Polímeros

Qué es un polímero
Poli mero
muchos unidad repetida

repeat repeat repeat

unit unit unit
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)
Adapted from Fig. 14.2, Callister 7e.
 Historia de los polímeros
• Al principio se utiizaban polímeros naturales
– Madera – Caucho
– Algodón – Lana
– Cuero – Seda

• Usos más antiguos de “polímeros modernos”

– Pelotas de goma utilizadas por los aztecas
– Noé utilizó brea (polímero natural) para
recubrir arca –como todos los marineros de la
antigüedad
 Composición de los polímeros
La mayoría están constituidos por
hidrocarburos – Cadenas de C y H
(Existen también las siliconas –cadenas de
Si-O)
• Hidrocarburos saturados
– Cada carbon está enlazado a cuatro átomos
H H
H
CnH2n+2
C C

H H
H
 Hidrocarburos no saturados
• Enlaces dobles y triples relativamente reactivos – pueden romperse
para formar nuevos enlaces
– Enlace doble – etileno o eteno - CnH2n

H H
C C
H H

• 4 enlaces, pero solo 3 átomos enlazados al C

– Enlace triple – acetileno o etino - CnH2n-2

H C C H
 Isomerismo

• Isomerismo
– Dos compuestos con la misma fórmula química pueden tener
diferentes estructuras
Ex: C8H18
• n-octano
H H H H H H H H
H C C C C C C C C H = H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3
H H H H H H H H 
H3C ( CH2 ) CH3
6
• 2-metil-4-etil pentano (isooctano)
CH3
H3C CH CH2 CH CH3
CH2
CH3
 Química de los polímeros
• Polimerización con radical libre (polimerización por adición)
H H H H
R + C C R C C initiation
H H H H
free radical monomer
(ethylene)

H H H H H H H H
R C C + C C R C C C C propagation
H H H H H H H H
dimer

• Iniciador: ejemplo – peróxido de benzoilo

H H H
C O O C 2 C O =2R
H H H
Polimeración por condensación
Water is “Condensed out”
during polymerization of Nylon

• Una parte del monómero original se pierde (condensa)

durante el proceso de polimerización
• El proceso se lleva a cabo en presencia de un
catalizador
• Por lo general condensan agua, CO2 pero otros
compuestos pueden aparecer como el HCN u otros
ácidos
Polímeros comerciales típicos
NOTA: Ver en la Tabla 15.3 los polímeros comericales
más importantes incluyendo sus marcas
 Grado de polimerización, n
n = número de unidades repetidas por cadena

H H H H H H H H H H H H
H C C (C C ) C C C C C C C C H ni = 6
H H H H H H H H H H H H

Mn Mw
nn   xi ni  nw   wi ni 
m m

where m  average molecular weight of repeat unit

m  f i mi
Chain fraction mol. wt of repeat unit i
 PESO MOLECULAR
• Peso molecular, Mi: Masa de un mol de cadenas.

M bajo M alto

total wt of polymer
Mn 
total # of molecules

M n  x i M i
M w  w i M i

Mw is more sensitive to
higher molecular
weights Adapted from Fig. 14.4, Callister 7e.
 Cálculo del peso molecular
Ejemplo: masa promedio de un curso de estudiantes
Ni Mi xi wi
# of students mass (lb)
1 100 0.1 0.054
1 120 0.1 0.065 M n   xi M i
2 140 0.2 0.151
3 180 0.3 0.290
2 220 0.2 0.237
M w   wi M i
1 380 0.1 0.204 Ni
xi 
N
all i
i

Mn Mw
Ni  M i
186 lb 216 lb wi 
N M
all i
i i
 Estructura molecular

• Configuración de las cadenas covalentes y resistencia:

secondary
bonding

Lineal Ramificada Reticulada Malla

Resistencia creciente
Adapted from Fig. 14.7, Callister 7e.
 Forma de las moléculas de polímeros

Conformación – Orientación molecular

puede cambiar por rotación en los enlaces
– nota: no es necesario que se rompan los enlaces

Adapted from Fig.

14.5, Callister 7e.
 Forma de las moléculas de polímeros
Configuraciones – para cambiar se deben romper
los enlaces

• Estereoisomerismo
H H H H H R
C C C C or C C
H R
H R H H

A A

C C
E E
B D D B
Plano
especular
 Tacticidad
Tacticidad – estereorregularidad de la cadena
H H H H H H H H
Isotáctica – all R groups on
C C C C C C C C
same side of chain
H R H R H R H R

H H H R H H H R
syndiotáctica – R groups
C C C C C C C C
alternate sides
H R H H H R H H

H H H H H R H H
atáctica – R groups random C C C C C C C C
H R H R H H H R
 Isomerismo cis/trans

CH3 H CH3 CH2

C C C C
CH2 CH2 CH2 H

cis trans
cis-isoprene trans-isoprene
(natural rubber) (gutta percha)
bulky groups on same bulky groups on opposite
side of chain sides of chain
 Copolímeros Adapted from Fig.
14.9, Callister 7e.

Dos o más monómeros Aleatorio

polimerizan al mismo tiempo
• Aleatorio – A y B varía de forma
aleatoria en la cadena
• Alternado – A y B alternan en la
cadena polimerizada
• En bloques – bloques de A Alternado
alternan con bloques de B
• Injerto – cadenas de B injertadas
en la cadena principal de A En bloques

A– B–

Injerto
 Polymer Crystallinity
Adapted from Fig.
14.10, Callister 7e.

Ex: polyethylene unit cell

• Crystals must contain the

polymer chains in some way
– Chain folded structure

Adapted from Fig.

14.12, Callister 7e.
 Polymer Crystallinity

Polymers rarely exhibit 100% crystalline

• Too difficult to get all those chains aligned
crystalline
region
• % Crystallinity: how much
is crystalline.
-- TS and E often increase
with % crystallinity.
-- Annealing causes
crystalline regions
to grow. % crystallinity
increases.
amorphous
region
Adapted from Fig. 14.11, Callister 6e.
(Fig. 14.11 is from H.W. Hayden, W.G. Moffatt,
and J. Wulff, The Structure and Properties of
Materials, Vol. III, Mechanical Behavior, John Wiley
and Sons, Inc., 1965.)
 Mechanical Properties
• i.e. stress-strain behavior of polymers

brittle polymer

FS of polymer ca. 10% that of metals

plastic
elastomer
elastic modulus
– less than metal

Adapted from Fig. 15.1,

Strains – deformations > 1000% possible Callister 7e.

(for metals, maximum strain ca. 100% or less)

 Tensile Response: Brittle & Plastic
(MPa) fibrillar
Near Failure structure
x brittle failure
near
onset of
failure
necking plastic failure
x
Initial
unload/reload

e
aligned, networked
cross- case crystalline
linked regions
case slide
semi-
crystalline amorphous
crystalline
case regions
regions align
elongate
Stress-strain curves adapted from Fig. 15.1, Callister 7e. Inset figures along plastic response curve adapted from
Figs. 15.12 & 15.13, Callister 7e. (Figs. 15.12 & 15.13 are from J.M. Schultz, Polymer Materials Science, Prentice-
Hall, Inc., 1974, pp. 500-501.)
 Predeformation by Drawing
• Drawing…(ex: monofilament fishline)
-- stretches the polymer prior to use
-- aligns chains in the stretching direction
• Results of drawing:
-- increases the elastic modulus (E) in the
stretching direction
-- increases the tensile strength (TS) in the
stretching direction Adapted from Fig. 15.13, Callister
-- decreases ductility (%EL) 7e. (Fig. 15.13 is from J.M.
Schultz, Polymer Materials
• Annealing after drawing... Science, Prentice-Hall, Inc.,
1974, pp. 500-501.)
-- decreases alignment
-- reverses effects of drawing.
• Comparable to cold working in metals!
 Tensile Response: Elastomer Case
(MPa)
x brittle failure Stress-strain curves
adapted from Fig. 15.1,
Callister 7e. Inset
figures along elastomer
curve (green) adapted
from Fig. 15.15, Callister
plastic failure
x 7e. (Fig. 15.15 is from
Z.D. Jastrzebski, The
Nature and Properties of
x Engineering Materials,
elastomer 3rd ed., John Wiley and
Sons, 1987.)
final: chains
are straight,
e still
cross-linked
initial: amorphous chains are Deformation
kinked, cross-linked. is reversible!

• Compare to responses of other polymers:

-- brittle response (aligned, crosslinked & networked polymer)
-- plastic response (semi-crystalline polymers)
 Thermoplastics vs. Thermosets
T
• Thermoplastics:
Callister,
rubber
-- little crosslinking viscous Fig. 16.9 Tm
-- ductile mobile liquid
-- soften w/heating liquid tough
plastic Tg
-- polyethylene
polypropylene
polycarbonate partially
crystalline
polystyrene crystalline
solid
solid

• Thermosets: Molecular weight

Adapted from Fig. 15.19, Callister 7e. (Fig. 15.19 is from F.W. Billmeyer,
-- large crosslinking Jr., Textbook of Polymer Science, 3rd ed., John Wiley and Sons, Inc.,
1984.)
(10 to 50% of mers)
-- hard and brittle
-- do NOT soften w/heating
-- vulcanized rubber, epoxies,
polyester resin, phenolic resin
 T and Strain Rate: Thermoplastics

• Decreasing T...
(MPa)
-- increases E 80 4°C Data for the
-- increases TS semicrystalline
-- decreases %EL 60 polymer: PMMA
20°C (Plexiglas)
• Increasing 40 40°C
strain rate...
-- same effects 20
as decreasing T. to 1.3
60°C
0
0 0.1 0.2 e 0.3
Adapted from Fig. 15.3, Callister 7e. (Fig. 15.3 is from T.S. Carswell and
J.K. Nason, 'Effect of Environmental Conditions on the Mechanical
Properties of Organic Plastics", Symposium on Plastics, American Society
for Testing and Materials, Philadelphia, PA, 1944.)
 Melting vs. Glass Transition Temp.
What factors affect Tm
and Tg?
• Both Tm and Tg increase with
increasing chain stiffness

• Chain stiffness increased by

1. Bulky sidegroups
2. Polar groups or
sidegroups
3. Double bonds or aromatic
chain groups

• Regularity (tacticity) – affects

Tm only

Adapted from Fig. 15.18,

Callister 7e.
 Time Dependent Deformation
• Stress relaxation test: • Data: Large drop in Er
-- strain to eo and hold. for T > Tg. (amorphous
5 polystyrene)
-- observe decrease in 10 rigid solid
Er (10s) 3 (small relax) Adapted from Fig.
stress with time. in MPa 10
15.7, Callister 7e.
transition (Fig. 15.7 is from
1
tensile test 10 region A.V. Tobolsky,
Properties and
Structures of
eo strain 10-1 Polymers, John
viscous liquid Wiley and Sons, Inc.,
(t) 10-3 (large relax) 1960.)

60 100 140 180 T(°C)

time Tg
• Relaxation modulus: • Sample Tg(C) values:
(t ) PE (low density) - 110
E r (t )  PE (high density) - 90
Selected values from
eo PVC + 87 Table 15.2, Callister
PS +100 7e.

PC +150
 Polymer Fracture
Crazing  Griffith cracks in metals
– spherulites plastically deform to fibrillar structure
– microvoids and fibrillar bridges form

alligned chains

Adapted from Fig. 15.9,

fibrillar bridges microvoids crack Callister 7e.
 Polymer Additives
Improve mechanical properties, processability,
durability, etc.
• Fillers
– Added to improve tensile strength & abrasion
resistance, toughness & decrease cost
– ex: carbon black, silica gel, wood flour, glass,
limestone, talc, etc.
• Plasticizers
– Added to reduce the glass transition
temperature Tg
– commonly added to PVC - otherwise it is brittle
 Polymer Additives
• Stabilizers
– Antioxidants
– UV protectants
• Lubricants
– Added to allow easier processing
– “slides” through dies easier – ex: Na stearate
• Colorants
– Dyes or pigments
• Flame Retardants
– Cl/F & B
 Processing of Plastics
• Thermoplastic –
– can be reversibly cooled & reheated, i.e. recycled
– heat till soft, shape as desired, then cool
– ex: polyethylene, polypropylene, polystyrene, etc.
• Thermoset
– when heated forms a network
– degrades (not melts) when heated
– mold the prepolymer then allow further reaction
– ex: urethane, epoxy
 Processing Plastics - Molding
• Compression and transfer molding
– thermoplastic or thermoset

Adapted from Fig. 15.23,

Callister 7e. (Fig. 15.23 is from
F.W. Billmeyer, Jr., Textbook of
Polymer Science, 3rd ed.,
John Wiley & Sons, 1984. )
 Processing Plastics - Molding

• Injection molding
– thermoplastic & some thermosets
Adapted from Fig. 15.24,
Callister 7e. (Fig. 15.24 is from
F.W. Billmeyer, Jr., Textbook of
Polymer Science, 2nd edition,
John Wiley & Sons, 1971. )
Processing Plastics – Extrusion

Adapted from Fig. 15.25,

Callister 7e. (Fig. 15.25 is from
Encyclopædia Britannica, 1997.)
 Polymer Types: Elastomers

Elastomers – rubber
• Crosslinked materials
– Natural rubber
– Synthetic rubber and thermoplastic elastomers
styrene
• SBR- styrene-butadiene rubber

butadiene

– Silicone rubber
 Polymer Types: Fibers

Fibers - length/diameter >100

• Textiles are main use
– Must have high tensile strength
– Usually highly crystalline & highly polar

• Formed by spinning
– ex: extrude polymer through a spinnerette
• Pt plate with 1000’s of holes for nylon
• ex: rayon – dissolved in solvent then pumped through
die head to make fibers
– the fibers are drawn
– leads to highly aligned chains- fibrillar structure
 Polymer Types
• Coatings – thin film on surface – i.e. paint, varnish
– To protect item
– Improve appearance
– Electrical insulation
• Adhesives – produce bond between two adherands
– Usually bonded by:
1. Secondary bonds
2. Mechanical bonding
• Films – blown film extrusion
• Foams – gas bubbles in plastic
Blown-Film Extrusion

Adapted from Fig. 15.26, Callister 7e.

(Fig. 15.26 is from Encyclopædia
Britannica, 1997.)
 Advanced Polymers
• Ultrahigh molecular weight
polyethylene (UHMWPE)
– Molecular weight
ca. 4 x 106 g/mol
– Excellent properties for UHMWPE
variety of applications
• bullet-proof vest, golf ball
covers, hip joints, etc.
Adapted from chapter-
opening photograph,
Chapter 22, Callister 7e.
The Stem, femoral head, and the AC socket are made from Cobalt-chrome metal alloy or ceramic, AC
cup made from polyethylene
 ABS – A Polymerized “Alloy”
ABS, Acrylonitrile-Butadiene-Styrene
Made up of the 3 materials: acrylonitrile, butadiene and styrene. The material is located under
the group styrene plastic. Styrene plastics are in volume one of the most used plastics.

Properties

The mechanical properties for ABS are good for impact resistance even in low temperatures.
The material is stiff, and the properties are kept over a wide temperature range. The
hardness and stiffness for ABS is lower than for PS and PVC.

Weather and chemical resistance

The weather resistance for ABS is restricted, but can be drastically improved by additives as
black pigments. The chemical resistance for ABS is relatively good and it is not affected by
water, non organic salts, acids and basic. The material will dissolve in aldehyde, ketone,
ester and some chlorinated hydrocarbons.

Processing

ABS can be processed by standard mechanical tools as used for machining of metals and wood.
The cutting speed need to be high and the cutting tools has to be sharp. Cooling is
recommended to avoid melting of the material. If the surface finish is of importance for the
product, the ABS can be treated with varnish, chromium plated or doubled by a layer of
acrylic or polyester. ABS can be glued to it self by use of a glue containing dissolvent.
Polyurethane based or epoxy based glue can be used for gluing to other materials.
A Processing Movie:

Calloway Golf:
 Summary
• General drawbacks to polymers:
-- E, y, Kc, Tapplication are generally small.
-- Deformation is often T and time dependent.
-- Result: polymers benefit from composite reinforcement.

• Thermoplastics (PE, PS, PP, PC):

-- Smaller E, y, Tapplication
And Remember:
-- Larger Kc
Table 15.3 Callister 7e
-- Easier to form and recycle
Is a Good overview of
applications and trade
• Elastomers (rubber): names of polymers.
-- Large reversible strains!

• Thermosets (epoxies, polyesters):

-- Larger E, y, Tapplication
-- Smaller Kc