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CHAPTER 14/15: POLYMER STUDIES

Issues:

• What are the basic microstructural features of a polymer?

• How are polymer properties affected by molecular weight? • How do polymeric materials accommodate the polymer chain?

• What are the tensile properties of polymers and how are they affected by

basic microstructural features?

• Changing Polymer Properties: Hardening, anisotropy,

and annealing in polymers.

• How does the elevated temperature mechanical response of

polymers compare to ceramics and metals?

• What are the primary polymer processing methods?

Chapter 14 Polymers

What is a polymer?

Poly

many

mer

repeat unit

repeat

unit

H H H H H H C C C C C C H H H H
H
H
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
H

Polyethylene (PE)

repeat

unit

H H H H H H C C C C C C H Cl H Cl
H
H
H
H
H
H
C
C
C
C
C
C
H Cl
H
Cl
H
Cl

Polyvinyl chloride (PVC)

repeat

unit

H H H H H H C C C C C C H CH 3 H
H
H
H
H
H
H
C
C
C
C
C
C
H
CH 3 H
CH 3 H
CH 3

Polypropylene (PP)

Ancient Polymer History

Originally many natural polymers were used

Wood Cotton Leather

Rubber Wool Silk

• Oldest known uses of “Modern Polymers” – Rubber balls used by Incas

Noah used pitch (a natural polymer) for the ark as had all ancient mariners!

Polymer Composition

Most polymers are hydrocarbons

i.e. made up of

H and C

(we also recognize Si-H „silicones‟)

Saturated hydrocarbons

Each carbon bonded to four other atoms

H

Polymer Composition Most polymers are hydrocarbons – i.e. made up of H and C (we also

H

H

C
C

H

C H H
C
H H
  • C n H 2n+2

Unsaturated Hydrocarbons

Double & triple bonds relatively reactive can form new bonds Double bond ethylene or ethene - C n H 2n

H H C C H H
H
H
C
C
H
H

4-bonds, but only 3 atoms bound to C‟s

Triple bond acetylene or ethyne - C n H 2n-2

H

C

Unsaturated Hydrocarbons • Double & triple bonds relatively reactive – can form new bonds – Double

C

H

Isomerism

Isomerism

two compounds with same chemical formula can have quite different structures

Ex: C 8 H 18 n-octane

H

H H H H H H H H C C C C C C C C
H
H
H
H
H
H
H
H
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H

H

=

H 3 C

CH 2 CH 2

CH 2

CH 2 CH 2

CH 2

CH 3

H 3 C

( CH 2

) 6 CH 3

2-methyl-4-ethyl pentane (isooctane)

CH 3 H 3 C CH CH 2 CH CH 2 CH 3 CH 3
CH 3
H 3 C
CH
CH 2 CH
CH 2
CH 3
CH 3

Chemistry of Polymers

Free radical polymerization

R

Chemistry of Polymers • Free radical polymerization R + free radical H H C C H

+

free radical

H H C C H H
H
H
C
C
H
H
  • R

monomer

(ethylene)

H H C C H H
H
H
C
C
H
H

R

H H C C H H
H
H
C
C
H
H

+

H H C C H H
H
H
C
C
H
H
Chemistry of Polymers • Free radical polymerization R + free radical H H C C H

R

H H H H C C C C H H H H
H
H
H
H
C
C
C
C
H
H
H
H

dimer

initiation

propagatio

Initiator: example - benzoyl peroxide

Chemistry of Polymers • Free radical polymerization R + free radical H H C C H
H H C O O C H H
H
H
C
O
O
C
H
H
Chemistry of Polymers • Free radical polymerization R + free radical H H C C H
Chemistry of Polymers • Free radical polymerization R + free radical H H C C H

2

Chemistry of Polymers • Free radical polymerization R + free radical H H C C H

H

C O
C
O

H

 

= 2 R

= 2

Chemistry of Polymers

Free radical polymerization (addition polymerization)

R

Chemistry of Polymers • Free radical polymerization (addition polymerization) R + free radical H H C

+

free radical

H H C C H H
H
H
C
C
H
H
  • R

monomer

(ethylene)

H H C C H H
H
H
C
C
H
H

initiation

R

H H C C H H
H
H
C
C
H
H

+

H H C C H H
H
H
C
C
H
H
Chemistry of Polymers • Free radical polymerization (addition polymerization) R + free radical H H C

R

H H H H C C C C H H H H
H
H
H
H
C
C
C
C
H
H
H
H

dimer

propagatio

Initiator: example - benzoyl peroxide

Chemistry of Polymers • Free radical polymerization (addition polymerization) R + free radical H H C
H H C O O C H H
H
H
C
O
O
C
H
H
Chemistry of Polymers • Free radical polymerization (addition polymerization) R + free radical H H C
Chemistry of Polymers • Free radical polymerization (addition polymerization) R + free radical H H C

2

Chemistry of Polymers • Free radical polymerization (addition polymerization) R + free radical H H C

H

C O
C
O

H

 

= 2 R

= 2

Condensation Polymerization

Condensation Polymerization Water is “Condensed out” during polymerization of Nylon • Some of the original monomer‟s

Water is “Condensed out”

during polymerization of Nylon

Some of the original monomer‟s materials are shed

(condensed out) during polymerization process Process is conducted in the presence of a catalyst

Water, CO 2 are commonly condensed out but other compounds can be emitted including HCN or other acids

Bulk or Commodity Polymers

Bulk or Commodity Polymers
NOTE: See Table 15.3 for commercially important polymers – including trade names
NOTE: See Table 15.3 for commercially important polymers – including trade names

NOTE: See Table 15.3 for commercially important polymers including trade names

MOLECULAR WEIGHT

Molecular weight, M i : Mass of a mole of chains.

MOLECULAR WEIGHT • Molecular weight , M : Mass of a mole of chains . Lower

Lower M

MOLECULAR WEIGHT • Molecular weight , M : Mass of a mole of chains . Lower

higher M

M n

total wt of polymer

total # of molecules

  • M x M

 

n

  • M w M

 

w

i

i

i

i

M w is more sensitive to higher molecular weights

MOLECULAR WEIGHT • Molecular weight , M : Mass of a mole of chains . Lower

Adapted from Fig. 14.4, Callister 7e.

Molecular Weight Calculation

Example: average mass of a class

0.054

0.1

100

1

  • 1 120

0.054 0.1 100 1 1 120 180 186 lb w n 0.204 0.1 380 1 0.2

180

186 lb

M w

M n

0.204

0.1

380

1

0.2

220

2

0.290

0.3

216 lb

3

0.151

0.2

140

2

0.065

0.1

N i

M i

x i

w i

# of students

mass (lb)

   
   

0.237

0.054 0.1 100 1 1 120 180 186 lb w n 0.204 0.1 380 1 0.2

  • M n x M

i

i

  • M w w M

i

i

  • x i

w

i

N i  N i all i N  M i i  all i
N
i
N
i
all i
N  M
i
i
all i

N M

i

i

Degree of Polymerization, n

n = number of repeat units per chain

H

H H H H H H H H H H H H C C ( C
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
H
H
H
H
H
H
H
H
H
H
H

H

n

n

M n x n  i i
M
n
x n
i
i

m

n

w

n i = 6 M w w n  i i
n i = 6
M
w
w n
i
i

m

where

m

average molecular weight of repeat unit

m   f m i i Chain fraction
m
 
f m
i
i
Chain fraction

mol. wt of repeat unit i

Molecular Structures

• Covalent chain configurations and strength:

secondary bonding
secondary bonding

Linear

Molecular Structures • Covalent chain configurations and strength: secondary bonding Linear B ranched Cross-Linked Network Direction

B ranched

Molecular Structures • Covalent chain configurations and strength: secondary bonding Linear B ranched Cross-Linked Network Direction

Cross-Linked

Molecular Structures • Covalent chain configurations and strength: secondary bonding Linear B ranched Cross-Linked Network Direction

Network

Molecular Structures • Covalent chain configurations and strength: secondary bonding Linear B ranched Cross-Linked Network Direction

Direction of increasing strength

Adapted from Fig. 14.7, Callister 7e.

Polymers Molecular Shape

Conformation Molecular orientation can be changed by rotation around the bonds

note: no bond breaking needed

Polymers – Molecular Shape Conformation – Molecular orientation can be changed by rotation around the bonds

Adapted from Fig.

14.5, Callister 7e.

Polymers Molecular Shape

Configurations to change must break bonds

Stereoisomerism

H H C C H R
H
H
C
C
H
R
H H C C H R
H
H
C
C
H
R

B

A

  • C E

Polymers – Molecular Shape Configurations – to change must break bonds • Stereoisomerism H H C

D

or

H R C C H H
H
R
C
C
H
H

E

A C B D
A
C
B
D

mirror

plane

Tacticity

Tacticity stereoregularity of chain

isotactic all R groups on same side of chain

syndiotactic R groups alternate sides

atactic R groups random

H

H

H

H

H

H

H

H

C

C

C

C

C

C

C

C

H

R

H

R

H

R

H

R

H

H

H

R

H

H

H

R

C

C

C

C

C

C

C

C

H

R

H

H

H

R

H

H

H

H

H

H

H

R

H

H

C

C

C

C

C

C

C

C

H

R

H

R

H

H

H

R

cis/trans Isomerism

CH H 3 C C CH 2 CH 2
CH
H
3
C
C
CH 2
CH 2

cis

cis-isoprene (natural rubber)

bulky groups on same side of chain

CH 3 CH 2 C C CH 2 H
CH 3
CH 2
C
C
CH 2
H

trans

trans-isoprene (gutta percha)

bulky groups on opposite sides of chain

Copolymers

two or more monomers polymerized together

random A and B randomly vary in chain

alternating A and B alternate in polymer chain

block large blocks of A alternate with large blocks of B

graft chains of B grafted on to A backbone

A

B

Copolymers two or more monomers polymerized together • random – A and B randomly vary in
Adapted from Fig. 14.9, Callister 7e. random alternating block graft
Adapted from Fig.
14.9, Callister 7e.
random
alternating
block
graft

Polymer Crystallinity

Ex: polyethylene unit cell

Crystals must contain the polymer chains in some way

Chain folded structure

Polymer Crystallinity Ex: polyethylene unit cell • Crystals must contain the polymer chains in some way

Adapted from Fig. 14.12, Callister 7e.

Adapted from Fig. 14.10, Callister 7e.

Polymer Crystallinity

Polymers rarely exhibit 100% crystalline • Too difficult to get all those chains aligned crystalline region
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 plastic elastic modulus – less than metal
brittle polymer
plastic
elastic modulus
– less than metal

FS of polymer ca. 10% that of metals

elastomer

Adapted from Fig. 15.1,

Strains deformations > 1000% possible (for metals, maximum strain ca. 100% or less)

Callister 7e.

Tensile Response: Brittle & Plastic

(MPa) fibrillar Near Failure structure x brittle failure near onset of failure necking plastic failure x
(MPa)
fibrillar
Near Failure
structure
x
brittle failure
near
onset of
failure
necking
plastic failure
x
Initial
unload/reload
e
aligned,
networked
crystalline
cross-
case
regions
linked
slide
case
semi-
amorphous
crystalline
crystalline
regions
case
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 -- decreases ductility (%EL) Annealing after drawing ... -- decreases alignment -- reverses effects of drawing.

Predeformation by Drawing • Drawing …(ex: monofilament fishline) -- stretches the polymer prior to use --

Adapted from Fig. 15.13, Callister 7e. (Fig. 15.13 is from J.M. Schultz, Polymer Materials Science, Prentice-Hall, Inc., 1974, pp. 500-501.)

• Comparable to cold working in metals!

Tensile Response: Elastomer Case

 (MPa) x brittle failure plastic failure x x elastomer final: chains e are straight, still
 (MPa)
x
brittle failure
plastic failure
x
x
elastomer
final: chains
e
are straight,
still
cross-linked
initial: amorphous chains are
kinked, cross-linked.
Deformation
is reversible!

Stress-strain curves

adapted from Fig. 15.1,

Callister 7e. Inset

figures along elastomer

curve (green) adapted

from Fig. 15.15, Callister

7e. (Fig. 15.15 is from

Z.D. Jastrzebski, The Nature and Properties of

Engineering Materials, 3rd ed., John Wiley and

Sons, 1987.)

• Compare to responses of other polymers:

-- brittle response (aligned, crosslinked & networked polymer) -- plastic response (semi-crystalline polymers)

Thermoplastics vs. Thermosets

Thermoplastics:

T

-- little crosslinking

-- ductile

-- soften w/heating -- polyethylene polypropylene polycarbonate

polystyrene

Callister, rubber viscous Fig. 16.9 mobile liquid T m liquid tough plastic T g partially crystalline
Callister,
rubber
viscous
Fig. 16.9
mobile
liquid
T m
liquid
tough
plastic
T g
partially
crystalline
crystalline
solid
solid

Thermosets:

-- large crosslinking

(10 to 50% of mers)

Molecular weight

Adapted from Fig. 15.19, Callister 7e. (Fig. 15.19 is from F.W. Billmeyer, Jr., Textbook of Polymer Science, 3rd ed., John Wiley and Sons, Inc.,

1984.)

-- hard and brittle -- do NOT soften w/heating -- vulcanized rubber, epoxies, polyester resin, phenolic resin

T and Strain Rate: Thermoplastics

• Decreasing T...

-- increases E -- increases TS -- decreases %EL

• Increasing

strain rate ...

-- same effects as decreasing T.

(MPa)

8 0 4°C Data for the semicrystalline 6 0 20°C polymer: PMMA (Plexiglas) 4 0 40°C
8
0
4°C
Data for the
semicrystalline
6
0
20°C
polymer: PMMA
(Plexiglas)
4
0
40°C
20
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 T m and T g ?

Both T m and

T g

Melting vs. Glass Transition Temp. What factors affect T and T ? • Both T and

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 T m only

Adapted from Fig. 15.18, Callister 7e.

Time Dependent Deformation

Stress relaxation test:

-- strain to eo and hold. -- observe decrease in

stress with time. tensile test e o strain (t) time
stress with time.
tensile test
e o
strain
(t)
time

Relaxation modulus:

E

r

 t ( ) ( )  t e o
 t
(
)
( ) 
t
e
o

Data: Large drop in E r

for T > T g .

(amorphous

E r (10s) in MPa

5 10 polystyrene) rigid solid (small relax) Adapted from Fig. 3 10 15.7, Callister 7e. transition
5
10
polystyrene)
rigid solid
(small relax)
Adapted from Fig.
3
10
15.7, Callister 7e.
transition
1
(Fig. 15.7 is from
A.V. Tobolsky,
10
region
Properties and
Structures of
-1
10
viscous liquid
Polymers, John
Wiley and Sons, Inc.,
-3
10
(large relax)
1960.)
60
100 140
180 T(°C)
T g

Sample T g (C) values:

PE (low density)

- 110

PE (high density)

-

90

PVC

+

87

PS

+100

PC

+150

Selected values from Table 15.2, Callister

7e.

Polymer Fracture

Crazing Griffith cracks in metals

spherulites plastically deform to fibrillar structure microvoids and fibrillar bridges form

alligned chains

fibrillar bridges microvoids crack Adapted from Fig. 15.9, Callister 7e.
fibrillar bridges
microvoids
crack
Adapted from Fig. 15.9,
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 T g 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

Processing Plastics - Molding • Compression and transfer molding – thermoplastic or thermoset Adapted from Fig.

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
Callister 7e. (Fig. 15.24 is from
F.W. Billmeyer, Jr., Textbook of
Polymer Science, 2nd edition,
John Wiley & Sons, 1971. )

Processing Plastics Extrusion

Processing Plastics – Extrusion Adapted from Fig. 15.25, Callister 7e . (Fig. 15.25 is from Encyclopædia

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

SBR- styrene-butadiene rubber

Polymer Types: Elastomers Elastomers – rubber • Crosslinked materials – Natural rubber – Synthetic rubber and

styrene

Polymer Types: Elastomers Elastomers – rubber • Crosslinked materials – Natural rubber – Synthetic rubber and

butadiene

Silicone rubber

Polymer Types: Elastomers Elastomers – rubber • Crosslinked materials – Natural rubber – Synthetic rubber and

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

Blown-Film Extrusion Adapted from Fig. 15.26, Callister 7e . (Fig. 15.26 is from Encyclopædia Britannica, 1997.)

Adapted from Fig. 15.26, Callister 7e. (Fig. 15.26 is from Encyclopædia Britannica, 1997.)

Advanced Polymers

UHMWPE Adapted from chapter- opening photograph, Chapter 22, Callister 7e.
UHMWPE
Adapted from chapter-
opening photograph,
Chapter 22, Callister 7e.

Ultrahigh molecular weight polyethylene (UHMWPE)

Molecular weight ca. 4 x 10 6 g/mol

Excellent properties for variety of applications

bullet-proof vest, golf ball covers, hip joints, etc.

The Stem, femoral head, and the AC socket are made from Cobalt-chrome metal alloy or ceramic,
The Stem, femoral head, and the AC socket are made from Cobalt-chrome metal alloy or ceramic,

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:

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 -- Larger Kc -- Easier to form and recycle

Elastomers (rubber):

-- Large reversible strains!

And Remember:

Table 15.3 Callister 7e Is a Good overview of applications and trade names of polymers.

Thermosets (epoxies, polyesters):

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