Mechanical Behavior of Polymers

Chapter 11 (Sperling)

Overview Materials
Glassy Polymers: I. Thermoplastics Glassy Polymers: II. Thermosets Semi-crystalline Polymers Elastomeric Polymers (preceding chapter) Toughened Multiphase Polymers Polymer Composites

Also: Fracture Behavior of Polymers (A.J. Kinloch, R.J. Young, 1982) Mechanical Properties of Solid Polymers (I.M. Ward, 1971, 1999)

Overview of Mechanical Properties

Mechanical Properties:
Thermodynamics: Conservation of energy Kinetics:
Deformation: Viscoelasticity (Strain or stress controlled experiments) Failure: Observed Strength << Calculated Strength Role of Defects Failure Process: Initiation + Growth of Cracks. Mechanism of Failure: Modes of Energy Absorption

Two principal tools: Why ?

Stress Strain Behavior (tensile, shear, flexural tests, etc) Impact (Charpy, Izod tests)

Overview of Mechanical Properties

Stress Strain Behavior of Polymers: Slow deformation (in/min) Five regions (at most)
Elastic region Yield (intrinsic, extrinsic) Strain softening Cold drawing Strain hardening Failure Youngs modulus Yield stress and strain Strength, Ultimate elongation Toughness

Mechanical Properties

Mechanical Properties
Homogeneous vs Inhomogeneous Deformation

Restraints in:

(a.) 0

(b.) 1

(c.) 2 directions

Plastic deformation rarely occurs homogeneously (in the body as a whole) Plastic deformation often occurs faster in localized regions Unstable homogeneous deformation (intrinsic material prop., geometry) a. 0-D: Necking: strain softening enhances inhomogeneous deformation. b. 1-D: Locally thinned zone: sz = 54.7 if isochoric c. 2-D: Isochoric sb = 45 true shear bands Dilational sb= 90 craze formation

Mechanical Properties
Glassy Polymers: Thermoplastics
Ductile Deformation Brittle Deformation

Microshear Bands
At-Polystyrene at 22C under compression (Optical Microscopy w/ Polarized Light)

Crazes (fibrils, = 20 nm) Mechanisms of Deformation

At-Polystyrene in tension. (Transmission Electron Microscopy)

Mechanical Properties
Glassy Polymers: Thermoplastics

Effect of Temperature on the Yield Behavior: Eyring Rate Theory Brittle vs Ductile Behavior

Mechanical Properties
Glassy Polymers: Thermoplastics

Effect of Deformation Rate on the Yield Behavior: Eyring Rate Theory Brittle vs Ductile Behavior

Mechanical Properties
Glassy Polymers: Thermoplastics
Effect of Molar Mass: The fracture energy for brittle failure (craze propagation) is increases with molar mass. Why ?

Effect of Orientation: Fracture energy (K1c, G1c) // orientation

K1c, G1c orientation ?

Mechanical Properties
Glassy Polymers: Thermoplastics

Shear Yielding is very important mechanically:

Yielding: plastic (unrecoverable, isochoric) deformation under stress. Factor limiting strength if no brittle fracture. High Y Tough Shear bands play a role in crack initiation.

Deformation Mechanisms:
Ductile Behavior: Shear Yielding in the form of Microshear bands Compression, low shear rate, higher T. Brittle Behavior: Crazing with localized yielding ahead of crack tip Tension, high shear rate, lower T. Aggressive liquids & internal or external stress. Environmental stress cracking Solvent crazing

Mechanical Properties
Thermosets: Cross-linked Polymers Used Below their Tg

Epoxy with Tg = 150C T < 30 C: Hookean, brittle. 30 C < T < Tg - 100 C: Non-linear, brittle 100 C < T: Limited ductility No cold drawing or necking Fracture by tearing (elastomers)

Mechanical Properties
Thermosets: Cross-linked Polymers Used Below their Tg
As Thermoplastic Materials Below Tg 1) Thermosets are more ductile in compression than in tension. 2) Thermosets undergo considerable plastic deformation in pure compression or shear. Inability to undergo crazing limits: 1) Extent of post-yield plastic strain which increases with decreasing cross-linking. 2) Toughness.

Mechanical Properties
Semicrystalline Polymers

Depend on: 1) Morphology: crystallinity level level of crystal orientation 2) Whether Tdef > Tg or Tdef > Tg Modeling of their Mechanical Properties 1) Difficult because of non-linear def. 2) Large scale yielding at crack tips 3) Non-brittle

Mechanical Properties
Semicrystalline Polymers vs Other Materials

Single Xtl Ecal (GPa) Emeas (GPa) PE PP POM 180-405 40-50 150 Esp 71 69 50 88 28-55 27 sp (GPa) > 0.3 0.49 1.3 1.8 0.15-0.7 0.07 1.0-1.5 240-360 42 54

d (g/cc) E (GPa) Highly drawn PE High modulus PE Polydiacetylene single crystal fiber Kevlar fibers Glass fibers Steel Carbon fibers 0.966 0.97 1.31 1.45 2.5 7.9 2.0 68 67 61 128 70-140 210

200-420 100-210

Mechanical Properties
Semicrystalline Polymers

Effect of Spherulite Size (caution ?)

Effect of Temperature (caution ?)

Mechanical Properties
Semicrystalline Polymers

Low molar mass it-PP

High molar mass it-PP

Number of interspherulite links increases with molar mass and purity. More links, more ductile deformation.

Mechanical Properties
Semicrystalline Polymers

Number of interlamellar links increases with molar mass and purity. More links, more ductile deformation and higher strength.

Mechanical Properties
Semicrystalline Polymers
Octene Content 8.2 mol%

12.3 mol%

13.6 mol%

Ethylene-Octene Copolymers (Constrained Geometry Catalysts) Fringed Micellar Crystals act as cross-link sites. Mechanical Behavior: Similar to a crosslinked elastomer.

Mechanical Properties
Semicrystalline Polymers
Effect of Temperature

Effect of Molar Mass

Mechanical Properties
Semicrystalline Polymers

Deformation Mechanism: Stretching of amorphous chains. Shear yielding of crystallites. Void formation (stress whitening). Recrystallization with orientation.

Mechanical Properties
Summary for Ductile / Brittle Behavior

Line A Right: brittle unnotched Left: ductile unnotched

Line B Right: brittle notched Left: ductile notched

Mechanical Properties
Multiphase Polymer Mixtures
Toughening of Brittle Polymers: INCREASING FRACTURE ENERGY (1) With rubbery particles Crazes are initiated at rubbery particles, grow normal to the applied stress and terminate at other rubber particles. Rubbery articles allow absorption of large amount of mechanical energy through controlled crazing.

TEM of a microtomed section of HIPS

Mechanical Properties
Multiphase Polymer Mixtures
Toughening of Brittle Polymers: INCREASING FRACTURE ENERGY (2) With brittle particles (matching thermal and elastic prop) Crack-pinning mechanism

SEM of fracture surface of a sample of epoxy resin with glass beads

Mechanical Properties
Multiphase Polymer Mixtures

Stress-Strain Behavior sometimes does not tell you about toughening. Need to measure fracture energy or do impact tests.

Mechanical Properties
Multiphase Polymer Mixtures

Stress-Strain Behavior sometimes does not tell you about toughening. Needs to measure fracture energy (total energy dissipated during crack growth) or do impact tests for toughness at high strain rates.

Mechanical Properties
Fracture Energy Measurements

Study the propagation of a crack in plane-strain conditions. Measuring the stress for which a crack of known length starts to grow, allows you to calculate K1c (stress intensity factor) and G1c (fracture energy)

Mechanical Properties
Fracture Energy Measurements
Material Rubber Polyethylene Polystyrene HIPS PMMA Epoxy Rubber Toughened Epoxy Glass Reinforced Thermoset Glass Wood Al alloy Steel (mild) Steel (alloy) E (GPa) 0.001 0.15 3 2.1 2.5 2.8 2.4 7 70 2.1 69 210 210 G1c (kJ.m-2) 13 20 0.4 15.8 0.5 0.1 2 7 0.007 0.12 20 12 107 1.1 0.5 2.2 7 0.7 0.5 37 50 150 1.1 K1c (MN.m-3/2)

Mechanical Properties
Impact Test Measurements

Test Method Charpy Izod Falling weight Tensile Pneumatic gun Hydrolically operated

Strain Rate (s-1) 10 60 0.1 10 0.001 0.1 100 10,000 1 100

Impact Velocity (m.s-1) 3 2 14 10-5 10-1 20 240 0.008 - 4

Mechanical Properties
Impact Test Measurements on Multiphase Polymer Mixtures

Toughening of a brittle SAN copolymer