Lecture:6

• Characteristics of Polymer
Physical properties of polymers
Thermal properties of polymers

1
 Characteristics of Polymer
• Physical property
– Density
Specific gravity (ASTM D792)
specific gravity with respect to de-ionized water at
230C

2
 Density of some polymers

Commodity Engg. Specialty

plastic plastic polymers

LDPE HDPE PP PC PSF PEEK Poly-

imide

0.91- 0.94- 0.90 1.2 1.25 1.263- 1.42

0.93 0.97 -.91 1.4

3
 Physical States/Phases
Single component Pure material

Liquid
Solid GAS
P
Vapour

4
 Crystalline Solid of Small
Molecules
On heating at Tm

No order
Molecules move as
A whole

Long range order

Only vibrational motion
No translational motion
5
 Transitions
Crystalline Solid
Crystalline polymer
Volume change, v

Liquid
Melt

Specific Volume
Tm

Temperature Tm

Temperature

6
 Characteristics of Polymer
• Thermal properties
-Flow temperature Tf
-Thermal decomposition temperature (Td)
-Heat Distortion temperature (HDT) ASTM D648
- Melting temperature (Tm)
- Glass transition temperature (Tg)
Temperature above which the polymer
remains soft, flexible and rubbery and
below which it becomes hard, brittle and
glassy.
7
Change of State with Temperature

Rubbery
Glassy Or Visco Viscous
State elastic Liquid
(Brittle State (Polymer
Plastic) (Tough plastic melts)
and rubbers)
Tg Tf

8
 Importance of Tg’s
• Elastomer: Tg less than room temperature
cross linked into a permanent network structure
they exhibit tremendous elasticity, as in the
rubber bands, gaskets and tyres.

Thermoplastics:Tgs ~ 1000C;
they are processed above Tg, but then are
solidified into plastic parts by cooling.

9
 Importance of Tg’s
• Engineering plastics: Tg ~2000C
high in demand for strenuous applications
and tend to be expensive.
• Polymers with Tgs between room
temperature and 1000C do not crystalizes
are rather less widely applicable as bulk
materials, but are useful as adhesives.

10
 Factors affecting the glass transition
Chemical Structure
temperature
• Hindrance to
segmental rotation Polymer Tg(oC) Tm(oC)
PE -120 137
to
[-CH2CH-]n
-125
R
PP -10 to 176
-18
PS 100 Amor-
phous

11
 Factors affecting the glass transition
Chemical Structure
temperature
• Comparable Polymer Tg(oC)
size: increasing
polarity CH3 PP -10 to
-18
[-CH2CH-]n Cl PVC 89
R
CN Polyacry- 100
lonitrile

12
 Factors affecting the glass transition
Chemical Structure
temperature
• Flexibility in Polymer Tg(oC)
side group
CH3
chain PMMA 105
CH3
CH3 CH2 PEMA 65
[-CH2C-]n
C=O CH3 CH2CH2 PPMA 35
O
R
13
 Factors affecting the glass transition
temperature
CH3 Polymer Tg(oC)
• Syndiotactity
[-CH2C-]n
i-PMMA 45

C=O
O
a-PMMA 105
CH3

s-PMMA 115
• Trans isomers have higher Tg than cis:
• cis polybutadiene (Tg=-1080C)
• Trans-polybutadiene(Tg=-180C)
14
Effect of backbone structure on TM
O O
Polyester derivative
of ethylene glycol
[-C-R-C-O-CH2-CH2-O-]n

R Group Tm(oC)
(CH2)4 50
-Ph- 270
-Ph-Ph- 355
-Ph-CH2-CH2-Ph 220
-Ph-CH=CH-Ph- 450
15
Tg and Mol. Wt.
•Mobility of chain segments

Tg
affect the Tg
•Small chain would have
higher number of end group, Molecular Weight
lower Tg
T 
Polymer g (K) K(K)
PVC 351 8.1x104
Flory-Fox equation
PS 373 1.2x105
 K PMMA 387 2.1x105
Tg  Tg 
Mn
16
Tg and Composition
For homogeneous mixture of two components
Tg  W1Tg1  W2Tg 2
Addition of Plasticizers:
Low mol wt. nonvolatile substance Improves
flexibility in polymer
Decreases the Tg

For Co polymers 1 WA WB
 
Tg ( AB ) Tg ( A) Tg ( B )
17
 Effect of crosslinks

• Crosslinking elevates Tg
Fox-Loshaek equation

Tg  Tg 0  K c c
Cross linking density

Low cross-link densities raise the viscosities of polymer melts.

Intermediate cross-link densities transform gummy polymers into materials that have
elastomeric properties and potentially high strengths.
Very high cross-link densities can cause materials to become very rigid or glassy.
20
Interelationship between the Tg and Tm
The factors affecting Tg also affect the Tm.
Experimental observation

Tg  1 / 2Tm For symmetrical polymers

Tg  2 / 3Tm For unsymmetrical polymers

These are not universal relations.

21
 Thermodynamic Aspects of Tg

• Phase equilibria e.g boiling and melting are first

order transitions

• S,V and H are discontinuous

• Glass Transition 2nd order transitions

• Slope of S,V and H changes with increasing
temperature

22
 1st order and 2nd order derivatives
qrev  U  PV dG  VdP  SdT

dqrev  dU  VdP  pdV  G 

V   ;
 P T
H  U  PV
 G 
S  T  
dH  dU  PdV  VdP  T  p
G  H  TS
dG  VdP  SdT
dqrev
 dS  H    2
G
T Cp     T  2 
 T  p  T  p

23
 Thermodynamic Aspects of Tg
Slope dependent Physical Quantities

• Coefficient of thermal 1  V 
  
expansion V  T  p

• Heat Capacity  H 
cp   
 T  p

• The Isothermal Compressibility 1  V 

  
V  p T
24
 Measurement of Tg
Dilatometer :
Measures change of volume upon heating

Differential Scanning Calorimeter (DSC)

Measures change in capacity with temperature

Dynamic Mechanical Analysis(DMA)

Measurement of local relaxation time versus temp.

25
 Dilatometer
Measures change of volume upon heating
Liquid used: Hg,  is known
Small Heating rate : 1-20 min-1
Tg:Change in slope of Volume
temperature curve
Tm: Discontinuity in volume temperature
curve

26
 Dilatometer
Dilatometric data of specific
volume of Poly(N, N’
sebacoyl piperazine)

27
Study of Kovac
using
dilatometer
Specific volume
of polyvinyl
acetate
measured at 0.2
and 100h after
cooling rapidly
well above the
glass transition
temperature

28
Thermal expansion coefficient

Discontinuity in 
l
     g
Simha & Boyer
suggested

0.113
  ;Tg in K
Tg

29
DSC

•Individual heaters maintain identical

temperatures of two small platinum holders
• a small (10-30 mg) polymer sample
mechanically sealed in a small aluminum pan
• Record the differential power needed to
maintain sample pans at equal temperatures

30
 Use of DSC analysis
– measure melting temperature,
– glass transition temperature,
– specific heat or heat capacity
– latent heat of fusion (area of the peak/heating rate)
– reaction energy and temperature,
– crystalline phase transition temperature and energy,
– % crystallinity
– denaturization temperatures, oxidation induction times

31
 DSC
A discontinuity in Cp is
the characteristics of 2nd
order transition.
Cp=Cpl-Cpg
The temperature at Mid
point of the step
Change in Cp is the Tg

For many amorphous

polymer
C p  Tg  115 Jg 1
32
DSC Semi-crystalline polymer

33
 Heat Distortion temperature
• It is the temperature at which a standard test
specimen at a standard rate of heating gets distorted
to a fixed extent under a given load. (ASTM D648)
• Specimen size:
A standard bar 5" x ½" x ¼" is used for ASTM
Test Procedure:
The bars are placed under the deflection measuring
device. A load of 0.45 MPa is placed on each
specimen. The specimens are then lowered into a
silicone oil bath where the temperature is raised at
2° C per minute until they deflect 0.25 mm for ASTM.

34
Thermal Transition temperatures
Polymer HDT (oC) Tg(oC) Tm(oC)

PE 29to 126 -120 to 137

-125
PP 40 to 152 -10 to -18 176

PC 39 to 148 150 Amorphous

35
 Vicat Softening Temp. (ASTM D1525)
• the temperature at which a flat-ended needle (1sq.mm)
penetrates the specimen to the depth of 1 mm under a
specific load. 
• Specimen Size:
The test specimen must be between 3 and 6.5 mm thick
and at least 10 mm in width and length. No more than three
layers may be stacked to achieve minimum thickness. 
• Test Procedure:
Penetrating needle rests on the surface at least 1 mm from
the edge. A load of 10N is applied to the specimen. The
specimen is then lowered into an oil bath at 230 C. The bath
is raised at a rate of 50° per hour until the needle
penetrates 1 mm. 

36
 Characteristics of Polymer
• Mechanical properties
Static : Tensile, Shear properties
Transient: Creep and stress relaxation
Impact : Izod and Charpy
Cyclic :fatigue tests

37
Tensile properties
Illustration of a typical tensile-dogbone sample
ASTM D 638
T0

A0 W0

L0

Gage Length: ~50mm

Initial Width : 19or 29 mm
Initial Thickness: 4 to 14 mm
Over all length 63.5mm to 246 mm

38
 Tensile properties
Stress
True Stress

F
 F L
A0   
T

A L0
L  L

L
dl
L0     ln 
T

L0
l  L0 
Hooke’s Law

  E   D
Young’s Modulus
Compliance
39
 Tensile Properties
• Elastic Limit
• Initial, secant Modulus
• Yield Stress, Stiffness, Resilience
• Ultimate/tensile Strength
• Elongation at break
• Toughness
• Strain softening; orientation hardening; cold
drawing

40
Typical stress strain curves of
Various plastic Materials

Weak and Soft

Strong and tough

Weak and brittle Strong and stiff

41
 Modulus vs temperature for
various polymers

109
Modulus (Pa)

106

Temperature

42
 Simple Shear Deformation
Stress

F

A0
X

C
Hooke’s Law

J=1/G
  G Shear Compliance
Shear Modulus
E=3G ; J=3D (incompressible material)

43
 Mechanical properties of
Representative polymers
Polymer Elastic Yield Ultimate Elongation
Modulus Strength strength at break
(GPa) (MPa) (Mpa) (%)
PC 2.4 55-69 55-69 60-120

LDPE 0.14-.28 6.9-14 10-17 400-700

PMMA 2.4-2.8 48-62 48-69 2-10

PP 1-1.6 23 24-38 200-600

44