MSE 470 / MAE 455

Polymers and /Composites

Topic 8-9 Effect of Structure on Thermal Properties

• How do chemical & structural factors affect thermal behavior?

• What are the relationships between a polymer’s structure and

its thermal & mechanical properties?

• How does strain rate affect a polymer’s thermal and

mechanical properties ?

• How does degree of crosslinking affect an elastomer’s

mechanical properties ?

• How does the amount of plasticizer in a polymer affect its

thermal and mechanical properties?
Effect of Structure & Morphology on Tensile Test

Polymer E (Mpa) TS (Mpa)

A
Natural
2.5 22
Rubber

HDPE 830 28

Polystyrene 3100 37 B

C
bakelite 6900 62

D
 Mechanical Properties
• i.e. stress-strain behavior of polymers

brittle polymer

TS of polymer ca. 10% that of metals

plastic
elastomer
elastic modulus
– less than metal

Adapted from Fig. 15.1,

Strains – deformations > 1000% possible Callister 7e.

(for metals, maximum strain ca. 10% or less)

 Tensile Response: Brittle & Plastic
Near Failure (MPa) fibrillar
structure
x brittle failure
near
onset of
failure
necking plastic failure
x
Initial
unload/reload

e
aligned, networked
cross- case crystalline
linked regions
case slide
semi-
crystalline amorphous
crystalline
case regions
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 Adapted from Fig. 15.13, Callister
-- decreases ductility (%EL) 7e. (Fig. 15.13 is from J.M. Schultz,
Polymer Materials Science, Prentice-
• Annealing after drawing... Hall, Inc., 1974, pp. 500-501.)

-- decreases alignment
-- reverses effects of drawing.
• Compare 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.
plastic failure
x 15.15 is from Z.D.
Jastrzebski, The Nature
and Properties of
x Engineering Materials, 3rd
elastomer ed., John Wiley and Sons,
1987.)
final: chains
e are straight,
still
cross-linked
initial: amorphous chains are Deformation
kinked, cross-linked. is reversible!

• Compare to responses of other polymers:

-- brittle response (aligned, crosslinked & networked polymer)
-- plastic response (semi-crystalline polymers)
 Thermoplastics vs. Thermosets

T
• Thermoplastics: Callister,
-- little crosslinking viscous rubber
Fig. 16.9
mobile liquid Tm
-- ductile tough
liquid
-- soften w/heating plastic
-- polyethylene Tg
polypropylene
partially
polycarbonate crystalline
polystyrene crystalline
solid
solid

• Thermosets: Molecular weight

Adapted from Fig. 15.19, Callister 7e. (Fig. 15.19 is from F.W. Billmeyer, Jr.,
-- large crosslinking 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

 (MPa)
• Decreasing T...
-- increases E 80 4°C Data for the
-- increases TS semicrystalline
-- decreases %EL 60 polymer: PMMA
20°C (Plexiglas)
• Increasing 40 40°C
strain rate...
-- same effects 20
as decreasing T. 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 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 – effects Tm only

Adapted from Fig. 15.18,

Callister 7e.
 The bulk state of polymers

• The crystalline state: long range order in three

dimensions (chapter 6);

• The amorphous state (or the melt state): large amount

of disorder (chapter 5);

• The liquid-crystalline state: long range order in one or

two dimensions (chapter 7);

• The glassy state: large amount of disorder; amorphous

polymers when they are stiff and glassy at low
temperature (chapter 8), less freedom of movement
(only vibrational and rotational stretches)
Polymer crystals
Polymer crystals
 Mechanisms of Plastic Deformation
- Semicrystalline Polymers

Two adjacent chain Elongation of

folded lamellae and amorphous tie Tilting of Separation of
interlamellar chains lamellar chain crystalline
Orientation of
amorphous material folds block segments
block segments
before deformation and tie chains
with tensile axis
Melting vs. Glass Transition Temp.
• Melting transition: first-
order transition,
demonstrating
discontinuities in enthalpy
and volume;
• Glass transition: second-
order transition,
demonstrating
continuities in enthalpy
and volume, showing
shift in heat capacity and
coefficient of expansion;
suggesting the onset of
long-range coordinated
molecular motion.
Adapted from Fig. 15.18,
Callister 7e.
Melting vs. Glass Transition Temp.
 Thermal Methods in the Study of Polymorphs
A group of techniques in which a physical property is measured as a function of
temperature, while the sample is subjected to a predefined heating or cooling
program.

Differential Thermal Analysis (DTA)

• the temperature difference between a sample and an inert reference material, DT

= TS - TR, is measured as both are subjected to identical heat treatments

Differential Scanning Calorimetry (DSC)

• the sample and reference are maintained at the same temperature, even during a
thermal event (in the sample)

• the energy required to maintain zero temperature differential between the

sample and the reference, dDq/dt, is measured

Thermogravimetric Analysis (TGA)

• the change in mass of a sample on heating is measured

Courtesy of Dr. Reutzel-Edens, Lilly Research Laboratories

 Basic Principles of Thermal Analysis
Modern instrumentation used for thermal analysis usually consists of four parts:

1) sample/sample holder

2) sensors to detect/measure a property of the sample and the temperature

3) an enclosure within which the experimental parameters may be controlled

4) a computer to control data collection and processing

DTA power compensated DSC heat flux DSC

Courtesy of Dr. Reutzel-Edens, Lilly Research Laboratories

 Differential Thermal Analysis

sample holder

• sample and reference cells (Al)

alumina block
sensors
heating
coil
• Pt/Rh or chromel/alumel thermocouples
• one for the sample and one for the reference
• joined to differential temperature controller sample reference
pan pan

furnace

• alumina block containing sample and reference inert gas

cells vacuum

temperature controller
Pt/Rh or chromel/alumel
thermocouples
• controls for temperature program and furnace
atmosphere

Courtesy of Dr. Reutzel-Edens, Lilly Research Laboratories

 Differential Scanning Calorimetry

• DSC differs fundamentally from DTA in that the sample and reference are both
maintained at the temperature predetermined by the program.

• during a thermal event in the sample, the system will transfer heat to or from the
sample pan to maintain the same temperature in reference and sample pans

• two basic types of DSC instruments: power compensation and heat-flux

power compensation DSC heat flux DSC

Courtesy of Dr. Reutzel-Edens, Lilly Research Laboratories

 Power Compensation DSC
individual
heaters
controller DP

sample reference
sample holder pan pan

• Al or Pt pans

sensors inert gas

vacuum
inert gas
vacuum

• Pt resistance thermocouples DT = 0
thermocouple

• separate sensors and heaters for the sample and reference

furnace

• separate blocks for sample and reference cells

temperature controller

• differential thermal power is supplied to the heaters to maintain the temperature

of the sample and reference at the program value

Courtesy of Dr. Reutzel-Edens, Lilly Research Laboratories

 Heat Flux DSC
heating
coil
sample holder

• sample and reference are connected by sample

pan
reference
pan
a low-resistance heat flow path constantan
• Al or Pt pans placed on constantan disc chromel/alumel
wires
sensors inert gas
vacuum thermocouples

• chromel®-constantan area thermocouples (differential heat flow) chromel wafer

• chromel®-alumel thermocouples (sample temperature)

furnace

• one block for both sample and reference cells

temperature controller

• the temperature difference between the sample and reference is converted to

differential thermal power, dDq/dt, which is supplied to the heaters to maintain the
temperature of the sample and reference at the program value

Courtesy of Dr. Reutzel-Edens, Lilly Research Laboratories

 Analysis of Heat-Flow in Heat Flux DSC
• temperature difference may be deduced by considering the heat flow paths in the
DSC system
heating block
Tfurnace

DTR DTS
temperature

TRP
TSP
thermocouple is not in physical
TR DTL contact with sample
reference
TS
sample

• thermal resistances of a heat-flux system change with temperature

• the measured temperature difference is not equal to the difference in temperature

between the sample and the reference
DTexp ≠ TS – TR

Courtesy of Dr. Reutzel-Edens, Lilly Research Laboratories

Typical Features of a DSC Trace for a Polymorphic System

endothermic events

melting
sublimation
solid-solid transitions
desolvation
chemical reactions

exothermic events

crystallization
solid-solid transitions
sulphapyridine decomposition
chemical reactions

baseline shifts

glass transition

Courtesy of Dr. Reutzel-Edens, Lilly Research Laboratories

 Sample: INDIUM CRIMPED PAN CHECK File: C:...\10C per min crimped\DSC010920A.3

Enthalpy of Fusion
Size: 7.6300 mg DSC Operator: Ron Vansickle
Method: indium Run Date: 20-Sep-01 09:13
Comment: P/N 56S-107 Instrument: 2920 MDSC V2.6A
0.5

156.50°C
28.87J/g
0.0

-0.5
Heat Flow (W/g)

-1.0

-1.5

-2.0

157.81°C

-2.5
140 145 150 155 160 165 170 175
Exo Up Temperature (°C) Universal V3.3B TA Instruments
 Purity by DSC

• eutectic impurities lower the melting

point of a eutectic system

• purity determination by DSC based on

Van’t Hoff equation

RTo2 c . 1 97%
Tm = To -
DHo f
99%
• applies to dilute solutions, i.e., nearly
pure substances (purity ≥98%)
benzoic acid 99.9%

• 1-3 mg samples in hermetically-sealed

pans are recommended
melting endotherms as a function of purity.
• polymorphism interferes with purity
determination, especially when a
transition occurs in the middle of the
melting peak

Plato, C.; Glasgow, Jr., A.R. Anal. Chem., 1969, 41(2), 330-336.
 Calculation of crystallinity%

What is crystallinity%

L.H. Sperling, page 244.

 Effect of molecular weight on Tg
For linear polymer:

K
Tg = Tg −
( R −  G ) M

Tg at a molecular weight M was related to the glass temperature at

infinite molecular weight Tg 

L.H. Sperling, page 398.

Effect of aliphatic side group on Tg

L.H. Sperling, page 409.

 Effect of tacticity on Tg

COOR COOR COOR COOR COOR CH3 COOR CH3

H H H H H3C ROOC H3CROOC

H HH HH HH H H HH HH HH H

Isotactic Syndiotactic
L.H. Sperling, page 409.
 Time Dependent Deformation
• Stress relaxation test: • Data: Large drop in Er
-- strain to eo and hold. for T > Tg. (amorphous
-- observe decrease in 10 5
rigid solid polystyrene)
stress with time. Er (10s) (small relax) Adapted from Fig.
3
in MPa 10 15.7, Callister 7e.
transition (Fig. 15.7 is from A.V.
tensile test 10 1 region Tobolsky, Properties
and Structures of
eo strain 10 -1
Polymers, John Wiley
and Sons, Inc., 1960.)
viscous liquid
(t) 10 -3 (large relax)
60 100 140 180 T(°C)
time Tg
• Relaxation modulus: • Sample Tg(C) values:
(t ) PE (low density) - 110
E r (t ) = PE (high density) - 90
eo PVC + 87
Selected values from
Table 15.2, Callister
PS +100 7e.

PC +150
 Log Modulus (E) vs. T Curve - Amorphous Polymer
I II

E changes 100-1000X

III
IV
E changes 100-1000X

Tg

• Region I – Glassy, a flat plateau from T <Tg up to T = Tg,

– polymer usually rigid and brittle
• Region II – Leathery, curves downward from T=Tg and then slope flattens
– polymer is less stiff and has some ductility with less strength
• Region III – Rubbery, a shallower, slightly sloping plateau region beyond Tg
– polymer is less stiff, rubbery, ductile and is a plateau in semicryst. polymers
• Region IV – Viscous, downward sloping region of a “sticky viscoelastic fluid”
– semicrystalline polymers on plateau Tg < T < Tm; melt at Tm
– amorphous polymers lose 3-D stability unless crosslinked & are very elastic
Log E vs. T for a Thermoset – Where’s T25C vs. Tg?
Log E vs. T for a Thermoset – Where’s T25C vs. Tg?
Log E vs. T - Amorphous Themoplastic – Where’s T25C vs. Tg?
Log E vs. T Semicryst. Thermoplastic - T25C vs. Tg & Tm?
Log E vs. T for a Lightly Xlinked Elastomer – Where’s T25C vs. Tg?
Log E vs. T Summary – Where’s T25C vs. Tg & Tm?
 Activity - Polymer Classification Thermal Properties
A E I

biker water bottle experimental airplane

greenhouse window
F
B

milk container
G
prohibition telephone J
C

jogging shoes
H
rubber band fishing line

rock climber rope

football helmet
 Effect of Addition Polymers’ Bulky Side Group
“Steric Hindrance” on Tg, Tm, & Log E vs. T Curve
High Temperature Commercial Polymer Resins
Polymer Chemical & Structural Characteristics
Affect the Tg & Tm with the Same Trends
Effect of Strain Rate on Log E vs. T Curves
and on Tensile Test Properties
Rate Effects
Stress – Strain Curve
Master curve
650

Increasing
Strain Rate
4.5

.007

.00012
Effect of Amount of Plasticizer Added
to PVC on its Log E vs. T Curves
Effect of Degree of Crosslinking of Elastomers on
Log E vs. T Curves & Tensile Properties
 Summary
• There are four main regions in the Log E vs. T curves for most polymers:
– Glassy
– Leathery
– Rubbery
– Viscous

• Log E vs. T and mechanical properties - general effects

– Chemical structure for higher Tg also gives higher Tm
– Greater plasticization of PVC lowers Tg & decreases mechanical props.
– Higher load rate increases Tg and Tm and increases mechanical props.

• Log E vs. T and mechanical properties - addition polymers

– Bulky substituents next to main chain raise Tg & Tm (steric hindrance)
– Greater crystallinity raises rubbery plateau height
– Greater plasticization decreases leathery plateau height & lowers Tg

• Log E vs. T and mechanical properties - condensation polymers

– Greater chain stiffness in characteristic linkages increases Tg and Tm