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Method: Anneal80
Polystyrene
Comment: MDSC.3/40@2; After Anneal @ 80øC various times
-0.3
2.0 -0.4
-0.5
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
Measuring/Reporting Glass Transitions
• The glass transition is always a temperature range
• The molecular motion associated with the glass
transition is time dependent. Therefore, Tg increases
when heating rate increases or test frequency (MDSC®,
DMA, DEA, etc.) increases.
• When reporting Tg, it is necessary to state the test
method (DSC, DMA, etc.), experimental conditions
(heating rate, sample size, etc.) and how Tg was
determined
– Midpoint based on ½ Cp or inflection (peak in derivative)
Glass Transition Analysis
Polystyrene
9.67mg
10°C/min
Glass Transition Analysis
Polystyrene
9.67mg
10°C/min
Step Change in Cp at the Glass Transition
PET
9.43mg
KauzmannTemp; Lowest Tg
Enthalpy Decreases (Entropy of Crystal)
Entropy Decreases Temperature
Where H = High relative cooling rate
M = Medium relative cooling rate
S = Slow relative cooling rate
Suggestions for Finding Weak
Glass Transitions
• Know your empty-pan baseline
• Get as much material in the amorphous state
• Cool slowly through the glass transition
region
• Heat rapidly through glass transition region
• Use MDSC®
• Or use Quasi-Isothermal MDSC
Glass Transition Summary
Extrapolated 156.60°C
-5 Onset
28.50J/g
Temperature
Indium
Heat of 5.7mg
Heat Flow (mW)
-10 10°C/min
Fusion
Extrapolated
-3
Onset
Heat Flow (mW)
Temperature 236.15°C
-4 52.19J/g
Heat of
-5 PET
Fusion 6.79mg
10°C/min
-6
249.70°C
Peak Temperature
-7
200 210 220 230 240 250 260 270
Exo Up Temperature (°C) Universal V4.0B TA Instruments
Comparison of Melting
0
156.60°C
28.50J/g PET 236.15°C
-5 6.79mg 52.19J/g
10°C/min
249.70°C
Heat Flow (mW)
-10
Indium
5.7mg
-15
10°C/min
-20
157.01°C
-25
140 160 180 200 220 240 260 280
Exo Up Temperature (°C) Universal V4.0B TA Instruments
Analyzing/Interpreting Results
• It is often difficult to select limits for
integrating melting peaks
– Integration should occur between two points on
the heat capacity baseline
– Heat capacity baselines for difficult samples can
usually be determined by MDSC® or by
comparing experiments performed at different
heating rates
– Sharp melting peaks that have a large shift in the
heat capacity baseline can be integrated with a
sigmoidal baseline
Baseline Due to Cp
Baseline Type
DSC of Polymer Blend
More on this sample in
the MDSC® section
Where is the
Cp baseline?
Is it a melt?
YES!
8 Melt
Heat Capacity (J/g/°C)
6
10°C/min
50°C/min
4
100°C/min
2
150°C/min
0
-40 0 40 80 120 160 200 240 280
Temperature (°C)
Effect of Heating Rate on Polymorph
DSC at 1C/min
DSC at 1C/min
DSC at 10C/min
DSC at 50C/min
Effect of Impurities on Melting
Effect of p-Aminobenzoic Acid Impurity Concentration
on the Melting Shape/Temperature of Phenacetin
Melting of
Eutectic Mixture 96.0% Pure
95.0% Pure
NBS 1514
Thermal Analysis
Purity Set
Approx. 1mg
Crimped Al Pans
2°C/min
Van't Hoff Purity Calculation
-0.8 135.0
125.20°C
137.75°C
-1.0
134.5
-1.2
Temperature (°C)
Heat Flow (W/g)
-1.4
134.0
-1.6
Purity: 99.53mol %
Melting Point: 134.92°C (determined)
Depression: 0.25°C
-1.8 Delta H: 26.55kJ/mol (corrected)
Correction: 9.381% 133.5
Molecular Weight: 179.2g/mol
Cell Constant: 0.9770
Onset Slope: -10.14mW/°C
RMS Deviation: 0.01°C
-2.0
0.0 40
Integral (J/g)
105.00°C
275.00°C
-0.5 20
127.68°C
0.6877J/g 230.06°C
-1.0 0
-1.5
-50 0 50 100 150 200 250 300 350
Exo Up Temperature (°C) Universal V4.0B TA Instruments
Crystallization
• Crystallization is a kinetic process which can be
studied either while cooling or isothermally
• Differences in crystallization temperature or time
(at a specific temperature) between samples can
affect end-use properties as well as processing
conditions
• Isothermal crystallization is the most sensitive
way to identify differences in crystallization rates
Crystallization
• Crystallization is a two step process:
Nucleation
Growth
0.0
1.0
-0.5
Heat Flow (W/g)
-1.0
melting
0.5
-1.5
60 80 100 120 140 160 180 200
Exo Up
Temperature (°C)
0.0
40 50 60 70 80 90 100 110 120 130 140 150 160
Exo Up
Temperature (°C)
What is Isothermal Crystallization?
• A Time-To-Event Experiment
Annealing Temperature
Melt Temperature
Isothermal Crystallization
Temperature
Zero Time
Time
Isothermal Crystallization
5
117.4 oC
Polypropylene
4
Heat Flow (mW)
3 117.8 oC
118.3 oC
2
118.8 oC
119.3 oC
1 119.8 oC
120.3 oC
0
-1 1 3 5 7 9
Time (min)
Specific Heat Capacity (Cp)
• Heat capacity is the amount of heat required to
raise the temperature of a material by 1°C from T1
to T2
• True Heat Capacity (no transition) is completely
reversible; the material releases the same amount
of heat as temperature is lowered from T2 to T1
• Specific Heat Capacity refers to a specific mass
and temperature change for a material (J/g/°C)
Why is Heat Capacity Important?
• Absolute thermodynamic property (vs. heat
flow) used by engineers in the design of
processing equipment
• Measure of molecular mobility
– Cp increases as molecular mobility increases.
– Amorphous structure is more mobile than crystalline
structure
– Sapphire run
– Sample run
Calculating Cp by Standard DSC
• Three experiments are run over a specific
temperature range
– Allow 5 minute isothermal at start
– Use 20°C/min heating rate
3. Sample run
– Typical weight is 10 – 15 mg
– Use same weight of pan/lid as before ± 0.05 mg
Cp by Traditional DSC – 3 Runs
Heat Flow
5 400
Baseline Run
0
300
-5
Sample Run
Temperature (°C)
Heat Flow (mW)
200
-10
Calibration Run
-15
100
-20
-25
-30 -100
0 10 20 30 40
Time (min)
Cp by Traditional DSC – 3 Runs
6 500
280.00 °C
454.6 J/g
Cp & Total Heat
for PET
400
4
Heat Capacity (J/g/°C)
300
2
50.00 °C
1.161 J/g/°C 280.00 °C
1.924 J/g/°C 100
150.00 °C
1.609 J/g/°C
50.00 °C
34.94 J/g
0 0
0 50 100 150 200 250 300
Temperature (°C)
Specific Heat Capacity
• MDSC® & Tzero™ DSC have the ability
to calculate a heat capacity signal directly
from a single run.
275.00°C
Latent Heat of 530.8J/g
4
Absolute integral Melting is Not Heat
calculates total heat(Single Run) Capacity 400
Heat Capacity
135.54°C
0.7311J/g
2
200
Running Integral Latent Heat of
0 Crystallization is Not
Heat Capacity
-2 0
0 50 100 150 200 250 300
Temperature (°C) Universal V3.8A TA Instruments
Heat Flow w/ Different Heating Rates
Sample: Polypropylene
Size: 9.21 mg
DSC Cycle @ 10 C/min
Thermoset Curing & Residual
Cure
• A “thermoset” is a cross-linked polymer
formed by an irreversible exothermic
chemical reaction
– A common example would be a 2 part epoxy
adhesive
• With a DSC we can look at the curing of
these materials, and the Tg of full or
partially cured samples
Curing of a Thermoset
12
Method Log:
1: Ramp 10.00 °C/min to 190 °C
135.26°C
10
Heat Flow (mW)
98.35°C
258.3J/g
4
40 60 80 100 120 140 160 180 200
Temperature (°C)
Partially Cured System
1.08min
Cure of a Photopolymer by PCA
200
150
Heat Flow (mW)
Method Log:
1: Equilibrate at 35.00 °C
2: Isothermal for 1.00 min
1.01min 3: Light: on @ 20mW/cm2
209.1J/g
100 4: Isothermal for 5.00 min
5: Light: off
6: Isothermal for 2.00 min
7: End of method
50
0 2 4 6 8
Time (min)
Use PDSC to Study Phenolic Curing
With ambient pressure, curing is not visible due to volatization of water. Water
comes from the condensation reaction during the curing of the phenolic
Decomposition