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Course Outline
Unit II (A)

Polymer Structure Properties Relationship

Open Elective Department of Petroleum Studies PK 428(D)

Mechanical Properties such as stress-strain relationship, modulus, toughness, strength, dy namic mechanical behavior etc.

Basic Concepts
Mechanical Prop. deformation. Response of material to applied force or

Applied force; 1. Tensile Load 2. Compressive Load 3. Shear loading 4. Bending or Flexural Loading 5. Impact Loading 6. Dynamic Loading

Types of Loading

LECTURE 1

Tensile Loading
Examples: Climbers rope, Fishing net, Fibers Etc.

Compressive Loading
Examples: Pipeline, Mounting Pads, Bushes Chair Shoes Etc.

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Shear Loading
Examples: Rivets, Adhesives, Tearing of Film Etc.

Bending or Flexural Loading

Load

Examples
Simply Supported beam Molded Chair Racks Aircrafts floor Etc.

Impact Loading
Shield

Dynamic Loading
When a body is subjected to transient (Changing with time) loading conditions. Examples;
Axel of motorcar Vibrational loading Cyclic loading

Examples
Helmet Shoe sole Cabinet (casing) of mobile. Policemens Shield Etc.
Fast Speed Stone

Tensile stress, :

ENGINEERING STRESS
Shear stress, :

Ft
Area, A

Ft
Area, A

Loading at an angle

F Fs

Properties of Materials

LECTURE - 2

F = t Ao
original area before loading

Ft

Fs F = s Ao
Stress has units: N/m2 or lb/in2
4

Ft

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ENGINEERING STRAIN
Tensile strain: Lateral strain:

LINEAR ELASTIC PROPERTIES

1. Modulus of Elasticity, E: (also known as Young's modulus) 2. Hooke's Law:

= Lo
Shear strain:

/2

wo
L/2

Lo
/2 L/2

L = L wo

F
E 1
Linearelastic

=E
3. Poisson's ratio, :

/2

= L
Strain is always dimensionless.

= tan
/2 - /2

metals: ~ 0.33 ceramics: ~0.25 polymers: ~0.40

Units: E: [GPa] or [psi]
8

F
simple tension test

/2

: dimensionless

10

OTHER ELASTIC PROPERTIES

Elastic Shear modulus, G:

YOUNGS MODULI: COMPARISON

simple torsion test
Metals Alloys
1200 1000 800 600 400

G
M

Graphite Composites Ceramics Polymers /fibers Semicond

Diamond

=G
Elastic Bulk modulus, K:

E(GPa)

200 100 80 60 40

P V Vo V Vo 1
P P P
10 9 Pa

Si carbide Tungsten Al oxide Molybdenum Si nitride Steel, Ni <111> Tantalum Si crystal Platinum <100> Cu alloys Zinc, Ti Silver, Gold Glass-soda Aluminum Magnesium, Tin Concrete

Carbon fibers only

CFRE(|| fibers)*
Aramid fibers only

Eceramics > Emetals >> Epolymers

AFRE(|| fibers)*
Glass fibers only

GFRE(|| fibers)* GFRE* Graphite CFRE* GFRE( fibers)* CFRE( fibers)* AFRE( fibers)*

P= -K

20 10 8 6 4 2

-K

Special relations for isotropic materials:

Polyester PET PS PC PP HDPE PTFE LDPE

Epoxy only

E G= 2(1 + )

K=

E 3(1 2 )

Pressure test: Init. vol =Vo. Vol chg. = V

12

1 0.8 0.6 0.4 0.2

Wood(

grain)

13

PLASTIC (PERMANENT) DEFORMATION

Simple tension test:
2000

YIELD STRENGTH: COMPARISON

Metals/ Alloys Graphite/ Ceramics/ Polymers Semicond Composites/ fibers
Steel (4140)qt

Yield strength, y (MPa)

700 600 500 400 300 200

Hard to measure,

Elastic initially
permanent (plastic) after load is removed

Ti (5Al-2.5Sn)a W (pure) Cu (71500)cw Mo (pure) Steel (4140)a Steel (1020)cd Al (6061)ag Steel (1020)hr Ti (pure)a Ta (pure) Cu (71500)hr

Hard to measure, since in tension, fracture usually occurs before yield.

tensile stress,

1000

in ceramic matrix and epoxy matrix composites, since in tension, fracture usually occurs before yield.

Elastic+Plastic at larger stress

y(ceramics) >>y(metals) >> y(polymers)

Room T values
Based on data in Table B4, Callister 6e. a = annealed hr = hot rolled ag = aged cd = cold drawn cw = cold worked qt = quenched & tempered

100 70 60 50 40 30 20
Tin (pure) Al (6061)a

dry

engineering strain,
plastic strain
15

PC Nylon 6,6 PET PVC humid PP HDPE

LDPE

10

17

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TENSILE STRENGTH, TS
Maximum possible engineering stress in tension.

TENSILE STRENGTH: COMPARISON

Metals/ Alloys 5000 3000 2000 1000 Graphite/ Ceramics/ Polymers Semicond Composites/ fibers
C fibers Aramid fib E-glass fib Steel (4140)qt Diamond W (pure) Ti (5Al-2.5Sn)a a Steel (4140) Si nitride Cu (71500)cw hr Cu (71500) Al oxide Steel (1020) Al (6061)ag Ti (pure)a Ta (pure) Al (6061)a Si crystal
<100>

Adapted from Fig. 6.11, Callister 6e.

Tensile strength, TS (MPa)

TS engineering stress

AFRE(|| fiber) GFRE(|| fiber) CFRE(|| fiber)

300 200 100 40 30 20 10

TS(ceram) ~TS(met) ~ TS(comp) >> TS(poly)

Room T values

Typical response of a metal

wood(|| fiber) Nylon 6,6 PC PET PVC PP HDPE GFRE( CFRE( AFRE(

Glass-soda Concrete Graphite

strain
Metals: occurs when noticeable necking starts. Ceramics: occurs when crack propagation starts. Polymers: occurs when polymer backbones are

LDPE

aligned and about to break.

18

wood(

Based on data in Table B4, Callister 6e. fiber) a = annealed fiber) fiber) hr = hot rolled ag = aged cd = cold drawn cw = cold worked qt = quenched & tempered AFRE, GFRE, & CFRE = aramid, glass, & carbon fiber-reinforced epoxy fiber) composites, with 60 vol% fibers.
19

DUCTILITY, %EL
Plastic tensile strain at failure:

Engineering tensile stress,

Adapted from Fig. 6.13, Callister 6e.

smaller %EL (brittle if %EL<5%) larger %EL (ductile if %EL>5%)

L Lo %EL = f x100 Lo

Lo

Ao

Af

Lf

Properties of Materials..........continued

Engineering tensile strain,

Another ductility measure: Note:

LECTURE 3

%AR =

Ao A f x100 Ao

%AR and %EL are often comparable. --Reason: crystal slip does not change material volume. --%AR > %EL possible if internal voids form in neck.
20

TOUGHNESS
Energy to break a unit volume of material Approximate by the area under the stress-strain curve.

Creep
Deformation at constant stress
Due to thermal fluctuations Breaking of hydrogen bonds
Load Constant load

Engineering tensile stress,

smaller toughness (ceramics) larger toughness (metals, PMCs) smaller toughnessunreinforced polymers

eg;
Climbers rope
deformation c

Load removed

Time

Engineering tensile strain,

a b = Instant extension b c = total creep d- e = Instant recovery e f = Primary creep (recoverable with time) g h = Secondary creep (non recoverable)
21

g a h

Time

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Stress Relaxation
Relaxation in stress at constant deformation
Due to rearrangement of chains Formation of new secondary bonds
deformation Constant Strain

Brittle vs. Ductile failure

(MPa)
60 xbrittle failure 40 20
Time
Stress-strain curves adapted from Fig. 15.1, Callister 6e. Inset figures along elastomer curve (green) adapted from Fig. 15.14, Callister 6e. (Fig. 15.14 is from Z.D. Jastrzebski, The Nature and Properties of Engineering Materials, 3rd ed., John Wiley and Sons, 1987.)

plastic failure

x
elastomer

0 0
initial: amorphous chains are kinked, heavily cross-linked.

final: chains are straight, still cross-linked

Stress Reducing stress

Deformation is reversible!

Compare to responses of other polymers:

Time

--brittle response (aligned, cross linked & networked case) --plastic response (semi-crystalline case)
25

Effect of Temperature on SSC

(MPa)
Decreasing T...

Effect of elongation rate on SSC

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

80 4C 60 40 20 20C 40C

Data for the semicrystalline polymer: PMMA (Plexiglas)

60C 0 0 0.1 0.2

to 1.3 0.3

26

Effect of Moisture on SSC

Effect of Orientation on SSC

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Elastic Deformation
1. Initial 2. Load
bonds stretch return to initial shape

3. Unload

Deformation of Materials

F
Return to the original shape when the applied load is removed. Elastic means reversible!

LECTURE 4

Linearelastic Non-Linearelastic

Plastic Deformation
1. Initial 2. Load
bonds stretch & planes shear

Viscous Deformation
p lanes still sheared

3. Unload

elastic + plastic

plastic

F F
Could not return to the original shape when the applied load is removed. Plastic means permanent!
linear elastic linear elastic

Plastic deformations in noncrystalline solids (as well as liquids) occurs by a viscous flow mechanism. Usually attributed to fluids. But solids may also behave like viscous materials under high temperature and pressure. Viscous materials deform steadily under stress. Deformations are time dependent.

plastic

elastic

Based on the above mentioned deformation characteristics, several material idealizations could be made. Such as:
1. 2. 3. 4. Elastic Materials Plastic Materials extensometer Elastoplastic Materials Viscoelastic Materials
specimen

1. Elastic Materials
Return to the their original shape when the applied load is removed.

Unloading Loading

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2. Plastic Materials
No deformation is observed up to a certain limit. Once the load passes this limit, permanent deformartions are observed. P
Limit

3. Elastoplastic Materials
Up to a limit shows elastic properties. Within this limit if the load is removed, returns to its original shape. If the load passes the limit, plastic deformations are observed.
P

Unloading Loading

Elastic Limit

Plastic deformation

Plastic Elastic deformation deformation

4. Viscoelastic Material
Deformations are time-dependent.
Stress

Fast Loading-Unloading

Dynamic Mechanical Behavior of Polymers

Slow Loading-Unloading
Strain

LECTURE 5

Parameters of DMA
f= stress; e= strain; t= time Sinusoidal loading;

Dynamic Modulus
1. In-phase modulus (Dynamic Modulus) 2. Out of phase modulus (Loss Modulus) 3. Loss factor or (Dissipation factor)
= f m .Cos = E' em

e = e0 + em sin t
em = strain _ amplitude e0 = static _ strain

= angular _ frequancy = (2 xfreq.) _ in _ Hz

f m .Sin = E" em
Sin( ) E" = tan( ) = Cos ( ) E'

Stress Response;
f = f 0 + f m sin(t + ) where f m = stress _ amplitude
=

= Angular _ Phase _ lag

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Transition of Dynamic Modulus (E)

Mechanism of deformation; (i). Stretching of atomic bonds leads to high stresses and small strain that occur at high speed. (ii). Uncoiling of chains leads to large strain under low stress but take long time owing to viscous drag
Max. Energy Loss

Freq. dependency of Modulus

At higher frequency the stiff mechanism operates. It shows higher modulus (E) At lower frequency soft mechanism operates and shows lower modulus (E)

Stretching of bonds Uncoiling Of Chain

Energy Dissipation
At extreme frequency, there is little energy loss; (a). At high freq. little viscous displacement. (b). At low frequency little viscous resistance. But near the transition, when structure just becoming mobile, maximum energy dissipation takes place.
Max. Dissipation At peak

Other parameters affecting transition

Transition is dependent on structural mobility of chains via;
Temperature Plasticizer content Filler etc. These factors can affect the inter-molecular forces hence mobility.

Temperature
Tg(tan) > Tg(E) Tg(E) ~ Tg(DSC) More accurate

Frequency
10Hz 1Hz When frequency is increased, the material behaves like a stiff material and Tg-peak shifts to right hand side at the same temperature

0.1 Hz

Temperature

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Moisture
0.1% Moisture acts as plasticizer and increases the chain mobility hence Tg goes down. Tg peak shifts to LHS with rise in moisture content. Tg=0C Tg=32C Tg=80C

Annealing
Annealing causes rise in crystallinity hence chains are packed in regular pattern and their mobility goes down. It causes increase in Tg. Tg-peak shifts to RHS on temperature scale

8.0% tan()

3.0%

Un-annealed tan()

Annealed

Temperature

Temperature

Plasticizer
Unplasticized PVC

DMA of Nylon

PVC with 20% DOP PVC with 40% DOP

Plasticizers increases chain mobility hence reduces (Tg).

Temperature

-transition: (Below -80C) Due to movement of CH2 groups in chain. transition: (-80C to 0C) Due to movement of chain segments and amide group NHCO). transition: (0C to 150C) Main Tg. Due to segmental mobility in amorphous zone. Melting - (above 270C) Melting of crystalline zone.

Q&A
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