Diffraction, Non-Crystallinity, and

the PDF Database

Cyrus E. Crowder, ICDD

Tim Fawcett, ICDD
 This document was presented at PPXRD -
Pharmaceutical Powder X-ray Diffraction Symposium
Sponsored by The International Centre for Diffraction Data

This presentation is provided by the International Centre for Diffraction Data in cooperation with the
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 Classical Diffraction

• Classic ‘Bragg’ scattering is characterized by discrete

peaks arising from long-range crystallographically
ordered planes:

λ = 2dhkl sinθhkl
• The 2009 PDF databases have > 660,000 entries based
on the concept of discrete Bragg peaks arising from
crystalline structures.
• The existing concept of ‘Phase Identification’ is based on
matching accurately-determined positions and intensities
of peaks in an experimental patterns to those for PDF
database entries.
 Classical XRPD
NaCl – An Example

222

111 200 220 311

 The XRPD Pattern of a Common
Pharmaceutical Excipient

The process of identifying this material by conventional XRPD search/match

techniques is compromised by the small number of clearly defined diffraction
maxima and the difficulty in specifying the precise positions of these maxima.
Further, these ‘maxima’ are likely shifted from the true underlying positions of the
major Bragg peaks due to the significant overlap.
 Use of full pattern matching for phase
identification

• The ICDD has begun compiling a database (PD3) of

XRPD profiles for such materials.
• Such a database can be used for manual comparison
with an experimental pattern, however manual
comparisons with larger databases for identifying true
unknown materials would be slow and subjective.
• An automated full-pattern comparison would be
desirable to screen the database for most-likely
matches.
 The Integral Index

• The Integral Index is a numerical value based on a point-by-

point comparison of two digitized X-ray diffraction pattern This
numerical value ranges from 0-100 and is based on the
Hofmann and Kuleshova similarity index [1]:
⎡ i0 calc i0
⎤
n ⎢∑ ∑I count
I i i⎥
1 ⎢ i =1
= ∑ n ⎥
i =1
Sint −
n i0 =1 ⎢ n
⎥
⎢∑ ∑
calc count
I j I j⎥
⎣ j =1 j =1 ⎦
• The lower the index value, the better the match, giving 0 a
perfect match and 100 a complete non-match.
• We can use this relationship to rank the match between full
patterns from a given database set with the pattern from the
unknown material
 Example Using Integral Index to
Identify Nanocrystalline Material

• To facilitate comparison, the

background is removed before
computing the integral indices.
• To facilitate speed, the
database is limited to a likely
subset of entries, in this case
anything with cellulose in the
name.
• If unsuccessful, other subfiles,
i.e., polymers, fillers, or
forensics, could be specified.
 Perform Integral Index Calculations

• An estimated crystallite size parameter

is used to compute comparible FWHMs
for peaks, in this case, 3.5 nm.
• The software simulates a pattern for
each database entry, using the d-space
and intensity values.
• Each simulated database pattern is
compared with the unknown pattern to
generate integral index values.
Patterns Generated from Crystal Structure
Where Available

PDF 00-056-1717 Cell II

PDF 00-056-1718 Cell I beta
PDF 00-056-1719 Cell I alpha

Via PDF-4+

Scardi, Leoni
Faber

References for Form I alpha, Simulation of microcrystalline

Form I beta and Form II states of cellulose
Patterns Generated from Experimental d-I list if
Crystal Structure is Not Available
 Use of Integral Index
Comparing with all 16 PDF
experimental entries that
contain ‘cellulose’ in the name,
the integral index values vary
from 2.26 up to 19.28 for these
entries.

The best integral index fit is

with 50-2241 – cellulose Iβ.

Integral Index = 2.26

Cellulose 1β
 Comparison of Simulated Cellulose
Patterns to Experimental Pattern

Red – experimental pattern

Blue – ‘Standard’ database pattern

Cellulose Iβ
Integral Index = 2.26

Cellulose II
Integral Index = 5.93

Clearly, the cellulose 1β polymorph

is a better match than the cellulose II
polymorph.
 Non-crystalline Material

This is an X-ray ‘diffraction’ pattern for amorphous cellulose (Sigma Cellulose ground 13
hours). The same pattern is obtained after long periods of grinding, regardless of whether
the starting cellulose was form Iα, Iβ, or II. (Courtesy Ewa Bucher, International Paper)

The lack of long range order means we have no conventional “Bragg” diffraction, but
instead, rather broad features based on the distribution of interatomic distances within the
disordered structure.
Nanocrystalline Cellulose Iα?

Comparison of X-ray diffraction patterns for amorphous cellulose and that for
the cellulose Iα crystalline form with a simulated crystallite size of 1.5 nm.
Nanocrystalline Cellulose Iβ?

Comparison of X-ray diffraction patterns for amorphous cellulose and that for
the cellulose Iβ crystalline form with a simulated crystallite size of 1.5 nm.
 Nanocrystalline Cellulose II?

Comparison of X-ray diffraction patterns for amorphous cellulose and that for
the cellulose II crystalline form with a simulated crystallite size of 1.5 nm.
 Amorphous Standards

• Clearly the database should be expanded to include full 
patterns for standard amorphous materials since these 
cannot be generated from Bragg peak positions or 
crystallographic information. 

• This would allow integral index comparisons to be 
performed for both amorphous standards as well as 
nanocrystalline variations of crystalline materials 
already in the database.
Raw Polymer Pattern for Identification
using Integral Index

Background
Removal
 Integral Index Calculations for
Polymer Pattern

PDF-4+ 2009 database searched for entries containing ‘poly’ in the

name and having elements only within the set of C, H, N, O, F, and
Cl. Found: 651

Using a crystallite size of ~15 nm, Integral Index values were

computed for this experimental pattern that ranged from ~2.5 to 45.
(Roughly 20 seconds to compute on a 2-year-old Dell Inspiron.)

The top three are examined closer on the next slide.

Integral Index Results for Polymer
 Semi-crystalline Polypropylene

Crystalline Polypropylene
Polymers such as these are really 2-
phase systems, one being crystalline,
the other being amorphous.

Unlike polypropylene, many have only

one or two significant Bragg peaks
making conventional search/match
identification difficult.

Semi-crystalline Polypropylene Automated full pattern comparisons

have the potential to be a better
identification tool for XRPD patterns of
many polymers.
 Disordered Structures

Faulted clay materials

 The Editorial Challenge of a “Full
Pattern” Database

• How many ‘different’ entries are needed for

a given material (i.e. chain branching,
molecular weight, melting point, degree of
crystallinity, etc)?
 Nanomaterials
and blends

St. Johns Wort Powdered Bone

Echinacea Lipoic Acid

Benadryl Effexor
 Amorphous Materials and Blends

Cough Drop
Saw Palmetto

3 Sources
SunTheanine
Cellulose*

*Courtesy of Ewa Bucher

International Paper
 Tools that assist in identifying
materials with poor crystallinity

• Data and databases

• Simulations – crystallite size, pair distribution
functions, cluster analyses, total pattern fitting,
“random-walk”models, Rietveld refinement,
integral index
• Any knowledge of specimen chemistry,
processing and composition
• Complimentary data – melting point,
infrared,nmr, functional groups