Amorphous Materials

• Amorphous Structure –

– Randomly oriented molecules

– No long-range order

– Liquids, glassy or rubbery solids

– Most polymers are either amorphous or

semi-crystalline
Characterization of Amorphous Structure

• Glass Transition (Tg)

– Due to amorphous (non-crystalline) structure

– Due to macro-molecular motion (translational);

i.e., the entire molecule is free to move relative to
adjacent molecules.

– Extremely important transition because the

significant change in molecular mobility at Tg
causes significant changes in physical and
reactive properties.
 Glass Transition Analysis

• Reporting the Glass Transition (Tg) Temperature

– Tg is always a temperature range and never a
single temperature
– When reporting a single temperature, it is
necessary to state;
• What point in the step change (onset,
midpoint, end, etc.) is being measured
• The experimental conditions used to measure
Tg; such as technique (DSC, DMA, TMA, etc.),
heating rate, sample size or weight,
modulation conditions, etc.
 Changes at the Tg
Sample: Polystyrene File: C:\TA\Data\Len\FictiveTg\PSanneal80.002
Size: 14.0200 mg DSC
Method: Anneal80 Polystyrene - Modes of Molecular Motion/Mobility
Comment: MDSC.3/40@2; After Anneal @ 80øC various times
-0.3

Translation
2.0 -0.4

Rotation
-0.5
Vibration

[ ––––– · ] Heat Flow (mW)

Heat Capacity (J/g/°C)

1.5 Glass Transition is Detectable by DSC -0.6

Heat Capacity Because of a Step-Change in Heat Capacity

Heat Flow
-0.7
Temperature Below Tg
- lower Cp
- lower Volume
1.0 - lower CTE -0.8
- higher stiffness
- higher viscosity
- more brittle
- lower enthalpy
-0.9

0.5 -1.0
70 90 110
Exo Up Temperature (°C) Universal V3.8A TA Instruments
 Tg by DSC
Polystyrene - 9.67mg
10°C/min

Selected Start Extrapolated Onset

Temperature
 Heat Flow or
Cp Used to
Midpoint at ½ Calculate %
Cp or Heat Amorphous
Flow Change

Selected
End
 Glass Transition Analysis
Polystyrene - 9.67mg
10°C/min

Same data file,

same limits, only
Tg by infection
 What Affects the Tg by DSC?

• Heating Rate • Crystalline Content

• Heating & Cooling • Copolymers
• Aging • Side Chains
• Molecular Weight • Polymer Backbone
• Plasticizer • Hydrogen Bonding
• Filler

Anything that effects the mobility of the molecules,

affects the Heat Capacity, and in turn the Glass
Transition
Effect of Heating Rate on the Tg
10.04mg PMMA
 Effect of Heating Rate on the Tg

Heating Rate Heat Flow @ Tg Tg ½ Width of

(°C/min) 80°C Onset (°C) Midpoint (°C) Tg (°C)

2.5 -0.84 95.9 100.9 5.0

5.0 -1.66 96.0 102.0 6.0

10.0 -3.31 96.3 102.8 6.5

20.0 -6.62 98.3 105.1 6.8

 Glass Transition Detection

• The Tg is a low energy transition

– Due only to amorphous structure

– Can be hard to detect in semi-crystalline samples.

• To increase sensitivity:

– DSC

• Use larger (>10mg) samples and higher

(>10°C/min) heating rates
• Quench cool sample from above the melt

– Use MDSC®

– Use TMA or DMA

 Measuring Amorphous Structure
MDSC Conditions
• For “standard Tg”:

Sample Size: 10 – 15 mg Amplitude: 0.6-0.8°C

Period*: 60 seconds Heating Rate: 3°C/min

• If Tg is Hard to Detect

Sample Size: 10 – 20 mg Amplitude: 1.0°C-1.25°C

Period*: 80 seconds Heating Rate: 2°C/min

• If Tg has Large Enthalpic Relaxation

Sample Size: 5 – 10 mg Amplitude: 0.3°C-0.5°C

Period*: 60 seconds Heating Rate: 1°C/min

*With T zero™ pans & standard hermetic pans. You can subtract 20 sec
for low mass T zero™ pans & standard crimped pans.
Add 20 sec for 2900 series MDSC
 Is it a Tg?

• If not sure if a transition is a Tg

– Run Heat-Cool-Heat (H-C-H)
• If transition is a Tg then it should be present
on cooling curve and 2nd heat

– Run MDSC
• A Tg will always show up in the Reversing
Curve of a MDSC experiment

– Run TMA or DMA

 Is this a Tg or a Melt?
-1.5

-2.0
Heat Flow (mW )

-2.5

-3.0
100 120 140 160
Exo Up Temperature (°C) Universal V4.3A TA Instruments
 Now – Is this a Tg or a Melt?

Cool
2
Heat Flow (mW )

Polycarbonate 7.92mg
H-C-H @ 10°C/min
0

2nd Heat
-2

1st Heat

100 120 140 160

Exo Up Temperature (°C) Universal V4.3A TA Instruments
 Enthalpic Relaxation/Recovery at Tg

• Enthalpic relaxation, or aging, is the process of amorphous

material approaching equilibrium (never reached). Energy is
released as a function of time and temperature

• Enthalpic recovery is the endothermic transition seen at the

end of a glass transition in DSC experiments. It is the recovery
of energy that was dissipated during aging

• In traditional DSC, enthalpic recovery can appear as a melt

and make measurement of Tg difficult

• Since enthalpic recovery is a kinetic event, it can be separated

from the change in heat capacity by MDSC or the change in
length by MTMA
 2 Tg’s?
0.5

Thermoplastic Elastomer
3.21mg @ 10°C/min
Is this a
0.0
Tg? What
about
this?
-0.5
Heat Flow (mW )

-1.0

-1.5

-2.0

-2.5
-100 -50 0 50 100 150 200 250 300
Exo Up Temperature (°C) Universal V4.3A TA Instruments
 1 Tg
Thermoplastic Elastomer -- MDSC 0.48/60@3

0.5
Yes! 0.5 0.5

No!
0.0
0.0 0.0

Nonrev Heat Flow (mW )

Rev Heat Flow (mW )

Heat Flow (mW )

-0.5
-0.5 -0.5

-1.0

-1.0 -1.0
Tg’s occur in Rev Heat Flow 1st
transition clearly is a Tg 2nd one
-1.5 isn’t
-1.5 -1.5

-2.0
-100 -50 0 50 100 150 200 250 300
Exo Up Temperature (°C) Universal V4.3A TA Instruments
Partially Miscible Amorphous Phases
• If not miscible then Tg’s don’t shift
2.4

• If completely miscible then one Tg in the middle

2.2

2.0

Rev Cp (J/g/°C)
105.16°C(H) 140.13°C(H)
0.2657J/g/°C 0.1313J/g/°C
1.8

145.60°C(H)
ABS 108.59°C(H) 0.1715J/g/°C 1.6
0.1007J/g/°C
ABS-PC
1.4
ABS-PC Copolymer “Alloy”
PC
1.2
80 100 120 140 160
Temperature (°C)
 Semi-Crystalline Polymers
• Crystalline Structure –
– Molecules arranged in well defined structures
– Consists of repeating units
– Polymers can have crystalline phases
• Length of molecules prevents complete
crystallization
• Semi-crystalline Polymers –
– Both amorphous & crystalline solid phases
– Examples are most common thermoplastics
• Polyethylene, Polypropylene, etc
• Melting – The process of converting solid crystalline
structure to liquid amorphous structure

– Melting shows up as an endothermic peak in a

DSC scan

– The energy required to melt the crystalline phase

is proportional to the amount of crystalline phase

• In most cases sensitivity isn’t an issue with melting

transitions

• Heating rate doesn’t effect the onset of melting

(much), but will effect resolution
 Definitions

• Thermodynamic Melting Temperature – The

temperature where a perfect crystal would melt

• Metastable Crystals – Crystals that melt at lower

temperature due to imperfections

• Crystal Perfection – The process of metastable

crystals melting at a temperature below their
thermodynamic melting point and then (re)
crystallizing into larger, more perfect crystals that
will melt again at a higher temperature
 What is Heat Capacity (Cp)?

• Heat capacity is the amount of heat required to raise

or lower the temperature of a material

• Cp is the absolute value of heat flow divided by

heating rate (times a calibration factor)

• Most DSC’s do not measure absolute heat flow or

heat capacity

• Baseline subtraction is required on most DSC’s

when measuring Cp

• Q1000/Q2000 can measure Cp without baseline

subtraction
 Heat Capacity Baseline

• Knowledge of the heat capacity baseline is important for

almost all DSC and MDSC measurements because all
transitions must be analyzed between two points on the heat
capacity baseline for accurate temperatures and heats of
transition.

– It is often impossible to identify the heat capacity baseline

in DSC data

– The MDSC Reversing signals (Cp and Heat Flow) provide

the heat capacity baseline

– Although melting is primarily seen in the Reversing signal,

it is a latent heat (no change in sample temperature) and is
not heat capacity
 True Heat Capacity Baseline
Quenched PE/PET/PC Note: Melting has been removed
2.37 mg
MDSC .31840@3 from the Reversing Signal

Increasing
Enthalpic Crystallinity Prior to
Relaxatio Melting
Overlapping Tg
n
and Crystallization
Increasing
Crystallinity Prior
Enthalpic to Melting
Recovery

PE PET
Melting Melting
 Measuring Heat Capacity
• ASTM Method E1269
– Requires 3 runs
• Run Empty pans for baseline
• Run calibrate (typically sapphire)
• Run sample
• Typical Method
– Iso for 10 min
– Heat @ 10°C/min
– Iso for 10 min
• Generally considered to be accurate & repeatable to
within 5%
Conventional Heat Capacity of PET

Baseline

Sample

Calibration
 Direct Cp Measurement –Q2000/Q1000

• DSC’s with advanced Tzero™ technology measure

absolute heat flow:
– Baseline is flat
– Absolute zero heat flow value established as
– part of method
• By knowing absolute values of the heat flow and
heating rate, heat capacity is calculated in real time
and stored in data file
• Accuracy and precision is generally ± 2% with just
single run measurements
 Direct Cp Measurement

• Typical Method
– Heat @10°C/min

• Sample Size ~10mg

• Lowest mass pans possible

• Generally considered to be accurate &

repeatable to within 2-3%
 Direct Heat Capacity
1.5

97.00°C
1.0 0.9111J/g/°C
Heat Capacity (J/g/°C)

97.00°C
0.8758J/g/°C

0.5

Average Value of 8 Runs at 20°C/min in

a Hermetic Pan is 0.893 vs. a Theoretical
Value of 0.902 J/g°C at 97°C. Total Range
0.0 of Results Varied Less Than +/- 2%. Sample
Was Replaced At The End of Each Run.

-0.5
0 50 100 150 200
Temperature (°C) Universal V3.1B TA Instruments
General uses and applications

Determination of Tg and melting point of polymer system

Determination of degradation temperatures and rates

Determination of linear and volumetric expansion

Determination of modulus and mechanical properties

Determination of dielectric properties

Determination of the crystallinity level of polymeric system

Determination of the rate of crystallization