1984).
2. R.L. Martin and M.R. Niesman, Chem. Phys. Lipids, 34, 245
(1984).
3. B.J. Berne and R. Pecora,"Dynamic Light Scattering,"
John Wiley and Sons, N.Y., 1976.
4. S.W. Provencher, Makromol. Chem., 180, 201 (1979)
5. S.W. Provencher, Computer Physics Communications, 27, 229
(1982).
6. J.G. McWhirter and E.R. Pike, J. Phys. A: Math. Gen.,
11, 1729 (1978).
7. M. Kerker. "The Scattering of Light and Other
Electromagnetic Radiation," Academic Press N.Y., 1969.

RECEIVED July 17, 1986

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 6

Using Quasi-Elastic Light Scattering To Study Particle


Size Distributions in Submicrometer Emulsion Systems
1 1 1 2 2
C. A. Herb , E. J. Berger , . Chang , I. D. Morrison , and E. F. Grabowski
1
Technical Center, Owens-Corning Fiberglas Corporation, Granville, OH 43023
2
Webster Research Center, Xerox Corporation, Webster, NY 14580

Quasi-elastic ligh scatterin i excellen tech


nique for studyin
-micrometer emulsions. Improvements in the methods of
quasi-elastic light scattering data acquisition and
analysis that enable full particle-size distribution
studies of sub-micrometer emulsion systems are dis
cussed. Using several oil/water emulsion systems as
examples, we demonstrate the ability of these tech
niques to determine the effect of emulsifier concen
tration on the particle-size distribution produced by
an inversion method of emulsification. Some of the
benefits of obtaining the full distribution are also
discussed.

In addition to affecting its own stability and rheology, an emul


sion's particle-size distribution often influences the quality of
the products in which the emulsion is incorporated. The full
particle-size distribution is, therefore, of some concern to the
researcher trying to improve or modify the product properties. Once
the link between the properties and the particle-size distribution
is known, the goal of creating an acceptable distribution through
control of processing variables during the emulsification can be
addressed. The mean diameter, the width of the distribution, or
even the distribution shape may be affected by altering variables
such as the surfactant concentration, agitation intensity, and
temperature.) Thus, the ability to monitor the full distribution,
rather than just a mean diameter, allows better control of product
quality and provides valuable additional information for product
improvement and more fundamental emulsion studies.
When the particle sizes in question are below about 1 micro
meter, the techniques available for determining the distribution
become limited. The use of quasi-elastic light scattering (QELS)
for the measurement of these sub-micrometer particles is becoming
increasingly popular with the availability of several commercial
instruments capable of both gathering and analyzing data.(2) One of
the major advantages of using QELS for emulsion studies is the
0097-6156/87/0332-0089$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
90 PARTICLE SIZE DISTRIBUTION

a b i l i t y t o w o r k i n a n y medium. T h u s , b o t h w a t e r / o i l and o i l / w a t e r
emulsions are e a s i l y studied. I n a d d i t i o n , concentrated samples can
be d i l u t e d w i t h t h e o r i g i n a l c o n t i n u o u s p h a s e , t h u s m a i n t a i n i n g t h e
proper environment f o r the d r o p l e t s . L i k e w i s e , one c a n s y s t e m a t i
c a l l y a l t e r t h e environment t o study t h e e f f e c t s o f such changes on
the s t a b i l i t y o f t h e system. In addition, the preparation of the
s c a t t e r i n g samples i s f a s t and s i m p l e .
The a i m o f t h i s p a p e r i s t o d e s c r i b e t h e e x p e r i m e n t a l a n d
n u m e r i c a l t e c h n i q u e s t h a t , when c o m b i n e d , p r o v i d e a p r o c e d u r e t h a t
enables f u l l p a r t i c l e - s i z e d i s t r i b u t i o n s t u d i e s o f sub-micrometer
emulsion systems. We t h e n p r e s e n t d i s t r i b u t i o n r e s u l t s f o r s e v e r a l
o i l / w a t e r emulsions t o demonstrate the a b i l i t y o f these techniques
to monitor t h e e f f e c t o f p r o c e s s i n g v a r i a b l e s (such as s u r f a c t a n t
c o n c e n t r a t i o n ) on t h e f i n a l e m u l s i o n . F i n a l l y , we d i s c u s s some o f
the problems o f c o n v e r t i n g t h e i n t e n s i t y weighted d i s t r i b u t i o n t o a
mass w e i g h t e d d i s t r i b u t i o d t method f o minimizin
eliminating some o f t h e s

Background

Many e x c e l l e n t i n t r o d u c t i o n s t o q u a s i - e l a s t i c l i g h t s c a t t e r i n g c a n
be f o u n d i n t h e l i t e r a t u r e d e s c r i b i n g t h e t h e o r y a n d e x p e r i m e n t a l
t e c h n i q u e ( e . g . 3 - 6 ) . T h e u s e o f QELS t o d e t e r m i n e p a r t i c l e s i z e i s
based on t h e measurement, v i a t h e a u t o c o r r e l a t i o n o f t h e time de
pendence o f t h e s c a t t e r e d l i g h t , o f t h e d i f f u s i o n c o e f f i c i e n t s o f
suspended p a r t i c l e s undergoing Brownian motion. The measured a u t o
correlation function, G ( T ) , i s given by
< 2 >

( 1 ) 2
G < 2 ,
(T) = A[I + B | g (T)| ] (1)

A i s t h e base l i n e , which i s obtained e i t h e r from t h e long-time


asymptote o f t h e measured a u t o c o r r e l a t i o n f u n c t i o n o r from t h e
square o f t h e average photon f l u x . 3 i s an equipment-related con
( 1 )
s t a n t , and g () i s the normalized f i r s t - o r d e r autocorrelation
f u n c t i o n , which i s e a s i l y o b t a i n e d from t h e measured function,
C L )
G c 2 >
(x). F o r monodisperse systems g ( T ) i s a simple exponential
decay w i t h t h e d e s i r e d i n f o r m a t i o n being contained i n the decay
2
c o n s t a n t , , w h i c h i s e q u a l t o q D , w h e r e q i s t h e m a g n i t u d e o f t h e
s c a t t e r i n g v e c t o r ( q = ( 4 / ) s i n ( / 2 ) ) a n d D i s t h e t r a n s l a t i o n -
al diffusion coefficient. I f t h e sample i s d i l u t e enough t h a t t h e
motion o f a p a r t i c l e i s n o t a f f e c t e d by t h e presence o f t h e other
p a r t i c l e s i n t h e sample, o r i f i s obtained as a f u n c t i o n of con
c e n t r a t i o n and e x t r a p o l a t e d t o z e r o c o n c e n t r a t i o n , one o b t a i n s t h e
single-particle diffusion coefficient. I f t h e medium i s a N e w t o n i a n
f l u i d and one f u r t h e r assumes t h a t t h e p a r t i c l e s a r e s p h e r i c a l ( a n
excellent assumption f o r emulsions), the Stokes-Einstein r e l a t i o n
between t h e s i n g l e - p a r t i c l e d i f f u s i o n c o e f f i c i e n t and t h e h y d r o -
dynamic d i a m e t e r o f a p a r t i c l e c a n be used ( i . e . D = kT/(3irnd)),

2 2 2
= (^kTn sin |-)/(3riX d) (2)

where k i s t h e Boltzmann c o n s t a n t , i s temperature, i st h e


r e f r a c t i v e index o f t h e f l u i d , i s t h e s c a t t e r i n g angle, i st h e
v i s c o s i t y , i s t h e wavelength o f t h e l i g h t , and d i s t h e p a r t i c l e
diameter.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
6. HERB ET AL. Quasi-Elastic Light Scattering 91

( 1 >
For p o l y d i s p e r s e samples, g ( x ) i s a f u n c t i o n not only of the
d e l a y t i m e T, b u t a l s o o f t h e d i s t r i b u t i o n o f d e c a y c o n s t a n t s a s
shown i n E q u a t i o n 3 i n i n t e g r a l f o r m and i n E q u a t i o n 4 i n a l g e b r a i c
form.

g ( 1 <
(T) - / F () expC-) dT (3)
J
0

M
g ( 1 >
(T) = (-.) (4)
1
i=l

( 1 )
Thus, g i v e n g ( T ) , we n e e d t o d e t e r m i n e t h e p a r t i c l e s i z e
distribution. For narrow s i z e d i s t r i b u t i o n s , the a u t o c o r r e l a t i o n
function i s satisfactoril analyzed b th method f cumulant
g i v e t h e moments o f t h
a n a l y s i s o f QELS d a t a f o
d i s t r i b u t i o n s r e m a i n s an a r e a o f a c t i v e r e s e a r c h . ( 8 )
I n o r d e r t o o b t a i n t h e p a r t i c l e - s i z e d i s t r i b u t i o n , one must
i n v e r t E q u a t i o n 3 o r 4 n u m e r i c a l l y . When t h e d a t a a r e a n a l y z e d v i a
E q u a t i o n 4, o n e o b t a i n s a h i s t o g r a m d e s c r i b e d b y a p r o b a b i l i t y f o r
each decay c o n s t a n t , expressed by the v e c t o r s e t (^,^). A p a r t i
c l e d i a m e t e r d i s t r i b u t i o n c a n t h e n be o b t a i n e d f r o m t h i s v i a E q u a
t i o n 2. On f i r s t g l a n c e , i t w o u l d s e e m t h a t o n e c o u l d s i m p l y c h o o s e
a l a r g e number o f p a r t i c l e s i z e s , c a l c u l a t e t h e c o r r e s p o n d i n g d e c a y
c o n s t a n t s , a n d f i n d t h e b e s t s e t o f a^'s b y a l e a s t s q u a r e s f i t o f
( 1 )
the g ( T ) d a t a t o E q u a t i o n 4 f o r t h e assumed p a r t i c l e s i z e s . The
expectation i s t h a t only those s i z e s that are a c t u a l l y i n the d i s
p e r s i o n w i l l appear i n the f i n a l d i s t r i b u t i o n . U n f o r t u n a t e l y , the
i n v e r s i o n o f E q u a t i o n 4 i s known t o be i l l - c o n d i t i o n e d f o r t h e
standard l e a s t squares technique. That i s , s m a l l changes i n the
measured d a t a l e a d t o l a r g e v a r i a t i o n s i n the c a l c u l a t e d d i s t r i b u
t i o n s . (9) A more d e t a i l e d d i s c u s s i o n o f t h e p r o b l e m has been g i v e n
by P i k e ( 1 0 ) , i n w h i c h he s u g g e s t s t h a t t h e i l l - c o n d i t i o n e d n a t u r e
o f t h e i n v e r s i o n w i l l be r e d u c e d by l i m i t i n g t h e r a n g e o f t h e s o l u
t i o n s p a c e v i a a p r i o r i i n f o r m a t i o n a b o u t t h e d i s t r i b u t i o n , and by
i n c r e a s i n g the range of delay times over which the a u t o c o r r e l a t i o n
function i s obtained. The i n c r e a s e i n t h e r a n g e o f d e l a y t i m e s h a s
been s u c c e s s f u l l y a d d r e s s e d by t h e m a n u f a c t u r e r s o f d i g i t a l a u t o -
c o r r e l a t o r s by p r o v i d i n g n o n - l i n e a r s p a c i n g o f t h e c o r r e l a t o r
channels. The u s e o f r e a s o n a b l e a p r i o r i i n f o r m a t i o n t o l i m i t t h e
r a n g e o f t h e s o l u t i o n s p a c e w i l l be d i s c u s s e d i n t h e n e x t s e c t i o n .

The Inversion Algorithm

Requirements. A s u c c e s s f u l and y e t p r a c t i c a l n u m e r i c a l p r o c e d u r e
f o r o b t a i n i n g p a r t i c l e - s i z e d i s t r i b u t i o n s f r o m QELS d a t a m u s t :
1) b e s t a b l e a g a i n s t r a n d o m e x p e r i m e n t a l e r r o r , 2) c l e a r l y d i f f e r
e n t i a t e m u l t i m o d a l d i s t r i b u t i o n s from broad unimodal ones w i t h o u t
a p r i o r i k n o w l e d g e o f t h e s h a p e o f t h e d i s t r i b u t i o n , 3) r e q u i r e o n l y
m i n i m a l o p e r a t o r i n p u t , a n d 4) a p p l y t o b o t h n a r r o w a n d b r o a d
particle size distributions. An a d d i t i o n a l d e s i d e r a t u m i s t h a t t h e
c o m p u t e r r e q u i r e m e n t s be k e p t t o a r e a s o n a b l e l e v e l .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
92 PARTICLE SIZE DISTRIBUTION

Proposal. We h a v e r e c e n t l y d e s c r i b e d a p r o c e d u r e t h a t we b e l i e v e
m e e t s t h e r e q u i r e m e n t s l i s t e d a b o v e . ( 1 1 ) M o r e s p e c i f i c a l l y , we h a v e
s h o w n tha.t t h e p a r t i c l e s i z e d i s t r i b u t i o n c a n b e e x t r a c t e d f r o m t h e
QELS d a t a b y a c o m b i n a t i o n o f a ) a c o n v e r g e n t n u m e r i c a l a l g o r i t h m
t h a t makes use o f t h e f a c t t h a t t h e d i s t r i b u t i o n o f s i z e s must be
n o n - n e g a t i v e ( 1 2 ) , b) a n a l y s i s o f e a c h d a t a s e t w i t h m u l t i p l e b u t
e q u i v a l e n t b a s i s s e t s o f p a r t i c l e s i z e s ( 1 3 ) , and c) t h e a v e r a g i n g
of d i s t r i b u t i o n s o b t a i n e d from r e p e a t e d , independent measurements
f o r each sample analyzed.(11) Only a b r i e f d i s c u s s i o n of the proce
d u r e w i l l be g i v e n h e r e . More complete d i s c u s s i o n s are g i v e n e l s e
w h e r e . (.,12)

The N o n - N e g a t i v e C o n s t r a i n t . A s d i s c u s s e d a b o v e , t h e i n v e r s i o n o f
Equation 4 i s i l l - c o n d i t i o n e d . T h i s m a n i f e s t s i t s e l f most c l e a r l y
by p r o v i d i n g d i s t r i b u t i o n s w i t h n e g a t i v e components when o r d i n a r y
l e a s t squares algorithm used Th tendenc t produc thes
physically impossible solution
b e r o f assumed p a r t i c l e
the range of the s o l u t i o n space, thus reducing the i l l - c o n d i t i o n e d
n a t u r e o f t h e p r o b l e m as d i s c u s s e d i n t h e l a s t s e c t i o n . Unfortu
n a t e l y , i t has b e e n f o u n d t h a t t h e number o f s i z e s t h a t can be u s e d
s u c c e s s f u l l y i s s o f e w (5 o r 6 a t b e s t ) t h a t t h e s i z e r e s o l u t i o n i s
poor. A n o t h e r way t o s i g n i f i c a n t l y d e c r e a s e t h e r a n g e o f t h e s o l u
t i o n s p a c e i s t o d i s a l l o w a l l s o l u t i o n s t h a t c o n t a i n n e g a t i v e compo
nents. The u s e o f t h i s n o n - n e g a t i v e c o n s t r a i n t d u r i n g t h e c a l c u
l a t i o n s s u b s t a n t i a l l y reduces the i l l - c o n d i t i o n e d nature of the
inversion. The i n c r e a s e i n t h e s t a b i l i t y o f t h e i n v e r s i o n a l l o w s a
l a r g e r number o f unknowns t o be u s e d , t h u s i n c r e a s i n g t h e p o t e n t i a l
resolution. To i m p l e m e n t t h e m e t h o d o f n o n - n e g a t i v e l y constrained
l e a s t s q u a r e s , we c h o o s e t h e m e t h o d o f L a w s o n a n d H a n s o n ( 1 4 ) c a l l e d
NNLS ( f o r n o n - n e g a t i v e l e a s t s q u a r e s ) . The u s e o f t h i s a p r i o r i
i n f o r m a t i o n has not l i m i t e d the g e n e r a l n a t u r e of the d i s t r i b u t i o n
i n a n y way. The d e t a i l s o f u s i n g NNLS f o r t h e QELS p r o b l e m h a v e
been presented elsewhere.(12)

M u l t i p l e P a s s A n a l y s i s . P i k e and c o w o r k e r s (13) h a v e p r o v i d e d a
method t o i n c r e a s e the r e s o l u t i o n of the o r d i n a r y l e a s t s q u a r e s a l
g o r i t h m somewhat. I t was n o t e d t h a t a n y r e a s o n a b l e s e t o f a s s u m e d
p a r t i c l e s i z e s c o n s t i t u t e s a b a s i s set f o r the i n v e r s i o n ( w i t h i n
experimental error). T h u s , t h e d a t a c a n be a n a l y z e d a number o f
t i m e s w i t h a d i f f e r e n t b a s i s s e t e a c h t i m e , and t h e r e s u l t s c o m b i n e d .
A s t a t i s t i c a l l y m o r e - p r o b a b l e s o l u t i o n r e s u l t s f r o m an a v e r a g e o f
the s e v e r a l e q u a l l y - l i k e l y s o l u t i o n s . Although t h i s " m u l t i p l e pass
a n a l y s i s " helps l o c a t e the peaks of the d i s t r i b u t i o n w i t h b e t t e r
r e s o l u t i o n and p r o v i d e s a s m o o t h e r p r e s e n t a t i o n o f t h e r e s u l t , i t
can s t i l l o n l y p r o v i d e l i m i t e d r e s o l u t i o n w i t h o u t t h e use of a non-
n e g a t i v e l y constrained l e a s t squares technique. We h a v e s h o w n ,
however, t h a t the combination of both the n o n - n e g a t i v e l y constrained
c a l c u l a t i o n and t h e m u l t i p l e p a s s a n a l y s i s g i v e s t h e a d v a n t a g e s o f
both.
We i m p l e m e n t m u l t i p l e p a s s a n a l y s i s f o r a n a r b i t r a r y s p a c i n g o f
assumed s i z e s as f o l l o w s . L e t t h e r e be M assumed p a r t i c l e s i z e s
s u b m i t t e d t o t h e NNLS i n v e r s i o n r o u t i n e f o r e a c h o f p a s s e s . Thus,
t h e f i n a l h i s t o g r a m w i l l c o n t a i n MP d i f f e r e n t p a r t i c l e s i z e s s p a c e d
i n some f a s h i o n ( e . g . l o g a r i t h m i c a l l y , q u a d r a t i c a l l y , o r l i n e a r l y )

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
6. HERB ET AL. Quasi-Elastic Light Scattering 93

over the a p p r o p r i a t e range. The u p p e r and l o w e r l i m i t s o f t h e r a n g e


c a n be c h o s e n by t h e o p e r a t o r i f r e a s o n a b l e v a l u e s a r e known, o r
t h e y can be c h o s e n by t h e p r o g r a m f r o m t h e shape o f t h e f i r s t a u t o
correlation function. O n c e t h e r a n g e i s s e l e c t e d , a l l MP s i z e s a r e
c a l c u l a t e d a c c o r d i n g t o t h e c h o s e n s p a c i n g scheme.
We a c t u a l l y s u b m i t M+l s i z e s t o NNLS o n e a c h p a s s , t h e e x t r a
size corresponding to a "dust" signal ( i . e . i n f i n i t e p a r t i c l e s i z e
o r a z e r o d e c a y c o n s t a n t ) . T h u s , o n t h e f i r s t p a s s , we f i n d t h e
best f i t to the c o r r e l a t i o n f u n c t i o n using only the M f l p a r t i c l e
sizes:
d d d a n d d
l ' P + l ' 2P+l "W-P+l' dust

In g e n e r a l , on t h e j t h p a s s , we use t h e M+l particle sizes:

V d
P+j> 2P+j d
"W-P+j' a n d d
dust

The a n a l y s i s f r o m t h e
t i p l e pass a n a l y s i s of th
and a m e a s u r e o f t h e amount o f t h e s i g n a l t h a t i s due to "dust".

D i s t r i b u t i o n Averaging. Although the r e s o l u t i o n i s s i g n i f i c a n t l y


improved by t h e use o f a n o n - n e g a t i v e l y c o n s t r a i n e d l e a s t s q u a r e s
a l g o r i t h m , i t h a s two s h o r t c o m i n g s : 1) C o r r e l a t e d e x p e r i m e n t a l e r r o r
i s o f t e n i n t e r p r e t e d a s s m a l l s p u r i o u s p e a k s ; a n d 2) B r o a d unimodal
d i s t r i b u t i o n s t e n d t o be r e p r e s e n t e d by a s e t o f s e p a r a t e d p e a k s .
Although m u l t i p l e pass a n a l y s i s improves the p r e s e n t a t i o n of m u l t i
m o d a l d i s t r i b u t i o n s and u n i m o d a l d i s t r i b u t i o n s t h a t a r e n o t t o o w i d e ,
i t f a i l s t o c o r r e c t t h e s e two shortcomings.
We h a v e f o u n d t h a t b o t h t h e s e s h o r t c o m i n g s c a n b e r e d u c e d o r
e l i m i n a t e d b y t a k i n g m u l t i p l e d a t a s e t s o n t h e same s a m p l e , a n a l y z
i n g e a c h d a t a s e t i n d e p e n d e n t l y , and a v e r a g i n g a l l o f t h e r e s u l t i n g
size distributions. The c o r r e c t p e a k s a r e r e i n f o r c e d w h i l e s p u r i o u s
p e a k s a r e d i m i n i s h e d . A gap w i l l r e m a i n b e t w e e n t h e p e a k s o f a t r u e
bimodal sample. I f , however, the sample a c t u a l l y has a w i d e u n i
modal d i s t r i b u t i o n , the p o s i t i o n s of the separated peaks w i l l v a r y
f r o m one d a t a s e t t o a n o t h e r , t h u s f i l l i n g i n t o a s m o o t h u n i m o d a l
peak. Once a g a i n , a s t a t i s t i c a l l y m o r e - p r o b a b l e s o l u t i o n r e s u l t s
f r o m an a v e r a g e o f t h e s e v e r a l e q u a l l y - l i k e l y s o l u t i o n s . (The number
o f i n d e p e n d e n t d a t a s e t s u s e d s h o u l d b e g r e a t e r t h a n t w i c e t h e num
b e r o f p a r t i c l e s i z e s i n t h e b r o a d e s t p e a k d i v i d e d b y P, t h e n u m b e r
of passes.)
What i s p a r t i c u l a r l y s i g n i f i c a n t i s t h a t t h e QELS a n a l y s i s i s
enhanced by t h e c o m b i n a t i o n o f the t h r e e t e c h n i q u e s p r e s e n t e d h e r e
w i t h o u t i n t r o d u c i n g a n y new a s s u m p t i o n s o r r e q u i r i n g a n y unreasona
b l e a p r i o r i i n f o r m a t i o n , n o t even t h a t t h e d i s t r i b u t i o n must be
smooth.

Peak Broadening. The p e a k s o b t a i n e d b y t h e p r o c e d u r e o u t l i n e d a b o v e


c a n b e b r o a d e n e d b e y o n d t h e t r u e d i s t r i b u t i o n b y two t h i n g s . First,
t h e use o f t o o few assumed p a r t i c l e s i z e s f o r t h e i n v e r s i o n w i l l
o b v i o u s l y c a u s e t h e r e p o r t e d d i s t r i b u t i o n t o be b r o a d e r t h a n i t
s h o u l d be. T h i s p r o b l e m i s r e s o l v e d by c h o o s i n g a l a r g e r number o f
assumed s i z e s . (We t y p i c a l l y c h o o s e t w e n t y p a r t i c l e d i a m e t e r s f o r
e a c h i n v e r s i o n . ) The s e c o n d p r o b l e m i s t h a t t h e r e p o r t e d d i s t r i b u
t i o n w i l l be a r t i f i c i a l l y b r o a d e n e d by e x c e s s i v e n o i s e i n t h e a u t o -

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
94 PARTICLE SIZE DISTRIBUTION

c o r r e l a t i o n f u n c t i o n s o b t a i n e d . T h i s can o n l y be s o l v e d by i n c r e a s
ing the q u a l i t y of the data c o l l e c t e d , which implies longer data
c o l l e c t i o n times o r an i n c r e a s e i n t h e photon count r a t e , i f p o s s i
ble. We h a v e p r e v i o u s l y d e m o n s t r a t e d t h i s n o i s e r e l a t e d b r o a d e n i n g
w i t h a mixture of l a t e x standards (11,15). P r a c t i c a l l y , we h a v e
found that t h i s broadening i s n o t a s e r i o u s problem i f t h e t o t a l
p h o t o n c o u n t f o r e a c h a u t o c o r r e l a t i o n f u n c t i o n i s k e p t a b o v e 15 o r
20 m i l l i o n ( e . g . 10 m i l l i o n s a m p l e s w i t h a c o u n t r a t e o f 1.5 t o 2
photons p e r sample t i m e ) .

Emulsion Studies

As d i s c u s s e d e a r l i e r , i t i s known t h a t t h e s u r f a c t a n t c o n c e n t r a t i o n
present d u r i n g e m u l s i f i c a t i o n can a f f e c t the p a r t i c l e s i z e o f an
emulsion. I t h a s a l s o b e e n shown t h a t t h e s t a b i l i t y o f a n e m u l s i o n
can be a f f e c t e d i n r a t h e unexpected b changin th concentra
tion of the surfactant (16)
section allow the researche
t r i b u t i o n o f t h e emulsion system r a t h e r than j u s t an average diame
ter. U s i n g s e v e r a l o i l / w a t e r e m u l s i o n s y s t e m s a s e x a m p l e s , we dem
onstrate t h e a b i l i t y o f these techniques t o determine the e f f e c t of
e m u l s i f i e r c o n c e n t r a t i o n on t h e p a r t i c l e - s i z e d i s t r i b u t i o n produced
by a n i n v e r s i o n method o f e m u l s i f i c a t i o n . Some o f t h e b e n e f i t s o f
o b t a i n i n g t h e f u l l d i s t r i b u t i o n w i l l a l s o be d i s c u s s e d .

Experimental. P a r t i c l e - s i z e d i s t r i b u t i o n r e s u l t s were o b t a i n e d f o r
three emulsion systems, r e f e r r e d t o a s s y s t e m s A , B, a n d C. T h e
o i l phase o f e m u l s i o n systems A and C c o n s i s t s o f 70% by weight o f a
thermoset r e s i n i n an o r g a n i c s o l v e n t . The o i l phase o f e m u l s i o n
s y s t e m i s a d i f f e r e n t t h e r m o s e t r e s i n w i t h no s o l v e n t p r e s e n t . A
d i f f e r e n t n o n i o n i c e m u l s i f i e r was u s e d f o r e a c h o f t h e t h r e e e m u l
s i o n systems. The e m u l s i o n s were p r e p a r e d by s l o w l y a d d i n g w a t e r t o
the m i x t u r e o f o i l phase and s u r f a c t a n t i n a h i g h shear m i x e r . Fol
lowing i n v e r s i o n from the w a t e r / o i l t o o i l / w a t e r emulsion, a d d i t i o n
a l w a t e r was added t o b r i n g t h e f i n a l i n t e r n a l p h a s e t o 5 0 % b y
weight. The l i g h t s c a t t e r i n g s a m p l e s w e r e p r e p a r e d b y d i l u t i n g a
s m a l l p o r t i o n o f t h e e m u l s i o n t o 20 mg/L o i l p h a s e w i t h a d u s t f r e e ,
10 mg/L s o l u t i o n o f t h e e m u l s i f i e r . The s a m p l e was t h e n f i l t e r e d
t h r o u g h a 5 m i c r o m e t e r membrane f i l t e r d i r e c t l y i n t o t h e s c a t t e r i n g
cell.

Equipment. A l l s c a t t e r i n g e x p e r i m e n t s were done on a BI240 l i g h t


s c a t t e r i n g goniometer from Brookhaven Instruments C o r p o r a t i o n . T h i s
i n c l u d e s a l l t h e n e c e s s a r y o p t i c s , sample c e l l assembly, p h o t o m u l t i -
p l i e r tube, a m p l i f i e r / d i s c r i m i n a t o r , and t h e goniometer base i t s e l f .
The t e m p e r a t u r e o f t h e s a m p l e c e l l a n d i n d e x m a t c h i n g l i q u i d s u r
r o u n d i n g t h e c e l l w a s h e l d a t 25C w i t h a N e s l a b RTE-5DD c i r c u l a t i n g
bath. T h e l i g h t s o u r c e i s a S p e c t r a - P h y s i c s , M o d e l 1 2 4 B , 15 mW,
l i n e a r l y p o l a r i z e d , HeNe l a s e r . The l a s e r a n d o p t i c a l components
a r e mounted on a Newport R e s e a r c h C o r p o r a t i o n v i b r a t i o n i s o l a t i o n
table.
A BI2020 d i g i t a l c o r r e l a t o r , a l s o from Brookhaven Instruments,
r e c e i v e s t h e s i g n a l from t h e a m p l i f i e r / d i s c r i m i n a t o r . The c o r r e
l a t o r h a s 136 c h a n n e l s f o l l o w e d b y 4 b a s e l i n e c h a n n e l s s t a r t i n g a t
1024 s a m p l e t i m e s . I n our laboratory, the correlator i s controlled

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
6. HERB ET AL. Quasi-Elastic Light Scattering 95

by a H e w l e t t - P a c k a r d 236 m i c r o c o m p u t e r ( f o r m e r l y d e s i g n a t e d t h e
H P 9 8 3 6 ) , w h i c h a l s o p e r f o r m s t h e d i s t r i b u t i o n a n a l y s i s . The p r o g r a m
c o n t r o l s t h e BI2020 c o r r e l a t o r w h i l e c a l c u l a t i n g t h e d i s t r i b u t i o n
f r o m t h e l a t e s t a u t o c o r r e l a t i o n f u n c t i o n . I n t h i s way d a t a c a n be
collected while the i n d i v i d u a l d i s t r i b u t i o n s are being calculated
and a v e r a g e d . The s y s t e m r e q u i r e s no o p e r a t o r i n p u t once t h e r u n
has b e e n s t a r t e d . The f i n a l d i s t r i b u t i o n s a r e c o n v e r t e d f r o m l i g h t
i n t e n s i t i e s t o mass f r a c t i o n s u s i n g t h e M i e c o r r e c t i o n f a c t o r s a s i s
discussed i n a later section.

Results. F i g u r e 1 shows t h e d i s t r i b u t i o n s f o r e m u l s i o n s y s t e m A f o r
t o t a l e m u l s i f i e r c o n c e n t r a t i o n s r a n g i n g f r o m 3.5 t o 2 0 g / 1 0 0 g o i l
phase. I t c a n b e s e e n t h a t b o t h t h e mean d i a m e t e r a n d t h e w i d t h o f
the d i s t r i b u t i o n decrease w i t h i n c r e a s i n g s u r f a c t a n t l e v e l . The
same t r e n d w a s s e e n f o r s y s t e m o v e r t h e r a n g e o f 8 t o 21 g / 1 0 0 g
o i l phase. System c o u l d t b emulsified b th inversio tech
nique below t h i s range
ard deviations of both
tration. ( I t i s interesting, but only a coincidence, that both
s y s t e m s g i v e t h e same r e s u l t s o v e r t h e 8 t o 2 0 g / 1 0 0 g r a n g e . ) Thus,
f o r t h e s e s y s t e m s o n e c a n now p r e d i c t t h e mean d i a m e t e r a n d t h e
w i d t h o f t h e d i s t r i b u t i o n once t h e s u r f a c t a n t c o n c e n t r a t i o n i s known.
Conversely, i f t h e d i s t r i b u t i o n o f a sample were measured f o r q u a l i
t y c o n t r o l purposes and t h e d i a m e t e r and w i d t h were t o o h i g h , an i n
c o r r e c t s u r f a c t a n t c o n c e n t r a t i o n d u r i n g e m u l s i f i c a t i o n would be i n
d i c a t e d as a p o s s i b l e cause.
A m o r e i n t e r e s t i n g way t o l o o k a t t h e d a t a i s t o p l o t t h e s p e
c i f i c surface area of the emulsion droplets as a f u n c t i o n of the
s u r f a c t a n t c o n c e n t r a t i o n a s s h o w n i n F i g u r e 3. ( T h e s u r f a c e a r e a w a s
c a l c u l a t e d f r o m t h e f u l l d i s t r i b u t i o n r a t h e r t h a n f r o m a mean d i a m e
ter.) Thus, i t c a n be seen t h a t , o v e r t h e r a n g e s t u d i e d , a n i n
c r e a s e i n t h e amount o f s u r f a c t a n t p r e s e n t c a u s e s a p r o p o r t i o n a l i n
crease i n the surface area created.
Because a l l o f these d i s t r i b u t i o n s a r e unimodal and have r e l a
t i v e s t a n d a r d d e v i a t i o n s l e s s t h a n 3 5 % , t h e method o f c u m u l a n t s
c o u l d h a v e b e e n u s e d t o o b t a i n t h e d a t a o f F i g u r e 2. H o w e v e r , t h e
d i s t r i b u t i o n t e c h n i q u e used h e r e c a n d i s t i n g u i s h between b i m o d a l and
b r o a d u n i m o d a l d i s t r i b u t i o n s w i t h no o p e r a t o r i n t e r v e n t i o n o r a
p r i o r i knowledge about t h e sample. The i m p o r t a n c e o f t h i s a b i l i t y
i s d e m o n s t r a t e d b y t h e d i s t r i b u t i o n o f e m u l s i o n s y s t e m C shown i n
F i g u r e 4. T h i s s y s t e m w a s p r e p a r e d i n a n i d e n t i c a l f a s h i o n t o s y s
t e m s A a n d B, b u t w i t h a l o w c o n c e n t r a t i o n o f a d i f f e r e n t n o n i o n i c
emulsifier. The r e s u l t i n g b i m o d a l d i s t r i b u t i o n was c e r t a i n l y n o t an
expected r e s u l t . Note t h a t t h e broad unimodal o f F i g u r e l a and t h e
b i m o d a l o f F i g u r e 4 h a v e s i m i l a r mean d i a m e t e r s a n d s t a n d a r d d e v i a
tions. The a b i l i t y t o d i s t i n g u i s h b e t w e e n t h e two c a n b e o f s i g n i f
i c a n t a s s i s t a n c e i n t h e i n v e s t i g a t i o n o f emulsion systems. Indeed,
t h e d i s t r i b u t i o n shown i n F i g u r e 4 i s i n d i c a t i v e o f n o n - u n i f o r m
shear conditions during the e m u l s i f i c a t i o n rather than a s u r f a c t a n t
concentration problem.

F l o c c u l a t i o n versus Coalescence. The b r e a k i n g o f a n e m u l s i o n i s a


two s t e p p r o c e s s r e q u i r i n g t h e c o a l e s c e n c e o f t h e d r o p l e t s a f t e r
they a r e i n contact.(17) I f t h e system f l o c c u l a t e s b u t i s r e s i s t a n t
to coalescence, t h e system w i l l n o t phase separate. Over a p e r i o d

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
96 PARTICLE SIZE DISTRIBUTION

(a)

d = 754 nm
CO = 212 nm
< (excluding 5 bins
of n o i s e a g a i n s t
w
> upper bound)
M
H
<

100 400 1000 2000 3000

(b)

d = 5 6 9 nm
CO
CO = 149 nm
<!
S
W
>
M
H
:
-

100 400 1000 2000 3000

10
(c)

JUL d = 286 nm
CO
CO = 98 nm
<
w
II!
>
M
H
<

100 400 1000 2000 3000

PARTICLE DIAMETER (nm)

F i g u r e 1. P a r t i c l e s i z e d i s t r i b u t i o n s f o r e m u l s i o n s y s t e m A w i t h
v a r i o u s e m u l s i f i e r c o n c e n t r a t i o n s ( i n g/100g o i l p h a s e ) : ( a ) 3.5,
( b ) 5, ( c ) 10. E a c h f i g u r e i s a n a v e r a g e o f 15 d i s t r i b u t i o n s ,
e a c h o f w h i c h was o b t a i n e d u s i n g q u a d r a t i c s p a c i n g w i t h 20 p a r t i c l e
s i z e s p e r pass and 5 p a s s e s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
6. HERB ET AL. Quasi-Elastic Light Scattering

12

(d)
10

CO
IL d = 202 nm
CO
8 = 65 nm
<
w
6
>
M
H
<
W
PS - JnThj

100 400 1000 2000 3000

PARTICLE DIAMETER (nm)

14

(e)

CO
II d = 160 nm

1
CO
= 47 nm
<:
s
w
>
M
H

il
<U
hJ
W
ta

100 400 1000 2000 3000

PARTICLE DIAMETER (nm)

F i g u r e 1. Continued. P a r t i c l e size d i s t r i b u t i o n s f o r emulsion


s y s t e m A w i t h v a r i o u s e m u l s i f i e r c o n c e n t r a t i o n s ( i n g/100g o i l
phase): ( d ) 1 5 , ( e ) 2 0 . E a c h f i g u r e i s a n a v e r a g e o f 15
d i s t r i b u t i o n s , e a c h o f w h i c h was o b t a i n e d u s i n g q u a d r a t i c s p a c i n g
w i t h 20 p a r t i c l e s i z e s p e r p a s s a n d 5 p a s s e s *

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
98 PARTICLE SIZE DISTRIBUTION

800

MEAN DIAMETER
700h
EMULSION SYSTEM A
EMULSION SYSTEM

600! STANDARD DEVIATION


EMULSION SYSTEM A
EMULSION SYSTEM
> 500
LU


( 400
<

2
<
Q 300
2
<

LU
h-
LU
200
<

100

J L -L. -L
0 2 4 6 8 10 12 14 16 1 20 22 24

SURFACTANT CONCENTRATION <g/100g o i l phaco)

F i g u r e 2. Mean d i a m e t e r a n d s t a n d a r d d e v i a t i o n versus surfactant


concentration f o r e m u l s i o n s y s t e m s A a n d

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
6. HERB ET AL. Quasi-Elastic Light Scattering 99

55 ! I I

50 EMULSION SYSTEM A
EMULSION SYSTEM B
45

7 40
\
(M

351-
<
LU
< 3Qr
LU
CJ
<
u. 25
D
CO
U
- 20
U.

LU
CL 15
en

10

0 2 4 6 8 10 12 14 16 18 20 22

SURFACTANT CONCENTRATION <g/100g o i l p h a s o )

F i g u r e 3. S p e c i f i c s u r f a c e a r e a o f i n t e r n a l p h a s e v e r s u s surf
a c t a n t c o n c e n t r a t i o n f o r e m u l s i o n s y s t e m s A a n d B, a s c a l c u l a t e d
from the f u l l d i s t r i b u t i o n s .

7 OVER-ALL

6 d" = 778 nm
CO 0 = 235 nm
CO
5
<
4
>
M 3
H
<
J 2
W
P4
1

100 400 1000 2000 3000

PARTICLE DIAMETER (nm)

F i g u r e 4. P a r t i c l e - s i z e d i s t r i b u t i o n o f e m u l s i o n s y s t e m C w i t h
e m u l s i f i e r c o n c e n t r a t i o n o f 7 g/100g o i l p h a s e . The f i g u r e i s a n
a v e r a g e o f 10 d i s t r i b u t i o n s , e a c h o f w h i c h w a s o b t a i n e d u s i n g
q u a d r a t i c s p a c i n g w i t h 20 p a r t i c l e s i z e s p e r p a s s a n d 5 p a s s e s .
In Particle Size Distribution; Provder, T.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
100 p a r t i c l e size d i s t r i b u t i o n

o f t i m e , some o f o u r s a m p l e s f l o c c u l a t e d a n d s e t t l e d . I t was o f
i n t e r e s t t o d e t e r m i n e w h e t h e r t h e r e was a n y c o a l e s c e n c e o f t h e p a r -
t i c l e s under these c o n d i t i o n s . A f t e r s e v e r a l months, these samples
were re-examined t o determine t h e i r p a r t i c l e s i z e d i s t r i b u t i o n s . No
change i n t h e d i s t r i b u t i o n s was f o u n d , i n d i c a t i n g t h a t t h e samples
were, indeed, r e s i s t a n t t o coalescence. An example o f t h e a b i l i t y
o f t h e QELS t e c h n i q u e s p r e s e n t e d h e r e t o f o l l o w s l o w l y f l o c c u l a t i n g
e m u l s i o n samples c a n be found i n r e f e r e n c e 15.

Light Scattering Corrections

The d i s t r i b u t i o n o b t a i n e d f r o m t h e i n v e r s i o n o f E q u a t i o n 4 i s a n i n -
t e n s i t y weighted d i s t r i b u t i o n . That i s , i td i s p l a y s t h e percentage
o f l i g h t s c a t t e r e d f r o m e a c h p a r t i c l e s i z e i n t h e p o p u l a t i o n . What
i s d e s i r e d i s t h e amount o f mass a t e a c h p a r t i c l e s i z e (mass d i s t r i -
b u t i o n ) , o r t h e number o f p a r t i c l e s a t e a c h p a r t i c l e s i z e (number o r
frequency d i s t r i b u t i o n )
known, t h e o t h e r s c a n b
l i m i t s and n o i s e i n a c t u a l e x p e r i m e n t a l d a t a , however, i t i s n o t
that straightforward.
What i s r e q u i r e d i s a k n o w l e d g e o f t h e r e l a t i v e a m o u n t o f l i g h t
s c a t t e r e d from p a r t i c l e s o f d i f f e r e n t diameters i n t h e sample. I n
g e n e r a l t h i s depends n o t o n l y on t h e p a r t i c l e s i z e , b u t a l s o on t h e
r e f r a c t i v e i n d i c e s o f t h e p a r t i c l e s a n d t h e medium, t h e s c a t t e r i n g
a n g l e , t h e wavelength o f t h e i n c i d e n t l i g h t , and t h e shape o f t h e
particles.(18,19) The range o f p a r t i c l e s i z e s a c c e s s i b l e t o t h e
QELS t e c h n i q u e e x t e n d s up t o a b o u t 5 m i c r o m e t e r s , t h u s e x c e e d i n g t h e
l i m i t s o f b o t h t h e R a y l e i g h a p p r o x i m a t i o n and ( f o r any r e a s o n a b l e
r e f r a c t i v e index r a t i o ) t h e Rayleigh-Debye-Gans approximation. Be-
cause emulsion p a r t i c l e s a r e s p h e r i c a l , t h e exact s o l u t i o n o f t h e
a b s o r p t i o n and s c a t t e r i n g p r o b l e m f o r s p h e r e s , commonly r e f e r r e d t o
as t h e M i e t h e o r y , c a n be a p p l i e d . U n t i l r e c e n t l y , a l a r g e main-
frame computer was r e q u i r e d t o c a r r y o u t t h e n e c e s s a r y c a l c u l a t i o n s
involved. Tables o f M i e c o e f f i c i e n t s have been p u b l i s h e d by v a r i o u s
p e o p l e , a l l o w i n g t a b l e l o o k up methods t o b e u s e d . We o r i g i n a l l y
u s e d t h e 90 d e g r e e s c a t t e r i n g t a b l e s o f P a n g o n i s , e t a l . ( 2 0 ) f o r
t h e c o r r e c t i o n o f o u r QELS d a t a . W i t h t h e a d v e n t o f 16 b i t m i c r o -
p r o c e s s o r based desk t o p computers, however, t h e r e i s l i t t l e reason
not t o c a l c u l a t e t h e exact M i e c o e f f i c i e n t s needed f o r t h e d i s t r i -
b u t i o n b e i n g c o r r e c t e d . We now u s e a m o d i f i e d f o r m o f t h e s u b r o u -
t i n e BHMIE o f B o h r e n a n d H u f f m a n ( 1 9 ) t o c a l c u l a t e t h e r e q u i r e d
coefficients. T h i s a l l o w s us t o work e a s i l y a t any angle and w i t h
p a r t i c l e s o f any r e f r a c t i v e index ( i n c l u d i n g complex r e f r a c t i v e
indices).
H a v i n g o b t a i n e d t h e r e l a t i v e s c a t t e r i n g i n t e n s i t y p e r u n i t mass
f o r e a c h p a r t i c l e s i z e f r o m t h e M i e t h e o r y , t h e mass w e i g h t e d d i s -
t r i b u t i o n should be obtained by d i v i d i n g t h e histogram magnitude f o r
each p a r t i c l e s i z e by t h i s s c a t t e r i n g f a c t o r . F o r very narrow d i s -
t r i b u t i o n s (such as monodisperse l a t e x standards) o r bimodal d i s t r i -
b u t i o n s composed o f two n a r r o w d i s t r i b u t i o n s , t h i s w i l l w o r k v e r y
well. I f t h e sample has a broad unimodal d i s t r i b u t i o n and i n c l u d e s
diameters approaching o r l a r g e r than t h e wavelength of t h e i n c i d e n t
l i g h t , s m a l l e r r o r s i n the i n t e n s i t y weighted d i s t r i b u t i o n can lead
t o l a r g e e r r o r s i n t h e c a l c u l a t e d mass w e i g h t e d r e s u l t . In addition,
t h e p r e s e n c e o f c e r t a i n p a r t i c l e d i a m e t e r s may g o u n d e t e c t e d i n t h e

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
6. HERB ET AL. Quasi-Elastic Light Scattering 101

p r e s e n c e o f more h i g h l y s c a t t e r i n g p a r t i c l e s f o r any g i v e n a n g l e .
T h e s e p r o b l e m s a r e due t o t h e o s c i l l a t i o n s i n t h e s c a t t e r i n g i n t e n
s i t y as a f u n c t i o n o f p a r t i c l e s i z e a t a g i v e n a n g l e . Figure 5
shows t h e s c a t t e r i n g i n t e n s i t y p e r u n i t mass o f p a r t i c l e s as a f u n c
t i o n of diameter f o r a system i n which the p a r t i c l e s have a r e f r a c
t i v e i n d e x o f 1.59 ( e . g . p o l y s t y r e n e ) , t h e m e d i u m h a s a r e f r a c t i v e
i n d e x o f 1.33 ( e . g . w a t e r ) , a n d t h e l i g h t s o u r c e h a s a w a v e l e n g t h o f
6 3 2 . 8 nm ( i . e . a HeNe l a s e r ) . Note t h a t the f i r s t t h r e e minima are
a t a p p r o x i m a t e l y 4 5 0 nm, 760 nm, a n d 1080 nm. I t can be s e e n t h a t
i f t h e sample had a b i m o d a l d i s t r i b u t i o n w i t h n a r r o w d i s t r i b u t i o n s
a t 250 nm ( t h e f i r s t maximum) a n d 760 nm, i t w o u l d b e d i f f i c u l t t o
d e t e c t t h e 760 nm p e a k u n l e s s i t c o n t a i n e d a l a r g e p e r c e n t a g e o f t h e
mass. L i k e w i s e , i f a broad unimodal d i s t r i b u t i o n t h a t extended from
2 0 0 nm t o 1200 nm was m e a s u r e d a t 90 d e g r e e s a n d c o r r e c t e d u s i n g
F i g u r e 5, s m a l l a m o u n t s o f e r r o r a t t h e m i n i m a w o u l d l e a d t o l a r g e
e r r o r s i n t h e f i n a l mass w e i g h t e d result
We c u r r e n t l y a t t e m p
Mie s c a t t e r i n g f a c t o r ove
the c o r r e c t i o n . On e a c h p a s s o f t h e m u l t i p l e p a s s a n a l y s i s , t h e i n
v e r s i o n a l g o r i t h m c h o o s e s t h e two p a r t i c l e s i z e s t h a t b r a c k e t t h e
a c t u a l diameter. T h u s , t h e r e i s some " s p i l l i n g o v e r " i n t o a d j a c e n t
diameters. We a s s u m e t h a t f o r " g o o d " d a t a ( i . e . l o w n o i s e i n t h e
a u t o c o r r e l a t i o n f u n c t i o n s ) , t h i s w i l l go n o f a r t h e r t h a n o n e d i a m e
ter to either side. T h u s , t h e l i g h t s c a t t e r i n g f a c t o r may a l s o n e e d
t o be a v e r a g e d o v e r t h e t h r e e d i a m e t e r s . I f there are passes,
t h i s b e c o m e s a n a v e r a g e o v e r 3P d i a m e t e r s i n t h e f i n a l d i s t r i b u t i o n .
T h i s p r o c e d u r e t e n d s t o " s o f t e n " t h e e f f e c t o f t h e s h a r p maxima and
m i n i m a i n t h e f u n c t i o n s h o w n i n F i g u r e 5. Although t h i s provides
reasonable histograms, i t i s not a completely s a t i s f a c t o r y s o l u t i o n
b e c a u s e o f t h e a r b i t r a r y c h o i c e o f 3P d i a m e t e r s f o r t h e a v e r a g i n g .
Because the l i g h t s c a t t e r i n g versus p a r t i c l e s i z e r e l a t i o n s h i p
d e p e n d s on a n g l e , i t i s r e a s o n a b l e t o assume t h a t a s o l u t i o n t o t h e
p r o b l e m l i e s i n t h e j u d i c i o u s use of m u l t i a n g l e d a t a . We suggest
t h a t a p o s s i b l e s o l u t i o n w o u l d be t o o b t a i n a u t o c o r r e l a t i o n f u n c
t i o n s a t m o r e t h a n one a n g l e a n d t o f i t a l l a n g l e s s i m u l t a n e o u s l y
w i t h the Mie f a c t o r s i n c l u d e d i n the i n v e r s i o n . Such a c a l c u l a t i o n
w o u l d r e q u i r e no m o r e c o m p u t e r memory t h a n s i n g l e a n g l e d a t a a n d
should, i f the angles are chosen p r o p e r l y , help reduce the problems
d i s c u s s e d above.

Conclusions

We h a v e s h o w n t h a t t h e p a r t i c l e - s i z e d i s t r i b u t i o n s o f s u b - m i c r o m e t e r
e m u l s i o n s c a n b e s u c c e s s f u l l y o b t a i n e d f r o m QELS d a t a b y : 1) u s i n g a
least-squares technique that u t i l i z e s the n o n - n e g a t i v i t y c o n s t r a i n t
a s p a r t o f t h e i t e r a t i v e c a l c u l a t i o n , 2) a n a l y z i n g e a c h d a t a r u n
w i t h s e v e r a l s e t s o f assumed p a r t i c l e s i z e s and c o m b i n i n g t h e r e
s u l t i n g d i s t r i b u t i o n s , a n d 3) t a k i n g s e v e r a l s e t s o f d a t a o n t h e
same s a m p l e , a n a l y z i n g e a c h s e t i n d e p e n d e n t l y , a n d a v e r a g i n g t h e
final distributions. The c o m b i n a t i o n o f t h e s e t e c h n i q u e s p r o v i d e s
increased r e s o l u t i o n w h i l e minimizing the tendency to confuse b i
m o d a l and b r o a d u n i m o d a l d i s t r i b u t i o n s . In a d d i t i o n , the technique
r e q u i r e s v e r y l i t t l e i n p u t f r o m t h e o p e r a t o r , no a p r i o r i i n f o r m a
t i o n a b o u t t h e s h a p e o f t h e d i s t r i b u t i o n , and c a n be r u n on a d e s k
top computer.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
102 PARTICLE SIZE DISTRIBUTION

CO

<

2000 3000 4000 5000

PARTICLE DIAMETER (nm)

F i g u r e 5. S c a t t e r i n g i n t e n s i t y p e r u n i t mass o f p a r t i c l e s a s a
f u n c t i o n o f p a r t i c l e diameter f o r a system i n which the wavelength
o f t h e i n c i d e n t l i g h t i s 6 3 2 . 8 nm, t h e s c a t t e r i n g a n g l e i s 9 0 ,
t h e p a r t i c l e r e f r a c t i v e i n d e x i s 1.59, a n d t h e m e d i u m r e f r a c t i v e
i n d e x i s 1.33 ( f o r e x a m p l e p o l y s t y r e n e s p h e r e s i n w a t e r ) .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
6. HERB ET AL. Quasi-Elastic Light Scattering 103

We p r e s e n t e d d i s t r i b u t i o n r e s u l t s f o r s e v e r a l o i l / w a t e r e m u l
sions t o demonstrate t h e a b i l i t y of these techniques t o monitor t h e
e f f e c t o f p r o c e s s i n g v a r i a b l e s (such as s u r f a c t a n t c o n c e n t r a t i o n ) on
the f i n a l emulsion. The b e n e f i t s o f k n o w i n g t h e f u l l d i s t r i b u t i o n
r a t h e r t h a n a mean d i a m e t e r o n l y w e r e d i s c u s s e d . F i n a l l y , we d i s
c u s s e d some o f t h e p r o b l e m s o f c o n v e r t i n g t h e i n t e n s i t y w e i g h t e d
d i s t r i b u t i o n t o a mass w e i g h t e d d i s t r i b u t i o n and s u g g e s t e d methods
f o r m i n i m i z i n g these problems.
A FORTRAN i m p l e m e n t a t i o n o f t h i s technique i s available from
the authors.

Literature Cited
1. Walstra, P. In "Encyclopedia of Emulsion Technology"; Becher,
P., Ed.; Dekker: New York, 1983; Vol. 1, Chap. 2.
2. Brookhaven Instruments Corp. Ronkonkoma NY
Coulter Electronics
Hiac/Royco (Nicomp
Malvern Instruments Ltd., Malvern, Worcestershire, UK.
3. Pecora, R. In "Measurement of Suspended Particles by Quasi-
Elastic Light Scattering"; Dahneke, . ., Ed.; Wiley: New York,
1983; Chap. 1.
4. Ford, N. C. In "Measurement of Suspended Particles by Quasi-
Elastic Light Scattering"; Dahneke, B. E., Ed.; Wiley: New York,
1983; Chap. 2.
5. Berne, B. J.; Pecora, R. "Dynamic Light Scattering with Appli
cations to Chemistry, Biology and Physics"; Wiley-Interscience:
New York, 1976.
6. Chu, . "Laser Light Scattering"; Academic Press: New York,
1974.
7. Koppel, D. E. J. Chem. Phys. 1972, 57, 4814.
8. Dahneke, . ., Ed. "Measurement of Suspended Particles by
Quasi-Elastic Light Scattering"; Wiley: New York, 1983.
9. Tikhonov, A. N.; Arsenin, V. Y. "Solutions of Ill-Posed Prob
lems"; John, F., Translator; Wiley: New York, 1977.
10. Pike, E. R. In "Scattering Techniques Applied to Supramolecular
and Nonequilibrium Systems"; Chen, S.; Chu, .; Nossal, R.,
Eds.; NATO Advanced Study Institutes Series, Vol. B73, Plenum:
New York, 1981; pp. 179-200.
11. Morrison, I. D.; Grabowski, E. F.; Herb, C. A. Langmuir 1985,
1, 496-501.
12. Grabowski, E. F.; Morrison, I. D. In "Measurement of Suspended
Particles by Quasi-Elastic Light Scattering"; Dahneke, . .,
Ed.; Wiley: New York, 1983; Chap. 7.
13. McWhirter, J. G.; Pike, E. R. J. Phys. A. Math. Gen. 1978, 11,
1729.
14. Lawson, C. L.; Hanson, R. J. "Solving Least Squares Problems";
Prentice-Hall: Englewood Cliffs, NJ, 1974. A FORTRAN program
and subroutines called NNLS.
15. Herb, C. .; Morrison, I. D.; Grabowski, E. F. In "Magnetic
Resonance and Scattering in Surfactant Systems"; Magid, L.,
Ed.; Plenum: New York, (in press).
16. Fairhurst, D.; Aronson, M. P.; Gum, M. L.; Goddard, E. D.
Colloids and Surfaces 1983, 7, 153-159.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
104 P A R T I C L E SIZE DISTRIBUTION

17. Tadros, T. F.; Vincent, B. In "Encyclopedia of Emulsion Tech-


nology"; Becher, P., Ed.; Dekker: New York, 1983; Vol. 1,
Chap. 3.
18. Kerker, M. "The Scattering of Light and Other Electromagnetic
Radiation"; Academic Press: New York, 1969.
19. Bohren, C. F.; Huffman, D. R. "Absorption and Scattering of
Light by Small Particles"; Wiley: New York, 1983.
20. Pangonis, W. J.; Heller, W.; Economou, M. A. J. Chem. Phys.
1961, 34, 960-970.
RECEIVED June 27, 1986

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 7

Measuring Particle Size Distribution of Latex Particles


Using Dynamic Light Scattering
1
Ruth S. Stock and W. Harmon Ray
Chemical Engineering Department, University of Wisconsin, Madison, WI 53706

In a light-scattering experiment, particles that have


diameters on the order of the wavelength of incident
light and a large refractive index relative to that of
the medium, e.g. polymer latex in water, scatter light
according to Mie theory. The intensity of the scattered
light varies by an order of magnitude in an oscillatory
fashion with respect
to incorporate the mathematical description of Mie
theory into Provencher's constrained regularization
method to find the distribution by weight. Alternatively,
a simple linear least squares algorithm is used to
find the particle size distribution by intensity; this
is then transformed to a distribution by weight using
Mie theory. Measurements are made at multiple scattering
angles and the particle size distributions are compared.
A composite distribution formed by averaging the weight
distributions found at various angles is considered.
These methods are demonstrated on multimodal and broad
distributions.
Dynamiclightscatteringmaybeusedtodeterminethe particle size
distribution or molecular weight distribution in a wide variety of
applications. See rf. (1) for discussion of this literature.
There are special problems that occur when the particle diameter is
large relative to the wavelength of incident light. This is of
interest since many latex systems have particles with diameters of
300 to 1000 nm and a large ratio of particle to fluid refractive
index (1.2 for polystyrene latex). The most common wavelengths for
lasers used in light scattering are on the order of 500 nm.
Light entering a particle at two different points will
experience different path lengths. The refractive index difference
between the particle and the medium will also cause a phase shift in
the scattered light leaving the particle (see Figure 1). Due to
these effects, the intensity of light scattered by suspended spheri-
cal particles depends on the particle diameter relative to the wave-
length of incident light, the scattering angle and the refractive
index ratio. Plots of intensity as a function of angle for a
polystyrene/water system with 514.5 nm incident laser wavelength are
shown in Figure 2.

'Current address: General Motors Research Laboratories, Warren, MI 48090-9055


0097-6156/87/0332-0105$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
106 PARTICLE SIZE DISTRIBUTION

Mie Scattering
l-g

~* -{^
4
I
0 50 1000 1500 2000

Diameter (nm)

F i g u r e 2. P r e d i c t i o n s o f i n t e n s i t y p e r u n i t p a r t i c l e v o l u m e a s a
f u n c t i o n of p a r t i c l e diameter f o r three scattering angles given
i n c i d e n t w a v e l e n g t h 5 1 4 . 5 nm a n d r e f r a c t i v e i n d e x r a t i o
p o l y s t y r e n e / w a t e r o f 1.2.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
7. STOCK AND RAY Dynamic Light Scattering 107

I n o r d e r t o a c c o u n t f o r t h e s e e f f e c t s , one may u s e M i e t h e o r y t o
o b t a i n t h e v o l u m e o r mass ( i n t h e c a s e o f a h o m o g e n e o u s d e n s i t y
system) d i s t r i b u t i o n of l a t e x p a r t i c l e s i n s t e a d of the i n t e n s i t y
d i s t r i b u t i o n i n i t i a l l y o b t a i n e d from q u a s i e l a s t i c l i g h t s c a t t e r i n g
data, B e d w e l l e t . a l . ( 2 ) h a v e o b t a i n e d t h e mass d i s t r i b u t i o n o f
l a r g e p a r t i c l e s by i n c o r p o r a t i n g M i e t h e o r y i n t o t h e h i s t o g r a m
method. H e r e we p r o p o s e two m e t h o d s o f d a t a a n a l y s i s . First,
P r o v e n c h e r ' s method o f c o n s t r a i n e d r e g u l a r i z a t i o n has been m o d i f i e d
to i n c l u d e the Mie s c a t t e r i n g f a c t o r i n the k e r n e l of the i n t e g r a l
t o be i n v e r t e d . T h i s method i s s i m i l a r t o t h a t d e v e l o p e d i n d e p e n
d e n t l y by S. B o t t ( 3 ) . S e c o n d we c o n s i d e r u s i n g a s i m p l e n o n -
n e g a t i v e l y c o n s t r a i n e d l i n e a r l e a s t s q u a r e s f i t and c o m b i n i n g
i n f o r m a t i o n o b t a i n e d from data taken a t s e v e r a l s c a t t e r i n g a n g l e s .

Data Analysis

B o t h P r o v e n c h e r ' s metho
method f i r s t o b t a i n th square
f a c t P r o v e n c h e r ' s p r o g r a m u s e s t h e NNLS p r o g r a m a s p a r t o f t h e a n a
l y s i s procedure. P r o v e n c h e r ' s m e t h o d d e p a r t s f r o m t h e NNLS s o l u t i o n
by r e g u l a r i z i n g so t h a t t h e s m o o t h e s t p a r t i c l e s i z e d i s t r i b u t i o n
c o n s i s t e n t w i t h the data i s obtained. T h i s r e g u l a r i z a t i o n i s
a c c o m p l i s h e d by i n c l u d i n g a t e r m i n t h e o b j e c t i v e f u n c t i o n w h i c h i s
r e l a t e d to the second d e r i v a t i v e of the p a r t i c l e s i z e d i s t r i b u t i o n .
As t h e p a r t i c l e s i z e d i s t r i b u t i o n becomes s m o o t h e r t h i s t e r m becomes
s m a l l e r r e s u l t i n g i n t h e minimum v a l u e o f t h e o b j e c t i v e f u n c t i o n .
I n b o t h m e t h o d s t h e l e a s t s q u a r e s p a r a m e t e r s c o n s i s t e d o f 40
h i s t o g r a m s t e p h e i g h t s s p r e a d o v e r a two d e c a d e p a r t i c l e s i z e r a n g e .
T h e maximum n u m b e r o f p a r a m e t e r s a l l o w e d i n P r o v e n c h e r ' s p r o g r a m i s
50.
The i n t e n s i t y d i s t r i b u t i o n o f p a r t i c l e s i z e , G(a), i s r e l a t e d to
the e x p e r i m e n t a l l y observed e l e c t r i c f i e l d autocorrelation function,
g ^ ^ ( T ) as f o l l o w s
a
max
( 1 ) 2
g (t) - } G(a)exp(-k Tk T/3irna)da
B (1)
a
min

H e r e G ( a ) i s t h e i n t e n s i t y s c a t t e r e d by t h e p a r t i c l e s w i t h d i a m e t e r s
between a and a+da, k i s Boltzmann's c o n s t a n t , the temperature, k
R

t h e s c a t t e r i n g v e c t o r ( d e p e n d e n t on s c a t t e r i n g a n g l e and
w a v e l e n g t h ) , the c o r r e l a t i o n time and the v i s c o s i t y . To f i n d
t h e m a s s f r a c t i o n d i s t r i b u t i o n , F ( a ) , we u s e

a
max

g (D( ) T j F( )
a 1 a
3
(i ( )/a )exp(-k Tk T^na)da B
2
(2)
a
min

w h e r e i^(a) i s the s c a t t e r e d intensity per p a r t i c l e (6) and i s the


dimensionless p a r t i c l e size

- / (3)

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
108 PARTICLE SIZE DISTRIBUTION

H e r e i s t h e r e f r a c t i v e i n d e x o f t h e medium a n d i s t h e w a v e l e n g t h
o f i n c i d e n t l i g h t i n a vacuum. We m o d i f i e d P r o v e n c h e r ' ^ p r o g r a m t o
c a l l a subroutine which would supply values of ( i ^ ( a ) / a ) f o r the
k e r n e l of the i n t e g r a l . The i n i t i a l s o l u t i o n i s t h a t w i t h l i t t l e o r
no r e g u l a r i z a t i o n . A chosen s o l u t i o n where the i n c r e a s e i n the
o b j e c t i v e f u n c t i o n o v e r the I n i t i a l s o l u t i o n c o u l d about 50% of the
t i m e be due t o e x p e r i m e n t a l n o i s e a n d a b o u t 5 0 % o f t h e t i m e be due
t o o v e r s m o o t h i n g , i s s e l e c t e d by a s t a t i s t i c a l c r i t e r i o n ( 4 , 5 ) .
A s e c o n d a n a l y s i s p r o c e d u r e I n v o l v e s u s i n g t h e r e s u l t s f r o m many
s c a t t e r i n g a n g l e s t o e x t r a c t t h e mass f r a c t i o n d i s t r i b u t i o n o f p a r
t i c l e s i z e f r o m t h e d a t a . S i n c e i t w o u l d be h a r d t o f i n d a n o p t i m u m
s c a t t e r i n g a n g l e ( t h a t w h i c h has a r e l a t i v e l y h i g h i n t e n s i t y f o r the
p a r t i c l e s i z e ( s ) of i n t e r e s t ) w i t h o u t a l r e a d y knowing the p a r t i c l e
s i z e d i s t r i b u t i o n , one p o s s i b i l i t y i s t o a v e r a g e i n f o r m a t i o n f r o m
s e v e r a l s c a t t e r i n g a n g l e s . We u s e t h e n o n - n e g a t i v e l y c o n s t r a i n e d
l e a s t s q u a r e s method ( 6 ) w i t h o u f u r t h e regularization obtai
the p a r t i c l e s i z e d i s t r i b u t i o n
puted f o r each p a r t i c l e
c o n v e r t t h e i n t e n s i t y d i s t r i b u t i o n a t e a c h a n g l e t o a mass d i s t r i b u
t i o n of p a r t i c l e s i z e s . F i n a l l y , t h e 10 m a s s d i s t r i b u t i o n s ( o n e f o r
each angle) are averaged t o g e t h e r to form a composite d i s t r i b u t i o n .
O t h e r i n v e s t i g a t o r s (8,9,10) have used a s i m i l a r method i n w h i c h
i n t e n s i t y d i s t r i b u t i o n s f r o m NNLS a r e c o n v e r t e d t o m a s s d i s t r i b u
t i o n s u s i n g Mie f a c t o r s ; however, they o b t a i n d a t a f o r l o n g e r time
periods at a single scattering angle.

Experimental

F o u r s e p a r a t e l a t e x s a m p l e s w e r e a n a l y s e d . A b i m o d a l m i x t u r e was
c o m p o s e d by m i x i n g e q u a l p a r t s o f s o l u t i o n s w i t h 0 . 0 0 3 % s o l i d s o f
Dow l a t e x m o n o d i s p e r s e s t a n d a r d s w i t h n o m i n a l d i a m e t e r s 1 0 9 - a n d
497-nm h a v i n g s t a n d a r d d e v i a t i o n s o f 2.7 a n d 5.9 nm r e s p e c t i v e l y .
T h e m i x t u r e was s o n i c a t e d t o e l i m i n a t e a g g r e g a t e s . A p o l y s t y r e n e
l a t e x w i t h a b r o a d d i s t r i b u t i o n was o b t a i n e d f r o m K o d a k . This
d i s t r i b u t i o n h a d b e e n c h a r a c t e r i z e d p r e v i o u s l y by e l e c t r o n
m i c r o s c o p y , u l t r a c e n t r i f u g e and C o u l t e r c o u n t e r . A m o n o d i s p e r s e ,
s u r f a c t a n t f r e e , s u l f a t e d , p o l y s t y r e n e s t a n d a r d a n d a m i x t u r e o f 10
such monodisperse s t a n d a r d s were purchased from I n t e r f a c i a l Dynamics
Corporation. A p o l y v i n y l c h l o r i d e l a t e x w i t h a broad d i s t r i b u t i o n
was d o n a t e d by B. F. G o o d r i c h . T h i s s a m p l e h a d b e e n c h a r a c t e r i z e d
by J o y c e L o e b l d i s c c e n t r i f u g e . T h e s e s a m p l e s w e r e d i l u t e d t o 0.01%
s o l i d s and s o n i c a t e d t o e l i m i n a t e a g g r e g a t e s .
T h e c o r r e l a t i o n f u n c t i o n was m e a s u r e d u s i n g a M a l v e r n K 7 0 2 5
correlator. The w a v e l e n g t h o f t h e i n c i d e n t l i g h t ( a r g o n i o n l a s e r ,
L e x e l M o d e l 9 5 ) was 514.5 nm. The t e m p e r a t u r e o f t h e w a t e r b a t h
s u r r o u n d i n g t h e s a m p l e c e l l was 3 0 7 . 6 K. T h e same e q u i p m e n t was
used i n a p r e v i o u s p u b l i c a t i o n ( 1 ) . However, the d a t a c o l l e c t i o n
p r o g r a m was m o d i f i e d t o d i s c r i m i n a t e a g a i n s t d u s t ( 1 1 ) . I n t h i s
FORTRAN p r o g r a m t o t a l p h o t o n c o u n t f r o m s e v e r a l s h o r t ( 5 o r 10
second) runs were used t o e s t a b l i s h p h o t o n c o u n t a v e r a g e and s t a n
dard deviation. A f t e r e a c h s h o r t e x p e r i m e n t t h e d a t a was a c c e p t e d
o n l y i f i t s p h o t o n c o u n t was l e s s t h a n t h e mean p h o t o n c o u n t p l u s
three standard deviations. E a c h s h o r t e x p e r i m e n t was n o r m a l i z e d t o
i t s own b a s e l i n e . A s e r i e s o f 60 f i v e s e c o n d e x p e r i m e n t s w e r e

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
7. STOCK AND RAY Dynamic Light Scattering 109

a v e r a g e d t o y i e l d one a u t o c o r r e l a t i o n f u n c t i o n . Three c o r r e l a t i o n
sample times were used a t each a n g l e . The maximum a n d minimum w e r e
c o m p u t e d u s i n g R a c z e k ' s f o r m u l a ( 1 2 ) f o r t h e 4 9 7 - a n d 109-nm p a r -
ticles respectively. F o r the Kodak d i s t r i b u t i o n the e x p e c t e d upper
and l o w e r bounds o f the d i s t r i b u t i o n were used.
F o r t h e b r o a d d i s t r i b u t i o n s a n a l y s e d by t h e NNLS m e t h o d , d a t a
was t a k e n a t 10 s c a t t e r i n g a n g l e s : 20, 30, 40, 50, 60, 70,
8 0 , 9 0 , 100 a n d 110. A t each a n g l e t h r e e sample times were
used. These sample t i m e s were computed u s i n g R a c z e k ' s f o r m u l a w i t h
d i f f e r e n t v a l u e s f o r the bandwidth of the a u t o c o r r e l a t i o n f u n c t i o n :
v 2 , 4 a n d 8. F o r e a c h s e t o f c o n d i t i o n s a s e r i e s o f 30 t e n s e c o n d
e x p e r i m e n t s were averaged to y i e l d a s i n g l e a u t o c o r r e l a t i o n f u n c -
tion.

Results

We now d e m o n s t r a t e t h e s
c o n s i d e r P r o v e n c h e r ' s metho g example
b i m o d a l d i s t r i b u t i o n and b r o a d d i s t r i b u t i o n . T h e NNLS m e t h o d i s
d e m o n s t r a t e d o n a m o n o d i s p e r s e d i s t r i b u t i o n , a m i x t u r e o f 10 mono-
d i s p e r s e s t a n d a r d s and a b r o a d d i s t r i b u t i o n .
1
F o r P r o v e n c h e r s method as m o d i f i e d , the s t a t i s t i c s f o r the i n -
t e n s i t y a n d mass f r a c t i o n d i s t r i b u t i o n s f o u n d f o r t h e b i m o d a l m i x -
t u r e a r e s h o w n i n T a b l e I . We s e l e c t t h e s a m p l e t i m e s w h i c h g i v e
t h e i n t e n s i t y d i s t r i b u t i o n s h a v i n g t h e p e a k a r e a r a t i o o f t h e 109 nm
p e a k t o t h e 497 nm p e a k c l o s e s t t o u n i t y . T h e f i n a l mass d i s t r i b u -
t i o n s show o v e r a l l means w h i c h a r e q u i t e a c c u r a t e , s e e T a b l e I . F r o m
F i g u r e 3 one o b s e r v e s t h a t t h e r e l a t i v e p e a k a r e a s a n d p e a k l o c a -
t i o n s a r e q u i t e a c c u r a t e . F i g u r e 3 a l s o s h o w s t h a t t h e f i n a l mass
f r a c t i o n d i s t r i b u t i o n i s t h e same a t t h r e e d i f f e r e n t s c a t t e r i n g
a n g l e s a l t h o u g h the i n t e n s i t y d i s t r i b u t i o n f o r a s c a t t e r i n g a n g l e of
30 was v e r y d i f f e r e n t . T a b l e I I shows d a t a o b t a i n e d f r o m a b r o a d
p o l y s t y r e n e l a t e x s a m p l e d o n a t e d by K o d a k . The m a s s a v e r a g e a n d
s t a n d a r d d e v i a t i o n c o m p a r e w e l l w i t h t h e s t a t i s t i c s f r o m t h e mass
d i s t r i b u t i o n f o u n d by e l e c t r o n m i c r o s c o p y . The s o l u t i o n s f o r s c a t -
t e r i n g a n g l e s o f 30 a n d 90 r e p r e s e n t t h e m a j o r f e a t u r e s o f t h e
d i s t r i b u t i o n f a i r l y w e l l b u t they a r e too smooth. Note that the
d i s t r i b u t i o n f o u n d a t 60 h a s t h e h i g h e s t d u s t l e v e l o f a l l t h e s e
solutions; i t i s l i k e l y t h a t t h e low mean i s due t o o v e r c o m p e n -
s a t i o n o f the d u s t term. Thus P r o v e n c h e r ' s method as m o d i f i e d
y i e l d s s a t i s f y i n g r e s u l t s f o r b o t h the b i m o d a l and b r o a d d i s t r i b u -
t i o n e x a m p l e s e x c e p t when t h e d u s t t e r m i s l a r g e .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
110 PARTICLE SIZE DISTRIBUTION

Table I . Bimodal D i s t r i b u t i o n Results

Average Relative
D i a m e t e r ( nm) Standard Deviation
Angle Sample Time Intensity Mass Intensity Mass

Actual (microsec) 303 0.64

Chosen 30 140 478 281 0.23 0.74

Initial b
30 140

Chosen 0
60 8 337 243 0.80 0.89

Initial b
60 8 313 328 0.68 0.62

Chosen a
90 9 347 353 0.56 0.56

Initial b
90 9 346 348 0.55 0.57

* The c h o s e n s o l u t i o n h a s t h e o p t i m a l amount o f r e g u l a r i z a t i o n .
The i n i t i a l s o l u t i o n has l i t t l e o r no r e g u l a r i z a t i o n .

T a b l e I I . Kodak D i s t r i b u t i o n Results

Average Relative
D i a m e t e r ( nm) Standard Deviation
Sample Dust
Angle Time Intensity Mass Intensity Mass (%)

Actual (micro- 1050 0.30


sec)

Chosen 0
90 14 1000 1044 0.21 0.24 11

Chosen* 60 98 906 892 0.08 0.09 15

Chosen 0
30 28 1112 1075 0.13 0.16 0

The c h o s e n s o l u t i o n has the o p t i m a l amount o f regularization.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
7. STOCK A N D RAY Dynamic Light Scattering 111

700
Diameter (nm)

I I I I I
700
1 200 300 400 500
Diameter (nm)

F i g u r e 3. C o n s t r a i n e d r e g u l a r i z a t i o n solutions f o r the bimodal


d i s t r i b u t i o n f o r three s c a t t e r i n g a n g l e s shown.
( a ) No c o r r e c t i o n w i t h M i e f a c t o r .
(b) I n c l u d i n g c o r r e c t i o n w i t h M i e f a c t o r .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
112 PARTICLE SIZE DISTRIBUTION

F o r t h e second method, c o m p o s i t e d i s t r i b u t i o n r e s u l t s from t h e


n o n - n e g a t i v e l y c o n s t r a i n e d l e a s t s q u a r e s method u s i n g s e v e r a l a n g l e s
a r e shown i n T a b l e I I I . The c o m p o s i t e mass d i s t r i b u t i o n s l i g h t l y
u n d e r e s t i m a t e s t h e mean o f t h e b r o a d d i s t r i b u t i o n s s h o w n . However,
t h e e s t i m a t e o f t h e mean n e v e r d i s p l a y s a g r e a t e r e r r o r t h a n 5%. T h e
s t a n d a r d d e v i a t i o n o f t h e c o m p o s i t e mass d i s t r i b u t i o n o v e r e s t i m a t e s
t h a t o f a l l d i s t r i b u t i o n s . I n T a b l e I I I a n d i n F i g u r e 4 we c o n s i d e r
t h e r e s u l t s f r o m t h e B. F . G o o d r i c h s a m p l e . B o t h F i g u r e s 4 a and 4b
a r e t h e a v e r a g e o f 10 p a r t i c l e s i z e d i s t r i b u t i o n s e a c h f r o m a n a u t o -
c o r r e l a t i o n f u n c t i o n c o l l e c t e d f o r 15 m i n u t e s . I n Figure 4a each
a u t o c o r r e l a t i o n f u n c t i o n was f r o m s c a t t e r i n g a t a d i f f e r e n t s c a t -
t e r i n g a n g l e w h i l e i n F i g u r e 4b a l l t h e a u t o c o r r e l a t i o n f u n c t i o n s
w e r e f r o m s c a t t e r i n g a t 90. N o t e t h a t somewhat b e t t e r r e s u l t s a r e
o b t a i n e d by c o m b i n i n g d a t a f r o m s c a t t e r i n g a t s e v e r a l a n g l e s .

Table I I I . Modifie
Distributions from A l l Angles

Relative
Average diameter(nm) Standard Deviation
Intensity Mass A c t u a l Intensity Mass Actual

412-nm PS S t a n d a r d 451 428 412 0.181 0.077 0.02

Mixture of Standards 564 612 648 0.66 0.54 0.40

BFG PVC1 C o m p o s i t e 618 641 658 0.44 0.50 0.41

BFG P V C 1 90 only 571 617 658 0.46 0.39 0.41

Conclusion

By i n c o r p o r a t i n g t h e o r e t i c a l p r e d i c t i o n s o f t h e i n t e n s i t y a s a f u n c -
t i o n o f p a r t i c l e s i z e f o reach s c a t t e r i n g angle given the i n c i d e n t
w a v e l e n g t h and approximate r e f r a c t i v e i n d e x r a t i o i n t o t h e data ana-
l y s i s ( v i a c o n s t r a i n e d r e g u l a r i z a t i o n and NNLS), i t i s p o s s i b l e t o
o b t a i n t h e mass f r a c t i o n d i s t r i b u t i o n o f p a r t i c l e s i z e f r o m t h e p h o -
ton a u t o c o r r e l a t i o n function of Mie s c a t t e r e r s without separate
measurements o f i n t e n s i t y s c a t t e r i n g a s a f u n c t i o n o f a n g l e and
without extrapolation to zero angle. The M i e s c a t t e r i n g f a c t o r was
i n c l u d e d i n t h e k e r n e l o f t h e i n t e g r a l a n a l y s e d by c o n s t r a i n e d regu-
larization. F o r t h e NNLS m e t h o d , t h e i n t e n s i t y d i s t r i b u t i o n d e t e r -
m i n e d by a n a l y s i s o f t h e a u t o c o r r e l a t i o n f u n c t i o n was c o n v e r t e d t o a
mass d i s t r i b u t i o n by m u l t i p l y i n g e a c h h i s t o g r a m s t e p a r e a by t h e
appropriate s c a t t e r i n g f a c t o r (average over the p a r t i c l e s i z e repre-
s e n t e d by t h e s t e p ) . We h a v e s h o w n t h a t t h e c o m p o s i t e mass d i s t r i -
b u t i o n a v e r a g e d o v e r s e v e r a l s c a t t e r i n g a n g l e s i s s o m e t i m e s more
a c c u r a t e t h a n t h e c o m p o s i t e m a s s d i s t r i b u t i o n a v e r a g e d o v e r t h e same
t o t a l time from a s i n g l e s c a t t e r i n g angle. The m o d i f i c a t i o n o f t h e
NNLS m e t h o d i n v o l v e s s i m p l e r a n d f a s t e r c o m p u t a t i o n t h a n t h e m o d i f i -
c a t i o n o f t h e c o n s t r a i n e d r e g u l a r i z a t i o n method.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
7. STOCK AND RAY Dynamic Light Scattering 113

0 900 100 1900 2000

Diameter (nm)

F i g u r e 4. NNLS s o l u t i o n s f o r t h e B. F. G o o d r i c h s a m p l e . Both
s o l u t i o n s i n c l u d i n g the M i e f a c t o r (mass) and w i t h o u t c o r r e c t i o n
( i n t e n s i t y ) a r e shown.
(a) Average o f r e s u l t s from c o r r e l a t i o n f u n c t i o n s taken a t t e n
scattering angles,
(b) Average o f r e s u l t s from ten correlation functions t a k e n a t 90?

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
114 PARTICLE SIZE DISTRIBUTION

Literature Cited
1. R. S. Stock and W. H. Ray, J. Polym. Sci. Polym. Phys. Ed., 23,
1393, (1985).
2. . Bedwell, Erd. Gulari and D. Melnik in "Measurement of
Suspended Particles by Quasielastic Light Scattering",
. E. Dahneke Ed., Wiley, New York, p. 237, 1983.
3. S. Bott, in this volume.
4. S.W. Provencher, J. Hendrix, L. DeMaeyer and N. Paulussen,
J. Chem. Phys., 69, 4273 (1978).
5. S. W. Provencher, Comput. Phys. Commun., 27, 213 and 219,
(1982).
6. E. F. Grabowski and I. D. Morrison in "Measurement of Suspended
Particles by Quasielastic Light Scattering", . E. Dahneke Ed.,
Wiley, New York, p. 199, 1983.
7. H. H. Denman, W. Heller and W J Pangonis "Angular Scattering
Functions for Spheres"
1966.
8. C. A. Herb, I. D. Morrison and E. F. Grabowski, in this volume.
9. C. A. Herb, I. D. Morrison and E. F. Grabowski, in "Magnetic
Resonance and Scattering in Surfactant Systems", L. Magid, ed.,
Plenum Press, to be published.
10. I. D. Morrison, E. F. Grabowski and C. A. Herb, Langmuir, 1,
496, (1985).
11. Erd. Gulari, Es. Gulari, S. Tsunashima and B. Chu, Polymer, 20,
347, (1979).
12. J. Raczek, Eur. Polym. J., 18, 863 (1982).
RECEIVED August 7, 1986

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 8

Photon Correlation Spectroscopy, Transient Electric


Birefringence, and Characterization of Particle Size
Distributions in Colloidal Suspensions

Renliang Xu, James R. Ford, and Benjamin Chu


Department of Chemistry, State University of New York at Stony Brook,
Long Island, NY 11794-3400

By using a combinatio
scattering (LLS)
(TEB) we have been able to determine structural
characteristics and size distributions of polydisperse
disk-shaped particles (bentonite) in suspensions. In the
limit of low concentration and scattering angle we
obtained the weight-average molecular weight M w , the z
-average radius of gyration <R2G>1/2 and the second virial
coefficient A 2 from static light scattering measurements;
at higher scattering angles we were able to estimate an
average particle thickness. Photon correlation function
measurements of both the polarized and the depolarized
components of scattered light give us the average
diffusion coefficients DT (translational) and DR
(rotational) which can in turn be converted to average
particle dimensions. Detailed analysis of characteristic
linewidth distributions yield particle size distributions
consistent with direct observations using electron
microscopy. The TEB experiment provides us with the
average optical polarizability difference , the ratio
of permanent dipolar moment to electric polarizability
difference, and the average rotational diffusion
coefficient DR (TEB). Profile analysis of the decay
curve yields a distribution of particle sizes consistent
with the results from LLS.

Laser light scattering (LLS), which takes advantage of both static


(intensity) and dynamic (intensity correlation/linewidth)
measurements, has been used successfully in determining the
molecular weight distribution (MWD) of polymers in solution. The
essential steps are: 1. to use static light scattering to measure
the weight-average molecular weight Mw which calibrates the MWD, 2.
to use dynamic light scattering to measure the intensity-intensity

0097-6156/87/0332-0115$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
116 PARTICLE SIZE DISTRIBUTION

t i m e c o r r e l a t i o n . f u n c t i o n G^ ^(T), and 2
3 t o p e r f o r m a L a p l a c e
i n v e r s i o n of the '() i n o r d e r t o o b t a i n a n a p p r o x i m a t i o n t o the
c h a r a c t e r i s t i c l i n e w i d t h d i s t r i b u t i o n f u n c t i o n G(r) w h i c h i s r e l a t e d
t o t h e MWD by m e a n s o f a n e m p i r i c a l s c a l i n g r e l a t i o n .
I n c o l l o i d a l s u s p e n s i o n s of a n i s o t r o p i c p a r t i c l e s , the static
structure factor plays a prominent role i n p a r t i c l e s i z e analysis.
We h a v e u s e d t r a n s i e n t e l e c t r i c b i r e f r i n g e n c e ( T E B ) a n d electron
m i c r o s c o p y , i n a d d i t i o n to l a s e r l i g h t s c a t t e r i n g , to c o r r e l a t e our
a n a l y s i s of p a r t i c l e s i z e d i s t r i b u t i o n s of bentonite suspensions.
The c o m p l e m e n t a r y n a t u r e o f TEB and p h o t o n c o r r e l a t i o n s p e c t r o s c o p y
(PCS) i n p a r t i c l e s i z e a n a l y s i s w i l l be discussed.

Theory

TEB. Transient e l e c t r i c b i r e f r i n g e n c e (TEB) w i t h s i n g l e , r e v e r s e d


o r s i n u s o i d a l e l e c t r i c p u l s e s has become a u s e f u l t o o l f o r studying
the structure of l a r g
s u s p e n s i o n ) s i n c e i t wa
By a p p l y i n g l i n e a r l y p o l a r i z e d l i g h t t o a s y s t e m o f a n i s o t r o p i c
p a r t i c l e s a l i g n e d b y a n e x t e r n a l e l e c t r i c f i e l d and b y o b s e r v i n g t h e
depolarized i n t e n s i t y I of the t r a n s m i t t e d l i g h t as the system
r e l a x e s a f t e r r e m o v a l o f t h e e x t e r n a l f i e l d , we c a n o b s e r v e the
change i n the r e f r a c t i v e index difference of two orthogonal
d i r e c t i o n s w i t h r e s p e c t t o t i m e and t h e r e b y d e t e r m i n e t h e r o t a t i o n a l
diffusion c o e f f i c i e n t and obtain information on the optical
p o l a r i z a b i l i t y d i f f e r e n c e and t h e r a t i o o f p e r m a n e n t d i p o l e moment
to e l e c t r i c p o l a r i z a b i l i t y d i f f e r e n c e .
The r e l a t i o n s h i p between the depolarized time-dependent
t r a n s m i t t e d i n t e n s i t y l ( t ) and t h e r e f r a c t i v e i n d e x d i f f e r e n c e i n
t w o o r t h o g o n a l d i r e c t i o n s and y, i n w h i c h one i s i n t h e d i r e c t i o n
o f t h e a p p l i e d e l e c t r i c f i e l d and b o t h a r e p e r p e n d i c u l a r to the
d i r e c t i o n of p r o p a g a t i o n of the i n c i d e n t l i g h t , i s g i v e n b y (2)

2
I(t)-I b = k l p s i n ( a + ^ ) <D

w h e r e 1^ i s t h e i n s t r u m e n t s t r a y l i g h t i n t e n s i t y ; I p , t h e p o l a r i z e d
i n c i d e n t l i g h t i n t e n s i t y ; k, a l i g h t r e f l e c t i o n and a b s o r p t i o n loss
f a c t o r ; a, the a n g l e b e t w e e n the s l o w a x i s o f the q u a r t e r wave p l a t e
(Q) a n d t h e a x i s o f t h e t h i r d p o l a r i z e r ( B ^ ) ( s e e f i g u r e l ) ; a n d
<5(t), t h e o p t i c a l r e t a r d a t i o n d e f i n e d by

6(t) - - ( (t)-n (t))=^f-An(t) (2)


y

w i t h i L ^ and n ^ b e i n g t h e r e f r a c t i v e i n d i c e s o f t h e s o l u t i o n i n and
y d i r e c t i o n s ; s, t h e e f f e c t i v e l e n g t h o f t h e e l e c t r o d e s ; and X , theQ

w a v e l e n g t h of l i g h t i n vacuo.
For t h i n d i s k s , the r i s e and decay c u r v e s of optical
r e t a r d a t i o n (t) a r e r e l a t e d t o t h e p a r t i c l e r o t a t i o n a l m o t i o n b y
(D

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
8. X U ET AL. Particle Size Distributions in Colloidal Suspensions 117

TEB Instrumentation

w
1ZI

(O) (C)

zi : ED i
LASER P L , B 2 C Q B 3 PMT

L7 HV

LLS Instrumentation

I 1 ! 0 171 :
LASER P L BP

CL

CT

F i g u r e 1. S c h e m a t i c d i a g r a m s o f TEB a n d L L S i n s t r u m e n t a t i o n . ,
p i n h o l e s ; L , l e n s e s ; B, p o l a r i z e r s ; C, c e l l ; Q, q u a r t e r w a v e
p l a t e ; P M T , p h o t o m u l t i p l i e r t u b e ; HVG, h i g h v o l t a g e generator;
MP, m i c r o p r o c e s s o r ; TR, t r a n s i e n t r e c o r d e r ; C L , c o r r e l a t o r ; CT,
c o u n t e r ; , s c a t t e r i n g a n g l e . F o r t h e T E B s e t u p p o l a r i z e r s B^,
B 2 h a v e p o l a r i z a t i o n a x i s o r i e n t e d a t /4 w i t h r e s p e c t t o t h e x -
a x i s , as s h o w n i n ( a ) . A f t e r t h e l i g h t beam p a s s e d t h r o u g h t h e
cell with electric field i n the x - d i r e c t i o n containing a
s u s p e n s i o n o f a n i s o t r o p i c p a r t i c l e s and t h e q u a r t e r w a v e p l a t e
w i t h i t s f a s t a x i s o r i e n t e d a t /4 w i t h r e s p e c t t o t h e x - a x i s ,
t h e t r a n s m i t t e d l i g h t beam i s p o l a r i z e d i n t h e d i r e c t i o n o f /4
+ <S/2, a s s h o w n i n ( b ) . A n a l y z e r Bj h a s p o l a r i z a t i o n axis
o r i e n t e d a t 3 V 4 + as shown i n ( c ) .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
118 PARTICLE SIZE DISTRIBUTION

rise: 6(t) = Z S q 1 [1- e " 2 0


^ + . ^ , ( j )

decay: 6(t) - 6 o i e'^Ri* (4)

where 6 and D g
Q i are the steady state
i v a l u e o f 6j_(t) a n d t h e
rotational diffusion coefficient f o r the i t hf r a c t i o n of
polydisperse particles, respectively. i s the ratio of the
orientational p o l a r i z a b i l i t y (which i s r e l a t e d to the permanent
dipole m o m e n t u- a l o n g t h e s y m m e t r i c a x i s ) t o t h e e l e c t r i c a l
p o l a r i z a b i l i t y d i f f e r e n c e Q and has t h e f o r m

2
( /k T )
a P/Q = J (5
a a ) / k
( l- 3
where 3 and ^ a r e t h e e l e c t r i c a l p o l a r i z a b i l i t i e s a l o n g t h e m a j o r
a

and the minor p a r t i c l e axis, respectively; kg i s the Boltzmann


c o n s t a n t a n d T, t h e a b s o l u t e t e m p e r a t u r e . We h a v e t a k e n t h e
p e r m a n e n t d i p o l e moment a l o n g t h e m a j o r a x i s t o b e r e l a t i v e l y s m a l l
w h e n c o m p a r e d w i t h t h e i n d u c e d d i p o l e moment d i f f e r e n c e Q (16)
The steady state r e f r a c t i v e index difference o f each f r a c t i o n ,
A n , depends upon t h e e x t e r n a l
Q i f i e l d s t r e n g t h due t o t h e d i f f e r i n g
degrees of o r i e n t a t i o n o f each p a r t i c l e f r a c t i o n . A t l o w f i e l d
strengths,


= P E 6
" ( i ^ i > <>

When t h e e x t e r n a l f i e l d i ss u f f i c i e n t l y strong to f u l l y a l i g n a l l
particle fractions, An Q i reaches i t s saturation value ^ 3

2.
A = ( } ( 7 )
s i 8 - 3

where i s t h e v o l u m e f r a c t i o n o f t h e i t h p a r t i c l e f r a c t i o n and g^
and g-j a r e t h e m a j o r a n d t h e m i n o r p a r t i c l e a x i s o p t i c a l a n i s o t r o p y
f a c t o r s given by


.
g. = -2 (8)

w i t h a*? b e i n g t h e o p t i c a l p o l a r i z a b i l i t y i n t h e j t h d i r e c t i o n ; , 0

the p e r m i t t i v i t y i nvacuo; v, t h e volume o f a s i n g l e p a r t i c l e ; and


n, t h e r e f r a c t i v e i n d e x o f t h e s o l u t i o n .

Static Light Scattering. For a solution of polydisperse non-


absorbing particles, the Rayleigh r a t i o R (9) i s the excess v v

absolute scattered i n t e n s i t y o f the s o l u t i o n over that o f the pure

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
8. X U ET AL. Particle Size Distributions in Colloidal Suspensions 119

s o l v e n t a t s c a t t e r i n g a n g l e ft, w h e r e t h e s u b s c r i p t v v i n d i c a t e s
v e r t i c a l l y p o l a r i z e d i n c i d e n t and s c a t t e r e d l i g h t , and h a s t h e f o r m

R ()
vv
^ = [ ^ ) - 2 2 ( * ) ) 2
] (9)

where and P(KL^) a r e t h e c o n c e n t r a t i o n and t h e p a r t i c l e


s c a t t e r i n g f a c t o r o f s p e c i e s i h a v i n g m o l e c u l a r w e i g h t M^, i s t h e
m a g n i t u d e o f t h e momentum t r a n s f e r v e c t o r g i v e n b y = ( 4 f T A ) s i n ( 6
/2), L^ i s t h e e q u i v a l e n t d i a m e t e r o f t h e i t h p a r t i c l e f r a c t i o n , k 2

i s t h e second v i r i a l c o e f f i c i e n t , and t h e o p t i c a l constant i s


g i v e n by

2 2 2
4 /8
=

with N A and (3n/3c) being Avogadro's number and t h e r e f r a c t i v e


i n d e x i n c r e m e n t , r e s p e c t i v e l y . F o r s u f f i c i e n t l y s m a l l v a l u e s o f ,
e q u a t i o n (9) c a n be w r i t t e n a s ( 4 )

2 2
_ <R (C)> K
= i + OA r = + S-- h 2A M C l (10)
+ 2 A C + Z A L J u u ;
R () M (KL) 2 M 3 2 w
w w w

where M Wi s the weight-average molecular weight; C, the t o t a l


concentration of particles; P(KL), the z-average p a r t i c l e
scattering f a c t o r ; and < R | ( C ) > , t h e mean s q u a r e " r a d i u s o f z

g y r a t i o n " a t f i n i t e c o n c e n t r a t i o n C , w h i c h c a n be c o r r e c t e d f o r
c o n c e n t r a t i o n by

<Rg(0)> z - <R (C)> 2


Z [1 + 2 A M C ] 2 W (11)

2
with <Rg(0)> ^ being z the radius of gyration. For disk-like
p a r t i c l e s , s u c h a s t h e b e n t o n i t e p a r t i c l e s , e q s . (9), ( l O ) a n d ( l l )
are only approximate because of o p t i c a l anisotropy. In fact,
p o l a r i z e d l i g h t s c a t t e r i n g (vv-component) y i e l d s only apparent
v a l u e s f o rt h e m o l e c u l a r w e i g h t , t h e r a d i u s o f g y r a t i o n and t h e
second v i r i a l c o e f f i c i e n t . T h e c o r r e c t v a l u e s c a n b e c o m p u t e d i f we
know t h e d e p o l a r i z a t i o n r a t i o and t h e p a r t i c l e shape. For bentonite
p a r t i c l e s , t h e d e p o l a r i z a t i o n r a t i o i s v e r y s m a l l (~0.02). Thus,
t h e c o r r e c t i o n f a c t o r i s o f t h e o r d e r o f a f e w p e r c e n t w h i c h we
s h a l l ignore i n the present study.

D y n a m i c L i g h t S c a t t e r i n g . The m e a s u r e d s i n g l e c l i p p e d p h o t o e l e c t r o n
count a u t o c o r r e l a t i o n f u n c t i o n f o r the s e l f - b e a t i n g experiment has
the form (5)

2
G< )(T,K) = N <n Xn>[l
s k + b| g< >( , ) | ] x
K
2
(12)

w h e r e i s t h e d e l a y t i m e ; k, t h e c l i p p i n g l e v e l ; N , t h e t o t a l Q

n u m b e r o f s a m p l e s ; < n > a n d <n> t h e m e a n c l i p p e d a n d u n d i p p e d


k

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
120 PARTICLE SIZE DISTRIBUTION

counts, respectively; b i s a s p a t i a l coherence f a c t o r g e n e r a l l y


tak.en a s an u n k n o w n p a r a m e t e r i n t h e f i t t i n g p r o c e d u r e ; a n d
g** '(,) i s the n o r m a l i z e d first order electric field
autocorrelation function. E q u a t i o n (12) i s v a l i d f o r G a u s s i a n
s i g n a l s (6)
For monodisperse systems the normalized polarized and
d e p o l a r i z e d t i m e c o r r e l a t i o n f u n c t i o n s can be e x p r e s s e d as ( 7 )

^(,) - P (KL)exp[(-D K -m(m+l)D^T]


m T
2
(13)
m=0,even

2
^(,) - exp[(-D K -6D )x]
T R ()

w h e r e Dy and D are th
R

c o e f f i c i e n t s and t h e p a r t i c l
can be c a l c u l a t e d t h e o r e t i c a l l y f o r p a r t i c l e s o f d i f f e r e n t s h a p e s
( 7 , 8 ) . E q . ( 1 4 ) i s v a l i d o n l y f o r s m a l l KL. S c a t t e r i n g f a c t o r s f o r
d i s k - l i k e p a r t i c l e s h a v e b e e n p u b l i s h e d e l s e w h e r e ( 8 ) and we
r e c a p i t u l a t e them i n F i g u r e 2. At s u f f i c i e n t l y s m a l l s c a t t e r i n g
a n g l e s we can u s e e q u a t i o n s ( 1 3 ) and ( 1 4 ) t o d e t e r m i n e t h e v a l u e s o f
D and D
T Rf r o m t h e m e a s u r e d p o l a r i z e d and d e p o l a r i z e d i n t e n s i t y -
intensity autocorrelation f u n c t i o n s (^( , K ) a n d G ^ ( T , K ) . It
s h o u l d be noted t h a t the model ( 7 , 8 ) assumed i s o t r o p i c t r a n s l a t i o n a l
d i f f u s i v e m o t i o n , w h i l e i n r e a l i t y , we m u s t t a k e i n t o a c c o u n t
anisotropy in translational diffusion (9.). However, i n
e x t r a p o l a t i o n t o i n f i n i t e d i l u t i o n and z e r o s c a t t e r i n g a n g l e , we c a n
retrieve the correct translational diffusion coefficient
e x p e r i m e n t a l l y , r e g a r d l e s s o f model.
For polydisperse-particles, we can w r i t e

( l )
|g (x,K)| = / 0(,)- (15)

where G(r,K) i s the n o r m a l i z e d d i s t r i b u t i o n o f c h a r a c t e r i s t i c l i n e


w i d t h a t a g i v e n v a l u e o f K. I n v e r s i o n o f e q u a t i o n ( 1 5 ) i n t h e
presence of e x p e r i m e n t a l noise to o b t a i n the c h a r a c t e r i s t i c
l i n e w i d t h d i s t r i b u t i o n G(r,K) i s an i l l - c o n d i t i o n e d p r o b l e m w h i c h
has r e c e i v e d much a t t e n t i o n i n the r e c e n t l i t e r a t u r e ( 6 , 1 0 , 1 1 ) . F o r
the sake o f c l a r i t y we have o m i t t e d t h e p o l a r i z a t i o n s u b s c r i p t s ( w
o r vh) i n t h i s s e c t i o n . , .
1
The m e t h o d o f c u m u l a n t s (1 2) e x p a n d s g ' ' ( O i n t e r m s o f t h e
moments o f the c h a r a c t e r i s t i c l i n e w i d t h d i s t r i b u t i o n

f,\ ()9
2
.() 3

( )
| (,)| - A exp[-r(K)t + \ + ...] (16)

s 1
w h e r e i s t h e a v e r a g e l i n e w i d t h and yi <(r-F) >- A m o d i f i e d
M a r q u a d t - L e v e n b e r g n o n l i n e a r l e a s t s q u a r e s r o u t i n e was u s e d t o
d e t e r m i n e t h e b e s t v a l u e s o f a n d . A n o t h e r s t r a i g h t f o r w a r d
a p p r o a c h i n v o l v e d a p p r o x i m a t i n g G(r , K T a s t h e w e i g h t e d sum o f two
c h a r a c t e r i s t i c decay t i m e s ^"^ and 2

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
8. X U ET AL. Particle Size Distributions in Colloidal Suspensions 121

-
G(r,K)
1+ we9 (17)

The same nonlinear f i t t i n g routine could determine the best values


for w^ and which might not necessarily have physical meaning but
could be used to compute and W e
used a regularized inversion
2

of equation (15) that incorporates a p o s i t i v i t y constraint on G(r,K)


i n order to obtain more detailed information on the c h a r a c t e r i s t i c
linewidth p r o f i l e , A discussion of this approach may be pursued i n
reference (lO).

Experimental Methods

Sample P r e p a r a t i o n , The b e n t o n i t e powder obtained from F i s h e r


S c i e n t i f i c Company was dissolved i n doubly d i s t i l l e d and f i l t e r e d
water to make a stock s o l u t i o n with C = 365 x 10"^ g/g. T h i s stock
solution was further dilute
I. A l l measurements wer
i n order to avoid possible aging problems.

TEB. Our TEB apparatus c o n s i s t s of a 1 5 mW He-Ne l a s e r w i t h X = Q

6 3 2 . 8 nm., three Glan-Thomson p o l a r i z e r s and a q u a r t e r wave p l a t e


arranged as shown i n figure 1. The sample was contained i n a Beckman
1 cm q u a r t z c e l l w i t h two platinum electrodes, h e l d at
25+.50. The t r a n s m i t t e d l i g h t i n t e n s i t y was measured by a
photomultiplier tube (lP-28) and the output sent to a Biomation 8100
t r a n s i e n t recorder. The e x t e r n a l e l e c t r i c f i e l d was provided by a
Cober 605P high voltage pulse generator. The entire experiment was
under the control of a microcomputer.
High voltage square pulses from 0.5 to 33 KV/cm w i t h pulse
widths of around 2 msec were a p p l i e d to the f i v e b e n t o n i t e
suspensions. The p u l s e t r a c e s and the s i g n a l f r o m the
photomultiplier tube were simultaneously recorded at a resolution of
1 0 2 4 p o i n t s each i n the t r a n s i e n t r e c o r d e r using a sample time
increment of 40 usee and d i s p l a y e d on an o s c i l l o s c o p e . A f t e r 10
passes the data were transferred to the microcomputer and saved on
floppy disk f o r subsequent analysis. The entire measurement sequence
for one sample took a few minutes.

Light Scattering. The l i g h t scattering table consists of an argon


i o n l a s e r , s u i t a b l e lenses and p i n h o l e s to c o n d i t i o n the i n c i d e n t
beam, a sample c e l l i n a brass thermostat (2500_+ 0.05 C) and a
rotatable detector arm on which are mounted o p t i c a l parts to define
the s c a t t e r i n g geometry and the p h o t o m u l t i p l i e r tube as shown i n
f i g u r e 1. The s i g n a l from the p h o t o m u l t i p l i e r tube i s channeled
through a preamplifier/discriminator to either a pulse counter for
i n t e n s i t y measurements or a Malvern 7027 s i n g l e - c l i p p i n g correlator
for the time c o r r e l a t i o n measurements.
Intensity measurements of the f i v e suspensions were performed
u s i n g the l a s e r at an i n c i d e n t wavelength A = 5 1 4 . 5 nm over
Q an
angular range of 1 5 to 36 degrees. Dynamic measurements were done
using i n c i d e n t wavelengths of A = 5 1 4 . 5 and 488.0 nm over angular
Q

ranges of 1 5 to 5 4 degrees and of 3 5 to 80 degrees, respectively.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
122 PARTICLE SIZE DISTRIBUTION

1. 0

F i g u r e 2. S c a t t e r i n g f a c t o r o f d i s k - l i k e p a r t i c l e s w h e r e = 4n"
s i n ( 6 / 2 ) / X , and L, t h e p a r t i c l e d i a m e t e r . hP r e p r e s e n t s the
remaining higher order terms.

Table I. Sample Concentrations

S a m p l e Number Concentration (10"^ g/g water)

TEB 1 2.14

2 1.18

3 0.83

4 2.93

5 6.43

LLS 1 1.02

2 0.67

3 0.38

4 0.21

5 0.13

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
8. X U ET AL. Particle Size Distributions in Colloidal Suspensions 123

( g j i / j C ) . The r e f r a c t i v e i n d e x i n c r e m e n t (9n/3C) o f t h e b e n t o n i t e
s u s p e n s i o n was determined using a B r i c e Phoenix differential
r e f T a c t o m e t e r a t w a v e l e n g t h s 436 and 546 nm. By i n t e r p o l a t i o n , we
e s t i m a t e d (3n/3C) t o be 0.086 a t 514-5 nm. and 0.082 a t 488 nm, i n
r e a s o n a b l e a g r e e m e n t w i t h t h o s e v a l u e s r e p o r t e d by o t h e r a u t h o r s
(13,14,15).

R e s u l t s and D i s c u s s i o n

S t a t i c L i g h t S c a t t e r i n g Measurements. A Zimm p l o t f o r the b e n t o n i t e


s u s p e n s i o n s i s shown i n f i g u r e 3. H e r e we h a v e p l o t t e d HC/R (6 ) yv

2
a g a i n s t C K ' + s i n ( / 2 ) w h e r e K* i s an a r b i t r a r y c o n s t a n t , and
determined M = 3-57 x 10^ g / m o l e , A = 2.93 x 10"^ m o l e - g / g , and
w 2

9 2
<R|(0)> =1.51
Z x 10" cm from

lim HC _ 1 U |

00 R () M
w w

lim HC = _1 (19)
+0 R () M 2
w w
and

We h a v e a l s o b e e n a b l e t o e s t i m a t e t h e a v e r a g e t h i c k n e s s of
b e n t o n i t e d i s k s from t h e s l o p e o f t h e Zimm p l o t a t z e r o
c o n c e n t r a t i o n and h i g h s c a t t e r i n g a n g l e s . I f we take
2 J (KL )
1
P(KL ) = [ 1 - * ] (21 )
2
(KL.) ^ i

as t h e p a r t i c l e s c a t t e r i n g f a c t o r f o r a d i s k s h a p e d p a r t i c l e ( 8 ) ,
w h e r e J-j (KL^) i s t h e f i r s t o r d e r B e s s e l f u n c t i o n . F o r KL > 35,
e q u a t i o n (21; becomes

2
V(KL ) = 8/(KLi) (22)

w i t h an e r r o r o f l e s s than 13$. T h e r e f o r e , e q u a t i o n (9) becomes

8 C
R () , A
^ - = ^ 2 - 1 (23)
H C
CK L.
1
By assuming t h a t a l l the b e n t o n i t e p a r t i c l e s have the same t h i c k n e s s
d and d e n s i t y p, and u s i n g the r e l a t i o n
L? .
4
= (24)

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
124 PARTICLE SIZE DISTRIBUTION

we o b t a i n an e q u a t i o n from which the t h i c k n e s s d o f the b e n t o n i t e


d i s k s can be d e t e r m i n e d :

2
HC 8 2, , -\0

- = S i n ( ( 2 5 )
R ( 7 2 2>
w dpN A
A

I f we t a k e a v a l u e o f 2.0 g / m l f o r t h e d e n s i t y o f t h e b e n t o n i t e 0

disks, we o b t a i n an e s t i m a t e o f 30 A f o r t h e t h i c k n e s s o f a
b e n t o n i t e d i s k f r o m t h e s l o p e o f t h e Zimm p l o t i n f i g u r e 3 a t z e r o
c o n c e n t r a t i o n and h i g h s c a t t e r i n g a n g l e s .

Dynamic L i g h t S c a t t e r i n g Measurements. At s u f f i c i e n t l y low


s c a t t e r i n g a n g l e s where o n l y the f i r s t term o f t h e s t a t i c s t r u c t u r e
f a c t o r P Q ( K L ) i n e q u a t i o n ( 1 3 ) i s i m p o r t a n t , we c a n e x p r e s s t h e
linewidth obtained fro p o l a r i z e d dynami ligh scatterin
measurements as (17)

2 2 2
r v y (L,K) - D (L)K T (1 + f < R ( c ) ^ K ) (26)

where

D (L)
T = D(L) (1 + k C ) d (27)

with D ( L ) being T the t r a n s l a t i o n a l diffusion c o e f f i c i e n t of


p a r t i c l e s w i t h main d i m e n s i o n L e x t r a p o l a t e d t o i n f i n i t e d i l u t i o n .
kd i sa system s p e c i f i c second v i r i a l c o e f f i c i e n t which combines
h y d r o d y n a m i c and t h e r m o d y n a m i c f a c t o r s , and f i s a d i m e n s i o n l e s s
number d e p e n d e n t upon t h e p a r t i c l e s t r u c t u r e , p o l y d i s p e r s i t y and
solvent. _
By u s i n g t h e m e t h o d o f c u m u l a n t s , we d e t e r m i n e d r . With y v

v a l u e s o f <Rg(0)> , A and M ^ o b t a i n e d from s t a t i c l i g h t s c a t t e r i n g


z 2

m e a s u r e m e n t s , we o b t a i n e d D a n d f f r o m t h e s l o p e o f _ a p l o t o f
T

r /K
V Y v e r s u s a t d i f f e r e n t _ c o n c e n t r a t i o n s . By p l o t t i n g D a g a i n s t T

c o n c e n t r a t i o n , we e s t i m a t e d D ^ - 970 10"^ c m / s e c and k = -5-10 2


d

4
10 " g / g . T h e c o n c e n t r a t i o n d e p e n d e n c e o f t h e f v a l u e s s u g g e s t s
t h a t f o r l a r g e p a r t i c l e s , i n t e r n a l m o t i o n s have a m e a s u r a b l e e f f e c t
on t r a n s l a t i o n a l motions. T h u s , we e x p e c t that D has a R

c o n c e n t r a t i o n dependence.
We were a l s o a b l e to o b t a i n a c o n t i n u o u s l i n e w i d t h d i s t r i b u t i o n
c u r v e G ( r , K ) from t h e r e g u l a r i z a t i o n a p p r o a c h by i n v e r s i o n o f
Y V

e q u a t i o n (15) The r e s u l t o b t a i n e d f r o m t h e L a p l a c e inversion


R
procedure i s a s e t of d e l t a f u n c t i o n s G ( K ) which a p p r o x i m a t e t h e I F

continuous G ( T , K ) curve sampled at equal


V V i n t e r v a l s . The
s u b s c r i p t w s h a l l h e n c e f o r t h be o m i t t e d i n the i n t e r e s t o f c l a r i t y
in notation. I n o r d e r to o b t a i n a s i z e d i s t r i b u t i o n from G ( I ^ K ) we F

n e e d t o c o n v e r t b o t h t h e o r d i n a t e and t h e a b s c i s s a ( 1^) i n t h e
f o l l o w i n g way.
From e q u a t i o n s (26) and (27) we o b t a i n

k
2 2
- K ( l + k C ) ( l + f<Rg ( C ) > K ) d z (28)

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
8. X U ET AL. Particle Size Distributions in Colloidal Suspensions 125

where n Q i s the s o l v e n t v i s c o s i t y and we have used the r e l a t i o n (5)

k
D
T - 6^L <29)

W i t h v a l u e s f o r k , f and <R (0)> , we c o u l d c o n v e r t t h e a b s c i s s a


d g z

from space to L space. A f t e r h a v i n g d e t e r m i n e d the range i n L


space r e q u i r e d to a d e q u a t e l y c o v e r the s i z e d i s t r i b u t i o n , we chose
e q u a l l y s p a c e d v a l u e s o f L.^ and c a l c u l a t e d t h e corresponding
values. The amplitudes G(r ,K) f o r t h i s new set of i were
determined by i n t e r p o l a t i o n f r o m the o r i g i n a l continuous
d i s t r i b u t i o n curve. By t a k i n g i n t o account both the J a c o b i a n o f the
t r a n s f o r m a t i o n and t h e f o r m f a c t o r s c a l c u l a t e d f r o m t h e o r e t i c a l
p r i n c i p l e s ( 8 ^ ) , we c o u l d c o n v e r t the o r d i n a t e by s e t t i n g

F ( L ) = G ( r K ) ( 3 0 )
i pckir i '

The n o r m a l i z e d r e s u l t s f o r one b e n t o n i t e s u s p e n s i o n measured a t two


d i f f e r e n t s c a t t e r i n g a n g l e s a r e shown t o be s e l f - c o n s i s t e n t i n
figure 4
By f i t t i n g the d e p o l a r i z e d t i m e c o r r e l a t i o n f u n c t i o n d a t a w i t h
a double e x p o n e n t i a l model, we o b t a i n e d D v a l u e s i n c o n s i s t e n t w i t h R

t h e o t h e r r e s u l t s we o b t a i n e d . H o w e v e r , by p l o t t i n g t h e v a l u e s
o b t a i n e d f o r the f a s t e r component of the d o u b l e e x p o n e n t i a l f i t
a g a i n s t , and by p l o t t i n g t h e r e s u l t i n g i n t e r c e p t s and s l o p e s
a g a i n s t c o n c e n t r a t i o n , we o b t a i n e d Dj - 10.9 x 10"^ c m / s e c and D - 2
R

8 . 2 4 sec . The r e s u l t s a r e c o n s i s t e n t w i t h t h o s e o b t a i n e d f r o m
o t h e r methods. Thus, t h e r e may be a l o w - f r e q u e n c y component o f the
d e p o l a r i z e d t i m e c o r r e l a t i o n f u n c t i o n a r i s i n g p o s s i b l y from dust.

P a r a m e t e r s from TEB Measurements. By e q u a t i o n s (6) and (7) a t y p i c a l


2
r e t a r d a t i o n curve (<5 s E ) s h o u l d be l i n e a r at low f i e l d s t r e n g t h
Q

and r e a c h a p l a t e a u when the f i e l d s t r e n g t h i s s u f f i c i e n t to f u l l y


a l i g n a l l t h e p a r t i c l e s a l o n g t h e e l e c t r i c f i e l d v e c t o r . We f o u n d
t h e p l a t e a u a t f i e l d s t r e n g t h s h i g h e r t h a n 2.0 KV/cm. A p l o t of
6 S 0v e r s u s C a t a f i e l d s t r e n g t h o f 3.3 KV/cm y i e l d e d a s t r a i g h t
line. From the s l o p e o f 6 = 5*57xl0 C - 7-50x10 ^ we e s t i m a t e d
QQ
2

the o p t i c a l p o l a r i z a b i l i t i e s i n the f o l l o w i n g way.


From e q u a t i o n s ( 2 ) and ( 7 ) we have

5 ( 5 1 )
s o = ^ *1 ( -*1>
3

As the p a r t i c l e a n i s o t r o p y f a c t o r s g^ have a v a l u e per u n i t volume,


i t i s r e a s o n a b l e t o a s s u m e t h a t t h e s e q u a n t i t i e s a r e t h e same f o r
a l l particles. By changing to c o n c e n t r a t i o n u n i t s and by a c c o u n t i n g
f o r the f a c t t h a t the s h o r t a x i s of the p a r t i c l e s can be a l i g n e d i n
any d i r e c t i o n p e r p e n d i c u l a r to the f i e l d we have

C
* s o = n i ^ ^ < S 3 - - V > (32)
bento

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
126 PARTICLE SIZE DISTRIBUTION

TEB
P
/ \
c
D
(Arb.

^4--LLSl

_J

Ll

r-LLS2

0.5 1.0 1.5 2.0

L (jjm)

F i g u r e 4 S i z e d i s t r i b u t i o n s f r o m L L S s a m p l e 3 a t - 21 ( L L S l )
a n d a t 2 4 ( L L S 2 ) a n d f r o m T E B s a m p l e 4 I t s h o u l d be n o t e d
t h a t t h e s c a t t e r e d i n t e n s i t y f r o m L L S i s p r o p o r t i o n a l t o N^M^
w h i l e t h e t r a n s m i t t e d i n t e n s i t y f r o m TEB i s p r o p o r t i o n a l t o N j ^ .
I n t h i s c o m p a r i s o n , we h a v e c o n v e r t e d t h e TEB s i z e d i s t r i b u t i o n
t o t h e same w e i g h t i n g f a c t o r a s L L S .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
8. X U ET AL. Particle Size Distributions in Colloidal Suspensions 127

whereby we used an average v a l u e o f g^ and g-^ i n s t e a d o f s i m p l y g-^.


R e c a l l i n g t h a t from eq. (8)

Out
e n t o
g, = 3 A
* (33)
J 4 M

we c a l c u l a t e d Ag (=g^-g ) = 5.28x10"^ and = 1- = 1.24x10"33


2
Fm where we used M - 3.57x10^ g/mole and m /M ~ 14 w w n

The r a t i o o f o r i e n t a t i o n a l t o e l e c t r i c p o l a r i z a b i l i t y c a n be
e s t i m a t e d from the r a t i o o f two i n t e g r a t i o n s ( s e e e q u a t i o n s (3) and
(4))
(4+1)

/ (A An(t))dt
V 6D (B+1)
R _

r
fn(t)dt

We f i n d t h a t i s a c o n s t a n t independent of c o n c e n t r a t i o n and has


a v a l u e o f -0,248, t h e n e g a t i v e s i g n i n d i c a t i n g t h e d i r e c t i o n o f
o r i e n t a t i o n o f the p a r t i c l e s , i.e., the e l e c t r i c f i e l d ( x - d i r e c t i o n )
i s p e r p e n d i c u l a r to the symmetric a x i s o f the p a r t i c l e .
A n a l y s i s o f t h e TEB decay c u r v e s was c a r r i e d out u s i n g both the
c u m u l a n t s and t h e r e g u l a r i z a t i o n p r o c e d u r e s . F r o m t h e c u m u l a n t s
1
r e s u l t s , we p l o t t e d D a g a i n s t C and o b t a i n e d R = 74 s e c " , a s
shown i n f i g u r e 5
From the r e g u l a r i z a t i o n approach we o b t a i n e d the c h a r a c t e r i s t i c
linewidth distribution. We c o n v e r t e d the o r d i n a t e according to

(^) = . 4 / 3
GOV (35)

and the a b s c i s s a a c c o r d i n g t o

3k T-6(l+k C) .

- I
4 . d
J' 7 3
<*>
1

W i t h k = 1.35 x 10^ ( a n d [c]


d = g/g) o b t a i n e d f r o m t h e c u m u l a n t s
f i t , the r e s u l t i n g s i z e d i s t r i b u t i o n i s shown i n f i g u r e 4, which has
been c o n v e r t e d f u r t h e r t o a z-average f o r c o m p a r i s o n w i t h the
d i s t r i b u t i o n from LLS.

Comparison o f LLS and TEB R e s u l t s . By means o f e q u a t i o n (29) and

3 k T
B

4 L


we can compute an average p a r t i c l e d i a m e t e r <L> f r o m e i t h e r D o r Dm R

and t h e r e f o r e c o m p a r e d i r e c t l y t h e d i f f e r e n t r e s u l t s d e s c r i b e d
a b o v e . H o w e v e r , we s h o u l d be c a r e f u l t o a c c o u n t f o r t h e z - a v e r a g e

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
128 PARTICLE SIZE DISTRIBUTION

n a t u r e o f the d i s t r i b u t i o n curve from LLS measurements. Values of


<L> so d e t e r m i n e d a r e s h o w n i n T a b l e I I . We n o t e t h a t d i f f e r e n t
t e c h n i q u e s are q u i t e c o n s i s t e n t , the o n l y e x c e p t i o n b e i n g the
0
a v e r a g e v a l u e s computed from D , and Dm. The d i s c r e p a n c y i s p r o b a b l y
because we have n e g l e c t e d to c o r r e c t f o r a d d i t i o n a l c o n t r i b u t i o n s a t
f i n i t e s c a t t e r i n g a n g l e s due t o _ t h e p a r t i c l e s c a t t e r i n g f a c t o r s when
0 0
computing a v e r a g e s from D , ( o r Dm ). An average d i s k t h i c k n e s s <d>
can be computed from

2
4M <L >
<d> = (38)
7r P < J
^A bento ^

With the M w value obtained from static light scattering


m e a s u r e m e n t s , <d> = 35 A, i n r e a s o n a b l e a g r e e m e n t w i t h d 30 A
e s t i m a t e d from s t a t i c l i g h scatterin alone Ratio f
M :M :M can be c a l c u l a t e
n w z

s i z e d i s t r i b u t i o n s (PSD
a r e t h e same f o r a l l b e n t o n i t e p a r t i c l e s ( s e e T a b l e n ) . It i s also
i n t e r e s t i n g to use the p a r t i c l e s i z e d i s t r i b u t i o n o b t a i n e d f r o m TEB
t o g e n e r a t e a l i g h t s c a t t e r i n g t i m e c o r r e l a t i o n f u n c t i o n and t o
compare the t h e o r e t i c a l l y g e n e r a t e d c u r v e w i t h t h e m e a s u r e d d a t a .
F i g u r e 6 shows such a c o m p a r i s o n .

F r o m t h e v a l u e s o f ~D, and we can calculate the average


l i n e w i d t h u s i n g the e x p r e s s i o n (7)

2 2
^Vv(K) - p(!jy{P (KL)DK 0 + P (KL)[DK +6D ]
2 R

2
+P (KL)[DK +20D ]+...}
4 R (39)

and check the v a l u e s a g a i n s t the measured ones o v e r a wide a n g u l a r


r a n g e as s h o w n i n f i g u r e 7. The a g r e e m e n t s u g g e s t s t h a t p a r t i c l e
a b s o r b t i o n e f f e c t s a r e n e g l i g i b l e , and t h a t a l t h o u g h b e n t o n i t e
p a r t i c l e s a r e a l r e a d y on the edge o f the v a l i d i t y o f the R a y l e i g h -
Debye s c a t t e r i n g t h e o r y r e a s o n a b l e r e s u l t s can s t i l l be o b t a i n e d i f
e x p e r i m e n t s a r e done a t s m a l l enough s c a t t e r i n g a n g l e s .
F i n a l l y , we have examined the b e n t o n i t e p a r t i c l e s d i r e c t l y by
e l e c t r o n m i c r o s c o p y u n d e r a m a g n i f i c a t i o n o f a b o u t 24,000X. The
p a r t i c l e s a c t u a l l y appear to be e l l i p s o i d a l ones w i t h an a p p r o x i m a t e
a x i a l r a t i o o f 1.3 r a t h e r than p e r f e c t l y round d i s k s . We counted 266
p a r t i c l e s using p i c t u r e s at higher m a g n i f i c a t i o n s and o b t a i n e d <L>
0.97 ym. The d i s t r i b u t i o n (F'(L)) i s c l o s e t o the TEB r e s u l t w h i c h
i s c o n v e r t e d t o number d i s t r i b u t i o n f r o m t h e r e s u l t u s i n g t h e
r e g u l a r i z a t i o n approach, as shown i n f i g u r e 8.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
8. X U ET AL. Particle Size Distributions in Colloidal Suspensions 129

30. 0 L

a 20. -

10.0 L

0. 0 I 1 1 1

0.00 0.7

C ( 1 0 ~ g/g>

Figure 5 D versus C R from TEB m e a s u r e m e n t s . D = R

D (l+1.35xlO^C) s e c " - w i t h
R
1
DR * 7-4 1
s e c " and C expressed i n
Table I.

T a b l e I I . Average L e n g t h V a l u e s Computed From D i f f e r e n t Techniques


and M e t h o d s o f A n a l y s i s

1
Data Source orV <L2>l/2 <L-3>;i/3

LLS PSD 0.96 1.14 0.76

TEB PSD 1.04 1.18 0.78

D^ f r o m F w 0.79 - -
D from r v h 0.70 - -
f r o m TEB - - 0.78
2 -
<R > f r o m L L S
g z
- 1.10

* * *

Data Source Mw Mz

LLS PSD 1.00 1.47 2.10

TEB PSD 1.00 1.33 1.82

EM PSD 1.00 1.47 1.86

PSD denotes p a r t i c l e size distribution; l e n g t h i n u n i t s o f ym.


In Particle Size Distribution; Provder, T.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
130 PARTICLE SIZE DISTRIBUTION

1. 0

0. 0 0 -1.0
0.0 10.

X (msQc)

F i g u r e 6. A u t o c o r r e l a t i o n f u n c t i o n d a t a a t = 2 4 ( + ) f o r L L S
s a m p l e 3. Generated time c o r r e l a t i o n f u n c t i o n (continuous curve)
f r o m t h e s i z e d i s t r i b u t i o n c u r v e o f TEB a s s h o w n i n f i g u r e 4 w i t h
r e l a t i v e d e v i a t i o n b e t w e e n the two c u r v e s . D e v i a t i o n = 1.0 -
(^l^Ogenerated^ 8i(O m e ai \2
)g u r e <

0.0 3.0 6.0 9. G 12. G

2
(10 9
/cm 2
)

F i g u r e 7. A comparison of b e t w e e n the LLS e x p e r i m e n t a l d a t a


s
of sample 1 at C 1 . 0 2 x 1 0 " ^ g/g (+ : at \ = 514.5 nm, a n d *: a t Q

>^ = 4 8 8 . 0 nm) a n d a b e s t f i t c u r v e f r o m t h e o r y ( E q . 4 0 ) , w h i c h
2
w a s c o n s t r u c t e d b y _ u s i n g 15m 4 . 8 x 1 0 " c m / s e c [- 9 7 1 0 " ^ ( -
4 2 4
5xl0 C) cm /sec], D = 6 . 9 8 / s e c [> 8 . 2 4 ( 1 - 1 . 5 x l 0 C ) / s e c ] , L =
R

8 . 5 x 1 0 " ^ cm.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
8. X U ET AL. Particle Size Distributions in Colloidal Suspensions 131

0.0 G. 5 1.0 1.5 2.0

L (jjm)

F i g u r e 8. F'(L) n u m b e r s i z e d i s t r i b u t i o n f r o m EM and TEB


m e a s u r e m e n t s . M^-M^iM^ r a t i o s a r e l i s t e d i n T a b l e I I .

Acknowledgments

We g r a t e f u l l y a c k n o w l e d g e s u p p o r t of^ t h i s p r o j e c t b y t h e N a t i o n a l
S c i e n c e F o u n d a t i o n , P o l y m e r s P r o g r a m (DMR 8314193), a n d t h e U.S.
A r m y R e s e a r c h O f f i c e , Durham.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
132 PARTICLE SIZE DISTRIBUTION

Literature Cited

1. O'Konski, C. T.; Zimm, . H. Science 1950, 111, 113.


2. Fredericq, E.; Houssier, C. "Electric Dichroism and Electric
Birefringence"; Clarendon Press: Oxford, 1973; p.92.
3. Tinoco, I., Jr.; Yamaoka, K. J . Phys. Chem. 1959, 63, 423.
4. Huglin, M. B. Topics in Current Chemistry 1978, 77, 143.
5. Chu, . "Laser Light Scattering"; Academic Press: New York,
1974.
6. Chu. . Proceedings of the NATO ASI on the Application of Laser
Light Scattering to the Study of Biological Motions, J.C.
Earnshaw and M.W. Steer, Ed.; Plenum Press: 1983 pp.53-76.
7. Berne, B. J.; Pecora, R. "Dynamic Light Scattering"; John Wiley
& Sons, Inc., 1976.
8. Aragon, S. R.; Pecora, R. J . Chem. Phys. 1977, 66, 2506.
9. Maeda, T.; Fujime,
K.; Fujime, S. Macromolecules
10. Chu, .; Ford, J . R.; Dhadwal, H. In "Methods of Enzymology";
S. P. Colowick and N. O. Kaplan, Eds.; Academic Press: New
York, 1985; Vol. 104, pp. 256-297; Ford, J . R.; Chu, .
Proceedings of the 5th International Conference on Photon
Correlation Techniques in Fluid Mechanics, E. O. Schulz-
DuBois, Ed.; Springer-Verlag: 1983, pp. 303-314.
11. Pike, E. P. In "Scattering Techniques Applied to Supramolecular
and Non-Equilibrium Systems"; S. H. Chen; B. Chu; R. Nossal,
Ed.; 1981, pp. 179-200.
12. Koppel, D. E. J . Chem. Phys. 1972, 57, 4814.
13. Jennings, B. R.; Brown, B. L.; Plummer, H. J. C o l l . and Inter.
Sci. 1970, 32, 606.
14. Schweitzer, J . ; Jennings, B. R. J . C o l l . and Interface Sci.
1971, 37, 443.
15. Suong, Thai Thanh; Stoylov, S. Izv. Khim. Bulg. Akad.
Nauk.(Bulgaria) 1982, 15, 542.
16. Shah, M. J.; Thompson, D. C.; Hart, C. M. J . Phys. Chem. 1963,
67, 1170.
17. Stockmayer, W. H.; Schmidt, M. Pure & Appl. Chem. 1982, 54,
407.
RECEIVED July 17, 1986

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 9

Determination of Particle Size Distributions


Using Light-Scattering Techniques
1 1 2 2
Erdogan Gulari , A. Annapragad , Esin Gulari , andB.Jawad
1
Department of Chemical Engineering, University of Michigan, Ann Arbor,MI48109
2
Department of Chemical and Metallurgical Engineering, Wayne State University,

A comparison of the advantages and disadvantages of the


three light scattering based particle sizing techniques:
photon correlation spectroscopy (PCS), multiwavelength
turbidity spectra (TS) and Fraunhofer diffraction pattern
analysis (FDPA) in the overlap region of 0.5 m to 5 m
was made. Using monodisperse latex spheres, we observed
that in terms of the mean size the resolution of PCS and
TS were very good. Despite the manufacturer's claims of a
1 m lower limit, we found that commercial FDPA instru
ments cannot accurately measure the sizes below 2 m. Due
to the finite width and the fixed spacing of detector
diodes, the resolution was comparable to the mean size
measured. In terms of quantitative measurements of the
relative mass fractions in a bimodal mixture, both TS and
FDPA gave fairly accurate results with FDPA being closer
to the actual mass fractions. PCS results were not at a l l
quantitative. In terms of the ease of usage, FDPA was the
easiest followed by TS. PCS was the most difficult one,
both in sample preparation and data analysis.

Light scattering based p a r t i c l e s i z i n g techniques have the advantage


of nonintrusively measuring sizes of emulsions and dispersions. De
pending on the parameters involved, there are several techniques
which can be used and a choice of the most convenient method can be
made. Parameters governing the a p p l i c a b i l i t y of a given method are
the r e l a t i v e r e f r a c t i v e index m = n^/n.., and the r e l a t i v e size =
7/, where i s the wavelength o f the l i g h t i n the surrounding
medium, n^ i s the r e f r a c t i v e index of the p a r t i c l e and i s the re
f r a c t i v e index of the medium. When the p a r t i c l e s are small compared
to the wavelength of the incident l i g h t or < 0.4 one can use
either Photon Correlation Spectroscopy (PCS) (1,2) to measure p a r t i
cle size d i s t r i b u t i o n s or angular i n t e n s i t y measurements to obtain
the radius of gyration (3). When the p a r t i c l e s are large, 5 <

0097-6156/87/0332-0133$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
134 PARTICLE SIZE DISTRIBUTION

D < 5 0 0 , F r a u n h o f e r D i f f r a c t i o n P a t t e r n A n a l y s i s ( F D P A ) c a n b e
employed i n measuring p a r t i c l e s i z e d i s t r i b u t i o n s (4,5). For the
p a r t i c l e s i n the intermediate r a n g e , 0.7 < D < 10 , M i e t h e o r y
o f s c a t t e r i n g h o l d s and T u r b i d i t y S p e c t r a (TS) can f u r n i s h i n f o r m a
t i o n about p a r t i c l e s i z e s ( 6 ) .
Our o b j e c t i v e i n t h i s p a p e r i s t o compare a l l t h r e e methods i n
the overlap r e g i o n o f 0.5 t o 5 pm. We a r e p a r t i c u l a r l y i n t e r
e s t e d i n a c c u r a c y , n o i s e t o l e r a n c e , ease o f usage, and a b i l i t y t o
deal with multimodal d i s t r i b u t i o n s .

Theory

Photon C o r r e l a t i o n . P a r t i c l e s suspended i n a f l u i d undergo Brownian


m o t i o n due t o c o l l i s i o n s w i t h t h e l i q u i d m o l e c u l e s . T h i s r a n d o m mo
t i o n r e s u l t s i n s c a t t e r i n g and D o p p l e r b r o a d e n i n g o f t h e f r e q u e n c y
of the scattered l i g h t . Experimentally i t i s m o r e a c c u r a t e t o mea
sure the a u t o c o r r e l a t i o
the power spectrum i n t h
f i e l d a u t o c o r r e l a t i o n f u n c t i o n g ( t ) f o r a suspension o f monodisperse
p a r t i c l e s o r d r o p l e t s i s g i v e n by:

2
g(t) = exp(-Dq t) (1)

D = t h e d i f f u s i o n c o e f f i c i e n t o f t h e p a r t i c l e s i n t h e medium
q = s c a t t e r i n g v e c t o r = (4 /) s i n ( 6 / 2 ) where i s t h e s c a t t e r i n g
1

angle
t = time.
F o r a p o l y d i s p e r s e s y s t e m e q u a t i o n ( 1 ) must be i n t e g r a t e d o v e r
the s i z e d i s t r i b u t i o n w i t h t h e a p p r o p r i a t e w e i g h t i n g . For spherical
p a r t i c l e s the r e s u l t i s(7):

6 2
g(t) = / f(r)r exp(-Dq t)P(q,r)dr (2)

where f ( r ) i s t h e s i z e d i s t r i b u t i o n f u n c t i o n , P ( q , r ) i s the form


factor. The s i x t h power o f t h e p a r t i c l e r a d i u s appears because t h e
scattered electric f i e l d i s p r o p o r t i o n a l to the square o f the p o l a r
i z a b i l i t y which i n t u r n i s p r o p o r t i o n a l t o t h e volume o f the p a r t i
cle. E q u a t i o n (2) forms t h e b a s i s f o r o b t a i n i n g p a r t i c l e s i z e d i s
t r i b u t i o n s b y PCS.

Turbidity. T h e a t t e n u a t i o n o f a l i g h t beam t r a v e r s i n g a s c a t t e r i n g
medium c o n t a i n i n g p a r t i c l e s p e r u n i t v o l u m e i s e q u a l t o t h e t o t a l
scattered radiation; i . e . ,

-dl/I = NR dx (3)

where R i s t h e s c a t t e r i n g c r o s s s e c t i o n o f one p a r t i c l e . F o r an op
t i c a l p a t h l e n g t h o f and i n c i d e n t i n t e n s i t y I , Q

l n ( I / I ) = NRx
Q (4)

For a monodisperse system o f n o n a b s o r b i n g spheres i n t h e ab


sence o f m u l t i p l e s c a t t e r i n g , the t u r b i d i t y i s given by (8)

= N R(r,\,m) (5)

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
9. G U L A R I ET AL. Light-Scattering Techniques 135

R ( r , A , m ) i s t h e t o t a l e n e r g y s c a t t e r e d b y o n e s p h e r e when inci
d e n t wave i s o f u n i t i n t e n s i t y a n d i s g i v e n b y
2 2
2 l a | +|b I
R
= h \ 2n + 1 W

where a ^ and b a r e complex c o e f f i c i e n t s , c o m p u t a t i o n o f w h i c h a r e


d i s c u s s e d i n d e r a i l by H e l l e r and coworkers ( 8 , 9 ) .
For a p o l y d i s p e r s e system t h e t o t a l t u r b i d i t y a t a s p e c i f i c
w a v e l e n g t h c a n be w r i t t e n as an i n t e g r a l

= j-f(r.)T. ( X dr (7)

where i s t h e t u r b i d i t y o f p a r t i c l e s o f s i z e r . a t w a v e l e n g t h .
To e x t r a ' c t a n a v e r a g e p a r t i c l siz fro t h w a v e l e n g t h dependenc
of t u r b i d i t y has been aroun
m e t h o d s s u c h a s t h e maximu
t i e n t m e t h o d (11) a n d t u r b i d i t y a t t w o d i f f e r e n t w a v e l e n g t h s ( 1 2 )
have been used f o r p a r t i c l e s i z e measurement. Recently, inverting
t u r b i d i t y s p e c t r a by assuming a log-normal d i s t r i b u t i o n has been
proposed ( 1 3 ) . With t h e development o f automated spectrophotometers
and s c a n n i n g d i o d e a r r a y s as d e t e c t o r s , t u r b i d i t y measurements o f
v e r y h i g h p r e c i s i o n a t w a v e l e n g t h s t e p s o f 0.5 nm a p a r t c a n b e made
i n t h e u l t r a v i o l e t and v i s i b l e range. T h u s , more d e t a i l e d i n f o r m a
t i o n i s a v a i l a b l e and e q u a t i o n ( 7 ) c a n be i n v e r t e d t o o b t a i n m u l t i
modal p a r t i c l e s i z e d i s t r i b u t i o n s .

Fraunhofer D i f f r a c t i o n . For spherical particles with diameter


g r e a t e r t h a n t h e w a v e l e n g t h o f t h e i l l u m i n a t i n g r a d i a t i o n , t h e diam
eter of the d i f f r a c t i o n pattern i s inversely proportional to the
p a r t i c l e diameter. The l i g h t e n e r g y w i t h i n a n y r i n g o n t h e f o c a l
p l a n e bounded b y r a d i i , s due t o a p a r t i c l e o f r a d i u s r i s g i v e n
0

1 1
by:

L
s s
v 2
=
EiJo^krej/O+J^ikrSj/O-J^Ckrs^O-Jj 2
(krs /f)}
2 (8)

where f i s t h e f o c a l length, i s the energy f a l l i n g on t h e p a r t i c l e


and i s p r o p o r t i o n a l t o the cross sectional area o f the p a r t i c l e .

2
= CNTir (9)

where C i s a p r o p o r t i o n a l i t y constant. For a collection of parti


cles o f d i f f e r e n t sizes t h e t o t a l energy i s a sum o v e r a l l t h e s i z e s
and i s g i v e n b y :

M
2 2 2
L = C . { ( J

+ J 2) 1 s
- (J
0
+ J )
1 s
} (10)
s ,s1 2 i 2

For a d e t e c t o r which measures t h e l i g h t energy falling onto many


r i n g s we h a v e a m a t r i x e q u a t i o n

L(j) = N(i) T(j,i) (11)

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
136 PARTICLE SIZE DISTRIBUTION

T h i s e q u a t i o n c a n be s o l v e d assuming a d i s t r i b u t i o n c o n t a i n i n g M
f r a c t i o n s o f s i z e s and then i t e r a t i v e l y a d j u s t i n g t h e parameters o f
the d i s t r i b u t i o n u n t i l t h e d e v i a t i o n between t h e observed and c a l c u
l a t e d e n e r g y c u r v e s i s a minimum.

Experimental

L a t e x sphere s u s p e n s i o n s were p r e p a r e d u s i n g l a t e x spheres o f u n i


form s i z e purchased f r o m Duke S c i e n t i f i c a n d d i s t i l l e d - d e i o n i z e d
water. M e a s u r e m e n t s w e r e made i m m e d i a t e l y a f t e r r i g o r o u s s h a k i n g
and s o n i c a t i n g t o p r e v e n t s e t t l i n g .
A u t o c o r r e l a t i o n f u n c t i o n s were measured w i t h a Brookhaven I n
s t r u m e n t s 128 c h a n n e l m u l t i - t i m e f u l l c o r r e l a t o r . Other d e t a i l s o f
the spectrometer have been d e s c r i b e d p r e v i o u s l y ( 7 ) .
T u r b i d i t y m e a s u r e m e n t s w e r e made w i t h a n HP 8 4 5 1 A d i o d e a r r a y
UV-VIS s p e c t r o m e t e r . Sinc styren ha absorbanc k f 250
nm, o n l y t h e d a t a i n t h
Fraunhofer d i f f r a c t i o
2 6 0 0 HSD p a r t i c l e s i z e r . T h i s u n i t h a s 32 s e m i c i r c u l a r d e t e c t o r
units. The d e t e c t o r r i n g s p a c i n g i s r e l a t e d t o t h e most i n t e n s e
peak o f t h e d i f f r a c t i o n p a t t e r n o f p a r t i c l e s w i t h s i z e r . by 27tr.s./
A f = 1.375. Thus f o r a g i v e n d e t e c t o r t h e h i s t o g r a m s p a c i n g i s
f i x e d by t h e f o c a l l e n g t h o f t h e l e n s and t h e i n c i d e n t wavelength o f
radiation.

Results and D i s c u s s i o n

Monodisperse Suspensions. The a b s o l u t e a c c u r a c y o f t h e i n s t r u m e n t s


were t e s t e d w i t h a s e t o f monodisperse s o l u t i o n s . T a b l e I shows t h e
r e s u l t s o f t h i s comparative study.

Table I. Particle S i z e Measurements o f Monodisperse Systems U s i n g


D i f f e r e n t Techniques

I. Photon Correlation Spectroscopy

Nominal Diameter () S i z e Band () % wt. i n Band

0.15
- 0.17 7.1
0.17
0.19 -- 0.19
0.21
7.4
9.9
0.21
- 0.23 20.8
0.23
0.25 -- 0.25
0.27
50.8
4.1

1.92 1.96 9.1


1.96
2.00 -- 2.00
2.04
9.8
43.8
2.04
- 2.08 18.1
2.08
- 2.12 3.3
2.12
2.16 -- 2.16
2.20
3.4
11.6
2.20
- 2.24 0.8

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
9. G U L A R I ET AL. Light-Scattering Techniques 137

Table I (continued)

II. Turbidity Spectra

Nominal Diameter () S i z e o f Peak () % wt. of Peak

1.09 0.885 36.9


1.150 63.0

2.02 1.85 23.2


2.00 37.0
2.15 39.8

III. Fraunhofer D i f f r a c t i o n Pattern Analysis

Nominal Diameter (

1.09 1.2 - 1.5 9.2


1.5 - 1.9 46.9
1.9 - 2.4 42.2

2.99 1.9 - 2.4 2.6


2.4 - 3.0 12.7
3.0 - 3.8 46.2
3.8 - 4.8 37.5
4.8 - 6.2 0.3

5.0 3.8 - 4.8 1.6


4.8 - 6.2 67.8
6.2 - 7.9 30.5

We f o u n d o u t t h a t PCS i s r e l i a b l e up t o 7 p r o v i d e d t h a t d i s
p e r s i o n s o f p a r t i c l e s a b o v e one m i c r o n a r e d i l u t e e n o u g h t o m i n i m i z e
aggregation a n d m u l t i p l e s c a t t e r i n g . The l o w e r s i z e l i m i t f o r PCS
c a n go a s l o w a s 0.001 d e p e n d i n g o n s i g n a l - t o - n o i s e r a t i o s . Two
experimental d e t a i l s one n e e d s t o be a w a r e o f i n u s i n g PCS a r e t h e
low c o u n t s n e e d e d n o t t o s a t u r a t e t h e c o u n t e r s o f t h e c o r r e l a t o r and
l o n g data c o l l e c t i o n t i m e s n e c e s s i t a t e d by l o n g e r sample t i m e s f o r
the l a r g e r p a r t i c l e s .
A s s u m i n g t h e s u s p e n d e d p a r t i c l e s do n o t a b s o r b i n t h e w a v e
l e n g t h r a n g e , 2 5 0 - 8 5 0 nm, t h e l o w e s t s i z e t h a t c a n be m e a s u r e d u s i n g
TS i s 0.5 . T h i s i s d e t e r m i n e d by measurable d e v i a t i o n s from
d e p e n d e n c e o f t u r b i d i t y , i . e . , t h e p a r t i c l e m u s t be a M i e - s c a t t e r e r .
The upper l i m i t of approximately 7 i s i m p o s e d b y t h e numerical
problems a s s o c i a t e d w i t h c a l c u l a t i n g Bessel functions of l a r g e argu
ments. We h a v e a l s o t e s t e d t h e a c c u r a c y a n d n o i s e t o l e r a n c e o f TS
i n v e r s i o n by u s i n g s i m u l a t e d data (14). We f o u n d t h a t p a r t i c l e s i z e
d e t e r m i n a t i o n was n o t a p p r e c i a b l y a f f e c t e d w i t h n o i s e l e v e l s a s h i g h
as -10%.
Despite claims of 1 b y t h e e q u i p m e n t m a n u f a c t u r e r , the
s m a l l e s t s i z e t h a t c a n be s a m p l e d b y F D P A r e l i a b l y i s 2 . FDPA
r e s u l t s f o r 1.09 s p h e r e s l i s t e d i n T a b l e I i l l u s t r a t e s t h i s f a c t .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
138 PARTICLE SIZE DISTRIBUTION

I t i s due t o . l o w r e s o l u t i o n i m p o s e d b y t h e f i x e d s p a c i n g a n d w i d t h
o f 32 d e t e c t o r e l e m e n t s d e s i g n e d t o s a m p l e a v e r y w i d e r a n g e o f p a r
t i c l e s i z e s , 2 - 1 8 0 0 .

Polydisperse Suspensions. Polydisperse suspensions were a p p r o x i


mated by m i x t u r e s o f m o n o d i s p e r s e s u s p e n s i o n s . In order not to i n
t r o d u c e any b i a s i n t h e a n a l y s i s , a l l t h e d a t a from t h r e e d i f f e r e n t
i n s t r u m e n t s w e r e a n a l y z e d u s i n g t h e same p r o g r a m . The d i s t r i b u t i o n
f u n c t i o n s w e r e a s s u m e d t o b e a sum o f e q u a l l y s p a c e d h i s t o g r a m s f o r
PCS, d e l t a f u n c t i o n s f o r TS a n d l o g a r i t h m i c a l l y s p a c e d histograms
f o r FDPA. The h e i g h t a n d p o s i t i o n o f e a c h p a r a m e t e r was o p t i m i z e d
using a n o n l i n e a r l e a s t squares m i n i m i z a t i o n process (15).
I t i s i m p o r t a n t t o t a k e i n t o c o n s i d e r a t i o n t h e l i m i t a t i o n s im
p o s e d b y t h e s i z e d e p e n d e n c e o f t h e s i g n a l i n u s i n g a n y one o f t h e
three techniques to detect p o l y d i s p e r s i t y . F o r e x a m p l e , i n PCS,
when t h e s i z e s a r e i n t h Raylei^-Gan th siz dependenc
of the s c a t t e r e d i n t e n s i t
d i f f e r e n c e o f two i n d i a m e t e
weighting. For p a r t i c l e s i n the M i e - s c a t t e r i n g range, the r e l a t i v e
w e i g h t i n g i s n o t as s e v e r e b u t becomes s t r o n g l y angle-dependent.
F o r t u r b i d i t y measurements, the w e i g h t i n g f a c t o r s w i t h r e s p e c t t o
s i z e v a r y from r a t t h e s m a l l end t o r f o r the l a r g e r p a r t i c l e s .
F o r t h e case o f F r a u n h o f e r D i f f r a c t i o n , t h e w e i g h t i n g f a c t o r i s ap
proximately^ p r o p o r t i o n a l to the geometric cross s e c t i o n of the par
t i c l e or r . B a s e d o n t h e s e c o n s i d e r a t i o n s , PCS c a n e a s i l y d e t e c t
l a r g e p a r t i c l e s a t v e r y l o w c o n c e n t r a t i o n s w h e r e a s TS a n d F D P A a r e
r e l a t i v e l y more s e n s i t i v e t o s m a l l e r p a r t i c l e s i n t h e p r e s e n c e of
l a r g e r ones.
We h a v e a p p l i e d e a c h t e c h n i q u e t o s e v e r a l b i m o d a l s y s t e m s i n
the overlap r e g i o n . The n o m i n a l a n d m e a s u r e d d i a m e t e r s a n d t h e i n
p u t and m e a s u r e d mass f r a c t i o n s d e t e r m i n e d b y u s i n g t h e d i f f e r e n t
techniques are l i s t e d i n Table I I .

Table II. Bimodal D i s t r i b u t i o n Measurements U s i n g Different


Techniques

Nominal Diameter Measured Diameter I n p u t Mass M e a s u r e d Mass


() () Fraction Fraction

I. Photon C o r r e l a t i o n Spectroscopy

1.09 1.04 0.59 0.76


5.0 5.25 0.41 0.24

1.09 0.96 0.33 0.98


2.99 2.95 0.67 0.02

1.09 0.95 0.44 0.66


2.02 2.16 0.56 0.34

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
9. G U L A R I ET AL. Light-Scattering Techniques 139

Table I I (continued)
Nominal Diameter Measured Diameter I n p u t Mass M e a s u r e d Mass
() () Fraction Fraction
II. Turbidity Spectra

1..09 0.89 0.33 0.36


2..99 2.95 0.67 0.64

1..09 0.96 0.44 0.52


2,.02 2.04 0.56 0.48

III Franhofer D i f f r a c t i o n Pattern Analysis*

1..09 2.1 0.24 0.19


5..0 5.7 0.76 0.80

2..02 2.6
5..0 6.2

*63 mm focal l e n g t h l e n s was used.

F i g u r e 1 s h o w s t h e PCS r e s u l t s f o r t h r e e m i x t u r e s o f 1.09 a n d
5 . 0 , 1.09 a n d 2 . 9 9 , a n d 1.09 a n d 2.02 d i a m e t e r s p h e r e s . We s e e
t h a t t h e t w o f r a c t i o n s a r e r e s o l v e d i n a l l c a s e s a n d t h e means a r e
accurately determined. The u s e o f m u l t i p l e sample t i m e s c o r r e s p o n d
i n g t o t h e optimum t i m e s c a l e s o f i n d i v i d u a l peaks always improves
t h e a g r e e m e n t b e t w e e n PCS s i z e m e a s u r e m e n t s a n d n o m i n a l s i z e i n f o r
mation. The mass f r a c t i o n s d e t e r m i n e d b y PCS a r e n o t i n q u a n t i t a
t i v e a g r e e m e n t w i t h t h e a c t u a l mass f r a c t i o n s w h i c h i s a r e s u l t o f
v e r y uneven w e i g h t i n g o f t h e r e l a t i v e c o n t r i b u t i o n s o f t h e two f r a c
tions to the scattered intensity. Figure 2 i s a plot of the d i s t r i
b u t i o n s d e t e r m i n e d b y u s i n g TS o f t w o m i x t u r e s c o n t a i n i n g 1.09 a n d
2.99 a n d 1.09 a n d 2.02 d i a m e t e r s p h e r e s . The two c l o s e p e a k s a r e
r e s o l v e d and a r e a t t h e i r n o m i n a l r a d i i . I n b o t h cases t h e measured
mass f r a c t i o n s o f t h e s m a l l e r and t h e l a r g e r s i z e s p h e r e s compare
favorably with the input values. The b i m o d a l d i s t r i b u t i o n s from
FDPA f o r m i x t u r e s o f 1.09 a n d 5 . 0 , 2.02 a n d 2 . 9 9 , a n d 2.02 a n d 5.0
d i a m e t e r s p h e r e s a r e s h o w n i n F i g . 3. T h e s p a c i n g a n d t h e w i d t h
of t h e d e t e c t o r elements a r e such t h a t t h e spread o f a g i v e n peak i s
r o u g h l y e q u a l t o i t s mean. T h e r e f o r e , 2.02 a n d 2.99 s p h e r e s c a n
n o t be r e s o l v e d . I n b o t h t h e m o n o d i s p e r s e a n d b i m o d a l s y s t e m s , FDPA
m e a s u r e m e n t s o f 1.09 s p h e r e s y i e l d - 2 . 0 . T h i s i s a l i m i t a t i o n
o f t h e t e c h n i q u e and t h e geometry o f t h e d e t e c t o r . The i n p u t a n d
m e a s u r e d mass f r a c t i o n s b y FDPA a r e i n q u a n t i t a t i v e a g r e e m e n t . Fig
ure 4 i s a comparison o f t h e t h r e e d i f f e r e n t t e c h n i q u e s f o r a mix
t u r e o f 1.09 a n d 2.99 s p h e r e s . A g a i n 1.09 i s n o t d e t e c t e d b y
FDPA.
We a l s o a n a l y z e d t r i m o d a l s y s t e m s t o t e s t f u r t h e r t h e t h r e e
methods. T h e r e s u l t s f r o m P C S , TS a n d FDPA a r e s h o w n i n F i g s . 5, 6
a n d 7, r e s p e c t i v e l y . PCS d e t e c t s t h e p r e s e n c e o f t h r e e f r a c t i o n s .
Means s i z e s a r e i n good a g r e e m e n t w i t h n o m i n a l s i z e s b u t t h e r e i s
a g a i n p o o r a g r e e m e n t o f i n p u t a n d c a l c u l a t e d mass f r a c t i o n s . This
i s n o t s u r p r i s i n g when o n e c o n s i d e r s t h e f a c t t h a t t h e r e i s a n o r d e r
of magnitude d i f f e r e n c e i n t h e s i z e s which r e s u l t s i n v e r y uneven

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
140 PARTICLE SIZE DISTRIBUTION

O H

02

~ 1
" |
05 15 23 13 43 53

08H

03 H

04H

02H

I ' ' 'I


03 15 23 13 45 53

03-

06-

04-

02-

I 1
I
05 15 23 13 45 55

Dicrneter(^)
F i g u r e 1. Bimodal d i s t r i b u t i o n s o f suspensions c o n t a i n i n g mix
t u r e s o f a ) 1.09 a n d 5.0 , b ) 1.09 a n d 2.99 , c ) 1.09 a n d
2.02 l a t e x s p h e r e s m e a s u r e d b y P C S .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
9. G U L A R I ET AL. Light-Scattering Techniques 141

05-

oH

03H

02-

OH

00- J
05 15 25 15

05-

04-

oiH

02-

oH

oo-
05 15 25 15

DkiTieter(^)
F i g u r e 2. Bimodal d i s t r i b u t i o n s o f suspensions c o n t a i n i n g mix
t u r e s o f a ) 1.09 a n d 2.99 , b ) 1.09 a n d 2.02 pm l a t e x s p h e r e s
measured b y TS.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
142 PARTICLE SIZE DISTRIBUTION

OB H

08

o*H

02

I ' I I I ' I h
I ' I
0 1 2 3 4 5 6 7 8

03 H

0J6

04H

02

OB

OJH

02

I ' I ' 1
0 1 2 3 4 5 6 7 8

Dicrneter(/xiT^
F i g u r e 3. Bimodal d i s t r i b u t i o n s o f suspensions c o n t a i n i n g mix
t u r e s o f a ) 1.09 a n d 5.0 , b ) 2.02 a n d 2.99 , c ) 2.02 a n d 5.0
l a t e x s p h e r e s m e a s u r e d b y FDPA.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
9. GULARI ET AL. Light-Scattering Techniques 143

0.6 H

0.4H

02H

25 35
Diameter(/x)

F i g u r e 4. C o m p a r i s o n o f t h e m e a s u r e d d i s t r i b u t i o n s b y PCS ( s o l i d
h i s t o g r a m ) , TS ( d e l t a f u n c t i o n s ) , a n d FDPA ( d a s h e d h i s t o g r a m ) f o r
a m i x t u r e o f 1.09 a n d 2.99 s p h e r e s .

OA

0.6

0.4H

02H

0.0

Dicrneter(/xm)

Figure 5. Trimodal d i s t r i b u t i o n of a suspension containing


0.261, 1.09 a n d 2.99 l a t e x s p h e r e s m e a s u r e d b y P C S . F o r
e a c h n o m i n a l s i z e , t h e i n p u t a n d m e a s u r e d mass f r a c t i o n s w e r e a s
follows: F o r 0 . 2 6 1 , i n p u t = 0 . 0 7 , m e a s u r e d = 0 . 2 4 ; f o r 1.09
, i n p u t = 0 . 7 4 , m e a s u r e d = 0 . 0 3 ; f o r 2.99 , i n p u t = 0 . 1 9 ,
measured = 0.73.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
144 PARTICLE SIZE DISTRIBUTION

05-

05-

0.4H

02A

0.H

00-
05 1 15 2 25
Diameter(/inT)
Figure 6. Trimodal distribution o f a suspension containing
0 . 2 6 1 , 1.09 a n d 2.02 l a t e x s p h e r e s m e a s u r e d b y T S . F o r e a c h
n o m i n a l s i z e , t h e i n p u t a n d m e a s u r e d mass f r a c t i o n s w e r e a s f o l
lows: F o r 0 . 2 6 1 , i n p u t = 0 . 0 8 6 , m e a s u r e d = 0 . 0 8 3 ; f o r 1.09
, i n p u t = 0 . 3 4 , m e a s u r e d = 0 . 3 7 ; f o r 2.02 , i n p u t = 0 . 5 7 ,
measured = 0.55.

1n

05H

0.6

0.4

02H

2 3 4 5 6
Diameter(/x)
F i g u r e 7. Size distribution o f a suspension c o n t a i n i n g 2.02,
2.99 a n d 5.0 l a t e x s p h e r e s m e a s u r e d b y FDPA.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
9. G U L A R I ET AL. Light-Scattering Techniques 145

contributions o f each f r a c t i o n to the total signal. Turbidity


c l e a r l y s e p a r a t e s O.261, 1.09 a n d 2.02 f r a c t i o n s e v e n t h o u g h t h e
i n d i v i d u a l s i z e s o f t h e p e a k s a r e a b o u t 10 p e r c e n t h i g h e r t h a n t h e i r
normal s i z e s . A s e x p e c t e d f r o m t h e r e s u l t s o f FDPA d i s c u s s e d b e
f o r e , 2 . 0 2 , 2.99 a n d 5 f r a c t i o n s o f t h e t r i m o d a l s y s t e m a r e n o t
r e s o l v e d a n d i n s t e a d a b r o a d p e a k e x t e n d i n g f r o m 2 t o 8 i s d e
tected.

Conclusions

I t i s c l e a r t h a t P C S a n d FDPA a r e c o m p l e m e n t a r y p a r t i c l e s i z i n g
t e c h n i q u e s w i t h a d i v i d i n g s i z e l i m i t o f a b o u t 5 . TS o v e r l a p s
w i t h b o t h P C S a n d FDPA i n t h e r e g i o n o f O.5 t o 5 . P C S a n d TS
have comparable r e s o l u t i o n i n t h e o v e r l a p r e g i o n w h i l e t h e r e s o l u
t i o n f o r FDPA i s l o w e r . PCS n e e d s t h e m o s t c a r e i n s a m p l e p r e p a r a
t i o n and data a c q u i s i t i o n TS a n d FDPA c a n b e u s e d w i t h h i g h e r c o n
centrations of particles
tween lower r e s o l u t i o n an
and T S , t h e s i g n a l s a r e d e t e r m i n i s t i c i n n a t u r e a n d t h e t i m e s r e
q u i r e d t o o b t a i n d a t a i s t r i v i a l compared t o t h e a n a l y s i s t i m e s .
For PCS, data a c q u i s i t i o n c o u l d take l o n g e r than data a n a l y s i s be
cause o f t h e needed s t a t i s t i c a l a c c u r a c y .

Acknowledgments

We g r a t e f u l l y a c k n o w l e d g e t h e f i n a n c i a l support o f t h i s work b y
N S F a n d U.S. A r m y .

Literature Cited

1. Gulari, Es; Gulari, E r . ; Tsunashima, Y . ; Chu, . J . Chem.


Phys., 1979, 70, 3965.
2. McWhirter, J . G . ; Pike, E.R. J . Phys. A, 1978, 11, 1729.
3. Kerker, M. "The Scattering of Light and Other Electromagnetic
Radiation"; Academic: New York, 1969.
4. Swithenbank, J.; Beer, J . M . ; Taylor, D.S.; McCreath, G.C. Pro
gress in Astronautics and Aeronautics, 1977, 53, 421.
5. Burkholz, .; Polke, R. Particle Characterization, 1984, 1,
153.
6. Wallach, M.L.; Heller, W.; Stevenson, A.F. J . Chem. Phys.,
1961, 34, 1796.
7. Bedwell, B.; Gulari, E r . ; Melik, D.H. "Measurement of Sus
pended Particles by Quasi-Elastic Light Scattering"; Dahneke,
B.E., Ed.; Wiley: New York, 1983; p. 237.
8. Heller, W.; Pangonis, W.J. J . Chem. Phys.. 1957, 26, 498.
9. Denman, H.H.; Heller, W.; Pangonis, W.J. "Angular Scattering
Functions for Spheres"; Wayne State Univ. Press: Detroit,
1966.
10. Inn, E.C.Y. J . Colloid. S c i . , 1951, 6, 368.
11. Dezelic, G.; Dezelic, N; Tezak, B. J . Colloid. S c i . , 1963, 18,
888.
12. Melik, D.H.; Fogler, H.S. J . Colloid. Interface S c i . , 1983,
92, 161.
13. Zollars, R.L. J . Colloid. Interface S c i . , 1980, 74, 163.
14. Gulari, Es.; Bazzi, G.; Gulari, E r . ; Annapragada, A. Particle
Characterization, 1986.
15. Chu, . ; Gulari, Es.; Gulari, Er. Physica Scripta, 1979, 19,
476.
In Particle Size Distribution; Provder, T.;
RECEIVED July
ACS 15, 1986Series; American Chemical Society: Washington, DC, 1987.
Symposium
Chapter 10

Particle Size Determination Using Angular


Light Scattering
HaroldN.Frock
Leeds & Northrup Instruments, 3000 Old Roosevelt Boulevard,
St. Petersburg,FL33702

The size of particle


patterns of light scattere
light scattering (described by Fraunhofer Diffraction
Theory) can be applied to particles with dimensions large
compared to the wavelength of light producing the scatter.
The more complex Mie Theory (1) must be invoked to analyze
particles with dimensions near the wavelength of light.
Fraunhofer theory is an interference phenomenon, and is
described in various optics text books (2,3). It is ade-
quate for most particle sizing applications and will be
discussed in detail. Mie Theory requires a knowledge of
the refractive index of the material. A unique use of po-
larized side scatter at several wavelengths is employed to
obtain particle size channels in the submicron region.

Fraunhofer Light Scattering

The d i f f r a c t i o n p h e n o m e n o n , o n w h i c h m o s t l i g h t s c a t t e r i n g instru-
m e n t s a r e b a s e d , i s w e l l known. T h i s s e c t i o n p r o v i d e s a summary o f
the mathematical background. Considering the l i g h t which i s s c a t -
t e r e d f r o m a s i n g l e i l l u m i n a t i n g beam, o n e f i n d s t h a t t h e infor-
mation r e g a r d i n g the p a r t i c l e dimension i s found i n the angular
d i s t r i b u t i o n o f s c a t t e r e d l i g h t f l u x , and t h a t i n f o r m a t i o n r e l a t -
i n g t o the c r o s s s e c t i o n a l a r e a o f the p a r t i c l e i s c o n t a i n e d i n a
measure o f the t o t a l s c a t t e r e d f l u x . However, i t i s d e s i r a b l e t o
h a v e a m e a s u r e o f some q u a n t i t y d i r e c t l y r e l a t e d t o t h e mass o f t h e
p a r t i c l e , namely the volume o f the p a r t i c l e . The approach t h a t h a s
been t a k e n i s t o e x t r a c t volume i n f o r m a t i o n from the s c a t t e r e d f l u x
s i g n a l b y forming the Fraunhofer d i f f r a c t i o n p a t t e r n i n the focal
plane o f a positive lens. An o p t i c a l f i l t e r i s p l a c e d i n t h e p l a n e
of the Fraunhofer d i f f r a c t i o n p a t t e r n , w h i c h i s shaped so as t o pass
a f r a c t i o n o f the c o l l e c t e d f l u x p r o p o r t i o n a l t o the cube o f the
diameter o fthe p a r t i c l e which produces the scattering.
A convenient d e s c r i p t i o n o f l i g h t scatter, o r d i f f r a c t i o n as i t
r e l a t e s t o p a r t i c l e s i z e m e a s u r e m e n t {k_,5.), i s shown i n F i g u r e 1.
In the s i m p l e s t c a s e , one can v i s u a l i z e t w o p a r t i c l e s o n e l a r g e

0097-6156/87/0332-0146$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
10. FROCK Angular Light Scattering 147

F i g u r e 1. C o m p a r i s o n o f s c a t t e r e d l i g h t f l u x a n g l e a n d i n t e n s i t y
for large andsmall p a r t i c l e s . Reproduced w i t h permission from
R e f . 9. C o p y r i g h t 1980 A m e r i c a n C e r a m i c S o c i e t y .

American Chemical Society


Library
1155 16th St., N.W.
In Particle Size Distribution; Provder, T.;
ACS Symposium Series; Washington, D.CSociety:
American Chemical 20036Washington, DC, 1987.
148 PARTICLE SIZE DISTRIBUTION

and one s m a l l i l l u m i n a t e d b y a c o l l i m a t e d l i g h t s o u r c e . The a n g l e


through which l i g h t i s s c a t t e r e d by p a r t i c l e s i s i n v e r s e l y propor
t i o n a l t o the diameters o f the p a r t i c l e s . The s m a l l p a r t i c l e
s c a t t e r s l i g h t t h r o u g h w i d e r a n g l e s t h a n t h e l a r g e p a r t i c l e . Mea
surement o f s c a t t e r e d i n t e n s i t i e s a t v a r i o u s a n g l e s w i l l produce a
p r o f i l e which can be used t o p r e c i s e l y determine t h e dimensions o f
the s c a t t e r i n g p a r t i c l e . The c o l l i m a t e d l i g h t beam i t s e l f must b e
prevented from reaching t h e d e t e c t i o n a r e a , because o f i t s very
high i n t e n s i t y r e l a t i v e t o the scattered l i g h t . T h i s i s accom
p l i s h e d b y f o c u s i n g t h e m a i n beam t o a v e r y s m a l l i m a g e a n d b l o c k
ing i t i n t h e plane o f t h e o p t i c a l f i l t e r . Only t h e l i g h t s c a t
t e r e d a t a n g l e s t h a t t r a n s c e n d t h e e x t e n t o f t h e m a i n beam i s t r a n s
mitted through t h e o p t i c a l f i l t e r t o the detection area. The u n i q u e
shape o f t h e o p t i c a l f i l t e r t r a n s m i t s l i g h t , t h e i n t e n s i t i e s o f
w h i c h a r e p r o p o r t i o n a l t o t h e volume o f p a r t i c u l a t e m a t e r i a l . The
net r e s u l t o f t h i s optomechanical t i multi-channel
histogram of the p a r t i c l
a p p r o x i m a t e l y one m i c r o m e t e
whose r a d i u s i s s u f f i c i e n t l y l a r g e compared w i t h t h e w a v e l e n g t h ,
the i n t e n s i t y d i s t r i b u t i o n o f t h e Fraunhofer d i f f r a c t i o n pattern i s
given by t h e f a m i l i a r A i r y formula: {)

Equation 1

w h e r e i s t h e f l u x p e r u n i t a r e a o f t h e i n c i d e n t beam, k = 2 T ^ , a
is the particle radius, W = S i n with t h e angle r e l a t i v e t o the
d i r e c t i o n o f t h e i n c i d e n t beam, a n d J ^ i s t h e f i r s t o r d e r B e s s e l
function of the f i r s t kind.
I t i s w e l l known t h a t i f t h e t o t a l d i f f r a c t e d f l u x i s c o l l e c t e d
and m e a s u r e d , a s i g n a l w i l l b e g e n e r a t e d t h a t i s p r o p o r t i o n a l t o t h e
s q u a r e o f t h e p a r t i c l e r a d i u s , p e r m i t t i n g a d i r e c t measurement o f
the c r o s s - s e c t i o n a l o r surface area o f t h e sphere.

w dw

dx

and s i n c e f o r v a l u e s o f t h e p a r t i c l e r a d i u s f o r w h i c h E q u a t i o n (l_)
i s v a l i d , t h e i n t e g r a n d i s n e g l i g i b l y s m a l l beyond t h e upper l i m i t ,
t h i s may b e w r i t t e n

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
10. FROCK Angular Light ScatteHng 149

oo J.J 2
(x)
F (a)
2 = 2T a' dx
X

= a 2
Equation 2

Many i n d u s t r i a l p r o c e s s e s , h o w e v e r , r e q u i r e m e a s u r e m e n t o f t h e
t o t a l mass o r v o l u m e o f p a r t i c u l a t e s . Selective attenuation and
c o l l e c t i o n o f t h e d i f f r a c t e d f l u x can p r o d u c e a s i g n a l p r o p o r t i o n a l
t o t h e cube o f t h e p a r t i c l e r a d i u s , and hence a measure o f t h e
volume, or mass, i f the
p l a n e mask w h i c h p a s s e s
desirable. A t t e n u a t i o n o f t h i s k i n d can be a c c o m p l i s h e d by a f i x e d
s p a t i a l f i l t e r w h o s e p r o p e r t i e s t o a f i r s t a p p r o x i m a t i o n do n o t de
p e n d o n a. The r e a s o n i s t h a t , a s shown b y E q u a t i o n ( l } , t h e r a d i a l
v a r i a t i o n o f d i f f r a c t e d f l u x d e p e n d s o n l y on t h e p r o d u c t aw, s o t h a t
a t t e n u a t i n g t h e f l u x i s p r o p o r t i o n a l t o 1/a. Thus, a f t e r passage
t h r o u g h a f i l t e r h a v i n g t r a n s m i s s i o n T(w) = C/w, where C i s con
stant, the integrated f l u x , using Equation {l),

dw

and, a s s u m i n g as b e f o r e t h a t a i s l a r g e enough f o r t h e upper limit


o f t h e i n t e g r a l t o be t a k e n as i n f i n i t y , t h i s g i v e s

F (a) = E k C a Equation k

A c t u a l measurements d e v i a t e from t h e o r y at the l a r g e p a r t i c l e


end b e c a u s e t h e a n g l e o f t h e d i f f r a c t e d f l u x i s n o t s u f f i c i e n t t o b e
d i s t i n g u i s h a b l e f r o m t h e u n s c a t t e r e d beam f o r v e r y l a r g e p a r t i c l e s .
D e v i a t i o n a t t h e s m a l l p a r t i c l e end o c c u r s a s t h e p a r t i c l e s i z e
approaches the wavelength of the l i g h t source. These l i m i t a t i o n s

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
150 PARTICLE SIZE DISTRIBUTION

d e f i n e a w o r k i n g r a n g e o f p a r t i c l e s i z e f r o m a b o u t 2 t o 300 micro
meters f o r a standard "midrange" instrument design.

Mie Scattering

Submicron p a r t i c l e s i z e a n a l y s i s employs a s c a t t e r t h e o r y not


c o m p l e t e l y d e s c r i b e d by F r a u n h o f e r d i f f r a c t i o n . The s m a l l p a r t i c l e
r a n g e down t o a b o u t 0 . 1 m i c r o m e t e r i n d i a m e t e r u t i l i z e s a c o m b i n a
t i o n o f F r a u n h o f e r d i f f r a c t i o n and Mie t h e o r y f o r t h e f o r w a r d s c a t
tered l i g h t and 9 0 - d e g r e e Mie s c a t t e r a t t h r e e ( 3 ) w a v e l e n g t h s
and two ( 2 ) p o l a r i z a t i o n s o f e a c h w a v e l e n g t h . Because o f i t s need
f o r a t e c h n o l o g y more i n v o l v e d t h a n d i f f r a c t i o n t h e o r y , submicron
measurements a r e i n f l u e n c e d by t h e i n d e x o f r e f r a c t i o n o f t h e m a t e r
i a l m a k i n g up t h e p a r t i c u l a t e s t o b e s i z e d .
The i n d e x o f r e f r a c t i o n o f a m a t e r i a l i s a m e a s u r e o f t h e
change i n t h e v e l o c i t y
change i n a m p l i t u d e as
i n d e x (N) i s d e f i n e d m a t h m a t i c a l l
f
components; t h e r e a l i n d e x ( n ) , and t h e complex component ( n ) :

f
= - in

where: = the r e a l component, w h i c h i s t h e r a t i o of the


velocity of l i g h t i n the m a t e r i a l

a'= the extinction coefficient of the m a t e r i a l

For p a r t i c u l a t e m a t e r i a l s w i t h h i g h r e a l i n d i c e s , the r e p o r t e d s i z e
d e p e n d s l e s s on t h e c o m p l e x component ( T ) . A l s o , as t h e s i z e o f
p a r t i c l e s i n c r e a s e s , t h e t o t a l s c a t t e r i n g phenomenon s i m p l i f i e s t o
F r a u n h o f e r d i f f r a c t i o n , and becomes a v e r y weak f u n c t i o n o f r e
f r a c t i v e index.
F o r w a r d s c a t t e r , F r a u n h o f e r and M i e , i s u t i l i z e d f o r measure
ment t h r o u g h o u t most o f t h e p a r t i c l e s i z e r a n g e . As p a r t i c l e s b e
come v e r y s m a l l , h o w e v e r , i t i s d i f f i c u l t t o c o l l e c t t h e l i g h t
s c a t t e r e d at those extremely wide angles w i t h p r a c t i c a l o p t i c a l
systems. F o r t h i s r e a s o n , t h e 3 c h a n n e l s a t t h e l o w e r end o f t h e
s i z e range are produced u s i n g l i g h t s c a t t e r e d at 90-degrees. The
Mie c o n s t a n t s d i s c u s s e d i n t h e p r e v i o u s s e c t i o n s a r e e v a l u a t e d f o r
and a p p l i e d o n l y t o t h e f o r w a r d s c a t t e r e d l i g h t . Size determina
t i o n s made b y t h e l i g h t s c a t t e r e d a t a r i g h t a n g l e ( 9 0 - d e g r e e
s c a t t e r ) a r e computed s e p a r a t e l y by u s i n g o r t h o g o n a l p o l a r i z a t i o n
at d i f f e r e n c e wavelengths ( 8 J . To i l l u s t r a t e t h e o p e r a t i o n o f t h e
9 0 - d e g r e e s c a t t e r , F i g u r e s 2 and 3 a r e p l o t s o f t h e l o g a r i t h m s o f
i n t e n s i t y of s c a t t e r e d l i g h t v s . angle o f s c a t t e r from 0 t o l 8 0
degrees. F i g u r e 2 shows i n t e n s i t y v a l u e s ( i ) i n o n e p l a n e o f
p o l a r i z a t i o n , a n d F i g u r e 3 shows i n t e n s i t y v a l u e s ( 1 2 ) from t h e
orthogonal plane ( i . e . , the planes of p o l a r i z a t i o n are mutually
perpendicular).

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
FROCK Angular Light Scattering

INTENSITY I , FOR VALUES


1

OF "A" FROM 0.5 to 8.

0 90 180
ANGLE OF OBSERVATION
(IN DEGREES)

Figure 2. Right-angle scatter i nI - plane of polarization.

0 90 180
ANGLE OF OBSERVATION
(IN DEGREES)

F i g u r e 3. Right-angle i nI ? plane of polarization.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
152 PARTICLE SIZE DISTRIBUTION

In t h i s example, water d r o p l e t s are used. The curves themselves


a r e p l o t s o f t h e s i z e p a r a m e t e r , "A", w h e r e :

A =TTD/A
with D = p a r t i c l e diameter
and = wavelength of l i g h t

One o f t h e m o r e s t a b l e c h a r a c t e r i s t i c s o f t h e p a t t e r n s i n t h e t w o
f i g u r e s i s t h e n u l l a t 9 0 - d e g r e e s f o r s m a l l v a l u e s o f "A" w i t h i g ,
one o f t h e p l a n e s o f p o l a r i z a t i o n ( F i g u r e 3 ) . F o r s m a l l "A" v a l u e s ,
t h e d i f f e r e n c e between F i g u r e s 2 and 3 a r e g r e a t e s t a t 9 0 - d e g r e e s ,
making t h i s u s e f u l f o r measurement purposes.
T h i s p a r t i c u l a r e x e c u t i o n o f p a r t i c l e s i z e measurement, i n i t s
u t i l i z a t i o n o f F r a u n h o f e r d i f f r a c t i o n and Mie T h e o r y , measures t h e
volume o f p a r t i c u l a t e m a t e r i a l . I t i s , therefore, appropriate to
i n t r o d u c e t h i s volume concep
per u n i t volume. This i
90-degree s c a t t e r f o r any s i z e p a r a m e t e r i s d i r e c t l y p r o p o r t i o n a l
t o t h e number o f p a r t i c l e s o f t h a t s i z e . When t h e f l u x d i f f e r e n c e
p e r p a r t i c l e , i ^ , - l g i s d i v i d e d b y t h e v o l u m e o f one p a r t i c l e ,
a n d p l o t t e d a g a i n s t t h e l o g o f "A", a w e l l d e f i n e d p e a k o c c u r s .
F i g u r e h shows t h i s c u r v e , c o m p u t e d f o r s p h e r e s o f i n d e x 1.33
(water). The c u r v e i n F i g u r e k h a s a mean v a l u e s l i g h t l y g r e a t e r
t h a n 1. Using wavelengths generated by a wide-band white l i g h t
s o u r c e , t h r e e ( 3 ) c h a n n e l s a r e f o r m e d as shown i n F i g u r e 5 . It is
e v i d e n t f r o m t h e f i g u r e , and a l s o f r o m E q u a t i o n 5 , t h a t c h a n n e l
values s c a l e d i r e c t l y w i t h wavelength. These numbers a r e computed
f o r an i n d e x o f 1 . 3 3 (water). Other i n d i c e s produce curves t h a t
are s i m i l a r . For example, computations f o r g l a s s spheres produce
a s i z e p a r a m e t e r t h a t i s a b o u t t h e same, i n d i c a t i n g a m i n i m a l de
p e n d e n c e o f s i d e s c a t t e r on r e f r a c t i v e i n d e x , i n c o n t r a s t t o much
l a r g e r e f f e c t s on s m a l l p a r t i c l e s m e a s u r e d b y f o r w a r d s c a t t e r .
The t w o s e t s o f c o m p u t a t i o n s - f o r w a r d s c a t t e r a n d s i d e s c a t t e r
- a r e made s e p a r a t e l y . I n o r d e r t o d e t e r m i n e t h e c o m p l e t e s i z e d i s
t r i b u t i o n , t h e f o r w a r d a n d s i d e s c a t t e r d e t e r m i n a t i o n s m u s t b e com
bined. T h i s i s a c c o m p l i s h e d b y a d j u s t i n g t h e g a i n on t h e s i d e
s c a t t e r computations u n t i l those channels blend together w i t h the
d i s t r i b u t i o n i n c o r p o r a t i n g b o t h f o r w a r d and s i d e s c a t t e r d i s t r i
b u t i o n s i s t h e n r e n o r m a l i z e d and p r i n t e d out as a l 6 - c h a n n e l p a r
t i c l e s i z e d i s t r i b u t i o n f r o m 0 . 1 2 t o h2.2 m i c r o n s . Any M i e c o n s t a n t
a d j u s t m e n t i s made t o t h e f o r w a r d s c a t t e r c o m p u t a t i o n s a l o n e b e
cause the s i d e s c a t t e r channels are r e l a t i v e l y i n s e n s i t i v e t o v a r i
ations i n the r e f r a c t i v e index.
E x t e n s i v e a p p l i c a t i o n s e x p e r i e n c e h a s shown t h a t m o s t p a r t i
c u l a t e m a t e r i a l s can be a n a l y z e d w i t h o u t any c o n s i d e r a t i o n o f t h e
r e f r a c t i v e index. T h i s i s g e n e r a l l y t r u e b e c a u s e most p r a c t i c a l
m a t e r i a l s h a v e a h i g h i n d e x , o r a r e somewhat a b s o r b i n g . In the
e x c e p t i o n a l c a s e i n w h i c h r e f r a c t i v e i n d e x c o r r e c t i o n s must be
a p p l i e d , t h e v a l u e s o f t h e r e a l and c o m p l e x i n d i c e s must be d e t e r
mined c a r e f u l l y . A r b i t r a r y use o f index c o r r e c t i o n s t o a r b i t r a r i l y
a l t e r i n s t r u m e n t c a l i b r a t i o n may p r o d u c e h i g h l y e r r o n e o u s r e s u l t s .
Table I s e r v e s as a guide t o t h e e f f e c t s o f t h e r e f r a c t i v e i n d e x
on s m a l l p a r t i c l e m e a s u r e m e n t s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
10. FROCK Angular Light Scattering 153

( S I Z E PARAMETER)

F i g u r e 4. F l u x d i f f e r e n c e p e r p a r t i c l e p e r u n i t v o l u m e . Reproduced
w i t h p e r m i s s i o n f r o m R e f . 10. C o p y r i g h t 1980 Hemisphere P u b l i s h i n g .

WAVELENGTH .45 .60 .90

PARTICLE
.15 .2 .3
DIAMETER

All units In micrometers

F i g u r e 5. Wavelength/Channel center r e l a t i o n f o rthree lowest


channels.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
154 PARTICLE SIZE DISTRIBUTION

Table I.

I N D E X OF REFRACTION

Real Component Complex Component

High High (Absorbing Materials)

High Low (Transparent Materials)

Low- High (Absorbing Materials)

*Low Low (Transparent Materials)

( * MIE CORRECTIONS BECOME S I G N I F I C A N T )

Systems For Light Scatterin

I m p l e m e n t a t i o n o f F r a u n h o f e r and Mie s c a t t e r i n g i s a c c o m p l i s h e d
t h r o u g h t h e use o f v a r i o u s o p t i c a l and e l e c t r o n i c d e s i g n s . Sche-
m a t i c d i a g r a m s o f a c o m b i n e d s y s t e m a r e shown i n F i g u r e 6 . In one
c o n f i g u r a t i o n t h e forward s c a t t e r m o d e a helium=neon l a s e r i l l u m -
i n a t e s p a r t i c l e s f l o w i n g t h r o u g h a sample c e l l . The diffraction
p a t t e r n s g e n e r a t e d a r e d i r e c t e d t h r o u g h an o p t i c a l f i l t e r and s e n s e d
by a s i l i c o n p h o t o d e t e c t o r . Measurement o f the v e r y s m a l l p a r t i c l e s
i s c a r r i e d out by d e t e c t i n g t h e l i g h t s c a t t e r e d a t 9 0 d e g . t h e s i d e
s c a t t e r mode i n t h e f i g u r e .
Detection of the o p t i c a l l y - f i l t e r e d scattered l i g h t i s followed
by d i g i t a l p r o c e s s i n g o f t h e s i g n a l s t o compute t h e p a r t i c l e s i z e
distribution. The Z - 8 0 m i c r o p r o c e s s o r a c c e p t s d i g i t i z e d s i g n a l s
f r o m t h e ADC ( A n a l o g - t o - D i g i t a l c o n v e r t e r ) , s t o r e s them i n RAM
( R a n d o m - A c c e s s Memory) u n t i l t h e end o f t h e d a t a c o l l e c t i o n c y c l e ,
and t h e n p e r f o r m s t h e c o m p u t a t i o n o f t h e s i z e d i s t r i b u t i o n (see
Figure 7). A multi-channel histogram of the s i z e d i s t r i b u t i o n i s
d i s p l a y e d on a d i g i t a l p r i n t e r , a n d a l s o p r e s e n t e d t o a n R S - 2 3 2
p o r t f o r computer i n t e r f a c i n g .
The m e a s u r e m e n t d o e s n o t r e q u i r e p a r t i c l e s t o p a s s t h r o u g h t h e
l a s e r b e a m one a t a t i m e . I n f a c t , t h e r e a r e n o r m a l l y l a r g e num-
b e r s o f p a r t i c l e s i n t h e beam a t any p o i n t i n t i m e . Each p a r t i c l e
f o r m s i t s own d i f f r a c t i o n p a t t e r n , a n d t h e s y s t e m sums t h e r e s u l t s
from t h e s e p a t t e r n s o v e r t h e t o t a l measurement p e r i o d . I t i s im-
p o r t a n t t h a t t h e p a r t i c u l a t e c o n c e n t r a t i o n be l o w enough so t h a t
m u l t i p l e s c a t t e r i n g does not o c c u r . T h i s h a p p e n s when l i g h t w h i c h
i s s c a t t e r e d f r o m one p a r t i c l e s t r i k e s a n o t h e r p a r t i c l e and i s
s c a t t e r e d f u r t h e r b e f o r e i t i s c o l l e c t e d . T h i s phenomenon i s
e a s i l y d e t e c t e d , and t h e l o a d i n g r a n g e i s u s u a l l y q u i t e b r o a d .
P a r t i c l e s i z e r s e m p l o y i n g l i g h t s c a t t e r i n g do n o t r e q u i r e f i e l d
calibration. The m e a s u r e m e n t o f p a r t i c l e s i z e i s d e t e r m i n e d b y
f o c a l l e n g t h s o f l e n s e s and t h e a n g u l a r e x t e n t o f t h e o p t i c a l
f i l t e r s and d e t e c t o r s . T h i s f e a t u r e i s an i m p o r t a n t one f o r p r o -
d u c t i o n and q u a l i t y c o n t r o l s i t u a t i o n s i n w h i c h c a l i b r a t i o n c o u l d
b e e a s i l y s e t i n c o r r e c t l y o r d i s t u r b e d i n some way d u r i n g op-
eration. I t i s prudent, however, t o p e r i o d i c a l l y check the oper-
a t i o n o f t h e i n s t r u m e n t u s i n g a w e l l - k n o w n d i a g n o s t i c m a t e r i a l , and
t o p e r f o r m recommended p e r i o d i c m a i n t e n a n c e .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
TUNGSTEN HALOGEN TUNGSTEN HALOGEN
LIGHT S O U R C E LIGHT S O U R C E



CONO. LENS COND. LENS
UV FILTER UV FILTER
APERATURE - APERTURE
1
] FILTER-POLARIZER WHEEL J FILTER-POLARIZER WHEEL

I
PRISM MIRROR PRISM
+ v
REFERENCE DETECTOR X R E F E R E N C E DETECTOR

LENS LENS
GLASS
PLATE

In Particle Size Distribution; Provder, T.;


00 OETECTOR SAMPLE 90*DETECT0R
CELL ] OH
LENS LENS
LENS LENS

] OPTICAL FILTER OPTICAL FILTER

ACS Symposium Series; American Chemical Society: Washington, DC, 1987.


FORWARD DETECTOR FORWARD D E T E C T O R

F i g u r e 6. O p t i c s f o r l i g h t s c a t t e r i n g . R e p r o d u c e d w i t h permission
f r o m R e f . 10. C o p y r i g h t 1980 H e m i s p h e r e P u b l i s h i n g .
156 PARTICLE SIZE DISTRIBUTION

LED
(Display)

Photo
Detector

Analog to
Digital
Converter

Z~80 Microprocessor

Figure 7. Block diagram of e l e c t r o n i c s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
10. FROCK Angular Light Scattering 157

Data C o r r e l a t i o n

The t h e o r y a n d d e s i g n o f a l l p a r t i c l e s i z e m e a s u r e m e n t d e v i c e s a r e
"based o n t h e a s s u m p t i o n t h a t p a r t i c l e s a r e s p h e r i c a l . M o s t ma-
t e r i a l s submitted f o rsize a n a l y s i s a r e not s p h e r i c a l . When t h e s e
m a t e r i a l s a r e analyzed by instruments employing d i f f e r e n t p h y s i c a l
principles, the results are different. Figure 8 i l l u s t r a t e s t h i s
p o i n t by comparing t h e cumulative (percent passing) d i s t r i b u t i o n o f
t h r e e i d e n t i c a l samples a n a l y z e d on t h r e e d i f f e r e n t i n s t r u m e n t s ,
each employing a d i f f e r e n t measurement t e c h n i q u e . The a b s o l u t e
v a l u e s o f t h e d i s t r i b u t i o n s a r e d i f f e r e n t , b u t t h e i r shapes a r e
quite similar. Because these r e s u l t s u s u a l l y e x h i b i t d i f f e r e n c e s
w h i c h a r e c o n s i s t e n t , a c o r r e l a t i o n c a n b e d e t e r m i n e d between one
o r more p a r a m e t e r s o f t h e d i s t r i b u t i o n .
A c o r r e l a t i o n c a n b e d e t e r m i n e d b y c a r r y i n g o u t a n a l y s i s on a
number o f d i f f e r e n t s a m p l e
The s a m p l e s s h o u l d b e c h o s e
so t h a t a good c u r v e - f i y computed exampl
t i o n c u r v e f o r a s e t o f a l u m i n a s a m p l e s i s shown i n F i g u r e 9. A
s e d i m e n t a t i o n i n s t r u m e n t was c o r r e l a t e d w i t h a l i g h t s c a t t e r i n g
instrument. E a c h i n d i v i d u a l p o i n t on t h e g r a p h i s t h e r e s u l t o f one
parameter (the median i n t h i s case) o f t h e d i s t r i b u t i o n as r e p o r t e d
by each o f t h e two i n s t r u m e n t s f o r one sample. The 7 d a t a p o i n t s ,
r e p r e s e n t i n g t h e medians o f 7 d i f f e r e n t samples, were p l o t t e d t o
determine t h e c o r r e l a t i o n between t h e two i n s t r u m e n t s f o r t h a t type
o f sample m a t e r i a l . A b e s t - f i t l i n e a r r e g r e s s i o n produced t h e
s t r a i g h t l i n e on t h e g r a p h a s w e l l a s t h e e q u a t i o n shown.

Applications

L i g h t s c a t t e r i n g h a s been a p p l i e d t o t h e measurement o f p a r t i c l e i n
j u s t about every f i e l d . These i n c l u d e ceramics, m i n e r a l s , m e t a l
powders, food, energy, environmental, p h a r m a c e u t i c a l s , and t h e v e r y
important f i e l d o f chemicals. Some e x a m p l e s o f a p p l i c a t i o n s i n t h e
chemical industry a r e :

catalysts propellants explosives


pigments toners coatings
polymers titanium dioxide emulsions
adhesives manganese d i o x i d e phosphates
c o a l - o i l mixtures

Conclusions

P a r t i c l e s i z e a n d d i s t r i b u t i o n s c a n b e d e t e r m i n e d b y a number o f
d i f f e r e n t methods. The t e c h n i q u e d e s c r i b e d h e r e i s l i g h t s c a t t e r -
ing. D i f f e r e n t measurement methods produce d i f f e r e n t r e s u l t s w h i c h
can b e c o r r e l a t e d e x p e r i m e n t a l l y . The a b s e n c e o f d i s t r i b u t i o n
standards f o r l i g h t s c a t t e r i n g p a r t i c l e s i z i n g instruments precludes
any d e t e r m i n a t i o n o f s i z e a c c u r a c y . This i s f u r t h e r complicated by
p a r t i c l e s o f n o n - s p h e r i c a l shape w h i c h makes t h e c o n c e p t o f s i z e
v e r y d i f f i c u l t t o d e f i n e . However, f o r p a r t i c u l a t e m a t e r i a l s e n -
c o u n t e r e d i n most i n d u s t r i a l p r o c e s s e s , t h e a s s u m p t i o n t h a t p a r t i -
c l e s a r e spheres produces q u i t e u s e f u l r e s u l t s t h a t a r e repeatable
a n d r e l a t e t o i m p o r t a n t p a r a m e t e r s o f many p r o c e s s e s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
158 PARTICLE SIZE DISTRIBUTION

Figure 8. Comparison of three identical samples.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
I


r
I

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
160 PARTICLE SIZE DISTRIBUTION

References

1. Mie, Gustave, Annalen der Physik, Vol. 25, No. 3, (1908) p.377.
2. Jenkins & White, "Fundamentals of Optics"; McGraw-Hill,
Second Ed.
3. Born, M. and Wolf, . , "Principles of Optics"; (4th Ed.),
Pergammon Press, Oxford, 1970.
4. Muly, E. C. and H. N. Frock, Opt. Eng., Vol.19, No.6,
Nov/Dec 1980, p. 861.
5. Plantz, P . E . , "Modern Methods of Particle Size Analysis";
Chap. 6. p. 173, Edited by Howard G. Barth, copywright
1984 by John Wiley & Sons, Inc.
6. Wertheimer, A. L. and W. L. Wilcock, Appl. Opt., Vol. 15,
June 1976, p. 1616.
7. "International Critical Tables"; McGraw-Hill, 1929.
8. Wertheimer, A. L. , e t . a l . "Optical Measurement f
Particulate Size i
at the U.S.E.P.A., Triangl , , y ,
1978.
9. Frock, H. N. and Walton, R. L., Am. Ceramic Soc. B u l l . , Vol. 59,
No. 6, June 1980, pp. 650-651.

10. Muly, E. C. and Frock, H. N. "Submicron Particle Size Analysis


Using Light Scattering" presented at the Fine Particle Society
Conference at the University of Maryland, Sept. 16, 1980.

RECEIVED July 25, 1986

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 11

Averages from Turbidity Measurements


L. H. Garcia-Rubi

Department of Chemical Engineering, College of Engineering, University of South


Florida, Tampa,FL33620

The information content of turbidity measurements from


polydisperse particulate systems has been analysed on
the basis of Mie theory and reported approximations to
Mie theory. The results from the analysis suggest two
alternative interpretations of turbidity data for the
small and intermediate p a r t i c l e size regimes: an
interpretation in terms of moments of the particle size
distribution and an equivalent interpretation in terms
of the volume to surface average p a r t i c l e diameter. It
is also shown that in the intermediate particle size
regime, the effective average diameter that s a t i s f i e s
the mean surface average extinction efficiency does not
correspond to a particular average of the particle size
d i s t r i b u t i o n . The value of the effective particle
diameter depends on both the wavelength and the spread
of the p a r t i c l e size d i s t r i b u t i o n . It is possible,
however, to interpret turbidity data in terms of an
effective average diameter and the volume to surface
particle diameter. The results obtained explain some of
the discrepancies existing in the literature regarding
the interpretation of the average particle diameters
obtained from scattering measurements. The theoretical
and practical implications of the results are presented
and discussed.

0097-6156/87/0332-0161$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
162 PARTICLE SIZE DISTRIBUTION

The a n a l y s i s of p a r t i c u l a t e systems using l i g h t scattering


measurements i s o f g r e a t s c i e n t i f i c and i n d u s t r i a l importance and as
s u c h i t has been t r e a t e d e x t e n s i v e l y i n t h e l i t e r a t u r e ( 1 - 5 ) . F o r
m o n o d i s p e r s e p a r t i c u l a t e s y s t e m s , t h e t h e o r y and t h e p r a c t i c e o f
light scattering have been q u i t e s u c c e s s f u l and a r e w e l l
e s t a b l i s h e d . However, t h i s i s n o t t h e case f o r p o l y d i s p e r s e s y s t e m s ,
where t h e t u r b i d i t y a t a g i v e n w a v e l e n g t h i s r e l a t e d t o t h e p a r t i c l e
s i z e d i s t r i b u t i o n ( e q u a t i o n s 1-9). M i e Theory r e l a t e s the measured
t u r b i d i t y (), t o t h e number, s i z e and o p t i c a l constants of
suspended isotropic spherical p a r t i c l e s through the following
e q u a t i o n s (1-5) :

() - A JO - 2
D Q ( a , m ) f ( D ))dD
c (1)
1

or

2

J D 0 Q(a,m)f(D)dD
() (2)
rC
O j
2 P
j D f ( D ) )dD
0 c

W h e r e , () i s t h e t u r b i d i t y a t t h e w a v e l e n g t h , t h e n u m b e r o f
p a r t i c l e s / m l , C t h e c o n c e n t r a t i o n i n g/ml, D the p a r t i c l e d i a m e t e r ,
f(D) t h e frequency d i s t r i b u t i o n of p a r t i c l e sizes, the density of
t h e p a r t i c l e s , m i s t h e c o m p l e x r e f r a c t i v e i n d e x r a t i o a n d Q(a,m) i s
t h e M i e o v e r a l l e x t i n c t i o n e f f i c i e n c y . The e x t i n c t i o n e f f i c i e n c y i s
g i v e n by

Q(a,m) - ( 2 / a ) 2
(2n+1) Re(a + b ) (3)
n=

If the p a r t i c l e s a r e n o n - a b s o r b i n g , e q u a t i o n 3 becomes

2 2 2
Qscat - ( 2 / a ) \ y (2n+1)[|a | n + |b |
n ] (4)

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
11. GARCIA-RUBIO Averages from Turbidity Measurements 163

a (5)

()
^() - m (am) ^()

m () i|^(am) - ( a m ) ^() n

b (6)

m ()
^() - () ^()

( ) ( ) + 1 ( ) (7)
"

1 / 2

()
~ ( /2) Ja} (8)

1 /

()
- -( /2)

Where, m ( + i k ) / n and i s the r e f r a c t i v e index o f the


0 0

s u s p e n d i n g medium. J ( a ) and N(a) a r e h a l f o r d e r i n t e g r a l B e s s e l a n d


Neuman f u n c t i o n s .
The s o l u t i o n t o t h e i n t e g r a l e q u a t i o n s 1 o r 2-9 i s r a t h e r
d i f f i c u l t , the scattering c o e f f i c i e n t s ( a + b ) h a v e t o be

c a l c u l a t e d a t e v e r y measured w a v e l e n g t h and e v e r y p a r t i c l e d i a m e t e r
f o r a g i v e n f o r m o f t h e p a r t i c l e d i a m e t e r d i s t r i b u t i o n , where t h e
f o r m o f t h e d i s t r i b u t i o n i s g e n e r a l l y unknown. T h e p r o b l e m o f
s o l v i n g e q u a t i o n s 1 o r 2 f o r t h e p a r t i c l e s i z e d i s t r i b u t i o n i s known
as t h e " I n v e r s e S c a t t e r i n g Problem" a n d a l t h o u g h t h i s p r o b l e m h a s
b e e n t r e a t e d e x t e n s i v e l y , no g e n e r a l s o l u t i o n s have been r e p o r t e d
(3> 6, 7,)* A l t e r n a t i v e approaches t o t h e s o l u t i o n o f t h e i n t e g r a l
e q u a t i o n s i n c l u d e t h e assumption o f t h e shape o f t h e p a r t i c l e s i z e
d i s t r i b u t i o n (3, 8-12) a n d t h e e s t i m a t i o n o f " E f f e c t i v e Particle
D i a m e t e r s " (3, 13-15).
I f t h e form o f t h e p a r t i c l e s i z e d i s t r i b u t i o n i s known o r i t
can be assumed t h e n , the main problem i n t h e s o l u t i o n o f e q u a t i o n s 1
or 2 stems from t h e complex c a l c u l a t i o n s required t o evaluate the
integral

(10)

A number o f d i s t r i b u t i o n f u n c t i o n s h a v e b e e n identified
e x p e r i m e n t a l l y f o r a v a r i e t y o f systems (3) and, i n p a r t i c u l a r , t h e
Log-Normal d i s t r i b u t i o n i s e x t e n s i v e l y used f o r t h e c a l c u l a t i o n o f
t h e i n t e g r a l a n d f o r t h e e v a l u a t i o n o f t h e moments o f t h e p a r t i c l e
s i z e d i s t r i b u t i o n ( 8 - 1 2 ) . The problem w i t h t h i s approach i s t h a t , i n
g e n e r a l , t h e shape o f t h e p a r t i c l e s i z e d i s t r i b u t i o n i s unknown and
t h u s , t h e average p a r t i c l e d i a m e t e r s o b t a i n e d a r e c o n d i t i o n a l upon

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
164 PARTICLE SIZE DISTRIBUTION

the v a l i d i t y of the assumption regarding the form of the


distribution.
D i r e c t a p p l i c a t i o n o f the s c a t t e r i n g equations f o r monodisperse
systems t o p a r t i c u l a t e systems that a r e p o l y d i s p e r s e , w i l l clearly
r e s u l t i n the e s t i m a t i o n o f average o r e f f e c t i v e p a r t i c l e diameters.
The i n t e r p r e t a t i o n of these average diameters i s n o t
s t r a i g h t f o r w a r d . Q u o t i n g K e r k e r ( 3 ) , " t h e r e i s no s i m p l e m e t h o d o f
c o m p a r i n g t h e s i z e d e t e r m i n e d by t h e e l e c t r o n m i c r o s c o p e w i t h t h e
a v e r a g e s i z e o b t a i n e d from l i g h t s c a t t e r i n g . Indeed, not only w i l l
d i f f e r e n t l i g h t s c a t t e r i n g methods g i v e d i f f e r e n t a v e r a g e s , b u t each
particular d i s t r i b u t i o n o f s i z e s w i l l h a v e i t s own c h a r a c t e r i s t i c
average." Maron, P i e r c e and U l e v i t c h (V3) e x p e r i m e n t a l l y
i n v e s t i g a t e d t h i s p r o b l e m a n d r e p o r t e d good agreement between t h e
p a r t i c l e diameters obtained from s p e c i f i c t u r b i d i t y measurements
t a k e n a t s e v e r a l w a v e l e n g t h s , and t h e t u r b i d i t y average p a r t i c l e
diameters c a l c u l a t e d fro
s i z e d i s t r i b u t i o n . Dobbin
noted that f o r a wide v a r i e t
w i t h r a d i i comparable t o and l a r g e r t o t h e w a v e l e n g t h , t h e s p e c i f i c
t u r b i d i t y c a n be a d e q u a t e l y represented i n terms of the volume
s u r f a c e mean d i a m e t e r a n d t h e mean s u r f a c e s c a t t e r i n g efficiency.

2 D 3 2

w h e r e t h e mean s u r f a c e scattering efficiency i s given by

f CO 00
Q(a,m) - J 0 D 2
Q(a,m) f ( d ) dD/ J D 2
f ( D ) dD

Since t h e r a t i o Q(a,m)/ D 3 2 was s h o w n , n u m e r i c a l l y , t o be


i n d e p e n d e n t o f t h e shape o f t h e d i s t r i b u t i o n , D o b i n s and J i z m a g i a n
c o m p u t e d t a b l e s o f t h e mean s u r f a c e s c a t t e r i n g e f f i c i e n c y as a
f u n c t i o n o f t h e v o l u m e s u r f a c e mean d i a m e t e r f o r t h e e v a l u a t i o n o f
D 3 2 d i r e c t l y from t r a n s m i s s i o n measurements. More r e c e n t l y , Bagchi
and V o i d , a n a l y s e d l a t e x p a r t i c l e s c o n s i d e r a b l y l a r g e r than t h e
wavelength of the incident radiation where t h e extinction
c o e f f i c i e n t i s approximately independent of the p a r t i c l e s i z e . T h e i r
r e s u l t s suggest that, i n t h e p a r t i c l e range i n v e s t i g a t e d , t h e
s p e c i f i c t u r b i d i t y c a n be d i r e c t l y r e l a t e d to the f i r s t three
moments o f t h e p a r t i c l e s i z e d i s t r i b u t i o n a n d t o t h e v o l u m e t o
surface average p a r t i c l e diameter. U n f o r t u n a t e l y , the
polydispersities of the l a t i c e s investigated were r e l a t i v e l y s m a l l
p r e v e n t i n g any d e f i n i t i v e s t a t e m e n t as t o t h e average that best
correlates the data.
Ideally, i t i s desirable t o solve equations 1 or 2 f o r the
complete s i z e d i s t r i b u t i o n whenever p o l y d i s p e r s e s y s t e m s a r e b e i n g
a n a l y s e d . However, from t h e c o m p u t a t i o n a l point of view, t h e d i r e c t
application of the equations f o r monodisperse systems i s more

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
11. GARCIA-RUBIO Averages from Turbidity Measurements 165

appealing. I t i s therefore necessary t o establish both, the physical


meaning o f the " e f f e c t i v e " average diameters as well as t h e
i n f o r m a t i o n c o n t e n t o f t h e t u r b i d i t y d a t a i n t e r m s o f t h e moments o f
the p a r t i c l e s i z e d i s t r i b u t i o n .

Problem F o r m u l a t i o n And A n a l y s i s

By f i r s t c o n s i d e r i n g t h e R a y l e i g h r e g i m e a n d e x p a n d i n g t h e c o m p l e x
scattering c o e f f i c i e n t s i n power s e r i e s o f a , i t c a n be shown t h a t
t h e e x t i n c t i o n c a n b e a p p r o x i m a t e d b y ( 1 , 3t 1 7 )

Q(a,m) = V a + V a 3 1
+ I\ a* + V a 1 5
+ (12)

or

Q(a,m) = r D + x 3 D

Where t h e c o e f f i c i e n t s and r's are i m p l i c i t functions of the


o p t i c a l constants and thus o f the wavelength ( s e e Appendix I ) .
For monodisperse systems, replacement o f e q u a t i o n 13 i n t o
e q u a t i o n 2, y i e l d s a n a p p r o x i m a t i o n t o t h e t u r b i d i t y i n t e r m s o f
powers o f t h e p a r t i c l e d i a m e t e r

() = [ T x + 3 D 2
+ I\ D 3
+ 5
1
D* + ] (14)
2

F o r p o l y d i s p e r s e s y s t e m s , r e p l a c e m e n t o f e q u a t i o n 13 i n t o e q u a t i o n 2
for every p a r t i c l e diameter, y i e l d s an approximation t o the
t u r b i d i t y i n t e r m s o f r a t i o s o f moments o f t h e p a r t i c l e size
d i s t r i b u t i o n w i t h o u t h a v i n g t o make a s s u m p t i o n s r e g a r d i n g t h e s h a p e
of t h e d i s t r i b u t i o n :

() [ I\ D 3 + 3 D 5 + I\ D 6 + 5 D 7 + ] (15)
2p D 3

W h e r e Dn r e p r e s e n t s t h e n t h moment o f t h e p a r t i c l e diameter.

For monodisperse systems i n t h e large p a r t i c l e s i z e regime, where


t h e e x t i n c t i o n e f f i c i e n c y c a n be assumed c o n s t a n t and a p p r o x i m a t e l y
e q u a l t o 2, e q u a t i o n 2 b e c o m e s

() - 3 C I / ( p D)
(16)

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
166 PARTICLE SIZE DISTRIBUTION

For p o l y d i s p e r s e s y s t e m s i n the large particle size regime


e q u a t i o n 2 becomes

() - 3 C i /(p D )
3 2 (17)

Where D 3 2 i s the volume t o s u r f a c e average p a r t i c l e diameter.

E q u a t i o n s 15 a n d 17 p o i n t t o s o m e o f t h e d i f f i c u l t i e s i n the
i n t e r p r e t a t i o n o f t h e t u r b i d i t y d a t a i n t e r m s o f a v e r a g e s o r moments
o f t h e p a r t i c l e s i z e d i s t r i b u t i o n . F r o m e q u a t i o n 15 i t i s c l e a r t h a t
the i n t e r p r e t a t i o n of the diameter d e p e n d s on t h e l e v e l of
approximation used to evaluate the e x t i n c t i o n efficiency.
F u r t h e r m o r e , i t s u g g e s t s t h a t , i n p r i n c i p l e , a s i g n i f i c a n t number o f
moments a n d t h e r e f o r e t h shap f th particl siz distributio
c a n be e v a l u a t e d d i r e c t l
l i m i t a t i o n being the s i g n a
t h e o t h e r hand, i n t h e l a r g e p a r t i c l e s i z e regime (equation 17),
o n l y one a v e r a g e , t h e v o l u m e t o s u r f a c e a v e r a g e i s a v a i l a b l e . I f t h e
p a r t i c l e s i z e d i s t r i b u t i o n i s k n o w n , o n l y t w o moments ( t h e s e c o n d
a n d t h e t h i r d ) c a n be o b t a i n e d d i r e c t l y f r o m t u r b i d i t y experiments.
The p r o b l e m o f d e c i d i n g on a p a r t i c u l a r average diameter ( o r
d i a m e t e r s ) t o be u s e d i n t h e c a l c u l a t i o n of the extinction
e f f i c i e n c y c a n be f o r m u l a t e d a s f i n d i n g a v e r a g e p a r t i c l e d i a m e t e r s ,
Dav, s u c h t h a t

(18)

where aav = Dav/

subject t o the f o l l o w i n g constraints:

1. The a v e r a g e d i a m e t e r ( s ) , a s r e p r e s e n t a t i v e of the p o p u l a t i o n
behavior, should s a t i s f y the a n a l y t i c behavior of the scattering
equations ( i e : the r e s u l t i n g e q u a t i o n s s h o u l d have t h e same
functional f o r m as e q u a t i o n s 1*1 a n d 1 6 ) .

2. The e q u a t i o n s o b t a i n e d f o r t h e a v e r a g e p a r t i c l e diameter(s)
should reduce to the equations developed f o r monodisperse
systems ( i e : the r e s u l t i n g equations s h o u l d reduce t o e q u a t i o n s
14 a n d 16 f o r m o n o d i s p e r s e s y s t e m s ) .

N o t e t h a t t h e f o r m u l a t i o n s t a t e d by e q u a t i o n 18 i s d i f f e r e n t from
t h a t o f D o b b i n s e t a l ( E q u a t i o n 1 1 ) i n t h a t we a r e s e e k i n g a
s o l u t i o n t o t h e i n t e g r a l e q u a t i o n 18 i n t e r m s o f o n e o r s e v e r a l o f
the moments of the p a r t i c l e s i z e d i s t r i b u t i o n and i n t h a t ,
s i m u l t a n e o u s l y , we a r e i n q u i r i n g a s t o t h e i n f o r m a t i o n c o n t e n t o f
the s c a t t e r i n g function with regards to the p a r t i c l e size
distribution.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
11. GARCIA-RUBIO Averages from Turbidity Measurements 167

T h e r e a r e two r e g i o n s i n t h e diameter space where t h e b e h a v i o r


of t h e a v e r a g e d i a m e t e r ( s ) c a n e a s i l y b e i n v e s t i g a t e d : t h e r e g i o n
where t h e diameter i s s m a l l compared t o t h e wavelength o f t h e
incident r a d i a t i o n ( i e : the Rayleigh regime) a n d t h e r e g i o n where
t h e d i a m e t e r i s much l a r g e r t h a n t h e w a v e l e l e n g t h ( i e : t h e l a r g e
particle size regime). I n the l a r g e p a r t i c l e s i z e regime, i t i s
c l e a r f r o m e q u a t i o n 17 t h a t t h e o n l y a v e r a g e o b t a i n e d f r o m t u r b i d i t y
measurements i s t h e volume t o s u r f a c e average d i a m e t e r . I t i s a l s o
e v i d e n t t h a t e q u a t i o n 17 h a s t h e same f u n c t i o n a l f o r m a s e q u a t i o n 16
a n d t h a t i n f a c t r e d u c e s t o e q u a t i o n 16 f o r m o n o d i s p e r s e systems.
Thus s a t i s f y i n g t h e c o n s t r a i n t s imposed f o r the s e l e c t i o n o f the
average diameters. Note t h a t although r a t i o s o f s u c c e s s i v e moments
w i l l s a t i s f y t h e c o n s t r a i n t s imposed, o n l y D r e s u l t s d i r e c t l y from
3 2

e q u a t i o n 2.
For t h e a n a l y s i s i n t h e s m a l l p a r t i c l e s i z e regime, rather than
approximating the scatterin
was d o n e t o o b t a i n e q u a t i o
into equation 2 t o obtai

Q(aav,m)
( )
(19)
2 D 3 2

Then o n t h e b a s i s o f t h e f i r s t c o n s t r a i n t , t h e e x t i n c t i o n efficiency
i s expanded i n power s e r i e s o f a a v t o y i e l d

1
() = 3 C
[ Dav + 3 Dav 3
+ I \ Dav* + 5 Dav 5
+ ..] (20)
2 D 3 2

n o t e t h a t by f o l l o w i n g t h i s a p p r o a c h t h e e r r o r s i n t h e a p p r o x i m a t i o n
o f Q(a,m) a r e n o t i n t e g r a t e d .
T h e r e a r e many a v e r a g e s t h a t when s u b s t i t u t e d i n t o e q u a t i o n 20
w i l l r e d u c e i t t o e q u a t i o n 14 f o r m o n o d i s p e r s e distributions.
However, o n l y t h e D a v e r a g e y i e l d s t h e same f u n c t i o n a l f o r m a s
3 2

e q u a t i o n 14 f o r p o l y d i s p e r s e a n d m o n o d i s p e r s e p a r t i c l e size
d i s t r i b u t i o n s . T h e r e f o r e , i t f o l l o w s t h a t t h e volume t o surface
average diameter s a t i s f i e s t h e c o n s t r a i n t s imposed a t b o t h , t h e
s m a l l a n d t h e l a r g e p a r t i c l e s i z e r e g i m e s . E q u a t i o n s 15 a n d 20
provide twoequivalent i n t e r p r e t a t i o n s f o r the t u r b i d i t y data i nt h e
s m a l l p a r t i c l e s i z e r e g i m e . E q u a t i o n 20 i s p a r t i c u l a r l y a t t r a c t i v e
because a s i n g l e average c o u l d be used f o r t h e i n t e r p r e t a t i o n o f
t u r b i d i t y d a t a i n b o t h t h e s m a l l and l a r g e p a r t i c l e s i z e regimes.
However, i t r e m a i n s t o d e m o n s t r a t e i f t h i s i s a l s o t r u e f o r t h e
intermediate s i z e regime ( i e : D - ) .
To s e a r c h f o r t h e a v e r a g e d i a m e t e r ( s ) t h a t w o u l d satisfy
e q u a t i o n 18 i n t h e i n t e r m e d i a t e p a r t i c l e s i z e r e g i m e , a n u m e r i c a l
a p p r o a c h was t a k e n . T h e o b v i o u s a p p r o a c h i s t o c a l c u l a t e t h e r i g h t
h a n d s i d e o f e q u a t i o n 18 f o r a v a r i e t y o f d i s t r i b u t i o n s a n d a

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
168 PARTICLE SIZE DISTRIBUTION

s u f f i c i e n t l y broad range o f t h e i r parameter v a l u e s and t h e n , s e a r c h


for a d i a m e t e r t h a t when s u b s t i t u t e d i n t o t h e e x p r e s s i o n f o r t h e
e x t i n c t i o n e f f i c i e n c y ( i e : e q u a t i o n 3 ) , s a t i s f i e s e q u a t i o n 18. A
c o m p a r i s o n b e t w e e n D a v a n d t h e moments o r r a t i o s o f moments o f t h e
d i s t r i b u t i o n i n question w i l l indicate which average d i a m e t e r
s a t i s f i e s e q u a t i o n 1 8 . A m a j o r d i f f i c u l t y w i t h t h e above approach
stems from the diameter b e i n g a m u l t i v a l u e d f u n c t i o n o f t h e
e x t i n c t i o n e f f i c i e n c y ( 1-3). I n o t h e r words, t h e r e i s not a unique
v a l u e f o r t h e d i a m e t e r as a f u n c t i o n o f t h e e x t i n c t i o n efficiency.
An a l t e r n a t i v e a p p r o a c h t h a t c i r c u m v e n t s t h e u n i q u e n e s s p r o b l e m i s
to s u b s t i t u t e t h e moments a n d t h e r a t i o s o f moments o f t h e
d i s t r i b u t i o n i n t o t h e e x t i n c t i o n e f f i c i e n c y and then s e l e c t those
t h a t b e s t a p p r o x i m a t e t h e c o n d i t i o n s t a t e d by e q u a t i o n 18.
T h e e f f e c t o f t h e s h a p e o f t h e d i s t r i b u t i o n c a n be t a k e n i n t o
c o n s i d e r a t i o n , w i t h o u t l o s s o f g e n e r a l i t y , i f i t i s assumed t h a t t h e
shape o f the d i s t r i b u t i o i questio approximate wit
w e i g h t e d sum o f g a u s s i a

f(D) - ^ v ( j ) N(D, y ( j ) , o(j)) (21)

subject to j. v(j) 1

and where p ( j ) and o ( j ) a r e t h e p a r a m e t e r s f o r t h e j t h a p p r o x i m a t i o n


function.

Replacement o f e q u a t i o n 21 i n t o 18 yields

Q(aav,m) - ^ v( j ) Q ( a a v ( j ) , m) / ^ v(j) D (j) 2 (22)

E q u a t i o n 22 i n d i c a t e s t h a t t h e s u r f a c e a v e r a g e s c a t t e r i n g e f f i c i e n c y
c a n be e x p r e s s e d a s a a l i n e a r c o m b i n a t i o n o f t h e a v e r a g e e f f i c i e n c y
for each of the a p p r o x i m a t i o n f u n c t i o n s . T h e r e f o r e , i t i s only
necessary t o f i n d which averages s a t i s f y e q u a t i o n 8 f o r a g a u s s i a n
d i s t r i b u t i o n . E x t e n s i v e c o m p u t a t i o n s w i t h a v a r i e t y o f parameter
v a l u e s i n d i c a t e s t h a t Dav does n o t c o r r e s p o n d t o any p a r t i c u l a r
a v e r a g e o r r a t i o o f moments o f t h e p a r t i c l e s i z e d i s t r i b u t i o n . T h i s
c a n be s e e n i n f i g u r e s 1 - 4 . W h e r e t h e f r a c t i o n a l e r r o r s , b e t w e e n t h e
s u r f a c e average e x t i n c t i o n e f f i c i e n c y and t h e e x t i n c t i o n c a l c u l a t e d
with t r i a l averages of the p a r t i c l e s i z e d i s t r i b u t i o n ( 1 -
Q ( a a v , m ) / Q ( a , m ) ) , a r e s h o w n a s f u n c t i o n o f t h e s i z e p a r a m e t e r a.
C l e a r l y , i t appears t h a t d i f f e r e n t p a r t i c l e a v e r a g e s w i l l be m o r e
e f f e c t i v e a t d i f f e r e n t s i z e parameter v a l u e s . I n g e n e r a l , averages
i n c l u d i n g h i g h e r moments a p p e a r t o p e r f o r m b e t t e r o v e r a l l . The
r e a s o n f o r t h e o b s e r v e d p e r f o r m a n c e c a n be b e t t e r u n d e r s t o o d w i t h

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
11. GARCIA-RUBIO AveragesfromTurbidity Measurements 169

F i g . 1. A p p r o x i m a t e b e h a v i o r o f t h e f r a c t i o n a l e r r o r a s a f u n c t i o n
o f t h e m e a n s i z e p a r a m e t e r /\ and t h e f r a c t i o n a l standard
d e v i a t i o n . W h e r e i s t h e mean p a r t i c l e d i a m e t e r .
1

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
170 PARTICLE SIZE DISTRIBUTION

F i g . 2 . A p p r o x i m a t e b e h a v i o r o f t h e f r a c t i o n a l e r r o r as a f u n c t i o n
o f t h e mean s i z e p a r a m e t e r * D /X a n d t h e f r a c t i o n a l s t a n d a r d
2 2

d e v i a t i o n . Where D 2 i s the s u r f a c e average p a r t i c l e diameter.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
11. GARCIA-RUBIO Averages from Turbidity Measurements 171

0.4 J

F i g . 3. A p p r o x i m a t e b e h a v i o r o f t h e f r a c t i o n a l e r r o r a s a f u n c t i o n
o f t h e mean s i z e p a r a m e t e r 3 2 * D /X and t h e f r a c t i o n a l s t a n d a r d
3 2

d e v i a t i o n . Where D 3 2 i s t h e mean v o l u m e t o s u r f a c e average


p a r t i c l e diameter.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
172 PARTICLE SIZE DISTRIBUTION

r e f e r e n c e t o f i g u r e 5. A s s u m e t h a t f o r a m a t e r i a l h a v i n g a g a u s s i a n
p a r t i c l e s i z e d i s t r i b u t i o n and t h e e x t i n c t i o n p r o p e r t i e s r e p r e s e n t e d
1
i n t h e f i g u r e , m e a s u r e m e n t s a r e t o be t a k e n a t a w a v e l e n g t h
c o r r e s p o n d i n g t o a s i z e p a r a m e t e r - 4. N o t e t h a t , i n i t i a l l y , m o s t
of the p a r t i c l e s i z e d i s t r i b u t i o n l i e s b e f o r e t h e f i r s t extinction
2
maximum. T h i s i m p l i e s t h a t t h e w e i g h t i n g on D i n e q u a t i o n 18 w i l l
increase together w i t h the diameter squared. Therefore, the a v e r a g e
d i a m e t e r t h a t s a t i s f i e s e q u a t i o n 18 w i l l c o r r e l a t e b e t t e r w i t h
a v e r a g e s c o n t a i n i n g h i g h e r moments o f t h e p a r t i c l e s i z e d i s t r i b u t i o n
(ie: the t u r b i d i t y a v e r a g e DT). Now assume t h a t two more
f !
m e a s u r e m e n t s a r e t o be t a k e n a t w a v e l e n g t h s A / 2 a n d / 4 . For t h i s
p u r p o s e t h e p a r t i c l e s i z e d i s t r i b u t i o n i s mapped a g a i n o n t o t h e
domain. Note t h a t the p a r t i c l e s i z e d i s t r i b u t i o n has changed
r e l a t i v e t o the f i r s t measurement, the p a r t i c l e s i z e d i s t r i b u t i o n
a p p e a r s t o have been s h i f t e d and b r o a d e n e d as t h e w a v e l e n g t h was
reduced. C l e a r l y , the r e s u l t from changing the wavelength i s a
change i n t h e range o f v a l u e
18 t h u s r e s u l t i n g n o
average e x t i n c t i o n e f f i c i e n c y but a l s o , i n d i f f e r e n t v a l u e s of t h e
a v e r a g e d i a m e t e r t h a t w i l l s a t i s f y e q u a t i o n 18. A s t h e w a v e l e n g t h i s
reduced, the d i s t r i b u t i o n continues to s h i f t u n t i l the l a r g e
p a r t i c l e s i z e r e g i m e i s r e a c h e d a n d t h e v a l u e o f Q(a,ra) b e c o m e s
independent of the shape of the p a r t i c l e s i z e d i s t r i b u t i o n .
I n c r e a s i n g t h e v a r i a n c e o f the p a r t i c l e s i z e d i s t r i b u t i o n w i l l have
a s i m i l a r e f f e c t o n t h e a v e r a g e s s a t i s f y i n g e q u a t i o n 18 s i n c e t h e
i n c l u s i o n o f l a r g e r and s m a l l e r s i z e s w i l l a s y m m e t r i c a l l y a f f e c t t h e
2
w e i g h t i n g o n D . A n i n d i c a t i o n a s t o how d i f f e r e n t m o m e n t s o f t h e
p a r t i c l e s i z e d i s t r i b u t i o n a f f e c t the c a l c u l a t i o n of the e x t i n c t i o n
e f f i c i e n c y c a n be o b t a i n e d d i r e c t l y f r o m t h e i n t e r p r e t a t i o n of
Q ( a , m ) f o r a n o m a l o u s d i f f r a c t i o n ( i e : [m - 1]<<1 and a 1 ) . The
e x t i n c t i o n e f f i c i e n c y f o r the anomalous d i f f r a c t i o n case i s g i v e n
1 2
by

Q(a,m) 2 - 4 [ ( e x p ( - p t a n B ) cosg/p)(sin(p-g) +

2 2
(cose cos(p-2B)/p] + 4 (cos fl/p )cos(20) (23)

where tanfl k/(n - n )


0 and 2(/ 0 - 1).

By f i r s t r e p l a c i n g e q u a t i o n 23 i n t o 1 0 , i t c a n be r e a d i l y shown,
t h a t t h e r e s u l t i n g i n t e g r a l c a n be e x p r e s e d a s a w e i g h t e d sum of the
moments o f t h e p a r t i c l e s i z e d i s t r i b u t i o n

(24)

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
11. GARCIA-RUBIO Averages from Turbidity Measurements 173

F i g . 4. Approximate b e h a v i o r o f the f r a c t i o n a l e r r o r as a f u n c t i o n
o f t h e mean s i z e p a r a m e t e r * Di/ and t h e f r a c t i o n a l s t a n d a r d
d e v i a t i o n . Where Dx i s t h e t u r b i d i t y average p a r t i c l e d i a m e t e r .

F i g . 5. B e h a v i o r o f the p a r t i c l e s i z e d i s t r i b u t i o n r e l a t i v e t o t h e
e x t i n c t i o n as f u n c t i o n o f t h e s i z e p a r a m e t e r a . 1) p a r t i c l e s i z e
d i s t r i b u t i o n as s e e n a t -'; 2) p a r t i c l e s i z e d i s t r i b u t i o n a t
'/2; 3) p a r t i c l e s i z e d i s t r i b u t i o n a t - ' .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
174 PARTICLE SIZE DISTRIBUTION

I n t h i s c a s e , a n e i g t h o r d e r a p p r o x i m a t i o n was u s e d i n o r d e r t o
i n c l u d e some o f t h e h i g h e r m o m e n t s o f t h e d i s t r i b u t i o n . Kn(X,m)
r e p r e s e n t s t h e w e i g h t f o r t h e n t h moment o f t h e s i z e distribution.
The v a l u e s f o r K n a r e g i v e n i n A p p e n d i x I I . A s i m i l a r e x p r e s s i o n c a n
be o b t a i n e d i n t e r m s o f t h e D 3 2 a v e r a g e i f E q u a t i o n 24 i s a p p l i e d t o
Q(aav,m) i n e q u a t i o n 19.
Note that t h e r e l a t i v e i m p o r t a n c e o f t h e moments o f t h e
p a r t i c l e s i z e d i s t r i b u t i o n o r t h e p o w e r s o f D , as r e f l e c t e d by
3 2

Kn(A,m), w i l l v a r y as f u n c t i o n o f t h e o p t i c a l c o n s t a n t s a n d o f t h e
wavelength. Therefore, i t i s clear that, i n the intermediate
p a r t i c l e s i z e regime, t h e measured e x t i n c t i o n e f f i c i e n c y c a n n o t be
r e a d i l y i n t e r p r e t e d i n t e r m s o f s i n g l e c o m b i n a t i o n s o f moments o f
the p a r t i c l e s i z e d i s t r i b u t i o n . F u r t h e r m o r e , i t i s e v i d e n t t h a t t h e
e f f e c t i v e average p a r t i c l e diameter r o u t i n e l y determined from
t u r b i d i t y measurements w i l l a p p e a r t o be a f u n c t i o n o f t h e
wavelength used i n t h
reported literature d a t a
figures 1-4 e x p l a i n
c o r r e l a t i o n with the t u r b i d i t y average p a r t i c l e diameter whenever
the s c a t t e r i n g e q u a t i o n s have been a p p l i e d t o p o l y d i s p e r s e d s y s t e m s .

Discussion

T h e o v e r a l l c o n c l u s i o n f r o m t h e a n a l y s i s o f e q u a t i o n 18 o v e r t h e
complete domain o f i s t h a t , i n p r i n c i p l e , i n f o r m a t i o n a b o u t t h e
s h a p e o f t h e p a r t i c l e s i z e d i s t r i b u t i o n c a n be o b t a i n e d d i r e c t l y
from t u r b i d i t y , or i n g e n e r a l , from s c a t t e r i n g measurements.
H o w e v e r , t h e d i s c r i m i n a t i n g power o f t h e measurements i n terms o f
the p a r t i c l e s i z e d i s t r i b u t i o n d e p e n d s u p o n t h e w a v e l e n g t h r a n g e
s e l e c t e d f o r the a n a l y s i s . The major d i f f i c u l t y i n the
interpretation of the data a r i s e s from the behavior of the
e x t i n c t i o n i t s e l f as f u n c t i o n o f t h e s i z e p a r a m e t e r w h i c h causes t h e
measurements " s e e " a d i f f e r e n t average a t every w a v e l e n g t h .
In t h e l a r g e p a r t i c l e s i z e regime, the i n t e r p r e t a t i o n of the
average p a r t i c l e d i a m e t e r as D i s unambiguous. I n t h e i n t e r m e d i a t e
3 2

p a r t i c l e s i z e r e g i m e , t h e e f f e c t i v e a v e r a g e d i a m e t e r Dav w i l l v a r y
as f u n c t i o n o f t h e w a v e l e n g t h . M e a s u r e m e n t s o v e r a r a n g e o f
w a v e l e n g t h s w i l l y i e l d averages that a r e weighted according t o the
behavior of t h e s c a t t e r i n g f u n c t i o n over t h e c o r r e s p o n d i n g s i z e
p a r a m e t e r r a n g e . H o w e v e r , t h e g e n e r a l f o r m u l a g i v e n b y e q u a t i o n 19
s u g g e s t s t h a t two parameters aav and D , c a n be u s e d t o i n t e r p r e t
3 2

t u r b i d i t y d a t a o v e r a w a v e l e n g t h r a n g e . T h e v o l u m e s u r f a c e mean
diameter w i l l correspond t o the p a r t i c l e s i z e d i s t r i b u t i o n whereas
the a a v w i l l c o r r e s p o n d t o t h e a v e r a g e d i a m e t e r " s e e n " by t h e
measurements averaged over t h e wavelength range. T h i s approach
s i m p l i f i e s the a n a l y s i s and i n t e r p r e t a t i o n of the s c a t t e r i n g data
for p o l y d i s p e r s e d systems c o n s i d e r a b l y . F o r example, i t i s not
n e c e s s a r y t o c a l c u l a t e t h e mean s u r f a c e s c a t t e r i n g e f f i c i e n c y i n t h e
f o r m s u g g e s t e d by D o b b i n s a n d J i z m a g i a n . A s i n g l e e v a l u a t i o n u s i n g
aav and D
3 2 y i e l d s t h e d e s i r e d a v e r a g e e f f i c i e n c y . When o p t i c a l
constants a r e estimated from s c a t t e r i n g data, the m i n i m i z a t i o n
problem i s reduced t o the estimation o f : the o p t i c a l constants aav

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
11. GARCIA-RUBIO Averages from Turbidity Measurements 175

and, o n e a v e r a g e p a r t i c l e d i a m e t e r ( i e : D ) . 3 2 Two moments o f t h e


p a r t i c l e s i z e d i s t r i b u t i o n , the s e c o n d a n d the t h i r d c a n be o b t a i n e d
i f the form o f t h e p a r t i c l e s i z e d i s t r i b u t i o n i s known. T h i s i s
p a r t i c u l a r l y i m p o r t a n t f o r t h e e s t i m a t i o n o f o p t i c a l constants as
f u n c t i o n s o f t h ewavelength, since only one e v a l u a t i o n o f t h e
extinction e f f i c i e n c y p e r p a r a m e t e r p e r i t e r a t i o n w i l l be r e q u i r e d
and no p r i o r knowledge o f t h eshape o f t h ep a r t i c l e size
d i s t r i b u t i o n i s necesary.
In the s m a l l p a r t i c l e s i z e regime, two e q u i v a l e n t f o r m u l a t i o n s
l e a d t o t h e i n t e r p r e t a t i o n o f t h e d a t a i n t e r m s o f r a t i o s o f moments
of the p a r t i c l e s i z e d i s t r i b u t i o n o r i n terms o f p o w e r s o f t h e D 3 2

a v e r a g e ( e q u a t i o n s 15 a n d 2 0 ) . I ti s c l e a r that i n either case a


s u f f i c i e n t number o f t e r m s i n t h e s e r i e s h a s t o b e i n c l u d e d i n o r d e r
t o a c c o u n t f o r the b e h a v i o r o f the e x t i n c t i o n as f u n c t i o n o f a. The
number o f t e r m s r e q u i r e d c a n n o t be d e c i d e d a p r i o r i , r a t h e r t h e d a t a
i t s e l f has t o dictat
a p p r o x i m a t i o n the measurement
The variation of
the w a v e l e n g t h o r as f u n c t i o n o f the v a r i a n c e o f t h e p a r t i c l e size
d i s t r i b u t i o n i s o f great importance i n the a p p l i c a t i o n o f s c a t t e r i n g
measurements t o t h e d e t e r m i n a t i o n o f m o l e c u l a r weights because
t y p i c a l molecular weight distributions a r er a t h e r broad. F o r
e x a m p l e , a p o l y m e r w i t h a r a t i o Mw/Mn 1 . 5 h a s a f r a c t i o n a l
s t a n d a r d d e v i a t i o n e q u a l t o 0.71. F o r a 60 A mean p a r t i c l e d i a m e t e r
and a gamma d i s t r i b u t i o n , Dx = 2 1 0 A. T h e d i f f e r e n c e b e t w e e n a n d

Dx i n d i c a t e s a t l e a s t a t h r e e f o l d change i n the magnitude o f t h e


s i z e parameter thus r e q u i r i n g that high order terms be i n c l u d e d i n
t h e m e a s u r e m e n t e q u a t i o n ( i e : e q u a t i o n s 15 o r 2 0 ) . M e a s u r e m e n t s a t
o t h e r w a v e l e n g t h s w i l l c l e a r l y r e s u l t i n Mw a p p e a r i n g a s a f u n c t i o n
of t h ew a v e l e n g t h i f o n l y t h e l e a d i n g term i sused. F i n a l l y , i t
s h o u l d be n o t i c e d t h a t i ft h eD 3 2 average i sused for t h e
interpretation o f t u r b i d i t y d a t a , t h e r e s u l t i n g molecular weight
average i s the r a t i o Mn/M 32 which i s r e l a t e d t o t h em o l a r s u r f a c e
area. The i m p l i c a t i o n s o f t h i s i n t e r p r e t a i o n are c u r r e n t l y being
e x p l o r e d a n d t h e y w i l l be r e p o r t e d s e p a r a t e l y .

Acknowledgments

T h i s r e s e a r c h was s u p p o r t e d b y t h e N S F I n i t i a t i o n G r a n t R I I - 8 5 0 7 9 5 6
The author i s i n d e b t e d t o D r . J . Harwood from t h eUniversity o f
A k r o n f o r h i s c o n t i n u o u s encouragement and s u p p o r t .

REFERENCES

1. van de Hulst, H. C., "Light Scattering by Small Particles",


1957, Wiley, New York.
2. Kerker, M . , e d i t o r . , "Electromagnetic Waves", 1962, Pergamon
Press, New York.
3. Kerker, M . , "The Scattering of Light and Other Electromagnetic
Radiation", 1969, Academic Press, New York.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
176 PARTICLE SIZE DISTRIBUTION

4. Bohren, C. F.; Huffman, D. R., "Absorption and Scattering of


Light by Small Particles", 1983, Wiley, New York.
5. Huglin, M. B.," Light Scattering from Polymer Solutions".,
1972, Academic Press Inc. (London) LTD.
6. Deirmendjian, D . , "Electromagnetic Scattering on Spherical
Polydispersions", 1969, American Elsevier, New York.
7. Baltes, H. P . , ( E d i t o r ) . , "Inverse Scattering Problems in
Optics", 1980, Springer-Verlag, Berlin.
8. Gledhill, R. L., J. Phys. Chem., 1961, 66, 458.
9. Wallach, M. L.; Heller, W.; Stevenson, A. F., J. Chem. Phys.
1961, 32(2), 1796.
10. Maxim, D. L.; Klein, .; Meyer, M. E.;Kuist, C. H.; J. Polym.
Sci. Part C, 1969, 27, 195.
11. Husain, .; Vlachopulos, J.; Hamielec, A. E.; J. L i q . Chrom.
1979, 2(4), 517.
12. Zollars, R. L., J. Coll Int S c i . 1980 74 163
13. Maron, S. H.; Pierce
1963, 18, 470.
14. Dobbins, R. . ; Jizmagian, G. S., Opt. Soc. Amer., 1966, 56,
1345, 1351.
15. Bagchi, P.;Vold, R. D., J . Coll. Int. S c i . , 1975, 53(2), 194.
16. Sorenson, H , . W.; Alspach, D. L., Automatica., 1971, 7, 465.
17. Penndorf, R. B., J . Opt. Soc. Amer., 1962, 52, 896.
18. MAC'S Symbolic Manipulation System (Macsyma), 1985, Symbolics
Inc., Cambridge Massachusetts.

APPENDIX I

The c o e f f i c i e n t s o f t h epower s e r i e s expansion of the


e x t i n c t i o n e f f i c i e n c y , t o a 5 t h o r d e r a p p r o x i m a t i o n , were d e r i v e d by
Penndorf 0 7 ) and independently a t o u r l a b o r a t o r i e s u s i n g Macsyma
(18). The c o e f f i c i e n t s o f t h es e r i e s a r e :

24 k
1
2 2 2 2 2
(n + k ) + 4(n - k ) + 4

4 nk 20 nk
15 2 2 2 2 2
3 [ 4 (n + k ) + 12 ( n - k ) +

2 2 2 2 2 2
+ 4.8 n k [ 7 ( n + k ) + 4 (n - k - 5) ]
2 2 2 2 2 2
[(n + k ) + 4(n - k ) + 4]

2 2
-192 n k
2 2 2 2 2 2
[(n + k ) + 4(n - k ) + 4]

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
11. GARCIA-RUBIO AveragesfromTurbidity Measurements 111

r 5 - (PiR 2 + P R,)
a

2 2 2 2 2
20nk [4 ( n + k ) + 8 ( n - k ) + 21 ]
2 2 2 2 2 2
21 [ 4 ( n + k ) + 12(n - k ) + 9 ]

2 r I4nk >
0 2 2 2 2 2
9 ( n + k ) + 24(n - k ) + 16

+ ^ ( 2nk + 4nk ( n - k - 3 ) ) 2 2

Where:
2 2 2 2 2
(n + k ) + n - k - 2
Pi

_ 6nk


R l =
2 2
( - k ) " + 22( - k ) - -60( - k ) - 200( - k ) 2 2 3 2 2 2 2 2

2 2 2 2 2 2
+ 400 - 4 n k [24( - k ) + 4 n k + 39]

2 2 3 2 2 3 2 2
2nk[2(n - k ) - 12(n - k ) + 205(n ~ k )

2 2 2 2
+ 8n k (n - k + 9) - 198]

2 2 2 2 2
- ( + k ) + 4 ( - k ) + 4

Replacement of the value / i n t o equation 17, y i e l d s equation


17a. Where the i t h c o e f f i c i e n t i s now given by

1
- (/)

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
178 PARTICLE SIZE DISTRIBUTION

APPENDIX I I

T h i s a p p e n d i x r e p o r t s t h e w e i g h t s f o r t h e moments o f t h e
p a r t i c l e s i z e d i s t r i b u t i o n o b t a i n e d f r o m an e i g h t o r d e r T a y l o r
S e r i e s a p p r o x i m a t i o n t o t h e s c a t t e r i n g e f f i c i e n c y f o r t h e anomalous
d i f f r a c t i o n case

K l - -B ( A t - 0 A) x

2
K 2 = (B/2!)(A t 0 - 2A t x - A )2

3 2
K 3 = (-B/3!)(A t 0 - 3Ait - 3A t 2 * A,)

3 2
K * ( B A ! ) ( A e o - MA t - 6A t 2 + 4A t 3 + A J

5
K 5 = (-B/5!)(A t 0 -

6 5 3 2
K 6 (B/6!)(A t 0 - 6^ - 15A f 2 + 20A t 3 + 15At - 6A t 5 -

A.)

7 6 5 3 2
K 7 - (-B/7!)(A t 0 - 7A t x - 21A t 2 + 35A,t" + 35A t
H - 21A t
5 -

A t
6 A ) 7

8 7 6 5 H 3
K 8 =* ( - B / 8 ! ) ( A t 0 - 8A t t - 28A t 2 + 56A t 3 + 70A t
H - 56A t
5 -

2
28A t 6 + 8A t 7 - A )
8

where t * 2-nk/\ 0

2
4cos(6)/Y

= 2( - ) / 0 0

The A c o e f f i c i e n t s c a n be g e n e r a l i z e d f o r e v e n and odd i n d e c e s


n
for even An = ( c o s ( 2 B ) - n ) ( c o s 6 ) y


for odd An (cosB s i n ( 2 8 ) - s i n B )

R E C E I V E D November 12, 1986

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 12

An Improved Disc Centrifuge Photosedimentometer


and Data System for Particle Size Distribution Analysis
M. E. Koehler,R.A.Zander,T.Gill, Theodore Provder, andT.F.Niemann
The Glidden Company, DwightP.Joyce Research Center, Strongsville,OH44136

An improved disc centrifuge photosedimentometer


(DCP) was developed for use in the determination of
the particle siz d siz distributio f latices
pigments and othe
on Stokes Law fo
a centrifugal force field and does not rely on the
use of particle size calibrants or standards. The
DCP instrument provides accurate stable particle
size analyses over a wide range of conditions while
at the same time is rugged enough for heavy use in
both a research and quality control environment. A
stand-alone data collection, analysis and management
system was developed both for routine quality
control operation and for research use of the
instrument.

The d i s c c e n t r i f u g e p h o t o s e d i m e n t o m e t e r ( D C P ) i s a n i n s t r u m e n t
used t o determine t h e p a r t i c l e s i z e and s i z e d i s t r i b u t i o n o f
l a t i c e s , pigments and o t h e r p a r t i c u l a t e s . S e p a r a t i o n i s based on
S t o k e s Law f o r t h e s e d i m e n t a t i o n o f p a r t i c l e s i n a c e n t r i f u g a l
f o r c e f i e l d . P a r t i c l e s a r e assumed t o be s p h e r i c a l . I n t h e most
common mode o f o p e r a t i o n t h e s e p a r a t i o n t a k e s p l a c e i n a
c y l i n d r i c a l c a v i t y o f known d i m e n s i o n s a n d c o n t a i n i n g a known
volume o f f l u i d . A d i l u t e s u s p e n s i o n o f t h e p a r t i c l e s o f i n t e r e s t
i s i n j e c t e d onto t h e surface o f the f l u i d while t h e d i s c i s
s p i n n i n g and t h e p a r t i c l e s sediment i n t h e c e n t r i f u g a l f o r c e f i e l d
r a d i a l l y outward p a s t a d e t e c t o r system. The appearance t i m e o f
the p a r t i c l e a t t h e d e t e c t o r , t , i n minutes i s g i v e n by

k log 1 0 (R /2 R l ) ( 1 )

t
2 2
D

0097-6156/87/0332-0180$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
12. KOEHLER ET AL. Improved Disc Centrifuge Photosedimentometer 181

w h e r e D i s t h e d i a m e t e r o f t h e p a r t i c l e i n m i c r o m e t e r s , R. i s t h e
radius at the surface of the f l u i d i n centimeters, R i sthe 2

r a d i u s a t t h e d e t e c t o r i n c e n t i m e t e r s , i s t h e r o t a t i o n a l speed
of the d i s c i n r e v o l u t i o n s per minute, i s the v i s c o s i t y of the
f l u i d i n p o i s e , i s t^he d e n s i t y d i f f e r e n c e b e t w e e n t h e p a r t i c l e s
a n d t h e f l u i d i n gm^cm a n d k, a c o l l e c t i o n o f c o n s t a n t t e r m s , i s
e q u a l t o 6.299 10 . I t c a n b e s e e n t h e n t h a t t h e m e t h o d r e l i e s
o n l y on measureable p h y s i c a l parameters and t h e use o f p a r t i c l e
s i z e c a l i b r a n t s or standards i s not required.
The g o a l o f t h i s w o r k was t o d e v e l o p a DCP i n s t r u m e n t w h i c h
would provide accurate s t a b l e p a r t i c l e s i z e analyses over a wide
r a n g e o f c o n d i t i o n s w h i l e a t t h e same t i m e b e i n g r u g g e d e n o u g h f o r
heavy use i n both a r e s e a r c h and q u a l i t y c o n t r o l environment. I n
a d d i t i o n a r e l a t i v e l y inexpensive stand-alone system f o r data
c o l l e c t i o n , a n a l y s i s a n d management was n e e d e d f o r b o t h r o u t i n e
quality control operatio d fo h f th instrument
This paper d i s c u s s e
and d a t a s y s t e m . Instrumen
comparative p a r t i c l e s i z e analyses are discussed elsewhere i n t h i s
v o l u m e (1_,2).

Experimental

Instrument. The i n s t r u m e n t ( 3 ) i s shown s c h e m a t i c a l l y i n F i g u r e


1. ( A c o m m e r c i a l v e r s i o n o f t h e i n s t r u m e n t d e s c r i b e d i n t h i s p a p e r
i s now a v a i l a b l e f r o m B r o o k h a v e n I n s t r u m e n t s C o r p o r a t i o n ,
R o n k o n k o m a , New Y o r k a s t h e B r o o k h a v e n D C P - 1 0 0 0 P a r t i c l e S i z e
A n a l y z e r . ) I t i s based on t h e use o f a v a r i a b l e r a t i o t r a c t i o n
d r i v e t r a n s m i s s i o n ( K o p p M o d e l R1.0HS, A n d a n t e x USA I n c . , 1 8 0 0 - T
B r i e l l e A v e . , Wanamassa, Ocean T o w n s h i p , N J 07712) c o u p l e d w i t h a
one-half-horsepower ac-motor o p e r a t i n g a t e s s e n t i a l l y constant
s p e e d . The r o t a t i o n a l s p e e d o f t h e d i s c i s s e l e c t e d m a n u a l l y b y
means o f a d i a l a n d i s c o n t i n u o u s l y v a r i a b l e o v e r a r a n g e f r o m
a p p r o x i m a t e l y 1,200 t o 1 2 , 0 0 0 r p m . T h e r o t a t i o n a l s p e e d i s
c o n t i n u o u s l y m o n i t o r e d b y means o f a d i g i t a l t a c h o m e t e r l o c a t e d o n
t h e c o n t r o l m o d u l e . The d i s c c a v i t y i s m a c h i n e d f r o m a s u i t a b l e
p l a s t i c m a t e r i a l , t y p i c a l l y polymethylmethacrylate, and i s mounted
on a m e t a l h u b . T h e d i s c c a v i t y i s d y n a m i c a l l y b a l a n c e d o v e r t h e
o p e r a t i n g speed range t o i n s u r e v i b r a t i o n f r e e o p e r a t i o n . A Vortec
c o o l e r ( V o r t e c C o r p o r a t i o n , 1 0 1 2 5 C a r v e r R d . , C i n c i n n a t i , OH
45242) p r o v i d e s c h i l l e d a i r w h i c h c o o l s t h e t r a n s m i s s i o n as i t
passes t h r o u g h a heat exchanger i n t h e t r a n s m i s s i o n f l u i d and i s
then blown i n t o t h e d e t e c t o r block assembly. This c o o l i n g prevents
heat generated i n t h e t r a n s m i s s i o n and by t h e s p i n n i n g d i s c c a v i t y
from warming t h e s p i n f l u i d d u r i n g t h e course o f a l o n g a n a l y s i s
run.
D e t e c t i o n o f t h e p a r t i c l e s i s a c c o m p l i s h e d b y means o f t h e i r
a t t e n u a t i o n o f a l i g h t beam p r o v i d e d b y a h a l o g e n l a m p a n d
c o l l i m a t e d by two s l i t a s s e m b l i e s . A s i l i c o n p h o t o d i o d e and a n
o p e r a t i o n a l a m p l i f i e r c i r c u i t a r e used t o monitor the l i g h t
i n t e n s i t y . A d j u s t a b l e g a i n and o f f s e t potentiometers a r e l o c a t e d
o n t h e c o n t r o l m o d u l e . The s i g n a l c a n be d i s p l a y e d o n a s t r i p c h a r t
r e c o r d e r a n d i s m o n i t o r e d b y means o f a d i g i t a l p a n e l m e t e r .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
53
00

2
)

1
50

m
C/J

S3
tn

c

r

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
12. KOEHLER ET AL. Improved Disc Centrifuge Photosedimentometer 183

The a n a l y s i s m e t h o d e m p l o y e d i s t h e p a t e n t e d e x t e r n a l
g r a d i e n t m e t h o d d e s c r i b e d i n d e t a i l e l s e w h e r e (_1,4) The o v e r a l l
i n s t r u m e n t p e r f o r m a n c e was e v a l u a t e d u s i n g m o n o d i s p e r s e
p o l y s t y r e n e l a t e x s t a n d a r d s , c o v e r i n g a r a n g e f r o m 0.176 t o
1.09 , o b t a i n e d f r o m Dow D i a g n o s t i c s , I n d i a n a p o l i s , I n d i a n a .

Calibration. The i n s t r u m e n t i s c a l i b r a t e d b y u s i n g a c a t h e t o m e t e r
t o measure t h e d i a m e t e r o f t h e f l u i d s u r f a c e w i t h 5 ml and w i t h
15 m l o f w a t e r i n t h e s p i n n i n g d i s c c a v i t y . C a l i b r a t i o n was d o n e
w i t h t h e d i s c c a v i t y r o t a t i n g a t 5 0 0 0 rpm. V a r i a t i o n s i n t h e
d i a m e t e r o f t h e f l u i d s u r f a c e as a f u n c t i o n o f r o t a t i o n a l speed
w e r e f o u n d t o be n e g l i g i b l e . The d e t e c t o r b l o c k was a l i g n e d t o t h e
5 m l - p o s i t i o n o f t h e d i s c c a v i t y by p l a c i n g 5 m l o f w a t e r i n t h e
c a v i t y , a n d a d j u s t i n g t h e d e t e c t o r b l o c k p o s i t i o n u n t i l a maximum
a t t e n u a t i o n o f t h e l i g h t beam was o b s e r v e d i n d i c a t i n g s c a t t e r i n g
b y t h e m e n i s c u s . F o r a s p i n f l u i d v o l u m e o f 15 m l w i t h t h e
d e t e c t o r at the 5 m l - p o s i t i o n
15 m l y i e l d a n d R^ o
a n
f l u i d v o l u m e , V, t h e s e m e a s u r e d r a d i i , a t 5 a n d 15 m l , ^ ^ ^
R a r e u s e < t o e o m e t r c a
15 1 * g i l l y c a l c u l a t e t h e r a d i u s , R^, o f t h e
f l u i d surface using equation (2).

A d e r i v a t i o n of equation ( 2 ) i s shown i n t h e Appendix.

D a t a S y s t e m . An IBM-PC d e s k t o p c o m p u t e r i s i n t e r f a c e d t o t h e
i n s t r u m e n t c o n t r o l module t o p r o v i d e a u t o m a t e d d a t a c o l l e c t i o n and
a n a l y s i s . The d a t a c o l l e c t i o n a n d a n a l y s i s p r o g r a m s a r e menu
d r i v e n . A d a t a management f a c i l i t y i s a n i n t e g r a l p a r t o f t h e d a t a
system. A modeling u t i l i t y i s provided t o a i d the operator i n
chosing the o p e r a t i n g c o n d i t i o n s ( r o t a t i o n a l speed, s p i n f l u i d
v o l u m e , f l u i d d e n s i t y , e t c . ) f o r a s a m p l e . Programming i s done i n
c o m p i l e d BASIC and t h e 8087 math c o p r o c e s s o r i s u s e d t o i m p r o v e
computational speed.
To i n i t i a t e a n a n a l y s i s r u n , t h e o p e r a t o r i n t e r a c t i v e l y
e n t e r s t h e e x p e r i m e n t a l p a r a m e t e r s and s a m p l e i d e n t i f i c a t i o n
t h r o u g h t h e c o m p u t e r k e y b o a r d . When t h e s a m p l e i n j e c t i o n i s made
t h e o p e r a t o r s i g n a l s t h e c o m p u t e r t o b e g i n d a t a c o l l e c t i o n by
p u s h i n g a b u t t o n l o c a t e d o n t h e d e t e c t o r b l o c k . The r a w d a t a a r e
p l o t t e d on t h e computer s c r e e n i n r e a l t i m e d u r i n g d a t a
c o l l e c t i o n . The o p e r a t o r e n d s d a t a c o l l e c t i o n b y u s e o f a f u n c t i o n
k e y o n t h e c o m p u t e r k e y b o a r d . O p t i o n a l l y , t h e c o m p u t e r c a n be s e t
to stop data c o l l e c t i o n at a predetermined t i m e .
D a t a a n a l y s i s i s i n t e r a c t i v e . The o p e r a t o r c a n c o n t r o l t h e
s l o p e s e n s i t i v i t y of a computer s e l e c t e d b a s e l i n e , o r can manually
c h o o s e a b a s e l i n e by means o f a c r o s s h a i r c u r s o r o n t h e raw d a t a
d i s p l a y . When t h e c a l c u l a t i o n i s c o m p l e t e d , t h e r e s u l t s a r e
d i s p l a y e d on t h e s c r e e n . P l o t s o f t h e raw d a t a , and o f t h e number,
w e i g h t a n d s u r f a c e d i f f e r e n t i a l a n d c u m u l a t i v e d i s t r i b u t i o n c a n be
d i s p l a y e d on t h e s c r e e n and p r i n t e d a t t h e o p e r a t o r s o p t i o n .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
184 PARTICLE SIZE DISTRIBUTION

A d a t a management s y s t e m i s a n i n t e g r a l p a r t o f t h e p r o g r a m .
T h i s a l l o w s t h e o p e r a t o r t o s t o r e e x p e r i m e n t a l d a t a on t h e
c o m p u t e r ' s d i s k s and t o r e a n a l y z e s t o r e d d a t a , o r t o s i m p l y r e v i e w
r e s u l t s without r e a n a l y s i s . Using the c u r s o r c o n t r o l s , the
o p e r a t o r c a n s e l e c t s t o r e d r u n s f r o m t h e menu a n d p r i n t t h e
r e s u l t s f o r t h o s e r u n s i n t a b u l a r f o r m . S e l e c t e d r u n s c a n be
deleted i n a similar fashion.

Results

The r a w d a t a t r a c e f o r a m i x t u r e o f 6 s t a n d a r d p o l y s t y r e n e l a t e x
m i c r o s p h e r e s i s s h o w n i n F i g u r e 2. T h i s s e p a r a t i o n was d o n e i n 20
m i n u t e s a t 1 0 , 4 5 0 rpm. W h i l e p a r t i c l e s i z e d a t a i n t h e f i r s t f e w
m i n u t e s i s d i f f i c u l t t o q u a n t i t a t e a c c u r a t e l y w i t h t h e DCP, this
s e p a r a t i o n demonstrates the r e s o l u t i o n c a p a b i l i t y of the
i n s t r u m e n t . F i g u r e s 3-7 s h o typical data d number surfac
and w e i g h t d i f f e r e n t i a
by t h e d a t a s y s t e m a l o n
D a t a f r o m a number o f d i f f e r e n t p a r t i c l e s i z e a n a l y s i s
i n s t r u m e n t a l methods i n c l u d i n g l i g h t s c a t t e r i n g , f i e l d f l o w
f r a c t i o n a t i o n , h y d r o d y n a m i c c h r o m a t o g r a p h y and m i c r o s c o p y were
o b t a i n e d f o r a s e r i e s o f p o l y m e t h y l m e t h a c r y l a t e l a t e x e s and were
c o m p a r e d t o DCP r e s u l t s ( 2 ) . T h e s e a n d o t h e r c o m p a r a t i v e results
h a v e d e m o n s t r a t e d t h e a c c u r a c y o f t h e i n s t r u m e n t a n d m e t h o d . The
r e p r o d u c i b i l i t y and p r e c i s i o n o f t h e i n s t r u m e n t a l s o were s t u d i e d
and a r e r e p o r t e d e l s e w h e r e
The i n s t r u m e n t h a s p r o v e n t o be e x t r e m e l y r e l i a b l e t h r o u g h
many i n s t r u m e n t - y e a r s o f s e r v i c e i n o u r l a b o r a t o r i e s . R o u t i n e
maintenance c o n s i s t s o n l y o f an annual o i l change f o r the t r a c t i o n
drive.

Conclusions

T h i s i m p r o v e d i n s t r u m e n t and t h e d a t a s y s t e m p r o v i d e an a c c u r a t e
r e l i a b l e means o f p a r i c l e s i z e a n a l y s i s o f l a t e x m a t e r i a l s o v e r a
w i d e r a n g e o f sample t y p e s and s i z e s .

Appendix

The f l u i d v o l u m e i s t h e d i f f e r e n c e b e t w e e n t h e v o l u m e s o f t h e two
c y l i n d e r s o f t h e same h e i g h t h a v i n g t h e r a d i i o f t h e o u t e r a n d
i n n e r s u r f a c e s o f t h e f l u i d and i s g i v e n by

h R
v
fiuid * l - i>

w h e r e Rg i s t h e o u t e r r a d i u s , R^ i s t h e i n n e r r a d i u s , a n d h i s t h e
h e i g h t of the c y l i n d r i c a l s e c t i o n . S u b s t i t u t i n g f o r the case of
t h e two m e a s u r e d r a d i i a t f l u i d v o l u m e s o f 5ml a n d 15ml y i e l d s

v i 5 , a i 5 m i i T h R R )
fiui - d - - ( L- Li
w h i c h c a n be solved for h as

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
KOEHLER ET AL. Improved Disc Centrifuge Photosedimentometer

3
2| 4

8 10 12 14 16 18 20 22

MINUTES
F i g u r e 2. Raw D a t a T r a c e f o r a M i x t u r e o f S i x P o l y s t y r e n e
Latexes 1 - 1.091 , 2 - 0.822 y m , 3 - 0.600 y m , 4 - 0.497 y m ,
5 - 0.357 y m , 6 - 0.176 y m , S p i n F l u i d V o l u m e 15 m l , D i s c S p e e d
10,450 r p m .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
186 PARTICLE SIZE DISTRIBUTION

Sanple ID: ps nix


Operator: mh
Run Nimbe r : 9999 Job NtiNbei: 53
Date Run: 82-12-1986 Tine Run: 89:13:15

F i g u r e 3. Plot f r o m DCP-1000 D a t a System Raw D a t a with


Baseline.

.8 H L
1/

i!
I / \
/ \

i I
A
/ \
/ \
1 ^ 1*- i

.4 .6 1.1 .2 1.3 1.4


DIAMETER (urn)

Sanple ID: ps nix


Operator: mh
Run Nimber: 9999 Job Nimber: 53
Date Run: 82-12-1986 Tine Run: 89:13:15
Range: .5823 to 1.2283 UM

F i g u r e 4. Plot f r o m D C P - 1 0 0 0 D a t a S y s t e m - Number Distribution.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
12. KOEHLER ET AL. Improved Disc Centrifuge Photosedimentometer 187

.8

7
.6
0
h
h
.4

L
.2

DftMETER (um)

Sample ID: ps nix


Operator: mh
Run Nimber: 9999 Job Number: 53
Date Run: 82-12-1986 Tine Run: 89:13:15
Range: .5823 to 1.2283

F i g u r e 5. Plot f r o m DCP-1000 D a t a S y s t e m - Surface


Distribution.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
188 PARTICLE SIZE DISTRIBUTION

! y
h
1 * .4

f / \
/ /1
/ /I /
/ / ) / \
2 ' /
/ /
/ /
/ /
JcL -
.4 .5 .8 .9 1.1 1.2 1.3 1.4
f. \
tr

Sample ID: ps nix


Operator: mh
Run Number: 9999 Job Number: 53 1
Date Run: 82-12-1986 Tine Run: 89:13:15 j
Range: .5823 to 1.2283 UN
1

F i g u r e 6. Plot f r o m DCP-1000 Data System - Weight Distribution.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
12. KOEHLER ET AL. Improved Disc Centrifuge Photosedimentometer 189

SAMPLE ID: ps mix

OPERATOR: rmh

RUN 9999 JOB 53

DATE RUN: 02-12-1986 TIME RUN: 09:13:15

ANALYSIS RESULTS

STD DEV

NUMBER AVERAGE (Dn) 0.608


SURFACE AREA AVERAGE <Ds
WEIGHT AVERAGE (Dw) 0.6907 urn

TURBIDITY AVERAGE (Dt) 0.7387 urn


PCS AVERAGE (Dp) 0.7912 urn

POLYDISPERSITY (Dw/Dn) 1.1358


SPECIFIC SURFACE 87307 cm*/g

RUN PARAMETERS

DISC SPEED 4033 RPM


PARTICLE DENSITY 1.05 q/cm 3
TEMPERATURE 20 C
SPIN FLUID WATER SPIN FL VOL 15 ml
SPIN FL DENSITY .9982 q/cm 3
SPIN FL VIS 1.002

BASELINE PARAMETERS

SLOPE -.0021 v/min INTERCEPT .1826


STARTING TIME 2.25 min ENDING TIME 13.45 min
HIGH DIAMETER 1.2283 urn LOW DIAMETER .5023 urn
CURVE AREA 1.3232 v-min

NOTE LINE

a f t e r another r e a l l i g n m e n t a l a MEK

Figure 7. R e p o r t f r o m DCP-1000 D a t a System.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
190 PARTICLE SIZE DISTRIBUTION

1 0 m l
h - . , (A-3)

F o r a n y o t h e r v o l u m e , V, h a v i n g r a d i u s R j a t t h e f l u i d s u r f a c e ,
one c a n t h e n u s e h a n d one o f t h e measured r a d i i , > t o solve
f o r Rj^ a s f o l l o w s ,

" tTP R2 ( R
7 I 5i * R
i> ( A
" A )

( R R )
^ 5 m l 15ml

10m

2 2
/V - 5 m l \ ,2 2 . ,.
R
5ml " R
l " (^-lmT-j ( R
5ml " 15ml R ) ( A
" 6 )

2 / V - 5 m l \ .2 2 .11/2 ( A.. 6 )
\ " l 5ml Wj "
0

R
" ^lS-) 5ml ( R
"

yielding e q u a t i o n 2

Literature Cited

1. Holsworth, R. M.; Provder, T . ; Stansbrey, J. J. "A Novel


External Gradient Formation Method for Disc Centrifuge Photo-
sedimentometry Particle Size Distribution Analysis" This
Volume.
2. Koehler, M. E.; Provder, T. "Comparative Particle Size
Analysis" This Volume.
3. Koehler, M. E.; Provder, T.; Zander, R. A. U. S. Patent
4 311 039, 1982.
4. Holsworth, R. M.; Provder, T. U. S. Patent 4 478 073, 1985.

RECEIVED October 6, 1986

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 13

External-Gradient-Formation Method
for Disc Centrifuge Photosedimentometric Particle Size
Distribution Analysis
R. M. Holsworth, Theodore Provder, and J. J. Stansbrey
The Glidden Company, DwightP.Joyce Research Center, Strongsville,OH44136

A novel and alternative method for making centrifugal


disc photosedimentometric analyses has been developed
which allows simplificatio f previou method
including an industr
Line Start. In thi spi y
gradient is formed external to the disc cavity and
injected into the disc cavity while the disc is
spinning at a predetermined speed. The externally
formed spin fluid contains at least two miscible or
partially miscible liquids of different densities in a
substantially incompletely mixed condition. The
External Gradient Method is evaluated and statistically
compared to the Buffered Line Start method of analysis
using a variety of particle sizes and latex types. The
results of the statistical analysis are discussed
relative to method type, sample type and size range,
temperature and other operational variables.

The d i s c c e n t r i f u g e p h o t o s e d i m e n t o m e t e r ( D C P ) h a s p r o v e d t o b e a n
e x c e l l e n t instrument f o r providing p a r t i c l e s i z e and p a r t i c l e s i z e
d i s t r i b u t i o n i n f o r m a t i o n t o pigment and l a t e x manufacturers and
c o a t i n g s f o r m u l a t o r s . T h e DCP o p e r a t e s b y f o r c i n g p a r t i c l e s r a d i a l l y
outward through a s p i n f l u i d under h i g h c e n t r i f u g a l f o r c e . As they
move o u t w a r d l y t h e p a r t i c l e s a r e s e p a r a t e d b y s i z e a n d / o r d e n s i t y .
At a s p e c i f i c r a d i a l d i s t a n c e t h e moving p a r t i c l e s i n t e r r u p t and
a t t e n u a t e a l i g h t beam, t h e i n t e n s i t y o f w h i c h i s m e a s u r e d b y a
p h o t o d e t e c t o r . The p a r t i c l e s i z e i s r e l a t e d t o t h e appearance time
1
a t t h e p h o t o d e t e c t o r b y means o f S t o k e s L a w f o r c e n t r i f u g a t i o n . T h e
c o n c e n t r a t i o n o f p a r t i c l e s i s obtained from the photodetector
response and the a p p l i c a t i o n o f Mie s c a t t e r i n g t h e o r y . Q ) A very
important step i n t h i s operation i s the formation o f a density
gradient within the spin f l u i d t o allow a hydrodynamically stable
s e p a r a t i o n o f t h e suspended p a r t i c l e s . An a c c e p t e d method f o r
forming t h i s spin f l u i d density gradient within the disc cavity i s
the w i d e l y used and patented ( 2 ) J o y c e - L o e b l B u f f e r e d L i n e S t a r t

0097-6156/87/0332-0191$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
192 PARTICLE SIZE DISTRIBUTION

( B L S ) . T h i s p a p e r d e s c r i b e s a n o v e l and a l t e r n a t i v e m e t h o d f o r
p e r f o r m i n g DCP a n a l y s e s a n d i n p a r t i c u l a r a new p r o c e d u r e f o r t h e
f o r m a t i o n of the s p i n f l u i d d e n s i t y g r a d i e n t e x t e r n a l to the DCP
d i s c . T h i s new p a t e n t e d m e t h o d ( 3 ) , k n o w n a s t h e E x t e r n a l G r a d i e n t
M e t h o d ( E G M ) , w i l l be c o m p a r e d t o t h e BLS m e t h o d o f a n a l y s i s . The
q u a n t i t a t i v e p r e c i s i o n o f t h e r e s u l t s o b t a i n e d w i t h EGM a n d BLS w i l l
be c o m p a r e d by s t a t i s t i c a l a n a l y s i s . I n a d d i t i o n , q u a l i t a t i v e
a d v a n t a g e s o f t h e EGM o v e r t h e BLS m e t h o d w i l l be g i v e n .

M a t e r i a l s and Methods

The d i s c c e n t r i f u g e u s e d i n t h i s s t u d y h a s b e e n d e s c r i b e d p r e v i o u s l y
(4^5) ( A c o m m e r c i a l v e r i s o n o f t h e i n s t r u m e n t i s now a v a i l a b l e f r o m
B r o o k h a v e n I n s t r u m e n t s C o r p o r a t i o n , R o n k o n k o m a , NY, a s t h e B r o o k -
h a v e n DCP-1000 P a r t i c l e S i z e A n a l y z e r . ) The l a t e x e s u s e d i n t h i s
s t u d y a r e m o n o d i s p e r s e Do polystyren late standard coverin
r a n g e o f s i z e s a n d two c o m m e r c i a
b o t h o f w h i c h had a b r o a d e
standards. A l l of the l a t e x sample p r e p a r a t i o n s analyzed i n the
s t a t i s t i c a l s t u d y were p r e p a r e d i n a s i m i l a r manner. A l l the f l u i d s
w e r e h e l d i n a t h e r m o s t a t i c a l l y c o n t r o l l e d t e m p e r a t u r e b a t h a t 25C.
The t e m p e r a t u r e s a t t h e b e g i n n i n g and end o f e a c h r u n w e r e r e c o r d e d .
F o r t h e EGM a h y p o d e r m i c s y r i n g e w i t h a v o l u m e u s u a l l y g r e a t e r
than t h a t of the t o t a l s p i n f l u i d , i s used to form the d e n s i t y
g r a d i e n t e x t e r n a l t o the d i s c c a v i t y . For example, i f a t o t a l s p i n
f l u i d o f 15 m l i s u s e d i n t h e a n a l y s i s , 15 m l o f t h e m o r e d e n s e
f l u i d i s drawn i n t o t h e s y r i n g e f o l l o w e d by 1 ml o f t h e l e s s d e n s e
f l u i d . A t t h i s p o i n t t h e s y r i n g e c o n t a i n s two i n c o m p l e t l y m i x e d
m i s c i b l e l i q u i d s . This d e n s i t y g r a d i e n t , thus formed, i s i n j e c t e d
i n t o the c a v i t y of the s p i n n i n g d i s c r e s u l t i n g i n a s p i n
f l u i d / d e n s i t y g r a d i e n t ready f o r sample i n j e c t i o n .
F o r t h e B L S , 15 m l o f s p i n f l u i d ( d e i o n i z e d ( D I ) w a t e r ) w e r e
i n t r o d u c e d , p a r t l y f i l l i n g the d i s c c a v i t y . Then, 1 ml o f a 50%
m e t h a n o l - w a t e r s o l u t i o n , b u f f e r f l u i d , was a d d e d w h i l e t h e
c e n t r i f u g e was r u n n i n g . The d i s c was d e c e l e r a t e d f o r 0.40 to 0.60
s e c o n d s , d e p e n d i n g o n t h e s a m p l e , and r e a c c e l e r a t e d t o f o r m t h e
d e n s i t y g r a d i e n t w i t h i n t h e new s p i n f l u i d . The s a m p l e s w e r e made up
i n 5 0 % m e t h a n o l - w a t e r s o l u t i o n ; 2 d r o p s o f l a t e x t o 25 m l o f
s o l u t i o n . The amount o f s a m p l e i n j e c t e d i n t o t h e d i s c c a v i t y v a r i e d
f r o m 0,20 t o 0.40 m l , d e p e n d i n g o n t h e s a m p l e . F o r t h e p a r t i c l e
s i z e s and p a r t i c l e d e n s i t i e s i n v o l v e d , t h e d i s c s p e e d o f 4 0 0 0 rpm
was c o n v e n i e n t and u s e d f o r a l l r u n s . F o r t h e EGM, the c o n d i t i o n s
w e r e i d e n t i c a l , e x c e p t t h a t t h e f i n a l s p i n f l u i d was c r e a t e d i n t h e
s y r i n g e , u s i n g 15ml o f DI w a t e r and 1ml o f 100% m e t h a n o l , b e f o r e
b e i n g i n j e c t e d i n t o t h e d i s c c a v i t y . The s a m p l e s w e r e p r e p a r e d and
i n t r o d u c e d i n t o t h e d i s c c a v i t y t h e same way f o r b o t h m e t h o d s .
The d a t a f o r e a c h r u n w e r e a c q u i r e d and s t o r e d e v e r y 5 s e c o n d s
by a d e d i c a t e d m i c r o p r o c e s s o r . A t t h e c o m p l e t i o n o f a r u n t h e
a c c u m u l a t e d d a t a w e r e s e n t t o a D i g i t a l PDP-11/44 m i n i c o m p u t e r f o r
c o m p u t a t i o n and r e p o r t i n g . The b a s e l i n e was a u t o m a t i c a l l y d e t e r m i n e d
by the a n a l y s i s s o f t w a r e . These r e s u l t s were c r i t i c a l l y r e v i e w e d .
The b a s e l i n e was a d j u s t e d b y t h e o p e r a t o r , when n e c e s s a r y , and the
r e v i s e d d a t a c a l c u l a t e d . T h e s e r e s u l t s were computed on t h e b a s i s
o f t h e i n i t i a l s p i n f l u i d t e m p e r a t u r e o f 25C.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
13. HOLSWORTH ET AL. Disc Centrifuge Photosedimentometric Analysis 193

The a n a l y s e s o f v a r i a n c e a n d c o v a r i a n c e w e r e c a r r i e d o u t u s i n g
BMDP P 2 V . , BMDP S t a t i s t i c a l S o f t w a r e , 1 9 6 4 W e s t w o o d B l v d , s u i t e 2 0 2
L o s A n g e l e s , CA 9 0 0 2 5 .

Statistical Design

P r e l i m i n a r y s t u d i e s i n d i c a t e d t h a t t h e B L S a n d EGM g a v e v e r y s i m i l a r
r e s u l t s . To s u b s t a n t i a t e t h e s e r e s u l t s , a n e x p e r i m e n t a l d e s i g n was
s e t up t o compare t h e p e r f o r m a n c e o f t h e two methods w i t h a
r i g o r o u s , f o r m a l i z e d s e t o f e x p e r i m e n t s . The f a c t o r s c o n s i d e r e d were
( 1 ) t h e t w o m e t h o d s (METHOD), B L S a n d EGM, ( 2 ) t w o o p e r a t o r s
( O P E R A T O R ) , o n e w i t h e x p e r i e n c e , t h e o t h e r n e v e r h a v i n g u s e d EGM
b e f o r e , ( 3 ) two s i m i l a r d i s c c e n t r i f u g e photosedimentometers (DCP),
b o t h a t t h e same l o c a t i o n , a n d ( 4 ) t h r e e t y p i c a l l a t e x s a m p l e s
( S A M P L E ) ; #3, 0.497m_polystyrene_standard a n d #2, =0.282
(Dw/Dn=1.03) a n d #4, D w 0 . 3 8 6 p m ( D w / D n = l . 0 5 ) b o t h c o m m e r c i a l
latexes.
The e x p e r i m e n t a l d e s i g
p l u s two e x t r a r e p l i c a t e s p e r sample. E x c e p t f o r t h e f o u r
r e p l i c a t e s , r u n i n a d j a c e n t p a i r s , t h e o r d e r o f a l l t h e r u n s was
r a n d o m i z e d . T h i s r e s u l t e d i n 51 t o t a l r u n s f o r a n a l y s i s i n t h e
s t a t i s t i c a l design.
I t was n o t p r a c t i c a l t o i n c l u d e t i m e e x p l i c i t l y a s a f o u r t h
f a c t o r i n t h e e x p e r i m e n t a l d e s i g n . H o w e v e r , some i n f o r m a t i o n c o u l d
be o b t a i n e d o n t h i s b y c o m p a r i n g r e p l i c a t e s r u n a t random o v e r t h e
t o t a l t i m e o f t h e e x p e r i m e n t s w i t h t h o s e r u n i n p a i r s , one a f t e r t h e
o t h e r . T h e t o t a l t i m e s p a n f o r r u n n i n g t h e s e e x p e r i m e n t s was a
l i t t l e more t h a n a week. F o u r o f t h e r e p l i c a t e s f o r e a c h s a m p l e
were r u n i n random o r d e r o v e r t h i s p e r i o d , t h e n a second r e p l i c a t e
was p a i r e d w i t h i t a n d r u n i m m e d i a t e l y f o l l o w i n g t h e f i r s t . F i n a l l y ,
t h e l a s t r e p l i c a t e f o r e a c h s a m p l e was added a t random. T h e r e w e r e ,
t h e n , n i n e r e p l i c a t e s s p r e a d a t random t h r o u g h o u t t h e p e r i o d , u s i n g
the f i r s t o f each o f t h e p a i r e d r e p l i c a t e s . There were, a l s o , e i g h t
p a i r e d r e p l i c a t e s r u n one a f t e r t h e o t h e r . The v a r i a n c e s o f t h e s e
two s e t s o f r e p l i c a t e s f o r a l l t h e s a m p l e s w e r e t h e n c o m p a r e d . The
r e s u l t s i n d i c a t e t h a t a b s o l u t e l y n o e f f e c t was d i s c e r n a b l e b e t w e e n
t h e r e p l i c a t e s t h a t were r u n a t random t i m e s and t h o s e t h a t were r u n
in pairs.
These r e s u l t s were a n a l y z e d u s i n g b o t h A n a l y s i s o f V a r i a n c e and
a n a l y s i s o f c o v a r i a n c e w i t h t h e change i n temperature d u r i n g t h e
run, used as t h e c o v a r i a t e . S t a t i s t i c a l l y , t h i s i s a f i x e d - e f f e c t
model e x c e p t f o r t h e c o v a r i a t e w h i c h i s random. A n a l y s e s were a l s o
c a r r i e d o u t on t h e i n d i v i d u a l samples, b u t t h e c o n c l u s i o n s and
r e s i d u a l mean s q u a r e s w e r e e s s e n t i a l l y t h e same a s f o r t h e s a m p l e s
combined

R e s u l t s and D i s c u s s i o n

The s i m p l i c i t y o f o p e r a t i o n o f t h e EGM a n d i t s a c c u r a c y a r e b e s t
s e e n b y c o m p a r i n g p a r t i c l e s i z e d i s t r i b u t i o n c u r v e s b y t h e EGM a n d
t h e BLS method and comparing d a t a o b t a i n e d from b o t h methods. F i g u r e
1 shows t h e s e p a r a t i o n o f t h r e e l a t e x s t a n d a r d s b y t h e BLS m e t h o d .
T w e n t y m l o f w a t e r was u s e d a s s p i n f l u i d a n d 1 m l o f 5 0 % ( V / V ) _^
m e t h a n o l a s a d e n s i t y b u f f e r . A 0.25 m l s a m p l e o f d i l u t e l a t e x ( 1 0

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
194 PARTICLE SIZE DISTRIBUTION

w
t o 10 g/1) was a n a l y z e d a t a d i s c s p e e d o f 3 5 8 6 rpm. I t I s o b v i o u s
t h a t t h e s t a n d a r d s a r e s e p a r a t e d w i t h b a s e l i n e r e s o l u t i o n and t h a t
t h e r e p r o d u c i b i l i t y i s v e r y g o o d . The EGM s e p a r a t i o n o f t h e same
l a t e x s a m p l e , s h o w n i n F i g u r e 2, a l s o h a s e x c e l l e n t b a s e l i n e r e s o l u
t i o n and r e p r o d u c i b i l i t y . The s p i n f l u i d c o n s i s t e d o f 11 m l o f w a t e r
t o p p e d by a d e n s i t y g r a d i e n t m o d i f i e r c o n s i s t i n g o f 9 m l o f w a t e r
and 1 ml o f m e t h a n o l . The s a m p l e s i z e was 0.25 m l a n d t h e d i s c s p e e d
was 3 5 8 6 r p m e P a r t i c l e s i z e d i s t r i b u t i o n s shown i n F i g u r e 3 r e v e a l
t h a t s i z e s e p a r a t i o n b y t h e two m e t h o d s i s v i r t u a l l y i d e n t i c a l .
F i g u r e 4 shows t h e r e s u l t s o b t a i n e d on a n o t h e r s a m p l e c o n t a i n i n g
f o u r d i f f e r e n t s t a n d a r d l a t e x e s w i t h p a r t i c l e s i z e s o f 1.091, 0.822,
0 . 6 0 0 a n d 0.497, u s i n g a s p i n f l u i d o f 11 m l o f w a t e r t o p p e d w i t h
an e x t e r n a l g r a d i e n t o f 9 m l o f w a t e r and 1 m l o f m e t h a n o l and a
d i s c s p e e d o f 3 5 8 6 rpm. P e a k a p p e a r a n c e t i m e s o f 3.6 m i n u t e s , 7.1
m i n u t e s , 12.5 m i n u t e s and 19 m i n u t e s c o r r e s p o n d t o c a l c u l a t e d
p a r t i c l e s i z e values of
r e s p e c t i v e l y , which are
v a l u e s of the standards
R e s u l t s o b t a i n e d on two d i f f e r e n t s a m p l e s c o n t a i n i n g t h e f o u r
l a t e x e s m e n t i o n e d above p l u s an a d d i t i o n a l p o l y s t y r e n e l a t e x
s t a n d a r d , n a m e l y 0.357um, a r e s h o w n i n F i g u r e 5. U s i n g t h e same
p r o c e d u r e d e s c r i b e d p r e v i o u s l y , i n f o u r s e p a r a t e e x p e r i m e n t s and
u s i n g d i s c s p e e d s o f 4 0 0 4 , 6 0 1 5 , 8 0 5 7 , a n d 1 0 , 1 6 0 rpm, a d i s t i n c t
s e p a r a t i o n of the standards i s seen over t h i s wide range of A n a l y z e r
d i s c speeds.
F i g u r e 6 shows t h e s e p a r a t i o n o f t h e l a t e x m i x t u r e shown i n
F i g u r e 5 i n c l u d i n g a n a d d i t i o n a l 0.176 p o l y s t y r e n e s t a n d a r d . I n
t h i s case, the e x t e r n a l l y prepared s p i n f l u i d / d e n s i t y g r a d i e n t
c o n s i s t e d o f 15 m l o f w a t e r a n d 1 m l o f m e t h a n o l and t h e d i s c s p e e d
was 1 0 , 4 5 0 rpm. B a s e l i n e s e p a r a t i o n a n d p e a k r e s o l u t i o n a r e o b t a i n e d
o v e r a d e c a d e o f s i z e r a n g e i n l e s s t h a n 25 m i n u t e s .
The EGM h a s s e v e r a l a d v a n t a g e s o v e r t h e B L S : i m p r o v e d s p i n f l u i d
d e n s i t y g r a d i e n t s t a b i l i t y a t h i g h d i s c s p e e d s , e . g . , 8,000 rpm t o
1 0 , 0 0 0 rpm; s u c c e s i v e s a m p l e i n j e c t i o n w i t h o u t c h a n g i n g s p i n f l u i d ,
and t h e c a p a b i l i t y t o c h a n g e d i s c s p e e d s d u r i n g r e p e a t e d injection
without d e s t r o y i n g the s p i n f l u i d / d e n s i t y g r a d i e n t e f f e c t i v e n e s s .
F o r e x a m p l e , d i s c s p e e d s c o u l d be c h a n g e d f r o m 3,000 t o 4 , 0 0 0 , 4,000
t o 5 , 0 0 0 , a n d 5,000 t o 6,000 rpm w i t h o u t u p s e t t i n g t h e d e l i c a t e l y
balanced s p i n f l u i d d e n s i t y g r a d i e n t needed f o r e f f e c t i v e p a r t i c l e
s i z e a n a l y s i s . T h i s c a n n o t be d o n e w i t h t h e B L S . N o t e t h a t f o r
q u a n t i t a t i v e a c c u r a c y m i n o r v o l u m e c h a n g e s n e e d t o be a c c o u n t e d f o r
a f t e r repeat i n j e c t i o n . However, f o r q u a l i t a t i v e a n a l y s i s or
" f i n g e r p r i n t i n g " t h i s procedure i s acceptable.
Subsequent experiments u s i n g dodecane (6) to i n h i b i t e v a p o r a t i v e
c o o l i n g a t t h e s p i n f l u i d / a i r i n t e r f a c e have d e m o n s t r a t e d e v e n more
i m p r o v e m e n t i n b a s e l i n e s t a b i l i t y and r u n - t o - r u n reproducibility
when u s i n g t h e EGM.

Statistical Analysis

T e m p e r a t u r e c o n t r o l i s an i m p o r t a n t f a c t o r i n d e t e r m i n i n g p a r t i c l e
s i z e by s e d i m e n t a t i o n m e t h o d s . D u r i n g a t y p i c a l r u n c h a n g e s i n s p i n
f l u i d t e m p e r a t u r e o f 2-4C w e r e common. T h i s t e m p e r a t u r e c h a n g e
( D E L T E M P ) was u s e d a s t h e c o v a r i a t e i n t h e a n a l y s i s o f c o v a r i a n c e .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
HOLSWORTH ET AL. Disc Centrifuge Photosedimentometric Analysis

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
196 PARTICLE SIZE DISTRIBUTION

LU
CO


a.
CO
LU
oc
ce

h-

LU

LU

TIME

F i g u r e 3. C o m p a r i s o n o f t h e DCP s e p a r a t i o n o f t h r e e l a t e x
s t a n d a r d s b y t h e B L S a n d EGM m e t h o d s a s s e e n i n F i g . l a n d F i g . 2 .

UD9IST .822Sill .600S7TX .497 sm


I.H2CALC .ei3CH. .6I3CALC .497CAl.

TIME

35S6RPM IIML WIER+(9ML WTER+IML MeOH)


I/4ML SAMPLE (POLYSTYRENE LATEX STANDARDS t

F i g u r e 4. DCP s e p a r a t i o n o f f o u r l a t e x s t a n d a r d s b y t h e EGM
method showing n o m i n a l s t a n d a r d and c a l c u l a t e d v a l u e s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
13. HOLSWORTH ET AL. Disc Centrifuge Photosedimentometric Analysis 197

I I 4004 RPM

2 4 6 6 0 * > 2 14 6 6 2 4 6 2 4 6 8
T I M E IN M I N U T E S +

F i g u r e 5 DCP s e p a r a t i o n o f s t a n d a r d latexes at four different


d i s c s p e e d s b y t h e EGM m e t h o d .

2 4 6 8 2 6 8 2 0 2 2
TIME IN MINUTES
10,450 RPM
I5ML SPIN FLUID VOLUME

F i g u r e 6. DCP s e p a r a t i o n o f l a t e x standards covering a decade o f


s i z e r a n g e b y t h e EGM m e t h o d .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
198 PARTICLE SIZE DISTRIBUTION

The m a g n i t u d e o f t h e t e m p e r a t u r e c h a n g e seemed t o h a v e n o e f f e c t .
The r e s u l t s w e r e a l m o s t i d e n t i c a l when t h e r u n s w i t h l a r g e
t e m p e r a t u r e e x c u r s i o n s were removed.
Analyses of_covariance f o r both t u r b i d i t y weight-average
p a r t i c l e s i z e (Dw) a n d p o l y d i s p e r s i t y (Dw/Dn) ( D n , n u m b e r - a v e r a g e
p a r t i c l e s i z e ) w e r e c a r r i e d o u t . The T a b l e s I a n d I I s h o w t h e
r e s u l t s f o r the t h r e e samples combined.

TABLE I . A N A L Y S I S OF COVARIANCE FOR P A R T I C L E S I Z E

Source ( a )
Degrees of Sum o f Mean F Tail Regression
Freedom Squares Square Prob. Coefficient

OPERATOR 1 712.6 712.6 0.27 0.6067


SAMPLE 2 13472409.6 6736204.8 2550.83 0.0000
DCP 1 17398.
METHOD 1 9005.
OS 2 50763.4 25381.7 9.61 0.0005
OD 1 1313.9 1313.9 0.50 0.4852
SD 2 65119.9 32560.0 12.33 0.0001
OM 1 2443.6 2443.6 0.93 0.3427
SM 2 28501.4 14250.7 5.40 0.0091
DM 1 1297.9 1297.9 0.49 0.4879
DELTEMP 1 128648.5 128648.5 48.72 0.0000 31.80684
ERROR 35 92427.7 2640.8

TOTAL 50 13870041.9

( a ) T h e i n t e r a c t i o n e f f e c t s a r e : OS, OPERATOR-SAMPLE; OD,


OPERATOR-DCP; SD, SAMPLE-DCP; OM, OPERATOR-METHOD; SM,
SAMPLE-METHOD; DM, DCP- METHOD.

TABLE I I . A N A L Y S I S OF COVARIANCE FOR P O L Y D I S P E R S I T Y

Source ( a )
Degrees of Sum o f Mean F Tail Regression
Freedom Squares Square Prob. Coefficient

OPERATOR 1 0.00039 0.00039 9.39 0.0042


SAMPLE 2 0.00834 0.00417 100.51 0.0000
DCP 1 0.00015 0.00015 3.54 0.0681
METHOD 1 0.00006 0.00006 1.53 0.2249
OS 2 0.00003 0.00002 0.37 0.6903
OD 1 0.00001 0.00001 0.19 0.6677
SD 2 0.00002 0.00001 0.23 0.7952
OM 1 0.00003 0.00003 0.70 0.4089
SM 2 0.00013 0.00007 1.62 0.2128
DM 1 0.00002 0.00002 0.59 0.4476
DELTEMP 1 0.00003 0.00003 0.73 0.3982 -0.00049
ERROR 35 0.00145 0.00004

TOTAL 50 0.01066

( a ) See T a b l e I f o r d i s c r i p t i o n s o f t h e i n t e r a c t i o n terms.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
13. HOLSWORTH ET AL. Disc Centrifuge Photosedimentometric Analysis 199

P o o l i n g t h e n o n - s i g n i f i c a n t sums o f s q u a r e s w i t h t h e residuals
in the c o v a r i a n c e t a b l e s above does not change the conclusions.
The i m p o r t a n t e f f e c t s c o n s i d e r e d h e r e a r e t h e METHOD and the
ERROR. The two M e t h o d s a r e n o t s i g n i f i c a n t l y d i f f e r e n t f o r e i t h e r
t h e p a r t i c l e s i z e o r t h e p o l y d i s p e r s i t y . The ERROR t e r m , a s w i l l be
s h o w n l a t e r , i s v e r y n e a r l y t h e same a s t h e r e p l i c a t i o n e r r o r .
The c o v a r i a t e , DELTEMP, i s h i g h l y s i g n i f i c a n t i n t h e
d e t e r m i n a t i o n of the P a r t i c l e S i z e . T h i s i n d i c a t e s t h a t temperature
c o n t r o l , f r o m the s t a t i s t i c a l p o i n t of v i e w , i s more i m p o r t a n t t h a n
has been p r e v i o u s l y c o n s i d e r e d . T h i s i s not s u r p r i s i n g p h y s i c a l l y ,
i n v i e w of the temperature dependence of the s p i n f l u i d v i s c o s i t y
and t h e d e n s i t y t e r m s c o n t a i n e d i n S t o k e s ' Law. The c o o l i n g capacity
o f t h e two DCPs w e r e k n o w n t o be d i f f e r e n t . B o t h i n s t r u m e n t s h a d
been p h y s i c a l l y r e c a l i b r a t e d p r i o r to r u n n i n g these e x p e r i m e n t s .
Y e t , t h e r e i s some e f f e c t u n a c c o u n t e d f o r i n t h e p a r t i c l e s i z e
a n a l y s i s t h a t l e a v e s th instrument statisticall somewha
different.
The t h r e e s a m p l e s s t a t i s t i c a l l y y
p a r t i c l e s i z e and p o l y d i s p e r s i t y . I n t h e c a s e o f t h e p a r t i c l e s i z e
d e t e r m i n a t i o n , t h e t w o - f a c t o r i n t e r a c t i o n s i n v o l v i n g t h e SAMPLE w e r e
a l l s i g n i f i c a n t , i n c l u d i n g t h e SAMPLE-METHOD i n t e r a c t i o n . R u n n i n g
t h e s a m p l e s i n d i v i d u a l l y d o e s n o t i n d i c a t e why t h i s m i g h t b e .
H o w e v e r , as n o t e d b e l o w , t h e e f f e c t s o b s e r v e d may be t h e r e s u l t o f
d i f f e r e n t o p e r a t o r t r a i n i n g , e s p e c i a l l y i n d e t e r m i n i n g the
b a s e l i n e s . Yet, from p r a c t i c a l c o n s i d e r a t i o n s , the f i n a l v a r i a t i o n s
are s t i l l a c c e p t a b l y s m a l l .
F o r p o l y d i s p e r s i t y , a s m i g h t be e x p e c t e d , SAMPLE was highly
s i g n i f i c a n t l y d i f f e r e n t . T e m p e r a t u r e , as s h o w n b y t h e v e r y
n o n - s i g n i f i c a n t c o v a r i a t e t e r m , h a s a n e g l i g i b l e e f f e c t on the
d e t e r m i n a t i o n of p o l y d i s p e r s i t y . However, f o r t h i s s e t of d a t a the
o p e r a t o r s were s i g n i f i c a n t l y d i f f e r e n t . T h i s i s p o s s i b l y r e l a t e d to
t h e i n d i v i d u a l j u d g e m e n t t h e o p e r a t o r s make i n r e p o s i t i o n i n g the
b a s e l i n e . I f t h i s i s c o r r e c t , t h i s e f f e c t s h o u l d be reducible
through b e t t e r t r a i n i n g of the o p e r a t o r s . In s p i t e of t h i s
d i f f e r e n c e , the s t a n d a r d e r r o r s of these d e t e r m i n a t i o n s remain
acceptably small.
The c o v a r i a t e , DELTEMP, i n t h e a n a l y s i s o f c o v a r i a n c e i s v e r y
s i g n i f i c a n t f o r p a r t i c l e s i z e , but not at a l l s i g n i f i c a n t f o r
p o l y d i s p e r s i t y . However, a n a l y s i s of v a r i a n c e of b o t h p a r t i c l e s i z e
and p o l y d i s p e r s i t y g a v e a v e r y d i f f e r e n t i n t e r p r e t a t i o n o f t h e
f a c t o r s o t h e r t h a n METHOD, w h i c h r e m a i n e d n o n - s i g n i f i c a n t . In
p a r t i c u l a r , t h e DCP i n s t r u m e n t s became e x t r e m e l y s i g n i f i c a n t
( e x p e c t e d ) a s d i d t h e OPERATOR ( n o t e x p e c t e d ) . The strong,
r e a s o n a b l e t e m p e r a t u r e e f f e c t , and t h e f a c t t h a t t h e e r r o r t e r m s
a g r e e d v e r y w e l l w i t h the r e p l i c a t i o n e r r o r s , l e d us t o b e l i e v e that
t h e c o v a r i a t e a n a l y s i s was t h e m o s t m e a n i n g f u l i n t e r p r e t a t i o n o f t h e
data.
S i n c e t h e m e t h o d s h a v e b e e n e s t a b l i s h e d t o be n o t s i g n i f i c a n t l y
d i f f e r e n t , the o t h e r i m p o r t a n t q u e s t i o n i s the e x t e n t of v a r i a t i o n
of the measurements. I t was p r e v i o u s l y e s t a b l i s h e d t h a t t h e two
m e t h o d s had a l m o s t i d e n t i c a l v a r i a n c e s , s o t h e f o l l o w i n g discussions
a r e b a s e d on t h e two m e t h o d s c o l l e c t i v e l y . T h e s e r e s u l t s a r e
summarized i n T a b l e I I I .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
200 PARTICLE SIZE DISTRIBUTION

TABLE I I I . REPLICATION ERROR


(Both Methods)

PARTICLE S I Z E , Dw

SOURCE DEGREES OF STANDARD COEFFICIENT


FREEDOM DEVIATION OF V A R I A T I O N

REPLICATES (
Sample 2 8 .0036 1.27 %
Sample 3 9 .0046 1.15
Sample 4 10 .0063 1.63

Mean o f 2, 3, 4 27 .0051

R E S I D U A L I N COVARIANCE
Residual 35 .0051
Pooled Residual 40 .0052

P O L Y D I S P E R S I T Y , Dw/Dn

REPLICATES
Sample 2 8 0.0038 0.37 %
Sample 3 9 0.0079 0.77
Sample 4 10 0.0045 0.43

Mean o f 2, 3, 4 27 0.0057

R E S I D U A L I N COVARIANCE
Residual 35 0.0064
Pooled Residual 45 0.0062

The c o e f f i c i e n t o f v a r i a t i o n g i v e s a g o o d m e a s u r e o f t h e
r e p r o d u c i b i l i t y of these determinations. I t i s the standard
deviation/mean r e p o r t e d as % v a r i a t i o n . These f i g u r e s o f l e s s than
2% f o r p a r t i c l e s i z e ( d w ) , a n d l e s s t h a n 1% f o r p o l y d i s p e r s i t y
a t t e s t t o the h i g h c a p a b i l i t i e s o f the methods.
I n summary, t h e e x p e r i m e n t a l d e s i g n s h o w s t h a t ( 1 ) t h e s a m p l e s
s e l e c t e d were h i g h l y d i f f e r e n t , ( 2 ) temperature c o n t r o l i s v e r y
i m p o r t a n t f o r p r e c i s e m e a s u r e m e n t , a n d ( 3 ) t h e r e a p p e a r s t o be some
o p e r a t o r e f f e c t i n t h e d e t e r m i n a t i o n o f p o l y d i s p e r s i t y . T h e r e a r e no
i n t e r a c t i o n e f f e c t s among o p e r a t o r s , DCP i n s t r u m e n t s , a n d m e t h o d s .
For p a r t i c l e s i z e measurement, however, d i f f e r e n t types o f samples
respond d i f f e r e n t l y t o the other f a c t o r s i n the experiment. In
s p i t e o f t h i s , t h e o v e r a l l p r e c i s i o n o f t h e measurements by b o t h t h e
B L S m e t h o d a n d t h e EGM i s e x c e l l e n t .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
13. HOLSWORTH E T A L . Disc Centrifuge Photosedimentometric Analysis 201

Conclusions

A n o v e l a p p r o a c h t o f o r m i n g a d e n s i t y g r a d i e n t f o r DCP a n a l y s i s h a s
b e e n d i s c u s s e d . T h e EGM h a s b e e n s h o w n t o b e s t a t i s t i c a l l y
e q u i v a l e n t t o t h e BLS method a n d i n t h e c a s e o f d e n s i t y g r a d i e n t
s t a b i l i t y n e c e s s a r y f o r h i g h s p e e d s e p a r a t i o n t h e EGM h a s b e e n
shown, q u a l i t a t i v e l y , t o have d e c i d e d a d v a n t a g e s .
The r e s u l t s o b t a i n e d f r o m t h e s t a t i s t i c a l a n a l y s i s o f t h e d a t a
were t y p i c a l o f o t h e r l a t i c e s t h a t have been a n a l y z e d . A n a l y s i s o f
v a r i a n c e i n d i c a t e d t h a t t h e r e were no s i g n i f i c a n t d i f f e r e n c e s
between ( 1 ) t h e two methods, ( 2 ) t h e two DCP's, ( 3 ) t h e two
o p e r a t o r s . A l s o , t h e r e were no s i g n i f i c a n t i n t e r a c t i o n s between
t h e s e v a r i a b l e s . The random e r r o r s i n t h e s e e x p e r i m e n t s , i n t e r m s o f
s t a n d a r d d e v i a t i o n s , w e r e ( 1 ) f o r p a r t i c l e s i z e , Dw, 0.050, a n d
( 2 ) f o r p o l y d i s p e r s i t y , Dw/Dn, 0 . 0 0 6 5 . T h e s t a n d a r d d e v i a t i o n s o f
the two methods, i n d i v i d u a l l y

References

1. Provder,T., Holsworth, R. ., Div.of Org. Coatings and Plastics


Chem. Preprint 36, 150(1976).
2. Jones, M. H . , U. S. Patent No. 3,475,968, November 4, 1969.
3. Holsworth, R. M., Provder, T . , U. S. Patent No. 4,478,073,
October 23, 1984.
4. Zander, R. . , Koehler, M. E., Provder, T . , U. S. Patent No.
4,311,039, January 19,1982.
5. Koehler, M. E., Zander, R. ., Gill, T.T., "An Improved Disc
Centrifuge Photosedimentometer and Data System", This Volume.
6. Coll, H . , Searles, C. G., J. Coll. Inter. S c i . , 1986, Vol 110,
No. 1, 65.

RECEIVED October 6, 1986

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 14

Improved Techniques in Disc Centrifugation


Hans Coll and LarryE.Oppenheimer
Research Laboratories, Eastman Kodak Company, Rochester,NY14650

Results obtained from the disk centrifuge have


been improved substantially by using preformed
density gradients in the rotor fluid rather than
the commonly used buffer-layer method, by protect
ing the fluid from evaporative cooling with a thin
oil layer, and by the proper correction of the
optical signal with the help of light-scattering
theory. We have found that the oil-covered
density gradient in the rotor is stable for hours,
even at high rotor speeds, and several samples can
often be injected consecutively onto the same
gradient with no degradation in the results. Size
distributions of spherical and near-spherical
particles have been determined with great preci
sion. The centrifugation method has been adapted
for determining the hydrodynamic thickness of
polymer layers (such as gelatin) adsorbed to
colloidal particles. More recently, particle size
analysis has been extended to nonspherical parti
cles and to nonaqueous media.

The d i s k c e n t r i f u g e i s a n e x c e l l e n t i n s t r u m e n t f o r d e t e r m i n i n g
p a r t i c l e s i z e d i s t r i b u t i o n s i n t h e s i z e range from s e v e r a l microme
t e r s t o somewhat b e l o w 0.1 . F o r b r o a d o r e s p e c i a l l y m u l t i m o d a l
size d i s t r i b u t i o n s , disk centrifugation i s , o v e r a l l , probably
s u p e r i o r t o any o t h e r s i z i n g method f o r t h e a f o r e m e n t i o n e d r a n g e .
The o n l y l i m i t i n g r e q u i r e m e n t i s a f i n i t e d e n s i t y d i f f e r e n c e
between t h e p a r t i c l e s and t h e suspending f l u i d .
The l i n e - s t a r t m e t h o d , w h i c h r e q u i r e s t h e p a r t i c l e s t o b e more
dense than t h e f l u i d , i s g e n e r a l l y used w i t h t h e d i s k c e n t r i f u g e .
I t has been r e c o g n i z e d t h a t s t a b l e s e d i m e n t a t i o n , as a r u l e ,
requires a density gradient i n the spin f l u i d (1). The b u f f e r - l a y e r
method (2) i s most o f t e n u s e d t o g e n e r a t e t h i s g r a d i e n t , b u t a t
times i t has been u n r e l i a b l e .

0097-6156/87/0332-0202$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
14. C O L L AND OPPENHEIMER Improved Techniques in Disc Centrifugation 203

To i n v e s t i g a t e t h e e f f e c t o f t h e d e n s i t y g r a d i e n t o n t h e
s t a b i l i t y o f s e d i m e n t a t i o n i n t h e d i s k c e n t r i f u g e , we generated,
externally, spin fluids containing well-defined density gradi
ents (3). I n t h i s m a n n e r p e a k b r o a d e n i n g was m i n i m i z e d a n d e x c e l
l e n t r e p r o d u c i b i l i t y c o u l d be a c h i e v e d . By i n t r o d u c i n g a t h i n
l a y e r of o i l onto the meniscus of the s p i n f l u i d t o prevent evapor
a t i o n , we c o u l d u s e t h e same s p i n f l u i d f o r s e v e r a l h o u r s , w h i c h ,
for a v a r i e t y of samples, allowed m u l t i p l e consecutive i n j e c t i o n s
t o be made t h r o u g h t h e o i l l a y e r .
The h i g h p r e c i s i o n o f t h e d i s k c e n t r i f u g e a l l o w e d t h e c o m p a r i
s o n o f s e d i m e n t a t i o n v e l o c i t i e s o f c o l l o i d a l p a r t i c l e s w i t h and
w i t h o u t an a d s o r b e d p o l y m e r l a y e r , f r o m w h i c h t h e h y d r o d y n a m i c
t h i c k n e s s o f t h e a d s o r b e d l a y e r c o u l d be c a l c u l a t e d ( 4 ) . H e r e t h e
d i s k c e n t r i f u g e , g i v i n g c o m p l e t e s i z e d i s t r i b u t i o n s , made t h e u s e
of monodisperse samples unnecessary.

Experimental

E x p e r i m e n t s were done w i t h a J o y c e - L o e b l Model I I I d i s k c e n t r i -


fuge-photosedimentometer ( V i c k e r s Instrument Co.). Preformed
d e n s i t y g r a d i e n t s w e r e made i n a L u c i t e g r a d i e n t a p p a r a t u s ( B u c h l e r
I n s t r u m e n t s , I n c . ) o r i n a s i m i l a r l y d e s i g n e d d e v i c e made o f g l a s s
(3). The t w o s o l u t i o n s w e r e pumped i n t o a n e a r - v e r t i c a l t u b e 1 cm
I.D. 35 cm l o n g b y u s i n g a p e r i s t a l t i c pump. The g r a d i e n t was
t h e n i n j e c t e d f r o m t h e t u b e i n t o t h e s p i n n i n g r o t o r b y means o f a
piston. F i g u r e 1 i s a schematic of the g r a d i e n t - f o r m i n g system.
S i n c e L u c i t e i s n o t w e t t e d b y w a t e r , 0.02% P l u r o n i c L 9 2 s u r f a c t a n t
(BASF W y a n d o t t e ) was a d d e d t o t h e a q u e o u s l i q u i d s i n t h e g r a d i e n t
maker.
S u c r o s e s o l u t i o n s w e r e u s u a l l y u s e d as aqueous s p i n f l u i d s .
N o n a q u e o u s m e d i a s u c h as d o d e c a n e / h e x a d e c a n e a n d d i e t h y l f o r m a -
mide/dimethylformamide m i x t u r e s have a l s o been used. The q u a l i t y
o f t h e g r a d i e n t s was c o n f i r m e d r e f r a c t o m e t r i c a l l y i n s e p a r a t e
experiments.

Preformed Density Gradients

Samples c o n t a i n i n g p a i r s o f p o l y s t y r e n e l a t e x e s w i t h narrow s i z e
d i s t r i b u t i o n s were used t o examine the e f f e c t o f d e n s i t y g r a d i e n t
s t e e p n e s s on peak shape. U n s t a b l e s e d i m e n t a t i o n , c h a r a c t e r i z e d by
p o o r l y r e s o l v e d , b r o a d p e a k s , u s u a l l y r e s u l t e d when t h e s a m p l e s
w e r e r u n b y t h e b u f f e r - l a y e r m e t h o d w i t h 4% s u c r o s e a s t h e s p i n
fluid. When t h e same s a m p l e s w e r e r u n i n 20 mL o f s p i n f l u i d w i t h
a p r e f o r m e d g r a d i e n t f r o m 0 t o 4% s u c r o s e ( a 0/4% g r a d i e n t ) , a s
shown i n F i g u r e 2a f o r a p a i r o f l a t e x e s w i t h n o m i n a l d i a m e t e r s o f
0.45 a n d 0.765 , s h a r p , w e l l - r e s o l v e d p e a k s w e r e o b t a i n e d . A
0/3% g r a d i e n t a l s o g a v e g o o d s e p a r a t i o n ( F i g u r e 2 b ) , b u t w i t h a
0/2% g r a d i e n t , t h e s e p a r a t i o n was s e v e r e l y d e g r a d e d ( F i g u r e 2 c ) .
A d d i t i o n a l e x p e r i m e n t s w i t h t r u n c a t e d g r a d i e n t s ( e . g . , 4/7.5%
s u c r o s e ) showed t h a t t h i s d e g r a d a t i o n o c c u r s o v e r a v e r y n a r r o w
r a n g e o f g r a d i e n t d e n s i t i e s . The l a t e x p a i r was w e l l s e p a r a t e d i n
a 4/7.5% g r a d i e n t but p o o r l y s e p a r a t e d i n a 4.25/7.5% g r a d i e n t w i t h
f u r t h e r degradation o c c u r r i n g i n l e s s steep g r a d i e n t s (Figures 3a-d).

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
204 PARTICLE SIZE DISTRIBUTION

F i g u r e 1. Schematic of the gradient-forming apparatus. Repro-


d u c e d w i t h p e r m i s s i o n f r o m R e f . 3. C o p y r i g h t 1985, A c a d e m i c
Press.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
14. C O L L A N D OPPENHEIMER Improved Techniques in Disc Centrifugation 205

F i g u r e 2. Sedimentation curves o f polystyrene latexes w i t h


n o m i n a l d i a m e t e r s o f 0.45 a n d 0.765 urn d i s k c e n t r i f u g e d a t 4 0 0 0
rpm i n 20 mL o f s p i n f l u i d w i t h g r a d i e n t s o f ( a ) 0/4%, ( b ) 0 / 3 % ,
( c ) 0/2% s u c r o s e . R e p r o d u c e d w i t h p e r m i s s i o n f r o m R e f . 3.
C o p y r i g h t 1985, Academic P r e s s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
206 PARTICLE SIZE DISTRIBUTION

F i g u r e 3. S e d i m e n t a t i o n c u r v e s r u n as f o r F i g u r e 2 b u t w i t h
g r a d i e n t s o f ( a ) 4/7.5%, (b) 4.25/7.5%, ( c ) 4.5/7.5%, (d) 5/7.5%
sucrose.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
14. C O L L AND OPPENHEIMER Improved Techniques in Disc Centrifugation 207

Gradient Protection

The p r e f o r m e d g r a d i e n t s i n t h e s p i n f l u i d b e c a m e u n s t a b l e i n l e s s
t h a n 1 h i f t h e r o t o r was r u n a t h i g h s p e e d . The i n s t a b i l i t y was
c h a r a c t e r i z e d by t h e a p p e a r a n c e o f a l a r g e peak i n t h e b a s e l i n e
a f t e r t h e c e n t r i f u g e had been r u n f o r about 1 h w i t h o r w i t h o u t a
sample h a v i n g been i n j e c t e d i n t o the r o t o r . I f a s a m p l e was
i n j e c t e d a f t e r the appearance of t h i s b a s e l i n e peak, a poor separa
t i o n , s u c h as t h a t shown i n F i g u r e 4 a , was a l w a y s o b t a i n e d . We
a t t r i b u t e d t h e s e phenomena t o c o n v e c t i v e m i x i n g o f t h e s p i n f l u i d
i n d u c e d by e v a p o r a t i v e c o o l i n g o f t h e s u r f a c e , w i t h t h e b a s e l i n e
p e a k b e i n g c a u s e d by t h e t r a n s i e n t r e f r a c t i v e i n d e x i n h o m o g e n e i t y
t h a t w o u l d accompany s u c h m i x i n g . To s u p p r e s s e v a p o r a t i o n a n d t h e
r e s u l t a n t c o o l i n g , we r a n e x p e r i m e n t s i n w h i c h t h e a q u e o u s s p i n
f l u i d was c o v e r e d w i t h 1 mL o f n - d o d e c a n e . G o o d r e s u l t s w e r e now
o b t a i n e d f o r samples i n j e c t e
3 h a t 6 0 0 0 rpm ( F i g u r
The g r a d i e n t - v a r i a t i o e x p e r i m e n t previou
s e c t i o n were repeated w i t h dodecane-protected gradients. Much
s h a l l o w e r g r a d i e n t s gave s t a b l e s e d i m e n t a t i o n under t h e s e c o n d i
tions. The l a t e x m i x t u r e c o u l d be s e p a r a t e d i n a 0/1% g r a d i e n t as
w e l l as i n a 4 / 4 . 5 % g r a d i e n t . This confirmed that evaporative
c o o l i n g o f t h e s p i n f l u i d was t h e p r i m a r y c a u s e o f c o n v e c t i o n a n d
hence of u n s t a b l e sedimentation.

Particle Size Distributions

P a r t i c l e r a d i i (R) a r e c a l c u l a t e d f r o m t h e s e d i m e n t a t i o n t i m e s ( t )
b y means o f t h e S t o k e s e q u a t i o n . F o r a s p i n f l u i d w i t h d e n s i t y and
viscosity gradients

(1)

where U i s the r o t o r speed ( r e v o l u t i o n s per second), is the


p a r t i c l e d e n s i t y , and p Q and are, r e s p e c t i v e l y , the position-
d e p e n d e n t d e n s i t y and v i s c o s i t y of the spin fluid. The i n t e g r a t i o n
e x t e n d s from x^, the distance of the fluid miniscus from the axis

of r o t a t i o n , t o x^, the radial distance of the o p t i c a l detector.

The c o n c e n t r a t i o n and h e n c e t h e v i s c o s i t y and d e n s i t y ( o f t h e


a q u e o u s s u c r o s e , e.g.) a t any p o i n t i n t h e s p i n f l u i d a r e c a l c u
l a t e d f r o m t h e c o n c e n t r a t i o n s and v o l u m e s i n t h e g r a d i e n t apparatus
and t h e d i m e n s i o n s o f t h e r o t o r .
The a c c u r a c y o b t a i n a b l e b y u s i n g t h i s a p p r o a c h c a n be s e e n
f r o m t h e r e s u l t s i n F i g u r e 5, w h i c h w e r e o b t a i n e d f o r p o l y s t y r e n e
l a t e x e s w i t h n o m i n a l d i a m e t e r s o f 0.804 a n d 1.09 um. The diameters
c a l c u l a t e d f r o m t h e p e a k p o s i t i o n s w e r e , r e s p e c t i v e l y , 0.789 a n d
3
1.093 ym, b a s e d o n a m e a s u r e d d e n s i t y o f 1.048 g / c m f o r t h e s e
latexes. The s m a l l p e a k a t 1.3 um i n F i g u r e 5 i s a t t r i b u t e d t o
d o u b l e t s o f t h e 1.09-um l a t e x . Although the r a t i o of the
s e d i m e n t a t i o n t i m e s o f t h e s e t w o p e a k s ( 1 . 0 9 a n d 1.3 ) i s c l o s e

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
208 PARTICLE SIZE DISTRIBUTION

Inject C^Hge
Inject
PS latex

1
F i g u r e 4. E f f e c t o f r u n n i n g a 2 / 6 % s u c r o s e g r a d i e n t a t 6 0 0 0 rpm
f o r ~3 h b e f o r e s a m p l e i n j e c t i o n ( a ) w i t h o u t o i l p r o t e c t i o n ,
( b ) w i t h p r o t e c t i o n . R e p r o d u c e d w i t h p e r m i s s i o n f r o m R e f . 3.
C o p y r i g h t 1985, Academic P r e s s .

Diameter (/ym)

F i g u r e 5. P a r t i c l e s i z e d i s t r i b u t i o n o f a m i x t u r e o f p o l y s t y r e n e
l a t e x e s w i t h n o m i n a l d i a m e t e r s o f 0.804 a n d 1.09 ym o b t a i n e d b y
d i s k c e n t r i f u g a t i o n a t 4 0 0 0 rpm i n a 1/4% s u c r o s e g r a d i e n t .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
14. C O L L AND OPPENHEIMER Improved Techniques in Disc Centrifugation 209

t o t h e 0.7 p r e d i c t e d f o r d o u b l e t s o r i e n t e d p a r a l l e l t o t h e
d i r e c t i o n o f s e d i m e n t a t i o n ( 1 ) , we e x p e c t t h a t B r o w n i a n m o t i o n
would randomize the o r i e n t a t i o n s o f the aggregates. I nt h i s case
t h e r a t i o o f t h e s e d i m e n t a t i o n t i m e s w o u l d b e s o m e w h a t b e l o w 0.7.
The i n s t a n t a n e o u s o u t p u t o f t h e d e t e c t o r (S) c a n b e r e l a t e d t o
the c o n c e n t r a t i o n o f m a t e r i a l o f a given s i z e by d i v i d i n g by the
t n e
extinction efficiency (Q ) f
e x t p a r t i c l e s present i n the
sa
detector (5). Q e x t *- f u n c t i o n o f the (known) p a r t i c l e size,the

r e l a t i v e r e f r a c t i v e i n d e x o f t h e p a r t i c l e s , and t h e wavelength-
dependent o p t i c a l response o f the d e t e c t i o n system. This treatment
i s exact o n l y f o r s p h e r i c a l p a r t i c l e s , but i t i s o f t e n used as an
a p p r o x i m a t i o n f o r o t h e r shapes as w e l l . For very narrow s i z e
distributions, Q may b e t r e a t e d a s a c o n s t a n t o v e r t h e r a n g e o f
e x t

p a r t i c l e s i z e s , a n d t h i s c o r r e c t i o n may b e i g n o r e d . This i s also


the case f o r p a r t i c l e s t h a
l e n g t h o f l i g h t , where

a d d i t i o n , i t has b e e n shown t h a t i f t h e r e l a t i v e r e f r a c t i v e i n d e x
o f t h e s a m p l e i s s u f f i c i e n t l y l o w (m < 1.25, e.g.) t h e wavelength
s e n s i t i v i t y o f t h e o p t i c a l s y s t e m and o f Q become u n i m p o r t a n t ,
e x t

and c a l c u l a t i o n s can be p e r f o r m e d f o r a s i n g l e w a v e l e n g t h (~700 nm


f o r our i n s t r u m e n t ) .
S i s r e l a t e d t o t h e n u m b e r c o n c e n t r a t i o n (N) o f p a r t i c l e s
viewed by the d e t e c t o r through

2
S = R ITN Q L (2)
ext

where L i s t h e p a t h l e n g t h . S i n c e t h e s i z e i n c r e m e n t AR s a m p l e d b y
t h e d e t e c t o r i s p r o p o r t i o n a l t o R, t h e o p t i c a l l y c o r r e c t e d d i s t r i
b u t i o n i s a volume d i s t r i b u t i o n (6, 7) w i t h l i n e a r increment o r an
area d i s t r i b u t i o n w i t h l o g a r i t h m i c increment:

3 2
S/Q e x t = const R /AR = c o n s t R /Alog R (3)

A Study R e q u i r i n g High P r e c i s i o n : Determination o f the Thickness o f


a G e l a t i n Layer Adsorbed on S i l v e r Bromide

W h i l e e x a m i n i n g t i m e - d e p e n d e n t phenomena o f s i l v e r b r o m i d e p a r t i
c l e s , we made many r e p e a t m e a s u r e m e n t s . With care, standard
d e v i a t i o n s c o u l d b e k e p t b e l o w 1%. F i g u r e 6, f o r i n s t a n c e , c o n t a i n s
t h e d i a m e t e r s c a l c u l a t e d f r o m t h e p e a k maxima f o r 44 i n j e c t i o n s o f
a s i l v e r bromide d i s p e r s i o n . F o u r c o n s e c u t i v e i n j e c t i o n s w e r e made
i n t o t h e same d o d e c a n e - p r o t e c t e d s p i n f l u i d , s o t h a t e x p e r i m e n t s i n
10 d i f f e r e n t s p i n f l u i d g r a d i e n t s a r e r e p r e s e n t e d h e r e . Monitoring
o f t h e s p i n f l u i d t e m p e r a t u r e was r e q u i r e d , s i n c e t h i s v a r i a b l e
a f f e c t s b o t h d e n s i t y and v i s c o s i t y . C o r r e c t i o n s w e r e a l s o made f o r
t h e volume change o f the s p i n f l u i d caused b y s u c c e s s i v e i n j e c t i o n s
(1, 3).
T h e a b i l i t y t o make v e r y p r e c i s e m e a s u r e m e n t s h a s a l l o w e d u s
t o use the d i s k c e n t r i f u g e t o determine the t h i c k n e s s o f adsorbed
g e l a t i n l a y e r s o n s i l v e r b r o m i d e p a r t i c l e s ( 4 ) . When p a r t i c l e s a r e
coated w i t h an adsorbed polymer l a y e r , the sedimentation time
r e f l e c t s t h e s i z e and d e n s i t y o f t h e p a r t i c l e c o r e a s w e l l a s t h e
t h i c k n e s s and d e n s i t y o f t h e a d s o r b e d l a y e r . An apparent (incor-

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
210 PARTICLE SIZE DISTRIBUTION

r e c t ) s i z e r c a n be c a l c u l a t e d f o r s u c h a p a r t i c l e by a s s u m i n g t h a t
t h e d e n s i t y i s u n i f o r m and e q u a l t o t h a t o f t h e c o r e . The s h e l l
t h i c k n e s s (L) i s c a l c u l a t e d from

2
L = R [(R /r)c c - 1] (4)

w h e r e R^ i s the radius of the core p a r t i c l e . V a l u e s o f R^ were

m e a s u r e d a f t e r t h e a d s o r b e d g e l a t i n was r e m o v e d f r o m t h e p a r t i c l e s
by e n z y m a t i c d i g e s t i o n . T y p i c a l s h i f t s , R^ - r , w e r e ~ 0 . 1 ym.

F i g u r e 7 c o n t a i n s t h e s i z e d i s t r i b u t i o n s c a l c u l a t e d f o r one
sample b e f o r e and a f t e r r e m o v a l o f t h e g e l a t i n l a y e r . A unique
advantage of u s i n g a d e v i c e t h a t generates t h e whole p a r t i c l e s i z e
d i s t r i b u t i o n , s u c h a s t h e d i s k c e n t r i f u g e , i s s h o w n i n F i g u r e 8.
Here, the g e l a t i n - c o a t e d s i l v e r bromide i s h i g h l y aggregated,
leading to a multimodal s i z e d i s t r i b u t i o n Nonetheless i t i s
possible to i d e n t i f y th
p a r t i c l e s f o r compariso
of the g e l a t i n .
The l a y e r t h i c k n e s s r a n g e d f r o m 0.025 t o 0.15 ym, d e p e n d i n g o n
t h e s a m p l e , t h e i o n i c s t r e n g t h , a n d t h e pH o f t h e s p i n f l u i d .
F i g u r e 9 shows p l o t s o f l a y e r t h i c k n e s s a s a f u n c t i o n o f s p i n - f l u i d
i o n i c s t r e n g t h o b t a i n e d f o r f o u r s i l v e r b r o m i d e s o l s a t pH ~ 6 .
S i m i l a r l y , we h a v e m e a s u r e d t h e t h i c k n e s s o f a n a d s o r b e d
s y n t h e t i c p o l y m e r l a y e r on t i t a n i u m d i o x i d e p a r t i c l e s i n a h y d r o c a r
b o n medium. S i n c e t h e p o l y m e r c o u l d n o t be removed f r o m t h e
p a r t i c l e s once adsorbed, t h e v a l u e s f o r t h e b a r e p a r t i c l e s were
o b t a i n e d by c e n t r i f u g i n g aqueous d i s p e r s i o n s o f t h e t i t a n i u m
d i o x i d e s t a b i l i z e d w i t h an i o n i c s u r f a c t a n t .

Nonspherical Particles

The s e d i m e n t a t i o n o f i s o m e t r i c p a r t i c l e s , s u c h as c u b e s and o c t a -
hedra, d e v i a t e s o n l y s l i g h t l y from the Stokes e q u a t i o n . Signifi
c a n t l y a n i s o m e t r i c p a r t i c l e s t h a t c a n be a p p r o x i m a t e d by e l l i p s o i d s
o f r e v o l u t i o n a r e amenable t o r i g o r o u s s i z i n g by c e n t r i f u g a t i o n i f
t h e a x i a l r a t i o s q a r e known. I f t h e major s e m i - a x i s i s a and t h e
m i n o r s e m i - a x i s i s c, t h e s e d i m e n t a t i o n v e l o c i t y d x / d t c a n be
w r i t t e n as

2ac(p - ) m

d t
*" - 9, f(q)
o

where i s t h e a n g u l a r a c c e l e r a t i o n and f ( q ) i s t h e f r i c t i o n
factor, a function of the a x i a l r a t i o . F o r a s p h e r e , a = c and
f ( q ) = 1. G i v e n 3, t h e a p p r o p r i a t e f r i c t i o n f a c t o r s c a n b e c a l c u
l a t e d ( 8 , 9 ) , once i t i s r e c o g n i z e d t h a t p a r t i c l e s w i t h dimensions
s m a l l e r t h a n a few m i c r o m e t e r s assume random o r i e n t a t i o n s d u r i n g
centrifugation. S i n c e q = c / a , t h e s e d i m e n t a t i o n t i m e c a n be
r e l a t e d t o a a n d / o r c. However, i n t h e g e n e r a l case where t h e
a x i a l r a t i o i s unknown, an i n d e p e n d e n t a s s e s s m e n t o f a i s n o t

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
C O L L A N D OPPENHEIMER Improved Techniques in Disc Centrifugation

F i g u r e 6. R e p r o d u c i b i l i t y o f p e a k p o s i t i o n s f o r s u c c e s s i v e r u n s
o n a s i l v e r b r o m i d e s a m p l e c e n t r i f u g e d a t 1500 rpm i n 20 mL o f a
4/8% s u c r o s e g r a d i e n t . = 4 4 i n j e c t i o n s , D = 0.694 , =
0.55%.


c

13
CT"
9>


c
"

0.1 0.2 0.4 0.8


Diameter (.)

F i g u r e 7. A p p a r e n t p a r t i c l e s i z e d i s t r i b u t i o n s o f a s i l v e r
b r o m i d e d i s p e r s i o n ( a ) i n 0.001 NaNO^ w i t h t h e g e l a t i n l a y e r

i n t a c t , (b) a f t e r removal o f t h e g e l a t i n . Reproduced w i t h


p e r m i s s i o n f r o m R e f . 4. C o p y r i g h t 1985, Academic P r e s s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
PARTICLE SIZE DISTRIBUTION

0.2 0.4 0.8 1.6

Diameter (/xm)

F i g u r e 8. Apparent p a r t i c l e s i z e d i s t r i b u t i o n s of a s i l v e r
b r o m i d e d i s p e r s i o n ( a ) i n 0.001 NaNO^ w i t h t h e g e l a t i n l a y e r

i n t a c t , (b) a f t e r removal o f t h e g e l a t i n . The a r r o w i n a i n d i


cates the peak f o r t h e unaggregated p a r t i c l e s . Reproduced w i t h
p e r m i s s i o n f r o m R e f . 4. C o p y r i g h t 1985, Academic P r e s s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
C O L L A N D OPPENHEIMER Improved Techniques in Disc Centrifugation

160 r

O U L _ J L _ J i _ J

, -3
0 3 6 , -2
0 3 6 , -l 0 3 6 , 0 Q

Electrolyte molarity

F i g u r e 9. G e l a t i n - l a y e r t h i c k n e s s v e r s u s s p i n - f l u i d ionic
strength f o r four s i l v e r halide dispersions. The s p i n f l u i d s
c o n t a i n e d NaNO^ a n d w e r e a d j u s t e d t o pH ~ 6 . R e p r o d u c e d w i t h

permission f r o m R e f . 4. Copyright 1985, Academic Press.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
214 PARTICLE SIZE DISTRIBUTION

possible. A s p e c i a l case i st h eo b l a t e e l l i p s o i d w i t h a c, a
t h i n p l a t e l e t , f o r w h i c h f a p p r o a c h e s 0.65 a n d t h e p r o d u c t a c c a n
be c a l c u l a t e d f r o m t h e s e d i m e n t a t i o n time.

Conclusion

The s t a b i l i t y o f s e d i m e n t a t i o n i n t h e d i s k c e n t r i f u g e i s g r e a t l y
enhanced by t h e presence o f a d e n s i t y g r a d i e n t i nt h e s p i n f l u i d ,
as e v i d e n c e d b y m i n i m a l p e a k b r o a d e n i n g . A g r a d i e n t w i t h known
p r o p e r t i e s c a n be formed e x t e r n a l l y and i n j e c t e d i n t o t h e s p i n n i n g
r o t o r by u s i n g an apparatus such as t h eone d e s c r i b e d here o r w i t h
an a p p r o p r i a t e l y d e s i g n e d s y r i n g e d e v i c e . Once i n j e c t e d , t h e
d e n s i t y g r a d i e n t i s s u b j e c t t od e g r a d a t i o n due t o thermal g r a d i e n t s
i n t h e s p i n f l u i d caused by evaporative c o o l i n g a t t h e meniscus.
This e f f e c t c a n be suppressed b y c o v e r i n g t h e s p i n - f l u i d s u r f a c e
w i t h a t h i n l a y e r o f a n o n v o l a t i l e o i l such as dodecane. A density
gradient protected i nthi
after injection into th
introduced i n t o t h e s p i n f l u i d through such an o i l l a y e r , consecu
t i v e r u n s c a n b e made w i t h t h e same s p i n f l u i d . The standard
d e v i a t i o n i n p a r t i c l e s i z e s c a l c u l a t e d from peak p o s i t i o n s c a n be
r e d u c e d t o <1% b y u s i n g t h e s e t e c h n i q u e s a l o n g w i t h c a r e f u l moni
t o r i n g o f t h es p i n - f l u i d temperature.
The o u t p u t o f t h e d i s k c e n t r i f u g e , a c u r v e o f o p t i c a l d e n s i t y
versus time, c a n be converted t o a p a r t i c l e s i z e d i s t r i b u t i o n b y
u s i n g Stokes' law t o convert t h etime a x i s t o a s i z e a x i s and by
the a p p l i c a t i o n o f l i g h t - s c a t t e r i n g theory t o c a l c u l a t e the p a r t i c l e
f r e q u e n c i e s from t h e o p t i c a l d e n s i t i e s . As d e s c r i b e d h e r e i n , one
o b t a i n s mass d i s t r i b u t i o n s w i t h l i n e a r s i z e i n c r e m e n t s o r t h e
equivalent area d i s t r i b u t i o n s w i t h l o g a r i t h m i c increments.
We h a v e d e m o n s t r a t e d t h a t t h e h i g h p r e c i s i o n o f t h e d a t a
allows t h ed i s k c e n t r i f u g e t o be used t odetermine t h ethickness o f
polymer layers adsorbed t od i s p e r s e d s u b s t r a t e s . Finally, although
the a n a l y s i s o f d i s k - c e n t r i f u g e data i sexact f o r s p h e r i c a l p a r t i
c l e s , s i g n i f i c a n t information can o f t e n be obtained f o r p a r t i c l e s
t h a t c a n be t r e a t e d as e l l i p s o i d s . When t h e a x i a l r a t i o i s k n o w n
and c o n s t a n t , a d i s t r i b u t i o n o f s i z e s c a n b e o b t a i n e d .

Literature Cited

1. Kaye, . H. "Direct Characterization of Fineparticles";


Wiley-Interscience: New York, 1981.
2. Beresford, J . J . Oil Colour Chem. Assoc. 1967, 50, 594.
3. Coll, H.; Searles, C. G. J. Colloid Interface S c i . , in press.
4. Coll, H . ; Oppenheimer, L. E.; Searles, C. G. J. Colloid
Interface Sci. 1985, 104, 193.
5. Oppenheimer, L. E., J. Colloid Interface Sci. 1983, 92, 350.
6. Allen, T. "Particle Size Measurement"; Chapman and Hall:
London, 1968; pp. 122-124.
7. Coll, H . ; Haseler, S. C. J. Colloid Interface Sci. 1984, 99,
591.
8. Tanford, C. "Physical Chemistry of Macromolecules"; Wiley: New
York, 1961; pp. 324-328.
9. Happel, J.; Brenner, H. "Low Reynolds Number Hydrodynamics";
Prentice Hall: Englewood C l i f f s , NJ, 1965.

RECEIVED June 27, 1986

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 15

Measuring Particle Size Distribution


of Simple and Complex Colloids Using Sedimentation
Field-Flow Fractionation
J. Calvin Giddings, KarinD.Caldwell, and HarlanK.Jones
Department of Chemistry, University of Utah, Salt Lake City,UT84112

This paper outline


of sedimentation f i e l d - f l o w fractionation (FFF) and
shows how the method is used for various p a r t i c l e
size measurements. For context, we compare sedimen-
tation FFF with other fractionation methods using
four criteria to judge effective p a r t i c l e
characterization. The application of sedimentation
FFF to monodisperse particle samples is then
described, followed by a discussion of polydisperse
populations and techniques for obtaining particle
size distribution curves and particle d e n s i t i e s . We
then report on preliminary work with complex c o l l o i d s
which have particles o f different chemical composi-
tion and density. I t is shown, with the help o f an
example, that sedimentation FFF is sufficiently
v e r s a t i l e to unscramble complex colloids, which
should eventually provide not only particle size
distributions, but simultaneous particle density
distributions.
S e d i m e n t a t i o n f i e l d - f l o w f r a c t i o n a t i o n ( s e d i m e n t a t i o n FFF) has
r e c e n t l y emerged as a powerful and v e r s a t i l e t e c h n i q u e f o r t h e
c h a r a c t e r i z a t i o n o f simple and complex p a r t i c l e p o p u l a t i o n s . I n
t h i s t e c h n i q u e , a p a r t i c u l a t e sample i s e n t r a i n e d i n a stream o f
l i q u i d , s u b j e c t e d t o a f i e l d a c t i n g p e r p e n d i c u l a r t o t h e stream
d i r e c t i o n , and washed down t h e l e n g t h o f a t h i n f l o w channel ( 1 ) .
The r a t e a t which p a r t i c l e s a r e d i s p l a c e d downstream (measured by
emergence t i m e s ) can be r e l a t e d by e x a c t t h e o r y t o p a r t i c l e
p r o p e r t i e s such as mass, s i z e , and d e n s i t y ( 2 ) . However, s i n c e
d i f f e r e n t k i n d s o f p a r t i c l e s move a t d i f f e r e n t v e l o c i t i e s i n t h i s
system, broad p a r t i c l e p o p u l a t i o n s a r e s o r t e d i n t o a graded s i z e
(or mass) d i s t r i b u t i o n a l o n g t h e l e n g t h o f t h e f l o w c h a n n e l .
O b s e r v a t i o n o f t h e shape o f t h e emerging d i s t r i b u t i o n ( r e c o r d e d as
a fractogram), together with theory, y i e l d s a p a r t i c l e size d i s -
t r i b u t i o n curve ( 3 - 6 ) .

0097-6156/87/0332-0215$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
216 PARTICLE SIZE DISTRIBUTION

Sedimentation FFF, a p p l i e d i n the above manner, y i e l d s h i g h l y


d e t a i l e d s i z e d i s t r i b u t i o n c u r v e s . I t i s convenient and a c c u r a t e .
Importantly, s e d i m e n t a t i o n FFF i s a h i g h l y f l e x i b l e t e c h n i q u e . I t
can be adapted t o n e a r l y a l l p a r t i c l e types i n v i r t u a l l y any
suspending medium. I t y i e l d s p a r t i c l e d e n s i t y as w e l l as s i z e and
s i z e d i s t r i b u t i o n . Our r e c e n t work has shown t h a t i t can be used
t o probe both s i z e and d e n s i t y d i s t r i b u t i o n s i n complex c o l l o i d s ,
d e f i n e d as systems having c o l l o i d a l p a r t i c l e s o f v a r i a b l e chemical
c o m p o s i t i o n . Complex c o l l o i d s are important i n many b i o l o g i c a l and
environmental s t u d i e s .
C l e a r l y , s e d i m e n t a t i o n FFF i s a s e p a r a t i o n t e c h n i q u e . I t i s
an important member o f the f i e l d - f l o w f r a c t i o n a t i o n (FFF) f a m i l y o f
t e c h n i q u e s . Although o t h e r members o f the FFF f a m i l y ( e s p e c i a l l y
thermal FFF) are more e f f e c t i v e f o r polymer a n a l y s i s , s e d i m e n t a t i o n
FFF i s advantageous f o r the s e p a r a t i o n o f a wide assortment o f
c o l l o i d a l p a r t i c l e s . S e d i m e n t a t i o n FFF not o n l y y i e l d s h i g h e r
r e s o l u t i o n than n e a r l y
but i t s simple t h e o r e t i c a
t i o n between observed p a r t i c l e m i g r a t i o n r a t e s and p a r t i c l e s i z e .
Thus s i z e d i s t r i b u t i o n curves are r e a d i l y o b t a i n e d on the b a s i s o f
t h e o r e t i c a l a n a l y s i s without the need f o r (and u n c e r t a i n t i e s o f )
calibration.
We note t h a t s e d i m e n t a t i o n FFF, although a s e p a r a t i o n t e c h -
nique, i s not a form of chromatography. Chromatography i s
u n i v e r s a l l y d e f i n e d as a method i n which s p e c i e s are s e p a r a t e d by
d i f f e r e n t i a l l y p a r t i t i o n i n g them between two phases, one s t a t i o n a r y
and one mobile ( 7 ) . In a l l FFF methods, by c o n t r a s t , s e p a r a t i o n i s
implemented withTn one phase, c o n s i s t i n g o f the l i q u i d continuum
w i t h i n the f l o w c h a n n e l . (We add here the o b s e r v a t i o n t h a t
hydrodynamic chromatography i s i n a p p r o p r i a t e l y named; s e p a r a t i o n i n
t h i s system a l s o t a k e s p l a c e i n the s i n g l e l i q u i d phase o c c u p y i n g
the i n t e r s t i t i a l space o f a packed column.)
In FFF systems, the s e p a r a t i o n along the f l o w a x i s i s caused
by the p e r p e n d i c u l a r f i e l d , whose c r u c i a l r o l e i s r e c o g n i z e d by the
word " f i e l d " i n f i e l d - f l o w f r a c t i o n a t i o n . The a p p l i e d f i e l d i n t e r -
a c t s w i t h e n t r a i n e d p a r t i c l e s , f o r c i n g them t o accumulate a t one
w a l l (the a c c u m u l a t i o n w a l l ) o f the c h a n n e l . S i n c e the f l o w
v e l o c i t y near any w a l l i s reduced by f r i c t i o n a l d r a g , the
downstream d i s p l a c e m e n t o f the p a r t i c l e s i s r e t a r d e d . R e t a r d a t i o n
(or r e t e n t i o n ) i s g r e a t e s t f o r those p a r t i c l e s f o r c e d most c l o s e l y
t o the w a l l . Consequently, p a r t i c l e s are s e p a r a t e d a c c o r d i n g t o
the d i f f e r e n t f o r c e s e x e r t e d on them by the a p p l i e d f i e l d . These
f o r c e s n o r m a l l y depend on p a r t i c l e s i z e , l e a d i n g t o a s i z e - b a s e d
separation.
The s e d i m e n t a t i o n FFF p r o c e s s i s i l l u s t r a t e d i n F i g u r e 1. In
t h i s f i g u r e , the FFF c h a n n e l , which has a r i b b o n - l i k e r a t h e r than a
t u b e - l i k e c o n f i g u r a t i o n , i s curved t o f i t w i t h i n a c e n t r i f u g e
basket. The c e n t r i f u g e i s r e s p o n s i b l e f o r the s e d i m e n t a t i o n f o r c e s
which impel p a r t i c l e s toward the a c c u m u l a t i o n w a l l . N a t u r a l l y , the
l a r g e s t and most massive p a r t i c l e s are i m p e l l e d by the g r e a t e s t
f o r c e s and end up c l o s e s t t o the w a l l , p r o v i d e d t h e i r d e n s i t y
d i f f e r s from t h a t o f the channel f l u i d .
The f l o w p r o f i l e i n the c h a n n e l , shown i n the f i g u r e , i s
p a r a b o l i c i n form. With t h i s f l o w p r o f i l e , the v e l o c i t y approaches

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
GIDDINGS ET AL. Sedimentation Field-Flow Fractionation

Spin

Flow profile

F i g u r e 1. S e p a r a t i o n o f l a r g e (A) p a r t i c l e s from i n t e r m e d i a t e -
s i z e d (B) and small (C) p a r t i c l e s i n a s e d i m e n t a t i o n FFF
c h a n n e l . The f i g u r e r e p r e s e n t s a s i d e view o f the c h a n n e l ,
which i s t y p i c a l l y 0.0254 cm t h i c k .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
218 PARTICLE SIZE DISTRIBUTION

z e r o near t h e w a l l , r e f l e c t i n g t h e above-mentioned f r i c t i o n a l d r a g .
Consequently, t h e l a r g e s t p a r t i c l e s , hugging t h e w a l l most c l o s e l y ,
are d i s p l a c e d most s l o w l y down t h e c h a n n e l . S e p a r a t i o n ensues, as
i l l u s t r a t e d i n the figure.
S e d i m e n t a t i o n FFF i s amenable t o r a t h e r e x a c t i n g t h e o r y ( 2 ) .
For l a m i n a r f l o w (which i n c l u d e s a l l FFF o p e r a t i o n ) , t h e p a r a b o l i c
p r o f i l e provides a concise d e s c r i p t i o n o f the flow d i s t r i b u t i o n .
The s e d i m e n t a t i o n f o r c e s , which a p p l y u n i f o r m l y throughout t h e
channel volume, a r e e q u a l l y w e l l - d e f i n e d i n terms o f p a r t i c l e s i z e ,
p a r t i c l e d e n s i t y , and f l u i d d e n s i t y . Thus m i g r a t i o n r a t e can be
r i g o r o u s l y r e l a t e d t o p a r t i c l e s i z e , as w i l l be shown i n t h e t h e o r y
section.
S e d i m e n t a t i o n FFF i s a p p l i c a b l e t o p a r t i c l e s r a n g i n g i n s i z e
from about 0.01 t o 1 pm. A s p e c i a l form o f s e d i m e n t a t i o n FFF
termed s t e r i c FFF extends t h i s range from 1 pm t o 100 pm ( 8 ) .

Comparison o f P a r t i c l e S i z
In o r d e r t o p r o v i d e c o n t e x t , we compare g e n e r a l l y t h e FFF methodol-
ogy w i t h o t h e r approaches used f o r measuring p a r t i c l e s i z e . Such
comparisons a r e d i f f i c u l t because t h e e f f i c a c y o f p a r t i c l e c h a r a c -
t e r i z a t i o n depends on t h e s p e c i a l needs a p p l i c a b l e t o each sample.
Thus sweeping g e n e r a l i z a t i o n s must be looked a t w a r i l y and a p p l i e d
w i t h d i s c r e t i o n . However, t h e s e g e n e r a l i z a t i o n s h e l p o r g a n i z e o u r
t h i n k i n g about such h i g h l y v a r i e d methodologies, and p o i n t us
toward d e s i r e d s o l u t i o n s .
For p r e s e n t purposes, p a r t i c l e c h a r a c t e r i z a t i o n methods a r e
d i v i d e d i n t o two major c a t e g o r i e s : those based on f r a c t i o n a t i o n
and t h o s e not. Some important t e c h n i q u e s f a l l i n g i n t h e s e two
c a t e g o r i e s a r e shown i n T a b l e I ; o t h e r t e c h n i q u e s a r e l i s t e d i n a
r e c e n t review ( 9 ) .

T a b l e I . Examples o f major p a r t i c l e c h a r a c t e r i z a t i o n
t e c h n i q u e s f a l l i n g i n two broad c a t e g o r i e s :
f r a c t i o n a t i o n and n o n f r a c t i o n a t i o n .
F r a c t i o n a t i o n methods N o n f r a c t i o n a t i o n methods""""
field-flow fractionation (FFF): light scattering: classical,
sedimentation, flow, s t e r i c , t u r b i d i m e t r i c , Fraunhofer,
etc. quasi-elastic, etc.
d i s c c e n t r i f u g a t i o n (DCF) neutron s c a t t e r i n g
hydrodynamic chromatography (HDC) electrozone
s i z e e x c l u s i o n chromatography (SEC) e l e c t r o n microscopy
s i e v i n g (SIV)

The n o n f r a c t i o n a t i o n t e c h n i q u e s , by themselves, use a v a r i e t y


o f phenomena t o probe p a r t i c l e c h a r a c t e r i s t i c s . In one c l a s s
( e . g . , most forms o f l i g h t s c a t t e r i n g ) , measurements a r e made on a
l a r g e , n o n d i f f e r e n t i a t e d p a r t i c l e p o p u l a t i o n . In another ( e . g . ,
e l e c t r o n microscopy and e l e c t r o z o n e methods), r e s u l t s a r e based on
a s t a t i s t i c a l a v e r a g i n g o f measurements made f o r i n d i v i d u a l
particles.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
15. GIDDINGS ET AL. Sedimentation Field-Flow Fractionation 219

As a c l a s s , f r a c t i o n a t i o n t e c h n i q u e s have c e r t a i n advantages
and d i s a d v a n t a g e s . A l i m i t a t i o n o f t h e f r a c t i o n a t i o n t e c h n i q u e s i s
t h a t adequate time must be taken t o c a r r y o u t t h e p a r t i c l e
s e p a r a t i o n . While t h i s time has been reduced t o o n l y a few minutes
i n some c a s e s , i t i s s t i l l slow compared t o t h e i d e a l case o f u s i n g
l i g h t as a probe, as i n l i g h t s c a t t e r i n g . (However, t o a c q u i r e
adequate d a t a t o c h a r a c t e r i z e broad p a r t i c l e d i s t r i b u t i o n s , l i g h t
s c a t t e r i n g experiments must o f t e n be c a r r i e d on f o r long p e r i o d s o f
time.)
A general advantage o f f r a c t i o n a t i o n i s t h a t i t breaks up
broad p a r t i c l e p o p u l a t i o n s i n t o component f r a c t i o n s , making i t
p o s s i b l e t o look a t t h e components i n d i v i d u a l l y and t o examine
t h e i r r o l e w i t h i n and c o n t r i b u t i o n t o t h e o v e r a l l p o p u l a t i o n .
Furthermore, each f r a c t i o n t y p i c a l l y c o n t a i n s a s u f f i c i e n t number
(10 - 10 ) o f p a r t i c l e s f o r v a l i d s t a t i s t i c a l r e p r e s e n t a t i o n .
The advantages o f f r a c t i o n a t i o n a r e a m p l i f i e d b important
c h a r a c t e r i s t i c s which ma
fractionation techniques
are:
1. High r e s o l u t i o n . The wealth o f d e t a i l about a p a r t i c l e
p o p u l a t i o n i n c r e a s e s w i t h t h e r e s o l u t i o n between p a r t i c l e
components.
2. Sample e l u t i o n . With e l u t i o n , d e t e c t i o n i s s i m p l i f i e d and
p a r t i c l e f r a c t i o n s can be c o l l e c t e d and subjected t o f u r t h e r
c h a r a c t e r i z a t i o n by a d d i t i o n a l f r a c t i o n a t i o n s t e p s , chemical
a n a l y s i s , e l e c t r o n microscopy, and o t h e r methods.
3. Exact t h e o r y . I f p a r t i c l e p r o p e r t i e s can be r e l a t e d
e x a c t l y t o t h e i r observed b e h a v i o r i n t h e f r a c t i o n a t i o n system,
then t h e p r o p e r t i e s can be deduced d i r e c t l y from e x p e r i m e n t a l
r e s u l t s without the uncertainties o f c a l i b r a t i o n procedures.
4. A d a p t a b i l i t y and f l e x i b i l i t y . A g r e a t e r v a r i e t y o f p a r -
t i c l e s can be t r e a t e d and more o f t h e i r p r o p e r t i e s measured i f t h e
f r a c t i o n a t i o n system i s a p p l i c a b l e t o a wide range o f p a r t i c l e
s i z e s , chemical t y p e s , and suspending media, and i f f r a c t i o n a t i o n
c o n d i t i o n s can be e a s i l y v a r i e d t o y i e l d complementary d a t a under
different conditions.
The f o u r c h a r a c t e r i s t i c s l i s t e d above a r e n o t a l l - i n c l u s i v e .
Other f a c t o r s i n c l u d e speed and ease o f o p e r a t i o n . However, t h e s e
f a c t o r s a r e n o t as i n t r i n s i c t o t h e method and a r e more s u b j e c t t o
changes, improvements, and t r a d e o f f s . Some o f t h e s e f a c t o r s w i l l
be d i s c u s s e d s h o r t l y .
In T a b l e I I , we show how t h e f i v e f r a c t i o n a t i o n t e c h n i q u e s
l i s t e d i n T a b l e 1 compare w i t h r e s p e c t t o t h e f o u r c h a r a c t e r i s t i c s
T a b l e I I . Comparison o f f r a c t i o n a t i o n t e c h n i q u e s
w i t h r e s p e c t t o f o u r i n t r i n s i c f e a t u r e s o f major importance.
exact
resolution elution theory flexibility
FFF high yes yes high
DCF high no yes medium
HDC low yes no low
SEC medium yes no low
SIV low no no low

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
220 PARTICLE SIZE DISTRIBUTION

l i s t e d above. The importance o f these c h a r a c t e r i s t i c s i s d i s c u s s e d


at g r e a t e r l e n g t h below.
R e s o l u t i o n i s without q u e s t i o n a key element i n a c c u r a t e and
detailed p a r t i c l e characterization. P a r t i c l e populations that
cannot be r e s o l v e d cannot, i n any sense, be d i s t i n g u i s h e d from one
another. While d e c o n v o l u t i o n t e c h n i q u e s can p r o v i d e p a r t i c l e s i z e
d i s t r i b u t i o n curves from low r e s o l u t i o n systems, t h e d e c o n v o l u t i o n
must be based on assumptions about i n s t r u m e n t a l band broadening and
band shape. In g e n e r a l , any d e t a i l e d i n f o r m a t i o n l o s t because o f
poor r e s o l u t i o n cannot be recovered by mathematical m a n i p u l a t i o n
a l o n e . I n a l l c a s e s , t h e q u a l i t y o f a s i z e d i s t r i b u t i o n curve w i l l
i n c r e a s e with t h e i n t r i n s i c r e s o l u t i o n e x h i b i t e d by t h e system.
We note t h a t FFF and d i s c c e n t r i f u g a t i o n both a c h i e v e high
r e s o l u t i o n r a n k i n g s i n T a b l e I I . T h i s comparable r e s o l u t i o n has
been p r e d i c t e d t h e o r e t i c a l l y ; any f i e l d (such as a s e d i m e n t a t i o n
f i e l d ) a p p l i e d d i r e c t l y t o a sample w i l l l e a d t o a p p r o x i m a t e l t h e
same r e s o l u t i o n as foun
p r o v i d i n g t h e displacemen
t h e o r y , r e s o l u t i o n i n FFF can be a m p l i f i e d by t h e a r b i t r a r y l e n g t h
of t h e s e p a r a t i o n path (channel l e n g t h ) , i n p r a c t i c e t h e two ap
proaches have comparable l e v e l s o f r e s o l u t i o n .
The r e s o l u t i o n a c h i e v a b l e by a system depends upon t h e number
o f t h e o r e t i c a l p l a t e s generated by t h a t system and upon t h e s e l e c
t i v i t y o f t h e system. The number o f t h e o r e t i c a l p l a t e s can be
v a r i e d w i d e l y with s e p a r a t i o n path l e n g t h , f l o w c o n d i t i o n s , f i e l d
s t r e n g t h , e t c . , and i s thus h i g h l y v a r i a b l e . However, s e l e c t i v i t y
i s a more i n t r i n s i c p r o p e r t y o f t h e f r a c t i o n a t i o n method and s e r v e s
as a b a s i s o f comparison o f t h e d i f f e r e n t systems.
S i z e s e l e c t i v i t y can be d e f i n e d by t h e e q u a t i o n

d In V d dV / n
S
d
= =
V 33 ( 1 )

where V i s p a r t i c l e v e l o c i t y and d i s p a r t i c l e diameter. T h i s


e x p r e s s i o n i s a p p l i c a b l e t o both e l u t i o n and n o n e l u t i o n systems.
(For e l u t i o n systems, V i s g e n e r a l l y used i n p l a c e o f V ( 1 1 ) ) .
The u s e f u l n e s s o f s e l e c t i v i t y as an index o f r e s o l u t i o n foTTows i f
we note t h a t a high S. i m p l i e s t h a t a small increment i n p a r t i c l e
diameter Ad g i v e s r i s e t o a l a r g e increment i n v e l o c i t y AV, which
l e a d s t o h i g h l y r e s o l v e d f r a c t i o n s . When t h e same small Ad i s
accompanied by a v e r y small AV, then d i s c r i m i n a t i o n i s l o s t .
In T a b l e I I I , we show t h e s e l e c t i v i t i e s c h a r a c t e r i s t i c o f f o u r
o f t h e f r a c t i o n a t i o n methods i n t h e i r normal working range.
Excluded from t h i s l i s t i s s i e v i n g , t o which t h e concept o f s e l e c
t i v i t y i s not a p p l i c a b l e . F o r completeness, we have s u b d i v i d e d t h e
FFF f a m i l y i n t o s e d i m e n t a t i o n F F F , thermal FFF, f l o w FFF, and
s t e r i c FFF t o show how t h e s e l e c t i v i t y o f each o f t h e s e s u b t e c h
niques compares t o t h a t o f t h e o t h e r f r a c t i o n a t i o n methods. The S.
v a l u e s r e p o r t e d here d i f f e r from S v a l u e s r e p o r t e d elsewhere ( 1 2 ) ,
which r e f e r t o mass r a t h e r than s i z e s e l e c t i v i t y .
The second c h a r a c t e r i s t i c l i s t e d i n T a b l e I I i s e l u t i o n .
E l u t i o n p r o v i d e s a c o n s i d e r a b l e advantage f o r d e t e c t i n g and
p r o c e s s i n g t h e sample a f t e r t h e f r a c t i o n a t i o n i s complete.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
15. GIDDINGS ET AL. Sedimentation Field-Flow Fractionation 221

T a b l e I I I . Comparison o f s e l e c t i v i t y S. f o r
p r i n c i p a l p a r t i c l e f r a c t i o n a t i o n methods.
method

FFF:*
sedimentation 3
flow 1
thermal 1.2
steric 0.5 - 1
DCF 2
HDC 0.02 - 0.03
SEC 0.03 - 0.22
*
values applicabl
+ carrier velocity
For polymers where we c o n s i d e r
p a r t i c l e diameter d = t w i c e hydro-dynamic radius.

However, not a l l samples r e q u i r e e l u t i o n , p a r t i c u l a r l y i f the


application is routine.
The t h i r d c h a r a c t e r i s t i c e n t e r e d i n T a b l e II r e f l e c t s the
e x a c t n e s s o f the t h e o r e t i c a l r e l a t i o n s h i p between p a r t i c l e
p r o p e r t i e s and experimental r e s u l t s . Except i n s p e c i a l c a s e s , a
r i g o r o u s t h e o r e t i c a l l i n k a g e w i l l improve the q u a l i t y o f i n f o r m a -
t i o n d e r i v e d from a f r a c t i o n a t i o n experiment.
The f i n a l c h a r a c t e r i s t i c o f T a b l e I I , f l e x i b i l i t y , p r o v i d e s an
index o f a system's a b i l i t y t o cope w i t h d i v e r s e p a r t i c u l a t e
m a t e r i a l s under v a r i e d c i r c u m s t a n c e s . While f l e x i b i l i t y i s not
important f o r r e p e t i t i v e runs o f the same m a t e r i a l , i t i s important
f o r e x p l o r i n g new p a r t i c l e t y p e s , measuring new p r o p e r t i e s ,
e v a l u a t i n g a c c u r a c y , and f o r o p t i m i z i n g the speed and r e s o l u t i o n
a s s o c i a t e d w i t h the p a r t i c l e c h a r a c t e r i z a t i o n . FFF ranks h i g h e s t
f o r f l e x i b i l i t y because o f the l a r g e number o f i n f l u e n t i a l
parameters s u b j e c t t o v a r i a t i o n : f i e l d t y p e , f i e l d s t r e n g t h , f l o w
v e l o c i t y , channel dimensions, and c a r r i e r p r o p e r t i e s . F i e l d
s t r e n g t h and f l o w v e l o c i t y are e s p e c i a l l y important; both a f f e c t
speed and r e s o l u t i o n and can be p l a y e d a g a i n s t one another f o r
o p t i m i z a t i o n . The v a r i a t i o n o f e i t h e r p r o p e r t y d u r i n g a run can
l e a d t o a v e r s a t i l e approach c a l l e d programming. We w i l l show
l a t e r t h a t the v a r i a t i o n o f c a r r i e r d e n s i t y l e a d s t o the measure-
ment o f p a r t i c l e d e n s i t y .
I t i s i n t e r e s t i n g t o compare the f l e x i b i l i t y o f t h r e e
t e c h n i q u e s F F F , HDC, and DCF. In HDC, f l o w i s a v a r i a b l e , but
t h e r e i s n o t h i n g e q u i v a l e n t t o f i e l d s t r e n g t h t o modulate the
e f f e c t o f f l o w ; thus f l o w r a t e s are not w i d e l y v a r i e d . In DCF,
f i e l d s t r e n g t h can be v a r i e d , but t h e r e i s no f l o w f o r compensating
adjustments and t h e r e i s l i t t l e p r o f i t i n v a r y i n g c o n d i t i o n s from
one run t o the next. In FFF, by c o n t r a s t , both f i e l d and f l o w are
w i d e l y and p r o f i t a b l y v a r i e d t o reach the d e s i r e d g o a l s o f speed,
a c c u r a c y , and redundancy.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
222 PARTICLE SIZE DISTRIBUTION

Theory
We have noted t h a t t h e combination o f r e g u l a r geometry, u n i f o r m
f i e l d s t r e n g t h , and w e l l - d e f i n e d p a r a b o l i c f l o w , make p o s s i b l e a
r i g o r o u s t h e o r e t i c a l treatment t o r e l a t e p a r t i c l e p r o p e r t i e s t o
experimental o b s e r v a t i o n s . T h i s t h e o r y s e r v e s as t h e b a s i s f o r
p a r t i c l e c h a r a c t e r i z a t i o n i n s e d i m e n t a t i o n FFF ( 2 ) . Here, we w i l l
b r i e f l y review t h e main t h e o r e t i c a l concepts and some o f t h e equa
t i o n s needed f o r p a r t i c l e s i z e c a l c u l a t i o n s .
We note f i r s t t h a t immediately f o l l o w i n g t h e i n j e c t i o n o f a
sample a t t h e head o f t h e c h a n n e l , t h e f l o w o f c a r r i e r i s stopped
b r i e f l y t o a l l o w time f o r t h e sample p a r t i c l e s t o accumulate near
the a p p r o p r i a t e w a l l . As t h e p a r t i c l e s c o n c e n t r a t e near t h e w a l l ,
the growing c o n c e n t r a t i o n g r a d i e n t l e a d s t o a d i f f u s i v e f l u x which
c o u n t e r a c t s t h e i n f l u x o f p a r t i c l e s . Because channel t h i c k n e s s i s
small ( a p p r o x i m a t e l y 0.25 mm) t h e s e two mass t r a n s p o r t p r o c e s s e s
q u i c k l y balance one a n o t h e r
near t h e accumulation w a l l
t i a l form

c(x) = c exp(-xAw)
Q (2)

where c ( x ) i s t h e c o n c e n t r a t i o n a t e l e v a t i o n above t h e w a l l , c
i s t h e c o n c e n t r a t i o n a t t h e w a l l (x = 0 ) , w i s t h e channel t h i c k
ness, and i s t h e r e t e n t i o n parameter. Q u a n t i t y i s a
d i m e n s i o n l e s s measure o f t h e t h i c k n e s s o f t h e e q u i l i b r i u m p a r t i c l e
c l o u d ; w i l l vary from one p a r t i c l e s i z e t o another as a r e f l e c
t i o n o f t h e f a c t t h a t t h e f o r c e d r i v i n g t h e p a r t i c l e s toward t h e
w a l l and t h e r e s u l t a n t c l o u d t h i c k n e s s i s a f u n c t i o n o f p a r t i c l e
d i a m e t e r . Thus t h e dependence o f on p a r t i c l e diameter d i s
ultimately responsible f o r particle separation.
S p e c i f i c a l l y , f o r sedimentation FFF, r e l a t e s t o d (along
w i t h f i e l d s t r e n g t h ( a c c e l e r a t i o n ) G and t h e d i f f e r e n c e i n
d e n s i t y between t h e p a r t i c l e and t h e c a r r i e r ) a c c o r d i n g t o t h e
expression
3
= 6kT/d ApGw (3)

For n o n s p h e r i c a l p a r t i c l e s , d r e p r e s e n t s an e f f e c t i v e d i a m e t e r ( t h e
diameter o f a sphere o f equal volume).
E q u a t i o n 3 can be r e a r r a n g e d as f o l l o w s t o y i e l d d i n terms o f

, 6kT .1/3 f 4 x

At t h e end o f t h e s t o p - f l o w p e r i o d i n which t h e p a r t i c l e
c l o u d s reach e q u i l i b r i u m , f l o w i s resumed and t h e p a r t i c l e s a r e
d i s p l a c e d downstream. The d i s p l a c e m e n t v e l o c i t y i s c h a r a c t e r i z e d
by t h e d i m e n s i o n l e s s r e t e n t i o n r a t i o R, which i s d e s c r i b e d by t h e
equation

R = v/<v> = V / V = 6 X [ c o t h ( l / 2 X ) - 2]
r (5)

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
15. GIDDINGS ET AL. Sedimentation Field-Flow Fractionation 223

T h i s e q u a t i o n shows t h a t R i s g i v e n by the r a t i o of p a r t i c l e d i s
placement v e l o c i t y V t o average c a r r i e r v e l o c i t y <v>, o r
e q u i v a l e n t l y t o the r a t i o o f channel v o i d volume V t o the r e t e n
t i o n volume V . Thus R i s e x p e r i m e n t a l l y a c c e s s i b l e because V i s
the measured volume r e q u i r e d t o d i s p l a c e a g i v e n p a r t i c l e s i z e
through the c h a n n e l . However, the e q u a t i o n a l s o shows t h a t R i s
r e l a t e d to , which i s r e l a t e d t o d through the p r e v i o u s e q u a t i o n .
Thus a l i n k a g e i s formed between p a r t i c l e diameter d and experimen
t a l r e t e n t i o n volume V . I t has been e s t i m a t e d t h a t p a r t i c l e
diameters a c c u r a t e t o 1-3* can be o b t a i n e d by u s i n g t h i s approach
(2).
In p r a c t i c e , we use as an i n t e r m e d i a t e parameter i n t h i s
c a l c u l a t i o n ; a v a l u e can be o b t a i n e d n u m e r i c a l l y from E q u a t i o n 5
f o r each measurement o f V and t h i s v a l u e used t o produce a p a r
t i c l e diameter d from E q u a t i o n 4.
We note t h a t a t hig
simpler equation
R = 6 (6)

While the p r i n c i p a l t o o l f o r p a r t i c l e c h a r a c t e r i z a t i o n i n
s e d i m e n t a t i o n FFF i s the f o r e g o i n g e q u a t i o n s a p p l i e d t o measured
retention levels, additional particle information, particularly f o r
narrow d i s t r i b u t i o n s , can be o b t a i n e d through the measurement o f
band broadening.
Band broadening a r i s e s from t h r e e p r i n c i p a l mechanisms, one o f
which depends on the mean v e l o c i t y <v> o f the c a r r i e r and two o f
which are independent o f <v>. The l a t t e r two r e p r e s e n t non-
i d e a l i t i e s i n instrument and sample. The t o t a l v a r i a n c e o f an
e l u t i n g peak i s the sum o f v a r i a n c e s c o n t r i b u t e d by each band-
broadening mechanism. Expressed as p l a t e h e i g h t H, which i s the
t o t a l v a r i a n c e d i v i d e d by column l e n g t h L ( 1 2 ) , the zone broadening
i s d e s c r i b e d by
2 2 g
2 2
= X j j - <v> + 81L(J (-^ + R - l ) ) (-ij) + H 1 (7)
36
By r e f i n i n g column d e s i g n , the i n s t r u m e n t a l band broadening H. has
been reduced t o a l e v e l i n s i g n i f i c a n t i n comparison w i t h the o t h e r
terms o f E q u a t i o n 7. The n o n e q u i l i b r i u m term, l i n e a r i n c a r r i e r
v e l o c i t y <v>, a l s o depends on channel t h i c k n e s s w and i n v e r s e l y on
p a r t i c l e d i f f u s i o n c o e f f i c i e n t D. The dependence o f c o e f f i c i e n t
on i s w e l l known, although the f u n c t i o n i s complex ( 1 4 ) . I t s
l i m i t i n g form i s d e s c r i b e d by
3
lim = 24 (8)
- 0
The remaining ( c e n t r a l ) term on the r i g h t o f E q u a t i o n 7 i s a
p o l y d i s p e r s i t y term. I t accounts f o r the broadening which r e s u l t s
from the a c t u a l f r a c t i o n a t i o n o f the d i f f e r e n t s i z e d p a r t i c l e s
which make up the narrow sample. T h i s term has a square dependence
on the standard d e v i a t i o n i n p a r t i c l e diameter

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
224 PARTICLE SIZE DISTRIBUTION

The above e q u a t i o n s may y i e l d u s e f u l p a r t i c l e parameters.


Thus both the s t a n d a r d d e v i a t i o n . i n p a r t i c l e diameter and d i f f u
s i o n c o e f f i c i e n t D can be r e l a t e d e x p e r i m e n t a l v a l u e s . A
procedure f o r o b t a i n i n g p a r t i c l e i n f o r m a t i o n v i a t h i s r o u t e w i l l be
d e t a i l e d i n our d i s c u s s i o n o f monodisperse p a r t i c l e p o p u l a t i o n s .
Monodisperse P a r t i c l e P o p u l a t i o n s
Narrow p a r t i c l e f r a c t i o n s approaching a monodisperse d i s t r i b u t i o n
are p a r t i c u l a r l y easy t o t r e a t and c h a r a c t e r i z e when the above
equations are a p p l i e d t o e x p e r i m e n t a l d a t a . F i g u r e 2 shows an
example o f the e l u t i o n p r o f i l e ( f r a c t o g r a m ) o b t a i n e d by r u n n i n g a
mixture o f f o u r samples o f "monodisperse" p o l y s t y r e n e l a t e x beads.
It i s c l e a r from the f i g u r e t h a t a r a t h e r p r e c i s e v a l u e o f r e t e n
t i o n volume V can be i d e n t i f i e d w i t h each bead s i z e . With V
r f

known, i t i s easy t o o b t a i
p a r t i c l e diameter d fro
y i e l d s d i a m e t e r s a c c u r a t e t o a p p r o x i m a t e l y 1-3%.
As s t a t e d p r e v i o u s l y , a d d i t i o n a l i n f o r m a t i o n on the sample i s
o b t a i n a b l e from band broadening ( p l a t e h e i g h t ) measurements. I f
p l a t e h e i g h t i s measured as a f u n c t i o n o f f l o w v e l o c i t y a t a f i x e d
r e t e n t i o n l e v e l , a l i n e a r r e l a t i o n s h i p i s o b t a i n e d , as p r e d i c t e d by
Equation 7. The s l o p e o f the l i n e y i e l d s the d i f f u s i v i t y D o f the
sample, and the i n t e r c e p t p r o v i d e s the p o l y d i s p e r s i t y .. The D
v a l u e t r a n s l a t e s i n t o a v a l u e f o r t h e average p a r t i c l e d i a m e t e r d
v i a the S t o k e s - E i n s t e i n r e l a t i o n s h i p

D = kT/3nd (9)

i n which k i s the Boltzmann c o n s t a n t , the temperature, and the


v i s c o s i t y o f the c a r r i e r . Thus, a combination o f r e t e n t i o n and
p l a t e h e i g h t measurements w i l l , i n t h e o r y , f u l l y c h a r a c t e r i z e a
narrow sample o f s p h e r i c a l p a r t i c l e s , y i e l d i n g p a r t i c l e d i a m e t e r ,
p o l y d i s p e r s i t y , and d e n s i t y , the l a t t e r by i n s e r t i n g d from
Equation 9 i n t o E q u a t i o n 3 t o o b t a i n . However, we note t h a t
parameters based on zone broadening measurements a r e p r e s e n t l y l e s s
a c c u r a t e than those based on r e t e n t i o n measurements, so we seek
a d d i t i o n a l i n f o r m a t i o n from r e t e n t i o n .
P a r t i c l e d e n s i t y can a l t e r n a t i v e l y be e v a l u a t e d from a s e t o f
r e t e n t i o n measurements made i n c a r r i e r s o f d i f f e r e n t d e n s i t y ( 1 5 ) .
Such d e n s i t y m o d i f i c a t i o n s are t y p i c a l l y accomplished by s u c c e s s i v e
a d d i t i o n s o f s u c r o s e t o the c a r r i e r . The observed r e t e n t i o n v a l u e s
y i e l d p a r t i c l e s i z e and d e n s i t y through E q u a t i o n 2. A r e a r r a n g e
ment o f t h i s e q u a t i o n l e a d s t o a g r a p h i c a l procedure f o r
s i z e / d e n s i t y e v a l u a t i o n . The r e a r r a n g e d form i s
6kT 1 n r n
= - - -
s
(10)
d\Gw

Here, from the o r i g i n a l e q u a t i o n i s e x p l i c i t l y e x p r e s s e d as


- , the d i f f e r e n c e between the d e n s i t y o f the sample p a r
t i c l e and the d e n s i t y o f the c a r r i e r . By p l o t t i n g the r e c i p r o c a l
of the r e t e n t i o n - d e r i v e d a g a i n s t t h e d e n s i t y o f t h e c a r r i e r i n
which r e t e n t i o n i s o b s e r v e d , a l i n e i s o b t a i n e d whose s l o p e g i v e s

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
15. GIDDINGS ET AL. Sedimentation Field-Flow Fractionation 225

the p a r t i c l e diameter and whose i n t e r c e p t y i e l d s i t s d e n s i t y . T h i s


method has been shown t o y i e l d a c c u r a t e s i z e and d e n s i t y v a l u e s f o r
monodisperse p o l y s t y r e n e l a t e x spheres ( 1 5 ) .
Polydisperse P a r t i c l e Populations
Most p a r t i c u l a t e samples o f i n t e r e s t c o n t a i n p a r t i c l e s d i s t r i b u t e d
over a broad s i z e range. Sedimentation FFF s o r t s such p o l y d i s p e r s e
m a t e r i a l s i n t o n e a r l y monodisperse p o p u l a t i o n s . These are con
t i n u o u s l y e l u t e d from the FFF channel b e g i n n i n g w i t h the s m a l l e s t
p a r t i c l e s and ending w i t h the l a r g e s t . A d e t e c t o r a t the end o f
the channel m o n i t o r s the p a r t i c l e content as a f u n c t i o n o f e l u t i o n
( r e t e n t i o n ) volume. A p l o t o f d e t e c t o r response vs e l u t i o n volume
i s shown i n F i g u r e 3. T h i s p l o t i s c a l l e d a f r a c t o g r a m . The
r e t e n t i o n volume f o r each volume element, emerging at a s p e c i f i c
v a l u e o f V , can be converted valu f retentio
through E q u a t i o n 5, which
p a r t i c l e diameter d o f th y Equatio
the t h e o r e t i c a l r i g o r o f s e d i m e n t a t i o n FFF makes i t p o s s i b l e t o
a s s i g n a d v a l u e t o each volume f r a c t i o n . In the example shown i n
F i g u r e 3, the a s s i g n e d p a r t i c l e diameters c a l c u l a t e d i n t h i s way
are developed i n t o a d s c a l e p a r a l l e l i n g the V s c a l e . Note t h a t
the d s c a l e i s a s s i g n e d p u r e l y by t h e o r y , r e q u i r i n g no c a l i b r a t i o n .
A f r a c t o g r a m w i t h an a u x i l i a r y d s c a l e l i k e t h a t shown i n
F i g u r e 3 can be used d i r e c t l y t o c h a r a c t e r i z e p o l y d i s p e r s e
m a t e r i a l s at a high l e v e l o f r e s o l u t i o n / d e t a i l . Small changes i n
p a r t i c l e p o p u l a t i o n s , r e f l e c t i n g changes i n environmental c o n d i
t i o n s o r p r o c e s s c o n t r o l parameters, w i l l be r e f l e c t e d immediately
i n the f r a c t o g r a m and can be d i s t i n g u i s h e d by a comparison o f
f r a c t o g r a m s . The p a r t i c l e diameter range over which any such
change takes p l a c e can be d i r e c t l y i d e n t i f i e d from such a
comparison. Using t h i s approach, we have c h a r a c t e r i z e d d i v e r s e
m a t e r i a l s such as emulsions, p r o t e i n p a r t i c l e s , liposomes, and
waterborne c o l l o i d s .
The same g e n e r a l procedure a p p l i e s t o programmed s e d i m e n t a t i o n
FFF. In programming, the f i e l d s t r e n g t h i s reduced c o n t i n u o u s l y
d u r i n g the run t o condense broad p a r t i c l e d i s t r i b u t i o n s w i t h i n a
r e a s o n a b l e range o f e l u t i o n volumes. The g e n e r a l t h e o r y o f
programming (16) can be a p p l i e d t o c o n s t r u c t a p a r t i c l e diameter
s c a l e f o r any f r a c t o g r a m o b t a i n e d under a r b i t r a r y programming
c o n d i t i o n s . An example o f programmed o p e r a t i o n w i l l be d e s c r i b e d
by K i r k l a n d e t a l . i n another paper i n t h i s volume.
While the simple p r o c e s s o f comparing f r a c t o g r a m s w i t h ap
pended p a r t i c l e diameter s c a l e s w i l l p r o v i d e a l l the i n f o r m a t i o n
needed i n many p a r t i c l e c h a r a c t e r i z a t i o n s t u d i e s , the f r a c t o g r a m
does not c o n s t i t u t e a f i n i s h e d p a r t i c l e s i z e d i s t r i b u t i o n (PSD)
c u r v e . To o b t a i n a q u a n t i t a t i v e PSD c u r v e , c o r r e c t i o n s must be
a p p l i e d . The f i r s t c o r r e c t i o n , which we c a l l a s c a l e c o r r e c t i o n ,
i s n e c e s s a r y because e l u t i o n volume and p a r t i c l e diameter are not
p r o p o r t i o n a l t o one another. Thus the p a r t i c l e c o n t e n t o f a f i x e d
volume o f e l u t e d sample w i l l correspond t o a d i f f e r e n t increment i n
d depending upon the p o i n t o f c o l l e c t i o n . A simple c o r r e c t i o n
f a c t o r , d e t a i l e d elsewhere ( 3 ) , can be a p p l i e d t o t h i s s c a l e
problem.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
226 PARTICLE SIZE DISTRIBUTION

0.480um
r
0.357um

V (ml)
r

F i g u r e 2. F r a c t i o n a t i o n o f f o u r samples o f Dow p o l y s t y r e n e l a t e x
beads by s e d i m e n t a t i o n FFF. The nominal p a r t i c l e s i z e s are g i v e n
in the f i g u r e . F l o w r a t e = 12 ml/hr, channel t h i c k n e s s w = 0.0127
cm, v o i d volume V = 2.0 ml, and f i e l d s t r e n g t h G = 193.7 g r a v i t i e s .
Reproduced w i t h p e r m i s s i o n from Ref. 20. C o p y r i g h t 1980 John W i l e y .

0 0.15 0.20 0.25 0.30 0.35


PARTICLE DIAMETER ()
I . . . .
0 20 40 60 80
RETENTION VOLUME (ml)
F i g u r e 3. Fractogram o f PVC l a t e x w i t h superimposed p a r t i c l e
diameter s c a l e . F i e l d = 82.6 g , flow = 226 ml/hr, V = 2,0
ml, sample = 40 o f 6% PVC. Reproduced w i t h p e r m i s s i o n from
Ref. 20. C o p y r i g h t 1980 John W i l e y .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
15. GIDDINGS ET AL. Sedimentation Field-Flow Fractionation 227

A second c o r r e c t i o n may be needed f o r d i s t o r t i o n s i n the


d e t e c t o r r e s p o n s e . T h i s i s p a r t i c u l a r l y t r u e of the UV m o n i t o r s
commonly used f o r p a r t i c l e d e t e c t i o n . While the s i g n a l f o r any
g i v e n volume element i s p r o p o r t i o n a l to the p a r t i c l e c o n t e n t of
t h a t volume, the s i g n a l i s s e n s i t i v e to p a r t i c l e s i z e and thus
v a r i e s as we pass from one p a r t i c l e d i a m e t e r to a n o t h e r . The UV
monitor i s e s s e n t i a l l y a t u r b i d i m e t r i c d e t e c t o r whose s i g n a l i n
c r e a s e s s i g n i f i c a n t l y with p a r t i c l e d i a m e t e r . C o r r e c t i o n s based on
the Mie t h e o r y of l i g h t s c a t t e r i n g have been d e v e l o p e d . However, a
more s u i t a b l e approach has been p r e s e n t e d by Oppenheimer (17), who
has used a s p e c i a l l i g h t s c a t t e r i n g d e t e c t o r w i t h a s i g n a l no
l o n g e r dependent on p a r t i c l e s i z e . With t h i s d e t e c t o r , a second
c o r r e c t i o n f a c t o r i s no l o n g e r n e c e s s a r y .
While e i t h e r the f u l l y c o r r e c t e d PSD or the n o n c o r r e c t e d PSD
r e p r e s e n t e d by the f r a c t o g r a m w i l l p r o v i d e a l l of the i n f o r m a t i o n
needed by most u s e r s , s e d i m e n t a t i o FFF i s u f f i c i e n t l v e r s a t i l
t o p r o v i d e more i n f o r m a t i o
p h y s i c a l c o l l e c t i o n of smal
The f r a c t i o n s can then be s u b j e c t e d to a broad v a r i e t y of t e s t s
u s i n g m i c r o s c o p i c , c h e m i c a l , or subsequent FFF p r o c e d u r e s .
We have shown t h a t f r a c t i o n s c o l l e c t e d from broad p a r t i c l e
d i s t r i b u t i o n s can be r e i n j e c t e d i n t o the s e d i m e n t a t i o n FFF d e v i c e
f o r a second run (18). The emerging peaks are r e l a t i v e l y narrow,
r e f l e c t i n g t h e i r small p a r t i c l e s i z e range. Q u i t e o b v i o u s l y , a
r e i n j e c t e d f r a c t i o n run i n a c a r r i e r of a d i f f e r e n t d e n s i t y w i l l
emerge at a d i f f e r e n t volume because of the e f f e c t of on r e t e n
t i o n parameter (see E q u a t i o n 3 ) . The s h i f t i n r e t e n t i o n volume
(see next s e c t i o n ) can be used t o c a l c u l a t e the d e n s i t y of the
p a r t i c u l a t e m a t e r i a l e x a c t l y as o u t l i n e d f o r monodisperse
populations.
An a l t e r n a t e approach f o r d e t e r m i n i n g p a r t i c l e d e n s i t y i n
v o l v e s f r a c t i o n c o l l e c t i o n f o l l o w e d by the a p p l i c a t i o n of q u a s i -
e l a s t i c l i g h t s c a t t e r i n g (QEL) t o the f r a c t i o n (19). The QEL
t e c h n i q u e i s p a r t i c u l a r l y e f f e c t i v e i n p r o v i d i n g a mean p a r t i c l e
d i a m e t e r d f o r narrow p a r t i c l e d i s t r i b u t i o n s . With t h i s d and the
o b t a i n e d from V (the volume at which the f r a c t i o n was
c o l l e c t e d ) , can be c a l c u l a t e d d i r e c t l y from E q u a t i o n 3.
A d d i t i o n of the known c a r r i e r d e n s i t y t o then y i e l d s the p a r
t i c l e d e n s i t y . D e n s i t y v a l u e s a c c u r a t e to w i t h i n a few p e r c e n t
have been o b t a i n e d i n a p r e l i m i n a r y a p p l i c a t i o n of t h i s t e c h n i q u e
(1?).

Complex C o l l o i d s
E a r l i e r we d e s c r i b e d complex c o l l o i d s as those having p a r t i c l e s o f
v a r i a b l e chemical c o m p o s i t i o n . Most c o l l o i d s of b i o l o g i c a l and
environmental o r i g i n and some of i n d u s t r i a l o r i g i n are complex.
These c o l l o i d s r e p r e s e n t a s e v e r e c h a l l e n g e f o r c o l l o i d c h a r a c
t e r i z a t i o n methods.
To o b t a i n any depth of knowledge about complex c o l l o i d s ,
i n f o r m a t i o n of two types must be o b t a i n e d . F i r s t , p a r t i c l e s i z e
i n f o r m a t i o n must be a c q u i r e d . Second, f o r any g i v e n p a r t i c l e s i z e ,
i n f o r m a t i o n on the d i s t r i b u t i o n of chemical components or on the
d i s t r i b u t i o n of some important p r o p e r t y ( l i k e d e n s i t y ) t h a t

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
228 PARTICLE SIZE DISTRIBUTION

r e f l e c t s chemical composition must be c o l l e c t e d . The problem i s


a c t u a l l y a two-dimensional one, r e q u i r i n g f a r more i n f o r m a t i o n than
i s necessary t o c h a r a c t e r i z e c h e m i c a l l y homogeneous c o l l o i d s .
The v e r s a t i l i t y o f FFF, combined w i t h i t s f a c i l i t y f o r p r o v i d
ing narrow f r a c t i o n s , makes t h i s t e c h n i q u e a prime c a n d i d a t e f o r
the study o f complex c o l l o i d s . Work along t h i s l i n e has o n l y
r e c e n t l y s t a r t e d ; c o n s e q u e n t l y , we w i l l p r o v i d e o n l y an o u t l i n e
s u f f i c i e n t t o demonstrate a p p l i c a b i l i t y t o complex c o l l o i d s .
We r e t u r n f i r s t t o the p r o c e s s o f f r a c t i o n c o l l e c t i o n and note
t h a t subsequent t e s t i n g o f t e n y i e l d s the second dimension o f
i n f o r m a t i o n . I n t e r p r e t a t i o n i s somewhat c o m p l i c a t e d by the f a c t
t h a t any s i n g l e f r a c t i o n w i l l c o n t a i n a v a r i e t y o f p a r t i c l e s h a v i n g
d i f f e r e n t d e n s i t i e s and d i f f e r e n t s i z e s . However, f o r a g i v e n
f r a c t i o n ( g i v e n V and v a l u e s ) , diameter d and d e n s i t y a r e
connected by E q u a t i o n 3. T h e r e f o r e , any subsequent t e s t c a p a b l e o f
y i e l d i n g a second r e l a t i o n s h i p i n v o l v i n g d and/or w i l l y i e l d
i n f o r m a t i o n on both q u a n t i t i e s
copy i s used t o determin
the f r a c t i o n , then E q u a t i o n 3 can be used t o o b t a i n a d e n s i t y
distribution.
S i m i l a r l y , c o l l e c t e d f r a c t i o n s can be r e i n j e c t e d i n t o the
s e d i m e n t a t i o n FFF system o p e r a t e d w i t h a d i f f e r e n t c a r r i e r d e n s i t y .
The degree t o which the r e t e n t i o n volume f o r any p a r t i c l e type i s
s h i f t e d by t h i s o p e r a t i o n w i l l depend upon the d e n s i t y o f the
p a r t i c l e . In t h e o r y , the shape o f the f r a c t o g r a m f o l l o w i n g f r a c
t i o n r e i n j e c t i o n w i l l y i e l d a d e n s i t y d i s t r i b u t i o n curve f o r t h e
fraction.
I f the same measurements are made f o r each o f s e v e r a l f r a c
t i o n s c o l l e c t e d a l o n g the e l u t i o n volume a x i s , the d e n s i t y
d i s t r i b u t i o n f o r each f r a c t i o n w i l l be c a l c u l a b l e . In t h i s way, we
e n v i s i o n the p o s s i b i l i t y o f b u i l d i n g up a t r u e two-dimensional
r e p r e s e n t a t i o n t o c h a r a c t e r i z e the p a r t i c l e m i x t u r e . In t h i s
r e p r e s e n t a t i o n , the p a r t i c l e c o n c e n t r a t i o n would be d i s p l a y e d as a
f u n c t i o n o f p a r t i c l e diameter a l o n g one a x i s and p a r t i c l e d e n s i t y
a l o n g another a x i s .
C o n s i d e r a b l e e f f o r t would c l e a r l y be needed t o c h a r a c t e r i z e
complex c o l l o i d s i n such a complete way. In many c a s e s , i t i s
l i k e l y t h a t one would o n l y need t o f o c u s on a c e r t a i n l i m i t e d
r e g i o n o f the s i z e - d e n s i t y m a t r i x , thus c o n s i d e r a b l y r e d u c i n g the
e x p e r i m e n t a l l a b o r . In a d d i t i o n , o t h e r t e c h n i q u e s (such as chemi
c a l a n a l y s i s ) might be brought i n t o p l a y t o s i m p l i f y the
experiments and, a t the same time, extend the i n f o r m a t i o n base. We
are a l s o examining an approach t o the two-dimensional ( s i z e -
d e n s i t y ) c h a r a c t e r i z a t i o n o f complex c o l l o i d s without the
requirement f o r f r a c t i o n c o l l e c t i o n .
The p r a c t i c a l i t y o f r e i n j e c t i o n methodology f o r p r o b i n g com
p l e x c o l l o i d a l m i x t u r e s has o n l y r e c e n t l y been demonstrated. In
t h i s experiment, a s y n t h e t i c m i x t u r e o f a p o l y d i s p e r s e PVC c o l l o i d
and a r a t h e r narrow p o l y s t y r e n e sample were s u b j e c t e d t o f r a c t i o n a
t i o n , y i e l d i n g the f r a c t o g r a m a p p e a r i n g a t the top o f F i g u r e 4. A
f r a c t i o n c o n t a i n i n g both k i n d s o f p a r t i c l e s was then c o l l e c t e d o v e r
the volume range i n d i c a t e d i n the f i g u r e . T h i s f r a c t i o n was con
c e n t r a t e d and then r e i n j e c t e d i n t o a s e d i m e n t a t i o n FFF system whose
c a r r i e r d e n s i t y was i n c r e a s e d t o a p p r o x i m a t e l y 1.03 g/ml by the
a d d i t i o n o f sucrose t o the aqueous b u f f e r . Because o f the lower
d e n s i t y (1.05 g/ml) and l a r g e r s i z e o f the p o l y s t y r e n e p a r t i c l e s i n
the f r a c t i o n , the buoyancy f o r c e s i n c r e a s e much more r a p i d l y f o r
these p a r t i c l e s than f o r the denser (^1.40 g/ml) PVC p a r t i c l e s .
In Particle Size Distribution; Provder, T.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
GIDDINGS ET AL. Sedimentation Field-Flow Fractionation

RETENTION VOLUME (ml)

F i g u r e 4. Cross-hatched a r e a i n f r a c t o g r a m A denotes a 5 ml
f r a c t i o n c o l l e c t e d from a s y n t h e t i c mix o f p o l y s t y r e n e (PS) and
p o l y v i n y l c h l o r i d e (PVC) run at 43.4 g w i t h c a r r i e r d e n s i t y =
1.00 g/ml. Same f r a c t i o n i s r e r u n (B) at 111 g i n c a r r i e r o f
d e n s i t y = 1.03 g/ml.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
230 P A R T I C L E SIZE DISTRIBUTION

Consequently, t h e p o l y s t y r e n e peak i s d i s p l a c e d t o a much lower


r e t e n t i o n volume and i s thus s h i f t e d away from t h e PVC peak, which
i s o n l y s l i g h t l y d i s p l a c e d . Consequently, these two chemical
forms, although o r i g i n a l l y mixed, can be s e p a r a t e d and independ-
ently characterized.
While many e x p e r i m e n t a l c h a l l e n g e s and d a t a r e d u c t i o n problems
must be d e a l t w i t h i n o r d e r t o extend FFF methodology t o important
complex c o l l o i d s , no fundamental b a r r i e r appears t o e x i s t which
would b l o c k p r o g r e s s i n t h i s d i r e c t i o n .
Acknowledgments
T h i s work was supported by c o n t r a c t number DE-AC02-79EV10244
from t h e Department o f Energy.
Literature Cited
1. Giddings, J.C.; Yang
46, 1917.
2. Giddings, J.C.; Karaiskakis, G.; Caldwell, K.D.; Myers, M.N.
J. C o l l o i d Interface Sci. 1983, 92, 66.
3. Yang, F.-S.; Caldwell, K.D.; Giddings, J.C. J. C o l l o i d
Interface Sci. 1983, 92, 81.
4. Yang, F.-S.; Caldwell, K.D.; Myers, M . N . ; Giddings, J.C. J.
C o l l o i d Interface Sci. 1983, 93, 115.
5. Caldwell, K.D. In "Modern Methods of P a r t i c l e Size Analysis";
Barth, H.G., Ed.; Wiley-Interscience: New York, 1984; Chapter
7.
6. Kirkland, J.J.; Rementer, S.W.; Yau, W.W. Anal. Chem. 1981,
53, 1730.
7. Commission on Analytical Nomenclature, Analytical Chemistry
D i v i s i o n , International Union of Pure and Applied Chemistry,
1974, 37, 4.
8. Peterson, R.E., II; Myers, M . N . ; Giddings, J.C. Sep. Sci.
Technol. 1984, 19, 307.
9. Barth, H.G.; Sun, S.-T. Anal. Chem. 1985, 57, 151R.
10. Giddings, J.C. Sep. Sci. 1973, 8, 567.
11. Myers, M . N . ; Giddings, J.C. Anal. Chem. 1982, 54, 2284.
12. Giddings, J.C. Pure & Appl. Chem. 1979, 51, 1459.
13. Karaiskakis, G.; Myers, M . N . ; Caldwell, K . D . ; Giddings, J.C.
Anal. Chem. 1981, 53, 1314.
14. Giddings, J.C.; Yoon, Y.H.; Caldwell, K.D.; Myers, M.N.;
Hovingh, M . E . Sep. Sci. 1975, 10, 447.
15. Giddings, J.C.; Karaiskakis, G.; Caldwell, K.D. Sep. S c i .
Technol. 1981, 16, 607.
16. Yang, F.J.F.; Myers, M . N . ; Giddings, J.C. Anal. Chem. 1974,
46, 1924.
17. Oppenheimer, L.E.; Mourey, T.H. J. Chromatogr. 1984, 298, 217.
18. Giddings, J.C.; Yang, F.-S. J. C o l l o i d Interface Sci. 1985,
105, 55.
19. Caldwell, K . D . ; Jones, H . K . ; Giddings, J.C. Colloids and
Surfaces, submitted.
20. Giddings, J.C.; Myers, M. N.; Caldwell, K . D . ; F i s h e r , S.R.
In "Methods o f Biochemical Analysis"; G l i c k , David, Ed.;
John Wiley & Sons, Inc.: New York, 1980; V o l . 26.
RECEIVED June 27, 1986
In Particle Size Distribution; Provder, T.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 16

Comparative Particle Size Analysis


M.E.Koehler and Theodore Provder
The Glidden Company, DwightP.Joyce Research Center, Strongsville,OH44136

A series of monodispers
synthesized and respec
refractive index, percent solids, and solution
density. The particle size of each latex was
analyzed by Disc Centrifuge Photosedimentometry
(DCP), Sedimentation Field Flow Fractionation
(SFFF), Hydrodynamic Chromatography (HDC),
Quasielastic Light Scattering (QELS), Transmission
Electron Microscopy (TEM), and turbidity. A
comparison of the apparent particle size averages of
the latexes as measured by each method showed that
for small, more monodisperse latexes the various
methods agree more closely than for larger diameter
samples having higher polydispersities. The relative
ordering of the apparent sizes by method is
consistent. The light scattering methods gave higher
apparent particle sizes, TEM the lowest number,
while DCP and SFFF were in relatively good agreement
in the center of the range. This is explained in
terms of the assumptions made and the physical
parameters measured by each method.

A v a r i e t y o f d i f f e r e n t i n s t r u m e n t a l methods a r e a v a i l a b l e f o r t h e
measurement o f t h e s i z e a n d s i z e d i s t r i b u t i o n o f p a r t i c u l a t e s .
T h e s e i n s t r u m e n t s u t i l i z e d i f f e r e n t p h y s i c a l p h e n o m e n a a s a means
of a s s e s s i n g t h e p a r t i c l e s i z e . S e d i m e n t a t i o n methods measure a
1
'hydrodynamic r a d i u s and r e q u i r e a knowledge o f the d e n s i t y o f
the p a r t i c l e as w e l l as the d e n s i t y and v i s c o s i t y o f t h e
s u s p e n d i n g f l u i d . Dynamic L i g h t s c a t t e r i n g methods measure t h e
d i f f u s i o n c o e f f i c i e n t a n d t e n d t o w e i g h t t h e measurement t o l a r g e r
p a r t i c l e s a n d a g g l o m e r a t e s . H y d r o d y n a m i c C h r o m a t o g r a p h y (HDC) i s a
c h r o m a t o g r a p h i c method w h i c h s e p a r a t e s p a r t i c l e s o n t h e b a s i s o f
t h e i r diameter by t h e i r d i f f e r e n t i a l r e t e n t i o n i n the f l o w streams
through the i n t e r s t i t i a l channels o f a packed column. T r a n s m i s s i o n
E l e c t r o n M i c r o s c o p y (TEM) a l l o w s t h e m e a s u r e m e n t o f t h e p a r t i c l e

0097-6156/87/0332-0231$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
232 PARTICLE SIZE DISTRIBUTION

s i z e o f h a r d p a r t i c l e s . H o w e v e r , TEM i s s u s c e p t i b l e t o d i s t o r t i o n
o f s o f t p a r t i c l e s , s h r i n k a g e o f p a r t i c l e s i n t h e e l e c t r o n beam,
and c a n n o t r e a d i l y a s c e r t a i n i f a g g l o m e r a t i o n h a s o c c u r e d . T h e
t u r b i d i t y method measures t h e a p p a r e n t a b s o r b a n c e o f a d i l u t e
suspension o f p a r t i c l e s and t h e apparent diameter o f t h e
scattering p a r t i c l e s i scalculated using c l a s s i c a l light
scattering theory ( 1 ) .
The p a r t i c l e s m o s t f r e q u e n t l y u s e d a s s i z e s t a n d a r d s a r e
commercially obtained polystyrene latex microspheres. For
s e d i m e n t a t i o n methods where knowledge o f t h e d e n s i t y d i f f e r e n c e
between t h e p a r t i c l e and t h e suspending f l u i d (water) i s needed,
t h e u s e o f p o l y s t y r e n e a s a s t a n d a r d m a t e r i a l c a n be a s e r i o u s
problem due t o t h e s m a l l magnitude o f t h i s d e n s i t y d i f f e r e n c e . F o r
Sedimentation F i e l d Flow F r a c t i o n a t i o n (SFFF), t h e apparent
d i a m e t e r i s p r o p o r t i o n a l t o t h e cube r o o t o f t h e i n v e r s e o f t h e
density difference (2) Fo Dis Centrifug Photosedimentometr
(DCP) t h e a p p a r e n t d i a m e t e
the i n v e r s e o f t h e d e n s i t
i n F i g u r e 1 w h i c h shows t h e r e l a t i v e e r r o r i n a p p a r e n t p a r t i c l e
s i z e a s a f u n c t i o n o f t h e e r r o r i n t h e assumed d e n s i t y o f
p o l y s t y r e n e l a t e x i n w a t e r f o r DCP a n d f o r S F F F . F o r e x a m p l e , f r o m
F i g u r e 1 i t c a n b e s e e n t h a t a ^57 nm d i a m e t e r l a t e x p a r t i c l e w i t h
a n o m i n a l d e n s i t y o f 1.057 g/cm h a v i n g a n e r r o r o f - 2 0 % i n
(-0.01 g/cm ) w o u l d r e s u l t i n a n e r r o r o f + 1 2 . 4 % i n t h e DCP
p a r t i c l e s i z e d i a m e t e r (+44 nm). The c o r r e s p o n d i n g e r r o r i n SFFF
p a r t i c l e s i z e d i a m e t r i s +7.9% (+28 nm).
I n o r d e r t o make a b e t t e r e v a l u a t i o n o f t h e r e l a t i v e a n d
a b s o l u t e p e r f o r m a n c e o f v a r i o u s i n s t r u m e n t s , i t was n e c e s s a r y t o
o b t a i n w e l l c h a r a c t e r i z e d , monodisperse latexes having a density
greater than that o f polystyrene. Polymethylmethacrylate^(PMMA)
l a t e x w i t h a p o l y m e r d e n s i t y o f a p p r o x i m a t e l y 1.21 gm/cm was
selected f o r t h i s purpose.
A s e r i e s o f m o n o d i s p e r s e PMMA l a t e x e s was s y n t h e s i z e d a n d
characterized with respect t o r e f r a c t i v e index, percent s o l i d s ,
and s o l u t i o n d e n s i t y . T h e p a r t i c l e s i z e o f e a c h l a t e x was a n a l y z e d
by s e v e r a l d i f f e r e n t i n s t r u m e n t a l m e t h o d s . T h e m e t h o d s u s e d
i n c l u d e DCP, S F F F , HDC, Q u a s i e l a s t i c L i g h t S c a t t e r i n g ( Q E L S ) , TEM,
and t u r b i d i t y .

Experimental Methods

Synthesis. A s e r i e s o f l a t e x e s was p r e p a r e d b y s e m i c o n t i n u o u s
emulsion polymerization o f methyl methacrylate. A d i a l k y l ester o f
sodium s u l f o s u c c i n i c a c i d s u r f a c t a n t y i e l d e d t h e narrow p a r t i c l e
s i z e d i s t r i b u t i o n r e q u i r e d . A n ammonium persulfate/sodium
m e t a b i s u l f a t e / f e r r o u s s u l f a t e i n i t i a t o r s y s t e m was u s e d . T h e
i n i t i a t o r was f e d o v e r t h e p o l y m e r i z a t i o n t i m e , a l l o w i n g b e t t e r
control of thepolymerization rate. For thesmaller size latexes
( 2 0 0 t o 4 5 0 n m ) , a s e e d l a t e x was p r e p a r e d i n s i t u b y p o l y m e r i z i n g
10% o f t h e monomer i n t h e p r e s e n c e o f t h e ammonium p e r s u l f a t e .
P a r t i c l e s i z e was a d j u s t e d b y v a r y i n g t h e l e v e l o f s u r f a c t a n t
d u r i n g t h e h e e l r e a c t i o n . As t h e exotherm o f t h i s r e a c t i o n
s u b s i d e d , t h e monomer a n d t h e s o d i u m m e t a b i s u l f a t e / f e r r o u s s u l f a t e
f e e d s were s t a r t e d a n d c o n t i n u e d o v e r a p p r o x i m a t e l y one h o u r . The

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
16. KOEHLER AND PROVDER Comparative Particle Size Analysis 233

maximum p a r t i c l e s i z e a c h i e v a b l e by t h i s m e t h o d was 440 nm. To


a c h i e v e l a r g e r p a r t i c l e s i z e s a l a t e x o f s m a l l e r s i z e was u s e d a s
t h e s e e d . Ammonium p e r s u l f a t e was t h e n a d d e d a t p o l y m e r i z a t i o n
t e m p e r a t u r e , 80C, a n d t h e a d d i t i o n a l l e v e l o f monomer r e q u i r e d t o
a c h i e v e t h e d e s i r e d p a r t i c l e s i z e was f e d o v e r 1.5 h o u r s .

Analysis. The p e r c e n t s o l i d s o f e a c h o f t h e l a t e x e s was m e a s u r e d


u s i n g a D u P o n t M o d e l 950 T h e r m o g r a v i m e t r i c A n a l y z e r . S o l u t i o n
d e n s i t i e s w e r e d e t e r m i n e d u s i n g a P a r r M e t t l e r M o d e l DMA-60
p r e c i s i o n d e n s i t o m e t e r . The p a r t i c l e d e n s i t y was c a l c u l a t e d f r o m
t h e s o l u t i o n d e n s i t y and t h e p e r c e n t s o l i d s .
The DCP u s e d was a v a r i a b l e s p e e d u n i t d e v e l o p e d i n o u r own
l a b o r a t o r y ( 3 - 6 ) . ( A c o m m e r c i a l v e r s i o n o f t h i s i n s t r u m e n t i s mow
a v a i l a b l e a s t h e B r o o k h a v e n DCP-1000 P a r t i c l e S i z e A n a l y z e r f r o m
B r o o k h a v e n I n s t r u m e n t s C o r p o r a t i o n , R o n k o n k o m a New Y o r k . S F F F
measurements were performed u s i n prototyp instrument provided
by D u P o n t (_7). ( A c o m m e r c i a
a v a i l a b l e as t h e DuPon
m e a s u r e m e n t s w e r e made b y M i c r o m e r i t i c s o n t h e i r M o d e l HDC-5600
F l o w s i z e r i n s t r u m e n t . QELS m e a s u r e m e n t s w e r e made o n a n instrument
c o n s t r u c t e d by P r o f e s s o r A l e x J a m i e s o n a t C a s e W e s t e r n R e s e r v e
U n i v e r s i t y ( 8 ) . TEM m e a s u r e m e n t s w e r e made b y t h e P i g m e n t s
D i v i s i o n o f SCM C o r p o r a t i o n , A d r i a n J o y c e P l a n t , B a l t i m o r e ,
M a r y l a n d . T u r b i d i t y m e a s u r e m e n t s w e r e made u s i n g a B a u s c h a n d Lomb
Model Spectronic-20 spectrometer.

Results

A c o m p a r i s o n o f t h e a p p a r e n t p a r t i c l e s i z e a v e r a g e s o f t h e PMMA
l a t e x e s a s m e a s u r e d by e a c h m e t h o d i s s h o w n i n F i g u r e 2 ( n u m b e r
a v e r a g e s , DN) and F i g u r e 3 ( w e i g h t a v e r a g e s , DW). T h e s e d a t a ,
along w i t h the p a r t i c l e d e n s i t y , the r e f r a c t i v e index, the percent
s o l i d s , a n d t h e p o l y d i s p e r s i t y , (DN/DW), c a l c u l a t e d a s t h e r a t i o
o f t h e w e i g h t a v e r a g e p a r t i c l e s i z e t o t h e number a v e r a g e p a r t i c l e
s i z e , a l s o a r e s h o w n i n T a b l e 1.

D i s c u s s i o n and Conclusions

B a s e d o n t h e TEM d a t a , i t a p p e a r s t h a t t h e s m a l l l a t e x e s a r e more
m o n o d i s p e r s e , a n d i t c a n be s e e n t h a t t h e v a r i o u s m e t h o d a g r e e
more c l o s e l y f o r t h o s e s a m p l e s . I n a l l c a s e s h o w e v e r , t h e r e l a t i v e
o r d e r i n g o f t h e a p p a r e n t s i z e s by method i s c o n s i s t e n t . T h a t i s ,
the l i g h t s c a t t e r i n g methods g i v e h i g h e r a p p a r e n t p a r t i c l e s i z e s ,
TEM g i v e s t h e l o w e r n u m b e r , a n d t h e DCP a n d S F F F a r e i n r e l a t i v e l y
good agreement i n t h e c e n t e r o f the r a n g e .
F i g u r e s 4 a n d 5 show p l o t s o f t h e a p p a r e n t number and w e i g h t
a v e r a g e s d e t e r m i n e d by SFFF p l o t t e d a g a i n s t t h e c o r r e s p o n d i n g data
f r o m DCP m e a s u r e m e n t s . F o r p e r f e c t a g r e e m e n t , t h e d a t a w o u l d l i e
a l o n g a l i n e w i t h s l o p e o f one w i t h a n i n t e r c e p t o f z e r o . The
d e v i a t i o n of these p l o t s from l i n e a r i t y at l a r g e r p a r t i c l e s i z e s
i s p r o b a b l y due t o a s t e r i c e f f e c t w h i c h o c c u r s i n S F F F when t h e
p a r t i c l e d i a m e t e r becomes a s i g n i f i c a n t f r a c t i o n o f t h e c h a n n e l
t h i c k n e s s (2) The p a r t i c l e s i z e l i m i t a b o v e w h i c h t h e S F F F
c h a n n e l used i n t h i s work i s e x p e c t e d t o e x h i b i t t h i s e f f e c t i s

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
234 PARTICLE SIZE DISTRIBUTION

F i g u r e 1. R e l a t i v e E r r o r i n P a r t i c l e D i a m e t e r v s . R e l a t i v e
E r r o r i n D e n s i t y Difference^ - P o l y s t y r e n e L a t e x i n Water:
s
d 3 5 7 nm, - 1.057 g/cm .

HDC DN DC DW
UR I D I TURB I D I Y
QELS


-+
x
S F F F DN
DCP DN
8
-+
x
QELS
S F F F DW
DCP DW
TEM DN TEM DW
0


^

+

X ce
UJ + UJ +


UJ
<

g <

m


$

00
" s l * w X
00
s*
m


I I I 1
' ' i l
68B 68A 73B 93A 8A 8C 68B 68A73B 93A 8A 8C
SAMPLE NUMBER SAMPLE NUMBER

Figure 2 ( l e f t ) . A p p a r e n t Number A v e r a g e , T u r b i d i t y , QELS


P a r t i c l e S i z e s o f PMMA L a t e x e s .

Figure 3 (right). Apparent Weight Average, Turbidity, QELS


P a r t i c l e S i z e s o f PMMA L a t e x e s 0

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
TABLE 1 g
r
P A R T I C L E S I Z E AVERAGES FOR PMMA L A T E X E S 3
>

DIAMETERS I N NANOMETERS

SAMPLE TEM DCP SFFF HDC SOLUTION S


ID DN DW DW/DN DN DW DW/DN DN DW DW/DN DN DW DW/DN TURBIDITY QELS % SOLIDS DENSITY(g/cc) |

68B 160 162 1.01 1 8 2 1 9 2 1.05 2 0 5 2 2 2 1.08 2 5 5 2 5 7 1.01 237 223 24.56 1.221

68A 2 3 9 2 4 1 1.01 2 3 3 2 4 7 1.06 2 6 1 2 6 7 1.02 3 2 2 3 4 2 1.06 2


27755 3
30055 23.05 1.213
1.213

357 413 22.59 1.218


I
9 3A
73B 2
3973
7239
88 1.02
3 1.02 3
4414
8345
31 1.03
2 1.02 3
4416
0345
20 1.03
1 1.01 4
5242
0452
43 1.00
2 1.00 4
3
4 55 9
597 4
4
4 61 8
683 22 26 .. 52 90 1.211
1.211
1.218 jIy

8A 4 4 8 4 6 9 1.05 5 5 0 5 6 6 1.03 5 2 1 5 2 9 1.02 6 6 4 6 6 8 1.01 667 578 26.26 1.217



817 746 9.88 1.221
8C 5 7 4 6 1 1 1.06 6 5 8 6 8 6 1.04 6 0 0 6 0 5 1.01 8 9 3 9 0 1 1.01 817 746 9.88 1.221

In Particle Size Distribution; Provder, T.;


Average P a r t i c l e D e n t i t y - 1.215 .


Average R e f r a c t i v e Index 1.48

ACS Symposium Series; American Chemical Society: Washington, DC, 1987.


)
Ut
PARTICLE SIZE DISTRIBUTION

200 400 600 800


DIAMETER (nm)
DCP

F i g u r e 4. A p p a r e n t Number A v e r a g e P a r t i c l e S i z e s o f PMMA
L a t e x e s - S F F F v s . DCP.

fc8
"*
<

200 400 600 800


DIAMETER (nm)
DCP
F i g u r e 5. A p p a r e n t W e i g h t A v e r a g e P a r t i c l e S i z e s o f PMMA
L a t e x e s - S F F F v s . DCP.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
16. KOEHLER AND PROVDER Comparative Particle Size Analysis 237

a p p r o x i m a t e l y 0.5 um. S F F F and DCP w e r e f o u n d t o be h i g h l y


complementary methods. A h i g h e r p a r t i c l e s i z e range i s a c c e s s i b l e
t o DCP and a l o w e r r a n g e i s a c c e s i b l e t o S F F F . The m e t h o d s y i e l d e d
s i m i l a r r e s u l t s i n the r e g i o n over w h i c h t h e i r ranges o v e r l a p .
B o t h methods are c a p a b l e of p r o v i d i n g d e t a i l e d distribution
information over t h e i r respective ranges.
F i g u r e 6 shows a c o m p a r i s o n o f the p a r t i c l e s i z e d i s t r i b u t i o n
c u r v e s f o r s a m p l e s 68-B and 8-A o b t a i n e d by SEM, S F F F , and DCP,
t h o s e methods d i r e c t l y y i e l d i n g d i s t r i b u t i o n i n f o r m a t i o n . For
s a m p l e 68-B, b a s e d on t h e SEM number d i s t r i b u t i o n , t h e s a m p l e i s
u n i m o d a l w i t h a s m a l l s h o u l d e r on t h e l a r g e d i a m e t e r s i d e . The DCP
n u m b e r d i s t r i b u t i o n c u r v e s h o w s t h e same c h a r a c t e r i s t i c s . The SFFF
number d i s t r i b u t i o n c u r v e a p p e a r s t o be b r o a d e r and t h e s m a l l
p o p u l a t i o n o f l a r g e r p a r t i c l e s i s n o t d i s c e r n a b l e . The s h o u l d e r on
t h e s m a l l e r d i a m e t e r s i d e i n t h e S F F F d i s t r i b u t i o n a p p e a r s t o be
an i n s t r u m e n t a r t i f a c t and d i th distribution f l
samples
F o r s a m p l e 8-A, show
d i s t r i b u t i o n i n d i c a t e s a b r o a d e r d i s t r i b u t i o n w i t h a s h o u l d e r on
t h e l a r g e p a r t i c l e s i z e s i d e and a t a i l w i t h a h i n t o f one o r more
s e c o n d a r y p e a k s on t h e s m a l l p a r t i c l e s i z e s i d e . The DCP number
d i s t r i b u t i o n f o r t h i s s a m p l e s h o w s a s y m e t r y and a s m a l l s h o u l d e r
on t h e l a r g e p a r t i c l e s i z e s i d e q u a l i t a t i v e l y s i m i l a r t o t h e SEM
c u r v e . On t h e s m a l l p a r t i c l e s i z e s i d e , t h e DCP s h o w s a t a i l and a
s m a l l p e a k , a g a i n q u a l i t a t i v e l y s i m i l a r t o t h e SEM c u r v e . The SFFF
number d i s t r i b u t i o n c u r v e f o r t h i s s a m p l e d o e s not show a s h o u l d e r
on t h e l a r g e p a r t i c l e s i z e s i d e . W h i l e t h e r e i s a s h o u l d e r on the
s m a l l p a r t i c l e s i z e s i d e , the problem w i t h a r t i f a c t u a l peaks i n
t h i s r e g i o n w i t h t h e S F F F i n s t r u m e n t u s e d makes i t d i f f i c u l t t o
s a y i f t h e t a i l and s h o u l d e r o b s e r v e d a r e r e a l .
The a v e r a g e d i a m e t e r s o b t a i n e d by HDC are c o n s i s t e n t l y high.
T h i s may be due t o a c o m b i n a t i o n o f a s m a l l c a l i b r a t i o n e r r o r and
the r e l a t i v l y c o a r s e (10 p e r c e n t ) s p a c i n g of s i z e c l a s s i f i c a t i o n s
u s e d i n t h e HDC q u a n t i f i c a t i o n by M i c r o m e r i t i c s .
The r e l a t i v e o r d e r i n g o f a p p a r e n t p a r t i c l e s i z e s i s n o t too
s u r p r i s i n g when one c o n s i d e r s t h e a s s u m p t i o n s made and the
p h y s i c a l p a r a m e t e r s m e a s u r e d by e a c h m e t h o d . What may be
s u r p r i s i n g i s the l a r g e s p r e a d of v a l u e s o b t a i n e d f o r the slightly
l e s s monodisperse l a t e x e s . T h i s demonstrates the need f o r c a u t i o n
when c o m p a r i n g p a r t i c l e s i z e d a t a o b t a i n e d by different
i n s t r u m e n t a l methods, e s p e c i a l l y f o r samples h a v i n g broad p a r t i c l e
s i z e d i s t r i b u t i o n s . For a c c u r a t e comparisons i n t h e s e cases i t i s
p r e f e r a b l e t o h a v e b o t h t h e s i z e a v e r a g e s and t h e distribution
curves

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
238 PARTICLE SIZE DISTRIBUTION

a
/ DCP

1I
1i \ SFFF

TEM

I I 1 1 1 1
0 100 200 300 400 0 200 400 600 800
DIAMETER (nm) DIAMETER (nm)

F i g u r e 6 C o m p a r i s o n o f P a r t i c l e Number D i s t r i b u t i o n Curves by
DCP, S F F F a n d TEM a ) S a m p l e 6 8 - B b ) S a m p l e 8-A

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
16. K O E H L E R AND P R O V D E R Comparative Particle Size Analysis 239

Acknowledgments

The a u t h o r s w i s h t o a c k n o w l e d g e S h a r o n K a f f e n f o r h e r s y n t h e s i s o f
t h e PMMA l a t e x e s , F a r r o k h M a l i h i f o r QELS a n d t u r b i d i t y
m e a s u r e m e n t s , C. M. N e a g f o r p e r c e n t s o l i d s a n a l y s i s b y
t h e r m o g r a v i m e t r y a n d C. B. R a k o w s k i o f SCM P i g m e n t s f o r t h e TEM
measurements

Literature Cited

1. Kerker, M. "The Scattering of Light and Other Electromagnetic


Radiation"; New York, 1969; Ch. 7.32.
2. Caldwell, K. C. "Field-Flow Fractionation of Particles", In
"Modern Methods of Particle Size Analysis", Chemical Analysis,
Vol. 73,; Barth, H G . Ed.; Wiley: New York 1984; Chapter 7
3. Koehler, M. E.; Zander
Improved Disc Centrifug
This Volume.
4. Koehler, M. E.; Provder, T . ; Zander, R. A. U. S. Patent
4 311 039, 1982.
5. Holsworth, R. M.; Provder, T. U. S. Patent 4 478 073, 1985.
6. Provder, T.; Holsworth, R. M. Div. of Org. Coatings and
Plastics Chem. Preprint 1976, 36, 150.
7. Blaine, R. "New Applications and Techniques: Sedimentation
Field Flow Fractionation", The TA Hotline, DuPont Company,
Summer 1986, 5.
8. Malihi, F. B.; Provder, T.; Koehler, M. E. Journal of Coatings
Technology, 1983, 55, 41-48.

RECEIVED October 6, 1986

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 17

Measuring Particle Size Distribution of Latex Particles


in the Submicrometer Range Using Size-Exclusion
Chromatography and Turbidity Spectra
T. Kourti,A.Penlidis,J.F.MacGregor, andA.E.Hamielec
Department of Chemical Engineering, McMaster Institute for Polymer Production
Technology, McMaster University, Hamilton, Ontario L8S 4L7, Canada

Turbidity spectra and size exclusion chromatography (SEC) are two


techniques which could be used for the on- and off-line monitoring of
polymer particle size during the polymerization. An experimental
evaluation of the two techniques is reported herein and it is shown that
they satisfactorily follow the change of the particle size during the
reaction. Information from SEC analysis is exploited to experimentally
evaluate the turbidity spectra technique and investigate its potential to
be used as an on-line measurement of particle size for latex reactor
control.

P a r t i c l e n u m b e r and particle size d i s t r i b u t i o n (PSD) are key p a r a m e t e r s i n e m u l s i o n


p o l y m e r i z a t i o n processes because they not only affect p o l y m e r i z a t i o n rate and p o l y m e r
properties d u r i n g the reaction, but they also d e t e r m i n e a p p l i c a t i o n properties of the final
latex such as s t a b i l i t y , viscosity, film forming, and others E f f o r t s to m a n i p u l a t e these
two i m p o r t a n t p a r a m e t e r s d u r i n g p o l y m e r i z a t i o n should precede any attempt to c o n t r o l
latex reactor performance and therefore there is a need for on-line m e a s u r e m e n t o f
particle n u m b e r and size d i s t r i b u t i o n . V a r i o u s techniques have been developed for the
d e t e r m i n a t i o n of PSD's of c o l l o i d a l dispersions but these are often t i m e c o n s u m i n g and
u n s u i t a b l e for on-line applications. L i g h t s c a t t e r i n g techniques are fast, simple,
reproducible a n d thus seem to be p r o m i s i n g for this purposed-2); c h r o m a t o g r a p h i c
techniques can be used c o m p l e m e n t a r y for off-line measurements. T h e measurement
techniques employed were t u r b i d i t y spectra and size e x c l u s i o n chromatography. T h e
scope of this study is to investigate the a b i l i t y of these two techniques to monitor latex
particle growth d u r i n g e m u l s i o n p o l y m e r i z a t i o n of v i n y l acetate and to evaluate the
potential of t u r b i d i t y spectra to be used for on-line p a r t i c l e size measurements.

TURBIDITY SPECTRA

Theoretical Background

The e x p e r i m e n t a l s i m p l i c i t y of t u r b i d i t y spectra i s the m a i n reason w h y the technique


has received so m u c h attention i n the past years (1-5). T u r b i d i t y gives a measure of the
a t t e n u a t i o n of a b e a m of l i g h t t r a v e r s i n g a d i s p e r s i o n of non-absorbing spheres:

0097-6156/87/0332-0242$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
17. KOURTI ET AL. Size-Exclusion Chromatography and Turbidity Spectra 243

I
where I a n d I represent intensity of the i n c i d e n t a n d the e m e r g i n g (from the s c a t t e r i n g
0

solution) beam, respectively, a n d is the l e n g t h of the optical path.


For a monodisperse suspension w i t h non-absorbing spherical particles per cm3,
i n absence of m u l t i p l e scattering, the t u r b i d i t y , , is g i v e n by:

2 n
nD / D \ p (2)
; = ,
4 V /
(D/X , n p / n ) , the extinction coefficient, is i n the general case a complicated function of
m m

the p a r t i c l e d i a m e t e r D, the w a v e l e n g t h i n the m e d i u m \ , a n d the refractive indices n m p

and n of the particles a n d the m e d i u m , respectively.


m c a n be calculated f r o m the
g e n e r a l M i e theory (3). For a polydisperse suspension:

i =
0 4 / \
m m
where f(D) is the suspension's n o r m a l i z e d p a r t i c l e size d i s t r i b u t i o n .
The concentration c of p o l y m e r i c solids i n the latex (gr/cm3 latex) is subsequently
g i v e n by:

3
nD (4)
Np f(D)dD
6

where i s the p a r t i c l e density i n gr/cm^.
C o m b i n a t i o n of equations (3) a n d (4) gives a ratio, the specific turbidity
independent of N, as:

2
D K( , - ^ W d D
(5)
V /
v
" m m
C 2p 0 0

3
D f(D)dD
Jo
It is evident f r o m the above equation that for a k n o w n size d i s t r i b u t i o n a l form, (/c) is a
f u n c t i o n of the refractive index and d e n s i t y of the particles, the w a v e l e n g t h of the i n c i d e n t
l i g h t a n d the p a r a m e t e r s d e s c r i b i n g the p a r t i c l e size d i s t r i b u t i o n .
Therefore, i n p r i n c i p l e , the p a r a m e t e r s of the particle size d i s t r i b u t i o n c a n be
e s t i m a t e d f r o m specific t u r b i d i t y m e a s u r e m e n t s a t different wavelengths. T h i s is not
true, however, i n the R a y l e i g h r e g i m e (i.e. s m a l l particles, ( D / \ ) less t h a n 0.1). In this m

4
case, the e x t i n c t i o n coefficient is p r o p o r t i o n a l to ( D / \ ) a n d m

f ( D ) d D
Jo * _ 3 (6,
= L = L D
3
D f(D)dD
'0
4 l 4 2 2 2
where D is a " t u r b i d i t y " average particle d i a m e t e r a n d L = 4 n p~ Am" ( m - 1/m -I- 2) ;
t

m = (np/n ). It is clear from equation (6) that use of different wavelengths w i l l not
m

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
244 PARTICLE SIZE DISTRIBUTION

provide a d d i t i o n a l information; hence, only a " t u r b i d i t y " average d i a m e t e r can be


d e t e r m i n e d i n the R a y l e i g h regime.

Experimental

P o l y i v i n y l acetate) ( P V A c ) latexes produced by batch and continuous e m u l s i o n


p o l y m e r i z a t i o n were used i n t h i s study. Details for the apparatus a n d the p o l y m e r i z a t i o n
procedure can be found i n P e n l i d i s et a l . (6,12,13). S a m p l e s t a k e n d u r i n g the reaction
were subsequently a n a l y z e d to follow conversion- and p a r t i c l e growth-time histories. The
batch e x p e r i m e n t a l runs were designed to y i e l d s i m i l a r conversion-time histories but
different particle sizes. C o n v e r s i o n was measured both off-line, by g r a v i m e t r i c analysis,
and on-line u s i n g an on-line densitometer (a U-tube D P R - Y W E model w i t h a Y-mode
oscillator w i t h a PTE-98 e x c i t a t i o n cell a n d a DPR-2000 electronic board by A n t o n P a a r ,
A u s t r i a ) . A n u m b e r of runs were repeated to check for r e p r o d u c i b i l i t y of the results. F o u r
batch runs are described i n T a b l e I below and t h e i r c o n v e r s i o n histories are plotted i n
F i g u r e 1.

T a b l e I. C l a s s i f i c a t i o n of B a t c h R u n s

Run# Emulsifier Level Expected P a r t i c l e D i a m e t e r

B7 low large
B10-B11 medium medium
(replications)
B8 high small

A B a u s c h and L o m b Spectronic-20 spectrophotometer (and occasionally, a


H e w l e t t - P a c k a r d 8450 A) was employed for the t u r b i d i t y measurements (cell l e n g t h
1.165 cm, b a n d w i d t h of 20 nm, w a v e l e n g t h f r o m 380 to 580 nm). F o r the t u r b i d i t y
measurements, the samples were d i l u t e d w i t h water s a t u r a t e d w i t h emulsifier. The same
degree of d i l u t i o n was used for a l l the samples of the b a t c h runs. A large n u m b e r of
m e a s u r e m e n t s were repeated to check for reproducibility.

D i s c u s s i o n of T u r b i d i t y R e s u l t s

Specific t u r b i d i t y histories for r u n s B7, BIO and B l l are shown i n F i g u r e 2. It is obvious


that the results are consistent; the r e p r o d u c i b i l i t y obtained i n r u n s B I O a n d B l l is c l e a r l y
shown, w h i l e it i s evident t h a t the latex particles formed i n r u n B 7 are larger, as expected.
Specific t u r b i d i t y histories are also plotted vs. d i m e n s i o n l e s s time for a
continuous e m u l s i o n p o l y m e r i z a t i o n run; the samples were w i t h d r a w n f r o m the second
reactor of a continuous t r a i n where the first reactor is a s m a l l seeding reactor. P a r t A of
F i g u r e 3 shows the p a r t i c l e size behaviour d u r i n g start up; a l l monomer, water, i n i t i a t o r
and soap feedrates were kept constant u n t i l the process reached a steady state. In part B,
the soap concentration i n the seed reactor was increased; a decrease i n the particle size
was expected and it is c l e a r l y shown from the specific t u r b i d i t y measurements.
H o p e f u l l y , it has become evident that specific t u r b i d i t y gives consistent and repro-
ducible q u a l i t a t i v e results. Two approaches have been used to translate the specific
t u r b i d i t y measurements f r o m the p r e v i o u s l y mentioned e x p e r i m e n t s into latex p a r t i c l e
size:

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
17. KOURTI ET AL. Size-Exclusion Chromatography and Turbidity Spectra 245

RUN B7
RUN
RUN BIO
RUN B l l

15 30 45 60 75 80
REACTION TIME (min.)

F i g u r e 1. Conversion h i s t o r i e s o f the batch v i n y l acetate


emulsion polymerizations (similar recipes; only the e m u l s i f i e r
concentration i s different).

REACTION TIME (min)

F i g u r e 2. S p e c i f i c t u r b i d i t y b e h a v i o r f o r three batch runs; runs


B10-B11 a r e r e p l i c a t i o n s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
246 PARTICLE SIZE DISTRIBUTION

(a) A n a p p r o x i m a t e (apparent) diameter, D , was determined. T h i s D


ap corresponds ap

to a monodisperse latex that would have g i v e n the same specific t u r b i d i t y


readings as the ones o b t a i n e d a n d it is u s u a l l y close to some average of the P S D
(4,7,18).
(b) U n d e r the f r e q u e n t l y v a l i d i n practice a s s u m p t i o n that the latex P S D is w e l l
represented by the l o g a r i t h m i c n o r m a l d i s t r i b u t i o n a l 8 )

l 2 2
f(D) = exp(-(nD-n D) /2o ), (7)
1/2
o D (2n)
the p a r a m e t e r s D a n d o of the d i s t r i b u t i o n were d e t e r m i n e d by a non-linear least squares
p a r a m e t e r e s t i m a t i o n technique based on Marquandt's compromise procedure. The
n u m b e r a n d weight average d i a m e t e r s of the latex P S D were t h e n c a l c u l a t e d from

2
D N = D exp(o /2)

w
F i g u r e 4 shows contours of constant sum of squares i n the space of the p a r a m e t e r s
D a n d o, for a set of specific t u r b i d i t y measurements, f r o m a batch run. The 9 5 %
a p p r o x i m a t e j o i n t confidence r e g i o n e s t i m a t e d as:

S(o, D ) = S(o, D ) . ( l + F n f t _(p,n-p)) (9)


0.95 min\ n p 005 /
corresponds to a s u m of squares e q u a l to 0.25. S(o, D ) i is the s u m of squares
m n

c o r r e s p o n d i n g to the s o l u t i o n o b t a i n e d by the search routine, is the n u m b e r of


p a r a m e t e r s t h a t were e s t i m a t e d (p = 2), is the n u m b e r of specific t u r b i d i t y
m e a s u r e m e n t s (n = 6), FQ.05(VI, V 2 ) gives the upper 5 % ofj i n F - d i s t r i b u t i o n w i t h v i , V 2
degrees of freedom. A h i g h n e g a t i v e c o r r e l a t i o n between D a n d o i s evident. It i s c l e a r
t h a t a whole l i n e of a l m o s t " e q u a l l y good" p a i r s of e s t i m a t e s exists. The d i s t r i b u t i o n s
w h i c h correspond to some of these " a l t e r n a t i v e " solutions (denoted by i n F i g u r e 4) are
plotted i n F i g u r e 5.
A l t h o u g h these r e s u l t s are not r e p r e s e n t a t i v e of b a t c h reactor operation, where
one w o u l d expect a l m o s t monodispersed latexes, a n d r e g a r d l e s s of the fact that the
d i s t r i b u t i o n i s c h a n g i n g as one moves a l o n g the confidence region, i t was observed,
however, t h a t the e s t i m a t e d weight average d i a m e t e r of these d i s t r i b u t i o n s was not
affected by t h i s shift. F u r t h e r m o r e , its n u m e r i c a l v a l u e r e m a i n e d close to that of U ap

c a l c u l a t e d i n (a) under the monodisperse assumption, as s h o w n i n F i g u r e 5 and T a b l e II.


S i m i l a r r e s u l t s were also observed (7) for p o l y v i n y l acetate) latexes w i t h l a r g e r particles;
a l l the " a l t e r n a t i v e " (D, o) solutions i n the elongated confidence r e g i o n correspond to
d i s t r i b u t i o n s w i t h a constant weight average d i a m e t e r w h i c h is n u m e r i c a l l y very close to
the a p p a r e n t d i a m e t e r of the suspension, o b t a i n e d under the monodisperse assumption.
The o b t a i n e d weight average d i a m e t e r s can r e a s o n a b l y w e l l follow the progress of
the r e a c t i o n as can be seen f r o m F i g u r e 6, where e x p e r i m e n t a l l y e s t i m a t e d weight
average d i a m e t e r s are plotted w i t h those t h e o r e t i c a l l y predicted by a m a t h e m a t i c a l model
for the b a t c h e m u l s i o n p o l y m e r i z a t i o n of v i n y l acetate.
F r o m the above discussion it has hopefully become clear that at the lower sub-
m i c r o n range, for p o l y ( v i n y l acetate) latexes, specific t u r b i d i t y m e a s u r e m e n t s can provide
a w e i g h t average p a r t i c l e d i a m e t e r w h i c h is r e a s o n a b l y close to the apparent d i a m e t e r
r e s u l t i n g under the monodisperse assumption. These r e s u l t s were f u r t h e r v e r i f i e d w i t h
s i m u l a t i o n studies; it was s h o w n j 7 ) t h a t the m a x i m u m e r r o r introduced by a s s i g n i n g the
U ap v a l u e to D
w was - 4 % for D a p v a l u e s up to 4000 and polydispersities up to 1.5.
Hence, w h e n low p o l y d i s p e r s i t y i s expected, one m i g h t have fast, on-line p a r t i c l e size

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
17. KOURTI ET AL. Size-Exclusion Chromatography and Turbidity Spectra 247

I .6

IO
wavelength

X 1.2 4 4 0 nm
k_



0.8
>
part


ce part A
TU

0.4

.

LU
0
SP

2 4 6 8 10
DIMENSIONLESS TIME(t/0 ) 2

F i g u r e 3. Specific t u r b i d i t y m e a s u r e m e n t s for the continuous r u n (2 = residence t i m e


i n the second reactor of the continuous train).

I " I 1 1

4.2
X
4.0 "

\
<
> 3.8 -
UJ

Q 3.6 -
<

3.4 * PROGRAM SOLUTION
16 5

? X EQUALLY GOOD PAIRS

1 1 1 1 1 1
405.0 425.0 445.0 465.0 485.0 505.0
M E A N OF L O G - N O R M A L DISTRIBUTION

F i g u r e 4. Contours^of constant s u m of squares ( S S = 1 6 , 5, 2) a n d possible, "equally


good", a l t e r n a t i v e (D,o) solutions.

American Chemical Society


Library
1155 16th St., N.W.
In Particle Size Distribution; Provder, T.;
Washington,
ACS Symposium Series; American ChemicalD.C. 20036
Society: Washington, DC, 1987.
248 PARTICLE SIZE DISTRIBUTION

3.01 1 1 1 r

F i g u r e 5. P a r t i c l e size d i s t r i b u t i o n s corresponding to some a l t e r n a t i v e solutions


( m a r k e d as x) of F i g u r e 4.

CONVERSION

F i g u r e 6. P a r t i c l e g r o w t h histories for the batch runs; model predictions (continuous


lines) and e x p e r i m e n t a l data. Reproduced w i t h p e r m i s s i o n f r o m Ref. 6. C o p y r i g h t
1985, M a r c e l D e k k e r Inc.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
17. KOURTI ET AL. Size-Exclusion Chromatography and Turbidity Spectra 249

measurements by d i s p e n s i n g w i t h p a r a m e t e r e s t i m a t i o n a n d a p p r o x i m a t i n g the weight


average d i a m e t e r w i t h D . In this case, concentration m e a s u r e m e n t (from on-line
ap

densitometer) a n d a t u r b i d i t y m e a s u r e m e n t at one w a v e l e n g t h would provide sufficient


data for the weight average d i a m e t e r c a l c u l a t i o n .

T a b l e II. A v e r a g e D i a m e t e r s f r o m Specific T u r b i d i t y M e t h o d

( R u n B7, wavelengths: 400, 440, 480, 500, 560 nm)

Sample # Conversion % D from(b),


w D from(a),
ap

5 49 715 785
6 66 805 900
7 84 870 985
8 97 890 1020
10 10

"Dap s h o u l d be c l o s e r t o

SIZE E X C L U S I O N C H R O M A T O G R A P H Y

Theoretical Background

P a r t i c l e chromatography u s i n g packed beds has attracted considerable a t t e n t i o n


of those interested i n m e a s u r i n g p a r t i c l e size d i s t r i b u t i o n of s p h e r i c a l p a r t i c l e s i n the
s u b m i c r o n range (8,9,11,14,16). T h e r e exist two c o m p l e m e n t a r y approaches to the use of
t h i s technique, according to the p a c k i n g m a t e r i a l employed:
a. H y d r o d y n a m i c C h r o m a t o g r a p h y ( H D C ) u t i l i z e s non-porous p a c k i n g a n d r e l i e s
m a i n l y o n the velocity profile i n the c a p i l l a r i e s formed by the p a c k i n g . L a r g e
particles a r e excluded f r o m regions near the c a p i l l a r y w a l l , where the a x i a l
velocities are s m a l l a n d hence, on the average, experience a h i g h e r velocity a n d
therefore a s m a l l e r r e t e n t i o n volume.
b. Size E x c l u s i o n C h r o m a t o g r a p h y ( S E C ) u t i l i z e s porous p a c k i n g m a t e r i a l ; steric
e x c l u s i o n of particles i n suspension from the pores i s a n a d d i t i o n a l force for size
separation. Suspended particles, s m a l l e r t h a n the d i a m e t e r i n the pore, c a n
diffuse into porous, g i v i n g a n efficient m e c h a n i s m of r e t a r d a t i o n a n d size
separation.
D e t a i l s c o n c e r n i n g the h y d r o d y n a m i c ( H D C ) a n d size e x c l u s i o n chromatography ( S E C ) as
a p p l i e d to separate particle suspensions a c c o r d i n g to t h e i r size a n d a n extensive l i t e r a t u r e
review can be found i n P e n l i d i s et al. (9) a n d they w i l l not be repeated here.
A detection system is connected to the outlet of the packed column for m o n i t o r i n g
the p a r t i c l e concentration. T h e passage of a n injected sample t h r o u g h the c o l u m n a n d
detector provides a n output trace o n the recorder, the chromatogram. A c h r o m a t o g r a m
can never f u l l y represent the d i s t r i b u t i o n of colloid sizes i n the injected sample;
i n s t r u m e n t a l s p r e a d i n g or a x i a l d i s p e r s i o n causes e l u t i o n of a single species to occur over
a range of retention volumes. T h e contents of the detector c e l l are not monodispersed, but
r a t h e r have a d i s t r i b u t i o n that is l i k e l y to be u n i m o d a l , a n d it is often quite broad (14).
Interpretation of a c h r o m a t o g r a m must therefore account for the a x i a l d i s p e r s i o n a n d
involves a n e v a l u a t i o n of i n s t r u m e n t a l s p r e a d i n g a n d correction of the detector response
to o b t a i n the true picture of the injected sample.
The detector response at retention v o l u m e v, F(v), can be expressed as (15)

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
250 PARTICLE SIZE DISTRIBUTION

( QO

0
W(y)G(v,y)dy ( 1 0 )

where W(y) is the true c h r o m a t o g r a m , that would have been obtained i n the absence of
a x i a l dispersion, a n d G(v, y) is the n o r m a l i z e d detector response for a t r u l y monodisperse
system w i t h mean retention v o l u m e y; G(v,y) i s c a l l e d the i n s t r u m e n t a l s p r e a d i n g
function
The solution of the above equation i n order to o b t a i n W(y) r e q u i r e s a n appropriate
form of the s p r e a d i n g f u n c t i o n a n d the n u m e r i c a l v a l u e s of its parameters. F u r t h e r m o r e ,
to convert W(y) into a size d i s t r i b u t i o n requires a r e l a t i o n s h i p between the m e a n
retention volume y and the p a r t i c l e d i a m e t e r D (i.e., a c a l i b r a t i o n curve).

S p r e a d i n g Function. A g e n e r a l s t a t i s t i c a l shape function, w h i c h accounts for skewed


chromatograms, i n i t i a l l y proposed by P r o v d e r and Rosen (16), has been used:

A3 A4
G(v,y) = G Q

vhere

( v - y r \
2

/
G
n< .y> =v
= = 2
e x
P ^ - 1 ~
2
)
V2no ' 2
(11)

(v-y)
=
0
H3(x) = 3-32
4 2
H4 () = - 6x + 3 (Hermite polynomials)
and

3 A 4
= - = - - 3 .

P2, P3 a n d 4 are the second, t h i r d a n d fourth moments of the d i s t r i b u t i o n . A3 i s a


measure of skewness and A4 a measure of kurtosis.

E s t i m a t i o n of the S p r e a d i n g Function. W h e n the injected sample is monodispersed, peak


b r o a d e n i n g occurs solely due to a x i a l dispersion; i f y is the m e a n r e t e n t i o n volume of the
c h r o m a t o g r a m , then the detector response is g i v e n by:

F(v) = WG(v, y) (12)

where W i s the a r e a under the chromatogram. T h e parameters (2, P3, P4) of the
d i s t r i b u t i o n c a n therefore be e s t i m a t e d f r o m the heights of c h r o m a t o g r a m s of s t a n d a r d
monodispersed latexes.

C a l i b r a t i o n Curve. T h e c h r o m a t o g r a m s of s t a n d a r d monodisperse samples m a y be used


to construct a c a l i b r a t i o n c u r v e r e l a t i n g the p a r t i c l e d i a m e t e r D w i t h its m e a n r e t e n t i o n
volume, y, by:

In D = a + by + c y 2
(13)

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
17. KOURTI ET AL. Size-Exclusion Chromatography and Turbidity Spectra 251

S o l u t i o n for A x i a l Dispersion. W i t h different degrees of success, numerous techniques


have been proposed for s o l v i n g e q u a t i o n (10). T h e most p r o m i s i n g method seems to be
that of Ishige et al. (10). It i s a n u m e r i c a l method that does not require s i g n i f i c a n t
c o m p u t i n g time.
The method uses the fact that any response F*(v) a l w a y s has a broader
d i s t r i b u t i o n t h a n the i n p u t d i s t r i b u t i o n W(y). Hence, i f a d i s t r i b u t i o n Fi(v) is broader
t h a n F*(v), the a s s u m e d Wi(y) must be sharpened to give a response closer to F*(v). U s i n g
F*(v) as the i n i t i a l guess for W(y), subsequent i m p r o v e d estimates are c a l c u l a t e d by:

W i + i = (F*/Fi)Wi (14)

where F j i s the c h r o m a t o g r a m c a l c u l a t e d u s i n g W[. T h e procedure is repeated u n t i l F t

satisfies a convergence c r i t e r i o n . W (y) is a l w a y s n o r m a l i z e d before use.


t

P a r t i c l e Size D e t e r m i n a t i o n . T h e corrected detector response at retention volume i s


g i v e n as

W(v) N ( v ) D ( v ) K ( v )
where a n d are the n u m b e r concentration a n d e x t i n c t i o n coefficient, respectively, of
particles of d i a m e t e r D a t retention volume v; indices and are defined as follows:

mass detector: = 3, = 0
t u r b i d i t y detector: = 2, = 1.

T h e e x t i n c t i o n coefficient c a n be c a l c u l a t e d from the general M i e theory (8).


The frequency d i s t r i b u t i o n of the p a r t i c l e size is related to the n u m b e r of particles
e l u t i n g at v o l u m e as follows:

N(v)dv
KD)dD = -
N(v)dv

N(v) (16)
D) = -

(I o
N(v)dv)(dD/dv)
/
F o r a n o n l i n e a r c a l i b r a t i o n curve

2
In D = a + bv + c v

and

dD/dv = D (b + 2cv) (17)

F r o m equations (15-17):

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
252 PARTICLE SIZE DISTRIBUTION

W(v)
D) = - (18)
/ W(v)dv \ v
Y
(dD/dv)(D (v) ())
V Y
J 0 D (v) ( ) /

Average Diameters. After the frequency distribution has been obtained, the following
average diameters can be calculated:

DfTD)dD
(19a)
number average:

4
D ftD)dD
(19b)
weight average D..

b
D ftD)dD

turbidity average: (19c)



D fl(D)dD

\l/2
surface average: 2
D ftD)dD (19d)

Experimental

A dry packed column with porous material was used for the characterization according to
size of the PVAc latex samples. The packing employed was CPG (Controlled Pore Glass),
2000 , 200-400 mesh size. Deionized water with 0.8 gr/lit Aerosol O.T. (dioctyl sodium
sulphosuccinate), 0.8 gr/lit sodium nitrate and 0.4 gr/lit sodium azide served as the carrier
fluid under a constant flowrate. The sample loop volume was 10 \xt. A Beckman UV
detector operating at 254 nm was connected at the column outlet to monitor particle size.
A particle size-mean retention volume calibration curve was constructed from
commercially available polystyrene standards. For reasons of comparison, the samples
previously characterized by turbidity spectra were also characterized by SEC. A number
of injections were repeated to check for the reproducibility of the method.

Discussion of SEC Results

As a preliminary indication of the capability of SEC to qualitatively follow particle


growth, the diameters corresponding to the peak retention volume were calculated
directly from the calibration curve (without any correction for axial dispersion). "Peak"
average particle diameters are plotted vs. conversion for the batch runs in Figure 7, where
it is clearly shown that runs B10 and B l l are replications, with latex particles smaller
than those produced from run B7, as expected. In the continuous run, shown in Figure 8,

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
17. KOURTI ET AL. Size-Exclusion Chromatography and Turbidity Spectra 253

.4

RUN B7
g
RUN BIO

L RUN B l l

or

LU

< 1.0

LU



<

OC
UJ
0.8h

<
LU

0.6 _1_
20 40 60 80 100
CONVERSION %

Figure 7. Size Exclusion Chromatography: peak average diameters for three batch
runs with different emulsifier levels; runs BIO - Bl 1 are replications.

2.0


1.6
X
o<
a:
UJ
1- 1.2
UJ

< part B
o part A
LU 0.8
-J

-
: CR2 (A + B)
<
L 0.4 O SEC
LU
S E C repeats
>
< Model

0.0 L _
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0
DIMENSIONLESS TIME, (t/0 )2

Figure 8. Size Exclusion Chromatography: peak average diameters for the


continuous run (17). (2 = residence time in the second reactor of the continuous
train).

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
254 PARTICLE SIZE DISTRIBUTION

a decrease in the particle size is observed during part B, where the emulsifier
concentration in the seeding reactor was higher than in part A (17). It can be seen that in
both cases SEC followed the course of the reaction reasonably well.
The chromatograms of the several injected PVAc samples were corrected for axial
dispersion (8-11) and number and weight average diameters were estimated. The
resulting distributions and diameter averages showed that the latex samples from the
batch runs were "almost" monodispersed (8). This was further supported by the fact that
estimated average diameters were very close to the "peak" average diameters (Table III).

Table III. Average Diameters from SEC

Sample # Conversion % Corrected "Peak" Diameters


D N Dw
(from SEC, )

Bll-11 47
13 63
16 86 960 980 1040
19 100 1010 1020 1080

B8-5 50 825 830 860


6 70 890 890 950
7 85 925 935 980
10 100 940 950 1020

SEC has been shown (7) to give satisfactory results for latexes with broad particle
size distributions as well. The method is particularly useful (7) in the determination of
distributions of small particles when specific turbidity would provide only a turbidity (or
weight) average diameter.

CONCLUSIONS

Turbidity measurements are simple, fast and reproducible. Specific turbidity can
successfully follow the particle size evolution during the course of emulsion
polymerization and can be translated into weight average diameters. A combination of an
on-line spectrophotometer with an on-line densitometer (to obtain concentration) would
provide the potential to estimate D on-line, as well An on-line determination of PSD's,
w

for small particles however, would seem quite difficult due to the high correlation of their
parameters. One should bear in mind that the above conclusions have been validated
only for polyvinyl acetate) latexes; the analysis is currently being extened to other
systems, such as polystyrene and poly(methyl-methacrylate).
At low conversions, the presence of monomer results in false particle size when
turbidity spectra is used (7). In this case, SEC can be used as a complementary technique
since it can also successfully follow particle growth and therefore yield particle sizes.
Both of the above techniques seem to give consistent results in the detection of
particle growth for latexes produced by continuous emulsion polymerization, as well.
More details and results from this ongoing research will be published shortly.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
17. KOURTI ET AL. Size-Exclusion Chromatography and Turbidity Spectra 255

LITERATURE CITED

1. Kiparissides,C.;MacGregor, J.F.; Singh, S.; Hamielec, A.E. CJChE 1980, 58, 65.
2. Zollars, R.L.; J. Colloid Interface Sci. 1980, 74, 163.
3. Heller, W.; Pangonis, W.J. J. Chem. Phy. 1957, 26, 498.
4. Meehan, E.J.; Beattie, W.H. J. Phys. Chem. 1960, 64, 1006.
5. Maxim, L.D.; Klein, .; Meyer, M.E.; Kuist, C.H. J. Polym. Sci., Part C 1969, 27,
195.
6. Penlidis, .; MacGregor, J.F.; Hamielec, A.E., Polym. Proc. Eng. 1985, 3(3), 185.
7. Kourti, T.; MacGregor, J.F.; Hamielec, A.E. unpublished results.
8. Kourti, T. Technical Report, Dept. of Chem. Eng., McMaster University,
Hamilton, Ontario, Canada, March 1984.
9. Penlidis, .; Hamielec,A.E.;MacGregor, J.F. J. Liquid Chromat. 1983, 6(S-2),
179.
10. Ishige, T.; Lee, S.I.; Hamielec, A.E. J. Appl. Poly. Sci. 1971, 15, 1607.
11. Husain, .; Hamielec A.E.; Vlachopoulos J In "Size Exclusion Chromatography
(GPC)"; Provder, Th.
Society: Washington,
12. Penlidis, .; MacGregor, J.F.; Hamielec, A.E., S. Proc. 189th ACS National
Meeting, Division of PMSE, Miami Beach, Florida, April 1985, p. 484.
13. Penlidis, .; MacGregor, J.F., Hamielec, A.E., AIChE J. 1985, 31(6), 881.
14. Hamielec, A.E. In "Modern Methods for Particle Size Analysis", Barth, H.G., Ed.;
J. Wiley & Sons, Inc.: NewYork, 1984; p. 251.
15. Tung, L.H. J. Appl. Polym. Sci. 1966, 10, 375.
16. Provder, T.; Rosen,E.M.,Separation Science 1970, 5(4), 437; 1970 5(4), 485.
17. Penlidis, A; MacGregor, J.F.; Hamielec, A.E. submitted for publication in
AIChE J.
18. Kerker, M. "The Scattering of Light and Other Electromagnetic Radiation";
Academic Press: New York, 1969.
RECEIVED June 27, 1986

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
Chapter 18

Particle Size Distribution Analysis of Colloidal Latices


Using Hydrodynamic Chromatography
AnthonyW.Thornton, JamesP.Olivier, CindyG.Smart, and Lee B. Gilman
Micromeritics Instrumen

The mass versus particle size distribution of several


polymer latices with diameters in the range of 30 nm
to 1500 nm was determined in less than 20 minutes
using an integrated hydrodynamic chromatograph. Dis-
tributions obtained were compared with those found
by other particle sizing techniques such as electron
microscopy to verify validity of the technique. The
instrument employed was able to analyze latices re-
producibly with different optical properties, even
though some of the injected particles may have been
trapped within the column. Latex properties were
correlated with particle size distribution data to
illustrate the benefit of this particle sizing
technique.

P a r t i c l e s i z e d i s t r i b u t i o n o f a l a t e x has a pronounced i n f l u e n c e on
i t s r h e o l o g i c a l p r o p e r t i e s , storage s t a b i l i t y , and f i l m forming
c a p a b i l i t i e s (_1). I n a d d i t i o n , l a t e x p a r t i c l e s i z e d i s t r i b u t i o n s
p r o v i d e i n f o r m a t i o n on p o l y m e r i z a t i o n mechanisms and k i n e t i c s ( 2 ) ,
a n d p r o v i d e a means o f p o l y m e r i z a t i o n c o n t r o l (_3,4).
It i s often d i f f i c u l t to define the size of a p a r t i c l e ,e s -
p e c i a l l y one w i t h a n i r r e g u l a r shape. Latex p a r t i c l e s suspended
i n a n aqueous phase a r e o f t e n n e a r l y p e r f e c t s p h e r e s . For this
case, p a r t i c l e s i z e can be described accurately using a s i n g l e
dimension, usually the diameter. The d i a m e t e r o f l a t e x p a r t i c l e s
can b e d e t e r m i n e d a c c u r a t e l y u s i n g m i c r o s c o p y ( u s u a l l y t r a n s m i s s i o n
electron microscopy) i f c l u s t e r s o f l a t e x spheres o r severely de-
formed p a r t i c l e s a r e excluded. Latex p a r t i c l e diameters a r e
determined r e l a t i v e t o the space between r u l i n g s on a c a l i b r a t e d
grid. S i m i l a r c a l i b r a t i o n s e x i s t f o r a number o f o t h e r t e c h n i q u e s
available f o r determination of latex p a r t i c l e size distributions
5,()). These t e c h n i q u e s i n c l u d e photon c o r r e l a t i o n s p e c t r o s c o p y ,
disk centrifuge photosedimentometry, sedimentation f i e l d flow
f r a c t i o n a t i o n , a n d h y d r o d y n a m i c c h r o m a t o g r a p h y , (HDC). The

0097-6156/87/0332-0256$06.00/0
1987 American Chemical Society

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
18. THORNTON ET AL. Analysis of Colloidal Latices 257

a c c u r a c y o f any one o f t h e s e t e c h n i q u e s c a n be s p e c i f i e d based upon


t h e o r e t i c a l models o r c a l i b r a t i o n u s i n g l a t i c e s t h a t have been s i z e d
by m i c r o s c o p y . T h e c a p a b i l i t i e s o f o n e o f t h e s e m e t h o d s , HDC, i s
the subject of t h i s paper.
H y d r o d y n a m i c c h r o m a t o g r a p h y was o r i g i n a l l y d e s c r i b e d b y S m a l l
(7) i n 1974. A number o f p u b l i c a t i o n s h a v e a p p e a r e d s i n c e t h e n
w h i c h d e s c r i b e t h e s e p a r a t i o n mechanism and sample d e t e c t i o n methods
u s e d w i t h HDC ( 5 , 8 - 1 8 ) . I n a d d i t i o n , Van G i l d e r , e t . a l . (19) used
HDC a s t h e p r i m a r y p a r t i c l e s i z i n g t e c h n i q u e i n r e s e a r c h o n t h e
p a r t i c l e s i z e versus v i s c o s i t y r e l a t i o n s h i p of h i g h s o l i d s paper
coating l a t i c e s .
The o r i g i n a l HDC a p p a r a t u s u s e d c o l u m n s p a c k e d w i t h p o l y m e r i c
i o n exchange spheres and s t a n d a r d l i q u i d chromatography components
to separate l a t e x p a r t i c l e s according t o s i z e . The d e v i c e was
c a l i b r a t e d u s i n g l a t i c e s whose p a r t i c l e s i z e h a d been d e t e r m i n e d
by m i c r o s c o p y . E l u t i o n tim found t regularly although
not l i n e a r l y , w i t h p a r t i c l
were r e q u i r e d f o reach s i z
18) h a v e l a r g e l y o v e r c o m e t h i s d r a w b a c k .
H y d r o d y n a m i c c h r o m a t o g r a p h y was c o m m e r c i a l i z e d b y M i c r o m e r i t i c s
I n s t r u m e n t C o r p o r a t i o n i n 1 9 8 4 . T h e F l o w S i z e r HDC 5 6 0 0 i s a n i n -
t e g r a t e d , computer c o n t r o l l e d l i q u i d chromatograph c o n s i s t i n g o f an
e l u a n t d e l i v e r y system, a sample i n j e c t i o n v a l v e , a s i z e s e p a r a t i o n
column, a sample d e t e c t o r , and an e l u a n t volume measuring d e v i c e
(see F i g u r e 1 ) . S i z e a n a l y s i s begins w i t h i n j e c t i o n of a l a t e x
sample i n t o a f l o w i n g stream o f e l u a n t w h i c h passes through t h e
s e p a r a t i o n column. The l a t e x p a r t i c l e s s e p a r a t e i n s i d e t h e column
such t h a t l a r g e p a r t i c l e s e x i t before s m a l l p a r t i c l e s . Presence of
sample i n t h e e l u a n t i s monitored as i t e x i t s t h e column u s i n g an
u l t r a v i o l e t l i g h t d e t e c t o r w i t h w a v e l e n g t h f i x e d a t 2 5 4 nm. Con-
s i d e r a t i o n o f d a t a treatment and i n s t r u m e n t d e s i g n i s r e q u i r e d t o
u n d e r s t a n d how t h e h y d r o d y n a m i c chromtograms a r e c o n v e r t e d i n t o
accurate, high resolution latex p a r t i c l e size distributions.

Accuracy i n HDC

Data Treatment. Hydrodynamic chromatograms can be r e p r e s e n t e d as


the c o n v o l u t e i n t e g r a l o f t h r e e p a r t i c l e s i z e dependent f u n c t i o n s .
T h i s i s s h o w n i n E q u a t i o n 1:

V
F(V) = / l {W(y) G ( V , y ) K ( y ) } d y (1)
V 2

where F ( V ) i s t h e sample d e t e c t o r response v e r s u s e l u a n t volume


s i n c e i n j e c t i o n , V ( t h e s a m p l e c h r o m a t o g r a m ) ; W(y) i s t h e mass o f
p a r t i c l e s w h i c h make up t h e s a m p l e w i t h mean e l u t i o n v o l u m e y ;
G(V,y) i s t h e band broadening f u n c t i o n d e s c r i b i n g s p r e a d i n g o f t h e
b a n d o f p a r t i c l e s w i t h mean e l u t i o n v o l u m e y a s i t p a s s e s t h r o u g h
the chromatograph; K ( y ) i s t h e d e t e c t o r response f o r a g i v e n con-
c e n t r a t i o n o f p a r t i c l e s w i t h mean e l u t i o n v o l u m e y ; a n d V i a n d V 2

d e f i n e t h e e l u a n t volume window d u r i n g w h i c h a l l p a r t i c l e s i n t h e
sample e l u t e . T h i s e q u a t i o n i s s i m i l a r t o t h a t u s e d b y Tung f o r
d e s c r i b i n g g e l - p e r m e a t i o n chromatograms ( 2 0 ) .
A m a t h e m a t i c a l t e c h n i q u e known as d e c o n v o l u t i o n c a n be u s e d

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
258 PARTICLE SIZE DISTRIBUTION

LEGEND.

A - RESERVOIR

PUMP

C O.I jum FILTER

D INJECTION VALVE

COLUMN

F DETECTO

G V O L UR A T OR

H RECYCLE VALVE

A I WASTE RESERVOIR

J COMPUTER

CONSOLE

L PRINTER

F i g u r e 1. B l o c k d i a g r a m o f c o m m e r c i a l h y d r o d y n a m i c c h r o m a t o -
graph. Solid l i n e s indicate f l u i d flow path. Broken l i n e s
i n d i c a t e data communication. Arrows i n d i c a t e f l u i d f l o w
direction.

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
18. THORNTON ET AL. Analysis of Colloidal Latices 259

to i n t e r p r e t chromatographic d a t a and s o l v e t h e c o n v o l u t e d i n t e g r a l
b a s e d o n k n o w n i n f o r m a t i o n . T h i s a l l o w s r e c o v e r y o f some r e s o l u t i o n
l o s t due t o t h e o v e r l a p o f sample b a n d s , and d e t e r m i n a t i o n o f t h e
mass-based p a r t i c l e s i z e d i s t r i b u t i o n . The m e a s u r e d c h r o m a t o g r a m ,
F ( V ) , i s r e p r e s e n t e d a s a sum o f c h r o m a t o g r a m s o f m o n o d i s p e r s e ma
t e r i a l s that f a l l w i t h i n the a n a l y t i c a l l i m i t s of the instrument,
and whose s i z e , band b r o a d e n i n g and l i g h t r e f r a c t i o n c h a r a c t e r i s t i c s
a r e known. An i n f i n i t e number o f l a t e x p e a k m o d e l s c o u l d be g e n e r
a t e d f o r t h e a n a l y s i s r a n g e o f HDC. However, summing a l a r g e number
o f p e a k m o d e l s becomes q u i t e t i m e c o n s u m i n g . The F l o w S i z e r t h e r e
f o r e u s e s 100 p e a k m o d e l s d u r i n g d e c o n v o l u t i o n . A l i n e a r combination
o f v a r y i n g a m o u n t s o f a l l t h e s e p e a k m o d e l s i s summed t o r e g e n e r a t e
the a c t u a l chromatogram o b t a i n e d . An i t e r a t i v e p r o c e s s , non-negative
l e a s t squares a n a l y s i s (21, 2 2 ) , i s used t o i n s u r e t h a t the best f i t
of the data i s obtained The r e l a t i v e amount o f e a c h peak m o d e l u s e d
i s then converted t o th
c l e s i z e of t h e models use
chromatogram.
E q u a t i o n 1 c a n b e r e p l a c e d w i t h t h e f i n i t e sum:

100
F(V) = Wi G ( V ) i K i (2)
1=1

w h e r e W i i s t h e m a s s o f p a r t i c l e s w i t h mean e l u t i o n v o l u m e c o r r e s
ponding t o chromatogram i , G ( V ) i i s t h e broadening f u n c t i o n f o r
p a r t i c l e s m a k i n g up c h r o m a t o g r a m i , a n d K i i s t h e d e t e c t o r r e s p o n s e
f a c t o r f o r those p a r t i c l e s . F(V) i s measured d u r i n g a p a r t i c l e
a n a l y s i s , G ( V ) i i s determined d u r i n g i n s t r u m e n t c a l i b r a t i o n , and
K i v a l u e s a r e measured f o r p o l y s t y r e n e l a t i c e s o f known s i z e . There
f o r e , d e c o n v o l u t i o n o f E q u a t i o n 2 g i v e s t h e v a l u e s o f Wi. The
p a r t i c l e s i z e v e r s u s mean e l u t i o n v o l u m e c a l i b r a t i o n i s t h e n u s e d
t o c o n v e r t Wi v a l u e s i n t o t h e p a r t i c l e s i z e d i s t r i b u t i o n o f t h e
sample.
The b a n d b r o a d e n i n g f u n c t i o n G ( V ) i c a n b e d e t e r m i n e d f o r
s e v e r a l p a r t i c l e s i z e s b y a n a l y z i n g l a t e x s a m p l e s o f known p a r t i c l e
s i z e w h i c h have v e r y narrow s i z e d i s t r i b u t i o n s , and then mathemati
c a l l y modeling t h e shape of t h e r e s u l t i n g chromatographic peaks.
The f u n c t i o n c a n t h e n b e i n t e r p o l a t e d f o r p a r t i c l e s i z e s b e t w e e n
t h o s e c o r r e s p o n d i n g t o t h e known l a t i c e s . The r e l a t i o n s h i p b e t w e e n
p a r t i c l e d i a m e t e r a n d y , t h e mean e l u t i o n v o l u m e o f t h e p a r t i c l e s ,
i s t h e p a r t i c l e s i z e versus e l u t i o n volume c a l i b r a t i o n . As d i s
c u s s e d e a r l i e r , a n HDC i s c a l i b r a t e d u s i n g p o l y s t y r e n e l a t i c e s ,
but t h e c a l i b r a t i o n i s v a l i d f o r o t h e r l a t i c e s ( 2 3 ) and even non-
?

latex materials. ( C o l l o i d a l g o l d t h a t h a d b e e n s i z e d a t 40 nm b y
e l e c t r o n m i c r o s c o p y w a s d e t e c t e d a t 39 nm u s i n g t h e F l o w S i z e r . )
K i , the d e t e c t o r response f a c t o r , describes the s i g n a l gener
a t e d when p a r t i c l e s a r e p r e s e n t i n t h e e l u a n t a s i t t r a n s i t s t h e
detector flow-through c e l l . Detector response a r i s e s p r i m a r i l y
from s c a t t e r i n g o f l i g h t by t h e l a t e x p a r t i c l e s ( 1 5 ) , although a
s m a l l c o n t r i b u t i o n f r o m l i g h t a b s o r p t i o n b y t h e s a m p l e may o c c u r
(16). P o l y s t y r e n e l a t e x s t a n d a r d s o f known s i z e a n d c o n c e n t r a t i o n
were used t o determine K i f a c t o r s f o r c o n v e r s i o n o f d e t e c t o r
r e s p o n s e i n t o mass c o n c e n t r a t i o n i n f o r m a t i o n .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
260 PARTICLE SIZE DISTRIBUTION

The q u a l i t y o f t h e d e c o n v o l u t i o n r e s u l t s w i l l b e l i m i t e d b y t h e
q u a l i t y of the g i v e n data. C h r o m a t o g r a p h i c d a t a , F ( V ) , must be c o l -
l e c t e d u n d e r t h e same c o n d i t i o n s a s t h e c a l i b r a t i o n d a t a . Detector
r e s p o n s e must change l i n e a r l y w i t h sample c o n c e n t r a t i o n w i t h i n t h e
o p e r a t i n g range of the chromatograph. I f n o t , Kj_ v a l u e s w i l l n o t
be c o n s t a n t f o r a g i v e n p a r t i c l e s i z e , a n d c a l c u l a t e d m a s s p e r c e n t
v a l u e s w i l l n o t be r e l i a b l e . The e l u a n t v o l u m e m e a s u r i n g d e v i c e
must g i v e r e p r o d u c i b l e e l u t i o n volume i n f o r m a t i o n . I f not, data
w i l l n o t b e c o l l e c t e d i n t h e same w i n d o w , t o V , o r a t t h e same
2

e l u a n t v o l u m e v a l u e s V, r e s u l t i n g i n i n c o r r e c t p a r t i c l e s i z e a s s i g n -
ment. Sample i n j e c t i o n and e l u t i o n must be r e p r o d u c i b l e . I f not,
the d e t e c t o r response w i l l not t r u l y represent the i n j e c t e d sample,
and c a l c u l a t e d p a r t i c l e s i z e d i s t r i b u t i o n s w i l l be i n a c c u r a t e . Cali-
b r a t i o n s a m p l e s must be m o n o d i s p e r s e and o f known s i z e . I f not,
band b r o a d e n i n g f u n c t i o n s , G ( V ) i , and p a r t i c l e s i z e v e r s u s e l u t i o n
v o l u m e , y, c a l i b r a t i o n s w i l l b inaccurate Th hydrodynami chroma
t o g r a p h and i t s o p e r a t i n
each of these c o n d i t i o n
p a r t i c l e s i z e d i s t r i b u t i o n s are determined.

Instrument Design. The F l o w S i z e r c o n s i s t s o f HPLC c o m p o n e n t s h o u s e d


i n a s i n g l e c a b i n e t a n d i n t e r f a c e d t o a n i n t e r n a l , d e d i c a t e d com-
1 1
puter. T h i s d e s i g n h e l p s t o m i n i m i z e "dead volumes i n the flow
p a t h s and e l e c t r i c a l n o i s e on s a m p l e d a t a l i n e s . The e l a p s e d
volume measuring d e v i c e , the V o l u R a t o r , i s connected t o the d e t e c t o r
flow outlet. The V o l u R a t o r g e n e r a t e s a s e r i e s o f p u l s e s p r o p o r t i o n a l
to the volume of f l u i d l e a v i n g the d e t e c t o r . The r e p e a t a b i l i t y o f
t h e V o l u R a t o r was d e t e r m i n e d t o b e 0.5% c o e f f i c i e n t o f v a r i a n c e
o f m e a s u r e d e l u t i o n v o l u m e (_24). R e p e a t a b i l i t y o f t h i s m a g n i t u d e
w i l l i n s u r e t h a t d e t e c t o r d a t a a r e a l w a y s c o l l e c t e d a t t h e same
e l a p s e d volume v a l u e s , r e g a r d l e s s of e l u a n t f l o w r a t e .

C a l i b r a t i o n Samples. Monodisperse p o l y s t y r e n e l a t i c e s are a v a i l a b l e


w i t h known, n a r r o w p a r t i c l e s i z e d i s t r i b u t i o n s . C o e f f i c i e n t s of
v a r i a n c e a b o u t t h e mean d i a m e t e r a r e t y p i c a l l y l e s s t h a n 6% o f
diameter measured u s i n g e l e c t r o n microscopy (25). HDC typically
c a n n o t r e s o l v e d i f f e r e n c e s i n d i a m e t e r o f o n l y 6%. Therefore,
t h e s e p o l y s t y r e n e s a r e s u f f i c i e n t l y n a r r o w t o b e u s e d a s HDC cali-
b r a t i o n reference samples. H o w e v e r , d o i n g s o may r e s u l t i n i n c o r -
p o r a t i o n of a s y s t e m a t i c e r r o r i n the p a r t i c l e s i z e versus e l u t i o n
volume c a l i b r a t i o n , a r i s i n g f r o m known e l e c t r o n m i c r o s c o p y e r r o r s
o f a s much a s 5% f o r p a r t i c l e s b e l o w 1 um ( 2 6 ) . Therefore,
a c c u r a c y can o n l y be s t a t e d as r e l a t i v e t o e l e c t r o n m i c r o s c o p y
r e s u l t s f o r the c a l i b r a t i o n samples. FlowSizer performance s p e c i f i -
c a t i o n s h a v e b e e n r e p o r t e d e l s e w h e r e (27) w i t h d i a m e t e r and mass
p e r c e n t r e s u l t s w i t h i n 5% o f t h o s e d e t e r m i n e d b y e l e c t r o n m i c r o -
scopy f o r a s e r i e s of these monodisperse p o l y s t y r e n e l a t i c e s .
T h i s i n v e s t i g a t i o n w i l l show t h a t r e p r o d u c i b l e p a r t i c l e s i z e
d i s t r i b u t i o n s are p o s s i b l e using hydrodynamic chromatography, even
t h o u g h a p o r t i o n o f t h e i n j e c t e d s a m p l e may b e t r a p p e d w i t h i n t h e
column m a t r i x . In a d d i t i o n , i t w i l l i l l u s t r a t e the e f f e c t s of using
f i x e d K-^ f a c t o r s f o r d i f f e r e n t t y p e s o f l a t e x w h o s e s c a t t e r i n g a n d
absorbing c h a r a c t e r i s t i c s d i f f e r e n t from those of p o l y s t y r e n e .
T h e s e two a r e a s d e t e r m i n e w h e t h e r o r n o t m a s s p e r c e n t p a r t i c l e s i z e

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
18. THORNTON ET AL. Analysis of Colloidal Latices 261

d i s t r i b u t i o n s c a n b e o b t a i n e d u s i n g HDC a n d do n o t a p p r e c i a b l y
a f f e c t t h e a b i l i t y o f HDC t o g i v e mean p a r t i c l e d i a m e t e r s . It is
t h e a b i l i t y o f HDC t o d e t e r m i n e t h e s i z e d i s t r i b u t i o n s o f s a m p l e s ,
a n d n o t j u s t mean d i a m e t e r s , w h i c h m a k e s i t a v a l u a b l e a n a l y t i c a l
technique.

Experimental

P a r t i c l e s i z e d i s t r i b u t i o n s and peak a r e a s o f i n j e c t e d l a t i c e s w e r e
d e t e r m i n e d u s i n g a s t a n d a r d F l o w S i z e r HDC 5 6 0 0 , M i c r o m e r i t i c s I n -
strument Corporation, Norcross, Georgia. The c o l u m n was r e p l a c e d
w i t h a s i n g l e open tube d u r i n g a p o r t i o n of p e r c e n t r e c o v e r y t e s t i n g .
P o l y v i n y l c h l o r i d e e x t i n c t i o n c o e f f i c i e n t s were s u b s t i t u t e d f o r
p o l y s t y r e n e c o e f f i c i e n t s d u r i n g a p o r t i o n of the K i f a c t o r t e s t i n g .
Ten m o n o d i s p e r s e p o l y s t y r e n e l a t i c e s w e r e p u r c h a s e d f r o m Duke
S c i e n t i f i c Corporation, Pal Alto California A particl siz
d i s t r i b u t i o n , determined usin
( T E M ) , was o b t a i n e d f o r e a c
columns).
The c o n c e n t r a t i o n o f e a c h l a t e x was d e t e r m i n e d gravimetrically.
T h r e e 1.0 m l s a m p l e s o f e a c h l a t e x w e r e w e i g h e d t o t h e n e a r e s t 0.1
mg. The s a m p l e s w e r e p l a c e d i n a v a c u u m o v e n (55 C, - 1 0 0 k P a ) f o r
two h o u r s . The d r i e d s a m p l e s w e r e a l l o w e d t o c o o l t o r o o m t e m p e r a -
t u r e i n a d e s e c c a t o r a n d w e i g h e d a g a i n t o t h e n e a r e s t 0.1 mg. Weight
percent v a l u e s were c a l c u l a t e d f o r the t h r e e samples of each l a t e x .
The a r i t h m e t i c mean o f t h e t h r e e w e i g h t p e r c e n t v a l u e s a n d t h e
s t a n d a r d e r r o r o f t h e means f o r e a c h l a t e x a r e l i s t e d i n t h e t h i r d
and f o u r t h c o l u m n s , r e s p e c t i v e l y , o f T a b l e I .

Table I. P o l y s t y r e n e L a t i c e s Used i n Mass R e c o v e r y Testing

a 1 3
Latex D i s t r i b u t i o n Latex Concentration
Mean Standard Weight Estimated
Diameter Deviation Percent Error
(nm) (nm) (%) (%)
43 7.5 12.9 0.1
91 5.8 10.38 0.02
176 2.3 10.79 0.03
198 3.6 10.49 0.02
261 3.1 10.40 0.02
305 8,4 10.91 0.08
624 5,2 10.77 0.03
804 4.8 9.86 0.09
913 5.9 10.2 0.1
1091 8,2 10.6 0.1
a, M a s s - w e i g h t e d d i s t r i b u t i o n b a s e d on m i c r o s c o p y d a t a s u p p l i e d
w i t h sample.
b. B a s e d on t h r e e g r a v i m e t r i c d e t e r m i n a t i o n s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
262 PARTICLE SIZE DISTRIBUTION

P a r t i c l e R e t e n t i o n i n Column. E a c h p o l y s t y r e n e l a t e x was agitated


a n d a 1.0 m l a l i q u o t o f e a c h was d i l u t e d w i t h F l o w S i z e r e l u a n t .
F i n a l s a m p l e c o n c e n t r a t i o n s r a n g e d f r o m 0 . 0 5 % t o 1.0% ( b y w e i g h t ) ,
d e p e n d i n g on l a t e x p a r t i c l e s i z e , i n o r d e r t o g e n e r a t e chromato
graphic s i g n a l s i n the l i n e a r range of the d e t e c t o r . Diluted
samples were p l a c e d i n a low power u l t r a s o n i c b a t h ( U l t r a s o n i c s ,
P l a i n v i e w , New Y o r k ) f o r 60 s e c o n d s j u s t p r i o r t o i n j e c t i o n . Peak
a r e a s w e r e d e t e r m i n e d f o r e a c h i n j e c t i o n . E a c h s a m p l e was i n j e c t e d
u n t i l t h r e e c o n s e c u t i v e a r e a s d i f f e r e d b y l e s s t h a n two p e r c e n t f r o m
one v a l u e t o t h e n e x t .
E q u a t i o n 3 was u s e d t o c a l c u l a t e m a s s p e r c e n t o f s a m p l e r e
covered, M , f o r each sample:
r

M r - C t x 100 (3)
At C c

where A c i s the average


i n j e c t i o n s of each sampl
A t i s t h e mean o f t h e l a s t t h r e e a r e a s d e t e r m i n e d f o r i n j e c t i o n s
t h r o u g h t h e open t u b e ; and C and Ct a r e t h e c o n c e n t r a t i o n s o f
c

the sample i n j e c t e d t h r o u g h t h e column and open t u b e , r e s p e c t i v e l y .


The m a s s % r e c o v e r e d f o r e a c h s a m p l e , a n d a n e s t i m a t e o f t h e e r r o r
i n e a c h v a l u e , a r e g i v e n i n T a b l e I I , s e c o n d and t h i r d columns,
respectively.

Table I I . Results of Percent Recovery Testing

Sample Recovered Retained Area


Mean Mass Estimated Mass Estimated Coefficient
Diameter 3
Percent Error Error of V a r i a n c e ^
(nm) (%) (%) (ug) (ug) (%)
43 100 1 0.00 0.00 0.7
91 95 4 1.75 0.08 1.0
176 82 2 3.8 0.1 1.1
198 72 2 17.6 0.6 1.1
261 62 2 22.5 0.8 1.5
305 64 2 47 1 0.5
624 78 3 122 5 1.7
804 72 2 208 7 1.2
913 70 2 193 6 0.9
1091 61 3 880 50 0.1
a. From T a b l e I .
b. Based on l a s t t h r e e i n j e c t i o n s o f e a c h sample.

E q u a t i o n 4 was u s e d t o c a l c u l a t e t h e m a s s o f s a m p l e retained
in t h e column, Mt, o f each o f t h e t e n l a t i c e s :

M t= M A j C VL
r c (4)
i =l (100) A c

where A i i s the a r e a of the i t h i n j e c t i o n of the sample; i s the


t o t a l number o f i n j e c t i o n s o f t h e s a m p l e ; and VL i s t h e volume o f
t h e i n j e c t i o n l o o p (10 uL f o r t h e F l o w S i z e r ) . Substitution of
E q u a t i o n 3 i n t o E q u a t i o n 4 f o l l o w e d by c a n c e l l a t i o n o f terms g i v e s :

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
18. THORNTON ET AL. Analysis of Colloidal Latices 263

M t
AjCt VL (5)
i=l A t

The m a s s o f e a c h s a m p l e r e t a i n e d a n d a n e s t i m a t e o f t h e e r r o r of
t h e c a l c u l a t e d v a l u e a r e g i v e n i n T a b l e I I , f o u r t h and fifth
columns, r e s p e c t i v e l y .

E f f e c t s of D e t e c t o r Response F u n c t i o n . Two s y n t h e t i c b l e n d s w e r e
made u s i n g t h r e e o f t h e p o l y s t y r e n e l a t i c e s (91 nm, 176 nm and
1091 nm). A s a m p l e o f c o m m e r c i a l l y a v a i l a b l e a c r y l i c l a t e x and one
o f b u t a d i e n e l a t e x w e r e o b t a i n e d and d i l u t e d w i t h e l u a n t . The two
b l e n d s a n d two c o m m e r c i a l s a m p l e s w e r e e a c h a n a l y z e d u s i n g t h e
F l o w S i z e r w i t h e a c h o f two d i f f e r e n t d e t e c t o r r e s p o n s e f u n c t i o n s .
The r e s u l t s o b t a i n e d w i t h t h e two d i f f e r e n t f u n c t i o n s a r e g i v e n i n
T a b l e I I I a n d F i g u r e 2.
The two r e s p o n s e f u n c t i o n
The p o l y s t y r e n e r e s p o n s
l a t i c e s o f known s i z e , a l o n g w i t h c u r v e f i t t i n g r o u t i n e s . Poly
s t y r e n e d e t e c t o r r e s p o n s e a r i s e s f r o m b o t h a b s o r b a n c e and s c a t t e r i n g
of i n c i d e n t u l t r a v i o l e t l i g h t . The p o l y v i n y l c h l o r i d e r e s p o n s e
f
c u r v e was c a l c u l a t e d a c c o r d i n g t o M i e s t h e o r y ( 1 5 ) u s i n g c o m p l e x
r e t r a c t i v e i n d e x v a l u e s g i v e n by Nagy ( 2 8 ) . Polyvinyl chloride
d e t e c t o r response a r i s e s almost e x c l u s i v e l y from s c a t t e r i n g of
incident ultraviolet light.

T a b l e I I I . C o m p a r i s o n o f HDC P a r t i c l e S i z e D i s t r i b u t i o n s
Obtained Using D i f f e r e n t D e t e c t o r Response F u n c t i o n s

A b s o r b a n c e and S c a t t e r i n g S c a t t e r i n g Only
Type o f Mean D i a m e t e r Mass % Mean D i a m e t e r Mass %
Distribution o f Mode i n Mode o f Mode i n Mode
(nm) (%) (nm) (%)
Narrow
Monomodal 136.3 100.0 135.7 100.0
Resolved 89.6 46.1 90.1 75.8
Bimodal 1029.0 53.9 1046.0 24.2
Overlapped 90.3 53.0 90.7 54.9
Bimodal 165.5 47.0 165.0 45.1

Results and Discussion

P a r t i c l e R e t e n t i o n i n Column. The r e s u l t s l i s t e d i n T a b l e I I i n
d i c a t e that a s i g n i f i c a n t p r o p o r t i o n of the l a t i c e s w i t h diameters
a b o v e 200 nm i s r e t a i n e d w i t h i n t h e HDC c o l u m n . However, the
p e r c e n t recovered f o r each sample i s v e r y r e p r o d u c i b l e once the
column i s c o n d i t i o n e d . The l a s t c o l u m n o f T a b l e I I l i s t s t h e c o
e f f i c i e n t o f v a r i a n c e (CV) o f t h e m e a s u r e d a r e a s f o r t h e l a s t t h r e e
i n j e c t i o n s of each sample. S u c h l o w CV v a l u e s a r e p o s s i b l e o n l y
i f t h e same a m o u n t o f s a m p l e i s r e a c h i n g t h e d e t e c t o r f o r e a c h i n
jection. P e r c e n t r e t e n t i o n o f l a t e x w i t h i n t h e c o l u m n must be
r e p e a t a b l e , and t h e r e f o r e , p r e d i c t a b l e . Any p r e d i c t a b l e ( s y s t e m a t i c )
e r r o r w h i c h may a f f e c t c a l c u l a t e d r e s u l t s c a n b e e l i m i n a t e d . The
e f f e c t s o f s a m p l e r e t e n t i o n c a n be overcome by m u l t i p l y i n g K i ( e x
t i n c t i o n c o e f f i c i e n t ) by p e r c e n t r e c o v e r y f o r e a c h sample and u s i n g

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
264 PARTICLE SIZE DISTRIBUTION

30 100 200 1 0 0 0 1500


PARTICLE DIAMETER.Bm

F i g u r e 2. P a r t i c l e s i z e d i s t r i b u t i o n o f a c o m m e r c i a l l y a v a i l a -
ble polybutadiene latex calculated using different detector
response f u n c t i o n s .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
THORNTON ET AL. Analysis of CoUoidal Latices

I I I I I 1 I 1 I I I I 1

30 100 200 1000/500

PARTICLE DIAMETER nm

F i g u r e 3. D e t e c t o r r e s p o n s e f u n c t i o n s f o r p o l y s t y r e n e ( P S )
a n d p o l y v i n y l c h l o r i d e ( P V C ) f o r 2 5 4 nm i n c i d e n t l i g h t .

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
266 PARTICLE SIZE DISTRIBUTION

the r e s u l t as an e f f e c t i v e e x t i n c t i o n c o e f f i c i e n t , K i . Equation 2
can t h e n be r e w r i t t e n a s :

F(V) - Wi G ( V ) i 4 (6)
i=l

to i n c l u d e the e f f e c t s of sample r e t e n t i o n . Deconvolucion of


Equation 6 w i l l then give accurate, reproducible p a r t i c l e s i z e
d i s t r i b u t i o n s , e v e n t h o u g h some o f t h e i n j e c t e d s a m p l e i s r e t a i n e d
w i t h i n the column.

E f f e c t s o f D e t e c t o r R e s p o n s e F u n c t i o n . The d e t e c t o r r e s p o n s e
f u n c t i o n s f o r p o l y s t y r e n e l a t i c e s and p o l y v i n y l c h l o r i d e l a t i c e s
d i f f e r s i g n i f i c a n t l y due t o a b s o r b a n c e o f u l t r a v i o l e t l i g h t b y
the polystyrene particles. The p o l y v i n y l c h l o r i d e p a r t i c l e s a b s o r b
e s s e n t i a l l y n o l i g h t a t 254 Th effect f usin different
detector functions i n Equatio
t r i b u t i o n determined. Th
bly o v e r t h e s m a l l s i z e r a n g e o f a n a r r o w monomodal a c r y l i c l a t e x .
T h e r e f o r e , changing d e t e c t o r response f u n c t i o n s has l i t t l e e f f e c t
on t h e c a l c u l a t e d p a r t i c l e s i z e ( s e e T a b l e I I I ) . The s i z e s o f
modes i n a w e l l r e s o l v e d b i m o d a l p o l y s t y r e n e s a m p l e ( 9 1 nm a n d
1091 nm) a r e s i m i l a r l y n o t a f f e c t e d b y c h a n g i n g r e s p o n s e f u n c t i o n s ,
a l t h o u g h t h e r e l a t i v e m a s s i n t h e two modes i s a f f e c t e d s i g n i f i c a n t
ly. H o w e v e r , i f t h e two modes a r e c l o s e t o g e t h e r i n s i z e ( 9 1 nm a n d
176 nm), o r o v e r l a p , e v e n t h e r e l a t i v e m a s s i n t h e two modes i s n o t
affected greatly. T h i s i s a g a i n due t o t h e s m a l l v a r i a t i o n i n
response f u n c t i o n over the w i d t h of the bimodal d i s t r i b u t i o n .
The r e s p o n s e f u n c t i o n v a r i e s s i g n i f i c a n t l y o v e r t h e w i d t h o f
a b r o a d l y d i s t r i b u t e d sample. Figure 3 illustrates particle size
d i s t r i b u t i o n s determined f o r the p o l y b u t a d i e n e sample. The r e s u l t s
are s i g n i f i c a n t l y d i f f e r e n t , w i t h b e t t e r d e f i n i t i o n o f modes
present i n the d i s t r i b u t i o n found u s i n g the non-absorbing response
function. The mean d i a m e t e r s o f t h e two d i s t r i b u t i o n s a r e 5 1 3 nm
a n d 405 nm f o r t h e p o l y s t y r e n e a n d p o l y v i n y l c h l o r i d e f u n c t i o n s ,
respectively. Polybutadiene i s expected to absorb v e r y l i t t l e
l i g h t a t 254 nm. T h e r e f o r e , t h e s c a t t e r i n g o n l y r e s u l t s would be
expected t o b e s t r e p r e s e n t the sample. I t s h o u l d be n o t e d t h a t t h e
e f f e c t s of using d i f f e r e n t response f a c t o r s are greatest f o r broad
sample d i s t r i b u t i o n s .
The e x a m p l e s s h o w n i n t h i s i n v e s t i g a t i o n a r e e x t r e m e d u e t o
s i g n i f i c a n t d i f f e r e n c e s i n the absorbance c h a r a c t e r i s t i c s i n the
two r e s p o n s e f u n c t i o n s . The d i f f e r e n c e s b e t w e e n t h e d i s t r i b u t i o n s
i n F i g u r e 3 a n d T a b l e I I I c a n b e u s e d a s a g u i d e t o t h e maximum
m a g n i t u d e o f e r r o r e x p e c t e d i n HDC p a r t i c l e s i z e d i s t r i b u t i o n s i f
the response f u n c t i o n used does not c o r r e s p o n d t o t h e o p t i c a l
p r o p e r t i e s of the l a t e x sample.

Applications

Q u a l i t y C o n t r o l o f L a t e x P o l y m e r i z a t i o n U s i n g Hydrodynamic Chroma
tography . L a t e x p o l y m e r s a r e most commonly m a n u f a c t u r e d i n a l a r g e
v e s s e l w i t h a l l t h e p r o d u c t b e i n g removed a t t h e end o f t h e p o l y
merization reaction. This so-called batch polymerization process

In Particle Size Distribution; Provder, T.;


ACS Symposium Series; American Chemical Society: Washington, DC, 1987.
18. THORNTON ET AL. Analysis of Colloidal Latices 267

y i e l d s a l a t e x product which has s l i g h t l y d i f f e r e n t l y p r o p e r t i e s f o r


each batch. M a n u f a c t u r e r s t y p i c a l l y b l e n d two o r more b a t c h e s o f
l a t e x t o g e t h e r t o i n s u r e a more u n i f o r m p r o d u c t . In addition,
l a t i c e s may b e b l e n d e d t o o b t a i n d e s i r a b l e p r o p e r t i e s a s c o n t r i b u t e d
by d i f f e r e n t s i z e s o f l a t e x p a r t i c l e s ( 1 9 ) . Latex m a n u f a c t u r e r s
w i l l a l s o on o c c a s i o n b l e n d s m a l l q u a n t i t i e s o f p o o r q u a l i t y b a t c h e s
w i t h good p r o d u c t s and s t i l l o b t a i n a m i x t u r e w i t h a c c e p t a b l e p r o
perties. I n t h e p a s t , b l e n d i n g o f l a t i c e s was m o n i t o r e d p r i m a r i l y
by v i s c o s i t y measurements, s u r f a c e t e n s i o n measurements, and end
use t e s t s . A l t h o u g h u s e f u l , s u c h t e s t s g i v e n o i n s i g h t i n t o why
a p a r t i c u l a r b a t c h o f m a t e r i a l b e h a v e s i n a g i v e n way. Thus,
v a l u a b l e g u i d a n c e i n how t o c o r r e c t a p r o b l e m i n b l e n d i n g o r p o l y
merization i s often not a v a i l a b l e . P a r t i c l e s i z e analysis of the
l a t e x c a n o f t e n y i e l d i n s i g h t i n t o why a p a r t i c u l a r b a t c h o f ma
t e r i a l i s not acceptable. I n many c a s e s , b a t c h p o l y m e r i z a t i o n s
r e q u i r e enough t i m e t h a t p a r t i c l siz b monitored b HDC
t h e l a t e x i s b e i n g made
c o r r e c t some p o l y m e r i z a t i o
product.
Two c o m m e r c i a l l y p r o d u c e d p o l y s t y r e n e l a t i c e s w e r e a n a l y z e d
u s i n g HDC. The m a n u f a c t u r e r r e p o r t e d t h a t t h e t w o b a t c h e s e x h i b i t e d
d i f f e r e n t r h e o l o g i c a l p r o p e r t i e s . Both samples o r i g i n a l l y had a
v i s c o s i t y i n the expected range. However, upon s t o r a g e f o r a few
h o u r s , t h e v i s c o s i t y o f one s a m p l e i n c r e a s e d t o an unacceptable
value. B o t h b a t c h e s w e r e d e t e r m i n e d t o h a v e t h e same c o n c e n t r a t i o n
of n o n - v o l a t i l e m a t e r i a l (percent s o l i d s ) . S i z e a n a l y s i s b y HDC
r e v e a l e d t h a t t h e g o o d b a t c h o f l a t e x was b i m o d a l a s e x p e c t e d . The
m a n u f a c t u r e r h a d b l e n d e d t o g e t h e r two s e p a r a t e b a t c h e s o f m a t e r i a l
( e a c h h a v i n g o n e s i z e mode) t o o b t a i n t h e g o o d m a t e r i a l . The u n
s t a b l e l a t e x was f o u n d t o c o n t a i n t h r e e m o d e s . Two o f t h e t h r e e
modes w e r e f o u n d a t t h e same d i a m e t e r s a s f o r t h e g o o d m a t e r i a l .
The t h i r d mode w a s f o u n d a t a l a r g e r p a r t i c l e s i z e . In addition,
t h e r e l a t i v e a m o u n t o f m a t e r i a l f o u n d i n t h e s e c o n d mode was much
g r e a t e r f o r t h e u n s t a b l e sample. T a b l e IV compares t h e r e s u l t s
f o u n d f o r t h e two s a m p l e s . The i n c r e a s e d v i s c o s i t y o f t h e u n s t a b l e
l a t e x a p p e a r s t o r e s u l t f r o m an i n c r e a s e i n t h e amount o f l a r g e
s i z e m a t e r i a l w i t h time. This indicates that smaller sized l a t e x
p a r t i c l e s were agglomerating d u r i n g s t o r a g e t o y i e l d l a r g e r s i z e
particles. Cause f o r t h i s a g g l o m e r a t i o n was n o t d i s c l o s e d b u t
c o u l d have r e s u l t e d from s e v e r a l f a c t o r s i n the p o l y m e r i z a t i o n
r e c i p e o r o p e r a t i o n of the p o l y m e r i z a t i o n equipment.

T a b l e I V . C o m p a r i s o n o f R e s u l t s O b t a i n e d b y HDC f o r Two Batches


of a Commercially A v a i l a b l e Polystyrene Latex

Good Sample Unstable Sample


Mean Mass Mean Mass
Mode Diameter Percent Diameter Percent
(nm) (%) (nm) (%)
A 133.2 62.2 136.2 55.4
251.2 37.8 248.1 42.1
C - - 463.4 2.5

In Parti