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
repeat unit repeat unit

mer
repeat unit
repeat unit

H H H H H H C C C C C C H H H H H H
Polyethylene (PE)

H H H H H H C C C C C C H Cl H Cl H Cl
Polyvinyl chloride (PVC)

H C H

H H C C CH3 H

H H C C CH3 H

H C CH3

Polypropylene (PP)

Adapted from Fig. 14.2, Callister 7e.

Ancient Polymer History

Originally many natural polymers were used Wood Rubber Cotton Wool Leather 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 H C H C H H H

CnH2n+2

Unsaturated Hydrocarbons
Double & triple bonds relatively reactive can form new bonds Double bond ethylene or ethene - CnH2n

H C C H

H H

4-bonds, but only 3 atoms bound to Cs Triple bond acetylene or ethyne - CnH2n-2

H C C H

Isomerism
Isomerism two compounds with same chemical formula can have quite different structures Ex: C8H18 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 H = H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3

H3C ( CH2 ) CH3

6

2-methyl-4-ethyl pentane (isooctane)

CH3 H3C CH CH2 CH CH3 CH2 CH3

Chemistry of Polymers
Free radical polymerization
H H R + C C H H monomer (ethylene) H H + C C H H H H R C C H H initiation

free radical

H H R C C H H

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

Initiator: example - benzoyl peroxide

H H H 2 H H C O H C O O C

= 2R

Chemistry of Polymers
Free radical polymerization (addition polymerization)
H H R + C C H H monomer (ethylene) H H + C C H H H H R C C H H initiation

free radical

H H R C C H H

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

Initiator: example - benzoyl peroxide

H H H 2 H H C O H C O O C

= 2R

Condensation Polymerization
Water is Condensed out during polymerization of Nylon

Some of the original monomers materials are shed (condensed out) during polymerization process Process is conducted in the presence of a catalyst Water, CO2 are commonly condensed out but other compounds can be emitted including HCN or other acids

Bulk or Commodity Polymers

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

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

total wt of polymer Mn total # of molecules

M n xi Mi M w w i Mi
Mw is more sensitive to higher molecular weights

Adapted from Fig. 14.4, Callister 7e.

Molecular Weight Calculation

Example: average mass of a class
Ni
# of students

Mi
mass (lb)

xi 0.1 0.1 0.2 0.3 0.2 0.1 Mn 186 lb

wi 0.054 0.065 0.151 0.290 0.237 0.204 Mw 216 lb

1 1 2 3 2 1

100 120 140 180 220 380

M n xi M i
M w wi M i
xi
wi

Ni

N
all i

Ni M i

N M
i all 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 C ) C C C C C C C C H H H H H H H H H H H H H

ni = 6

Mn nn xi ni m

Mw nw w i ni m

where m average molecular weight of repeat unit m fi mi

Chain fraction mol. wt of repeat unit i

Molecular Structures
Covalent chain configurations and strength:

secondary

bonding

Linear

Branched

Cross-Linked

Network

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
Adapted from Fig. 14.5, Callister 7e.

Polymers Molecular Shape

Configurations to change must break bonds

Stereoisomerism
H C C H R H H H C C H R or H R C C H H

A C B D
mirror plane

A E E D C B

Tacticity
Tacticity stereoregularity of chain
isotactic all R groups on same side of chain
H H H H H H H H C C C C C C C C H R H R H R H R

syndiotactic R groups alternate sides

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

atactic R groups random

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

cis/trans Isomerism
CH3 C C CH2 CH2 CH2 H CH3 C C H CH2

cis
cis-isoprene (natural rubber) bulky groups on same side of chain

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 random

Adapted from Fig. 14.9, Callister 7e.

alternating

block

graft

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

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

Adapted from Fig. 15.1, Callister 7e.

Tensile Response: Brittle & Plastic

Near Failure

(MPa)
x brittle failure
onset of necking

fibrillar structure
near failure

plastic failure

x
Initial unload/reload

e
aligned, networked crosscase linked case semicrystalline case amorphous regions elongate crystalline regions slide

crystalline regions align

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, PrenticeHall, 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.

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
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.)

plastic failure

elastomer

e
initial: amorphous chains are kinked, cross-linked. Deformation is reversible!

final: chains are straight, still cross-linked

Compare to responses of other polymers:

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

Thermoplastics vs. Thermosets

Thermoplastics:
-- little crosslinking -- ductile -- soften w/heating -- polyethylene polypropylene polycarbonate polystyrene

T
mobile liquid

viscous liquid

Callister, rubber Fig. 16.9

tough plastic

Tm
Tg

crystalline solid

partially crystalline 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...
-- increases E -- increases TS -- decreases %EL

(MPa)
80 4C

60
40 20 0

20C 40C

Data for the semicrystalline polymer: PMMA (Plexiglas)

Increasing strain rate...

-- same effects as decreasing T.

60C 0 0.1 0.2

to 1.3 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:
-- strain to eo and hold. -- observe decrease in stress with time. tensile test

Data: Large drop in Er

for T > Tg.
10
5

Er (10s) 3 in MPa 10 10
1

rigid solid (small relax)

(amorphous polystyrene)
Adapted from Fig. 15.7, Callister 7e. (Fig. 15.7 is from A.V. Tobolsky, Properties and Structures of Polymers, John Wiley and Sons, Inc., 1960.)

transition region

eo

strain (t) time

10-1 10-3 (large relax)

viscous liquid

60 100 140 180 T(C) Tg

Relaxation modulus:
(t ) E r (t ) eo

Sample Tg(C) values:

PE (low density) PE (high density) PVC PS PC - 110 - 90 + 87 +100 +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.

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 Encyclopdia Britannica, 1997.)

Polymer Types: Elastomers

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

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 1000s 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 Encyclopdia Britannica, 1997.)

Advanced Polymers
Ultrahigh molecular weight polyethylene (UHMWPE)
Molecular weight ca. 4 x 106 g/mol Excellent properties for variety of applications
bullet-proof vest, golf ball covers, hip joints, etc.
Adapted from chapteropening photograph, Chapter 22, Callister 7e.

UHMWPE

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 -- Larger Kc -- Easier to form and recycle
And Remember: Table 15.3 Callister 7e Is a Good overview of applications and trade names of polymers.

Elastomers (rubber):
-- Large reversible strains!

Thermosets (epoxies, polyesters):

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