2004 Training Seminars Interpreting Data

2004 Training Seminars
DSC
Interpreting DSC Data
Glass Transition & Melting
Glass Transitions
The glass transition is a step change in
molecular mobility (in the amorphous phase of

a sample) that results in a step change in heat
capacity
The material is rigid below the glass transition
temperature and rubbery above it. Amorphous
materials flow, they do not melt (no DSC melt
peak)
Glass Transitions
The change in heat capacity at the glass
transition is a measure of the amount of

amorphous phase in the sample
Enthalpic recovery at the glass transition is a
measure of order in the amorphous phase.
Annealing or storage at temperatures just
below Tg permit development of order as the
sample moves towards equilibrium
Heat Flow & Heat Capacity at

the Glass Transition
Sample: Polystyrene
Size: 14.0200 mg
Method: Anneal80
Comment: MDSC.3/40@2; After Anneal @ 80C various times
Polystyrene
DSC
File: C:\TA\Data\Len\FictiveTg\PSanneal80.002
-0.3
-0.4
-0.5
1.5
Glass Transition is Detectable by DSC

Because of a Step-Change in Heat Capacity
Heat Capacity
Heat Flow
-0.7
Temperature Below Tg
- lower Cp
- lower Volume
- lower CTE
- higher stiffness
- higher viscosity
- more brittle
- lower enthalpy
1.0
-0.6
[ ] H eat Flow (m W )
H eat C apacity (J/g/C )
2.0
-0.8
-0.9
0.5
Exo Up
70
90
110
Temperature (C)
-1.0
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 Cp or inflection (peak in derivative)
Glass Transition Analysis
Polystyrene
9.67mg
10C/min
Glass Transition Analysis
Polystyrene
9.67mg
10C/min
Step Change in Cp at the Glass Transition

PET
9.43mg
% Amorphous = 0.145/0.353= 41%
Aged Epoxy Sample
Effect of Annealing Time on Shape of Tg
Importance of Enthalpic Relaxation

Is enthalpic recovery at the glass transition important?
Sometimes
Glass transition temperature, shape and size provide useful
information about the structure of the amorphous component
of the sample.
This structure, and how it changes with time, is often
important to the processing, storage and end-use of a
material.
Enthalpic recovery data can be used to measure and predict
changes in structure and other physical properties with time.
Effect of Aging on Amorphous Materials

Physical Property Response on
S
Storage
Below Tg
Specific Volume Decreases
Modulus
Increases
Coefficient of
Expansion
Decreases
Heat Capacity
Enthalpy
Entropy
Decreases
Decreases
Decreases
Max Tg
Storage
V time
H
H
M
S
Equilibrium
Liquid
Equilibrium
Glass
KauzmannTemp; Lowest Tg
(Entropy of Crystal)
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

The glass transition is due to Amorphous
material
The glass transition is the reversible change
from a glassy to rubbery state & vice-versa
DSC detects glass transitions by a step
change in Cp
Melting Definitions
Melting the process of converting crystalline
structure to a liquid amorphous structure
Thermodynamic Melting Temperature the
temperature where a crystal would melt if it had a
perfect structure (large crystal with no defects)
Metastable Crystals Crystals that melt at lower
temperature due to small size (high surface area) and
poor quality (large number of defects)
Definitions (cont.)
Crystal Perfection the process of small, less perfect
crystals (metastable) 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
True Heat Capacity Baseline often called the
thermodynamic baseline, it is the measured baseline
(usually in heat flow rate units of mW) with all
crystallization and melting removed. assumes no
interference from other latent heat such as
polymerization, cure, evaporation etc. over the
crystallization/melting range
Melting of Indium
0
Heat Flow (mW)
Extrapolated
-5
Onset
Temperature
-10
156.60C
28.50J/g
Indium
5.7mg
10C/min
Heat of
Fusion
For pure, low

molecular weight
materials (mw<500
g/mol) use
Extrapolated Onset as
Melting Temperature
-15
-20
Peak Temperature
-25
150
Exo Up
157.01C
155
160
Temperature (C)
165
Universal V4.0B TA Instruments
Melting of PET
-1
For polymers, use Peak as Melting Temperature

-2
Heat Flow (m W )
-3
Extrapolated
Onset
Temperature
236.15C
52.19J/g
-4
Heat of
Fusion
-5
PET
6.79mg
10C/min
-6
Peak Temperature
-7
200
Exo Up
210
220
230
240
Temperature (C)
249.70C
250
260
270
Comparison of Melting
0
H eat Flow (m W )
-5
156.60C
28.50J/g
PET
6.79mg
10C/min
236.15C
52.19J/g
249.70C
-10
-15
Indium
5.7mg
10C/min
-20
157.01C
-25
140
Exo Up
160
180
200
220
Temperature (C)
240
260
280
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!
Onset shifts by only 0.3C
Is it a Melt?
NO!
Onset shifts by almost 30C
Effect of Heating Rate on Melting

10
Melt
Heat Capacity (J/g/C)
10C/min
50C/min
100C/min
2
150C/min
0
-40
40
80
120
160
Temperature (C)
200
240
280
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
99.3% Pure
Melting of
Eutectic Mixture
96.0% Pure
95.0% Pure
NBS 1514
Thermal Analysis
Purity Set
Approx. 1mg
Crimped Al Pans
2C/min
100% Pure
Van't Hoff Purity Calculation

135.0
125.20C
137.75C
-1.0
-1.2
Heat Flow (W/g)
-1.4
134.0
-1.6
-2.0
-1.8
134.5
Purity: 99.53mol %
Melting Point: 134.92C (determined)
Depression: 0.25C
Delta H: 26.55kJ/mol (corrected)
Correction: 9.381%
Molecular Weight: 179.2g/mol
Cell Constant: 0.9770
Onset Slope: -10.14mW/C
RMS Deviation: 0.01C
133.5
Total Area / Partial Area

-2.2
122
Exo Up
-2
10
124
126
128
130
132
134
136
Temperature (C)
133.0
138
Temperature (C)
-0.8
2004 Training Seminars

DSC
Interpreting DSC Data
Crystallization, Heat Capacity,
and Crosslinking
Crystallinity
Definitions
Crystallization the process of converting either
solid amorphous structure (cold crystallization on
heating) or liquid amorphous structure (cooling) to a
more organized solid crystalline structure
Crystal Perfection the process of small, less perfect
crystals (metastable) 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
Change in Crystallinity While Heating
Heat Flow (W/g)
0.5
60
0.0
40
-0.5
20
-1.0
-1.5
Exo Up
Integral (J/g)
Quenched PET
9.56mg
10C/min
1.0
134.63C
230.06C
71.96J/g
105.00C
275.00C
127.68C
0.6877J/g
230.06C
-50
50
100
150
Temperature (C)
200
250
300
350
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
The onset temperature is the nucleation (Tn)
The peak maximum is the crystallization
temperature (Tc)
Effect of Nucleating Agents

2.0
crystallization
POLYPROPYLENE
WITHOUT
NUCLEATING AGENTS
H eat Flow (W /g)
1.5
POLYPROPYLENE
WITH NUCLEATING
AGENTS
0.0
H eat Flow (W /g)
1.0
-0.5
-1.0
melting
0.5
-1.5
60
80
Exo Up
0.0
Exo Up
40
50
100
120
140
160
180
200
Temperature (C)
60
70
80
90
100
110
Temperature (C)
120
130
140
150
160
What is Isothermal Crystallization?

A Time-To-Event Experiment
Annealing Temperature
Melt Temperature
Temperature
Isothermal Crystallization
Temperature
Zero Time
Time
Isothermal Crystallization
5
117.4 oC
Polypropylene
H eat F lo w (m W )
117.8 oC
118.3 oC
118.8 oC
119.3 oC
119.8 oC
-1
120.3 oC
Time (min)
Specific Heat Capacity (Cp)

Heat capacity is the amount of heat required to
raise the temperature of a material by 1C 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
Provides useful information about the

physical properties of a material as a function
of temperature
Does DSC Measure Heat Capacity?

DSC or MDSC do not measure heat
capacity directly. They measure heat flow rate
which can be used to calculate heat capacity
which is more appropriately called apparent
heat capacity
DSC calculated Cp signals include all transitions because
the heat flow signal is simply divided by heating rate (an
experimental constant) to convert it to heat capacity units
A true value of Cp can only be obtained in temperature
regions where there are no transitions
Calculating Heat Capacity (Cp)

Depending on the DSC that you have there
are three different ways to calculate Cp
1) Three Run Method ASTM E1269
Applicable to all DSCs
2) Direct Cp Single Run Method

Applicable to Q1000 only
3) MDSC - Single Run Method

Any TA Instruments DSC w/ MDSC option
Most accurate determination
Cp by Standard DSC
Generally, three experiments are run in a
DSC over a specific temperature range
Empty pan run
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 20C/min heating rate
1. Empty pan run
Match pan/lid weights to 0.05 mg

Used to establish a reference baseline
Calculating Cp by Standard DSC

2. Sapphire run
Used to determine calibration constant

Use same weight of pan/lid as for baseline
0.05 mg
Typical weight is 20 25 mg
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
Heat Flow (mW)
200
-10
Calibration Run
-15
100
-20
0
-25
-30
-100
0
10
20
Time (min)
30
40
Temperature (C)
Sample Run
-5
Cp by Traditional DSC 3 Runs

6
500
280.00 C
454.6 J/g
Cp & Total Heat

for PET
400
300
150.00 C
174.6 J/g
200
2
50.00 C
1.161 J/g/C
280.00 C
1.924 J/g/C
150.00 C
1.609 J/g/C
100
50.00 C
34.94 J/g
0
0
0
50
100
150
Temperature (C)
200
250
300
Total Heat (J/g)
Heat Capacity (J/g/C)
Specific Heat Capacity

MDSC & Tzero DSC have the ability
to calculate a heat capacity signal directly
from a single run.
Benefits of using a heat capacity (instead of
heat flow) signal include:
The ability to overlay signals from samples run
at different heating rates
The ability to overlay signals from heating and
cooling experiments
Direct Cp from a Q1000

Sample: PET; Quenched
Size: 16.0000 mg
Method: Heat@20
Comment: Heat@20
DSC
File: C:...\Crystallinity\RIqPETcycle20.001
600
275.00C
530.8J/g
Latent Heat of
Absolute integral
Melting is Not Heat
Capacity
calculates total
heat(Single Run)
Heat Capacity
400
135.54C
0.7311J/g
Latent Heat of
Crystallization is Not
Heat Capacity
Running Integral
-2
50
100
150
Temperature (C)
200
250
200
[ ] In te g ra l (J /g )
H e a t C a p a c ity (J /g /C )
0
300
Universal V3.8A TA Instruments
Heat Flow w/ Different Heating Rates
Heat Flow Signals Increase in Size

with Increasing Heating Rate
Benefit of Plotting Heat Capacity

Heat Capacity Signals Are
Normalized for Heating Rate and
Permit Comparison of Experiments
Done at Different Heating Rates
Remember, DSC and MDSC

Cp signals are really
Apparent Cp signals;
crystallization and melting
are latent heats, not Cp
Heat Flow & Cp Signals

Polypropylene
Size: 9.21 mg
DSC Cycle @ 10degC/min
Heat Flow on Cooling
Heat Flow on Heating
Heat Capacity on Cooling
Heat Capacity on Heating
Weak Tg Visible in Cp Signal

Heat Capacity on Cooling
Heat Capacity on Heating
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
135.26C
H eat Flow (m W )
10
98.35C
258.3J/g
40
60
80
100
120
Temperature (C)
140
160
180
200
Partially Cured System
2nd heat shows increased

Tg, due to additional
curing during 1st heat
Note: Small exotherm due to residual cure
Photopolymer Cure by PCA

250
1.08min
Cure of a Photopolymer by PCA
H e a t F lo w (m W )
200
150
Method Log:
1: Equilibrate at 35.00 C
2: Isothermal for 1.00 min
3: Light: on @ 20mW/cm2
5: Light: off
7: End of method
1.01min
209.1J/g
100
50
0
0
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

2004 Training Seminars Interpreting Data

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2004 Training Seminars Interpreting Data

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2004 Training Seminars

molecular mobility (in the amorphous phase of

transition is a measure of the amount of

Heat Flow & Heat Capacity at

Glass Transition is Detectable by DSC

H eat C apacity (J/g/C )

Measuring/Reporting Glass Transitions

Glass Transition Analysis

Glass Transition Analysis

Step Change in Cp at the Glass Transition

% Amorphous = 0.145/0.353= 41%

Aged Epoxy Sample

Effect of Annealing Time on Shape of Tg

Importance of Enthalpic Relaxation

Effect of Aging on Amorphous Materials

Where H = High relative cooling rate

Suggestions for Finding Weak

Glass Transition Summary

Heat Flow (mW)

For pure, low

For polymers, use Peak as Melting Temperature

DSC of Polymer Blend

Onset shifts by only 0.3C

Onset shifts by almost 30C

Effect of Heating Rate on Melting

Heat Capacity (J/g/C)

Effect of Heating Rate on Polymorph

Effect of Impurities on Melting

Van't Hoff Purity Calculation

Heat Flow (W/g)

Total Area / Partial Area