Differential Scanning Calorimetry

(DSC)
Basic Theory &
Applications Training

2009 TA Instruments

Agenda

Understanding DSC
Experimental Design
Calibration
Optimization of DSC Conditions
Interpretation of Undesirable Events in DSC Data
Applications

DSC Training Course

2900 Series DSCs

DSC 2010

DSC 2910

DSC 2920

DSC Training Course

First Generation Q Series DSCs

Q1000
Q100
Q10
DSC Training Course

Second Generation Q-Series DSCs

Q2000

Q200

AutoQ20

Q2000 is top-of-the-line, research grade with all options

Q200 is research grade and expandable
Q20 is a basic DSC Available as an
Auto Q20 & also Q20P
DSC Training Course

Understanding DSC - Agenda

What does a DSC measure?

How does a DSC make that measurement?
How is a Tzero DSC different?
Tzero Results
Advanced Tzero

DSC Training Course

Agenda

What does a DSC measure?

How does a DSC make that measurement?
How is a Tzero DSC different?
Tzero Results
Advanced Tzero

DSC Training Course

What Does a DSC Measure?

A DSC measures the difference in heat flow rate (mW =
mJ/sec) between a sample and inert reference as a
function of time and temperature

DSC Training Course

Endothermic Heat Flow

0 .1

Heat flows into the sample as a result of either

Heat capacity (heating)
Glass Transition (Tg)
Melting
Evaporation
Other endothermic processes

0 .0

-0 .1

Heat Flow (W/g)

-0 .2

-0 .3

-0 .4

Endothermic

25

50

75

E xo U p

100

125

150

T e m p e r a tu re ( C )

DSC Training Course

Exothermic Heat Flow

Exothermic

Heat Flow (W/g)

0 .1

0 .0

Heat flows out of the sample as a result of either

Heat capacity (cooling)

Crystallization
Curing
Oxidation
Other exothermic processes

-0 .1
0

20

Exo U p

40

60

80

100

120

140

160

T e m pe ra tu re ( C )

DSC Training Course

Temperature

What temperature is being measured and displayed

by the DSC?

Sensor Temp: used by most DSCs. It is measured at the

sample platform with a thermocouple, thermopile or PRT.

Sample Platform
Chromel Area Detector
Reference Platform
Constantan Body

Thin Wall Tube

Base Surface
Constantan Wire
Chromel Wire
Chromel Wire

DSC Training Course

Temperature

What temperature is being measured and displayed

by the DSC?

Pan Temp: calculated by TA Q1000/2000 based on pan

material and shape

Uses weight of pan, resistance of pan, & thermoconductivity of

purge gas

What about sample temperature?

The actual temperature of the sample is never measured by DSC

DSC Training Course

Temperature

What temperatures are not typically being displayed?

Program Temp: the set-point temperature is usually not

recorded. It is used to control furnace temperature
Furnace Temp: usually not recorded. It creates the
temperature environment of the sample and reference

DSC Training Course

Understanding DSC Signals

Heat Flow

Relative Heat Flow: measured by all DSCs except TA
Q1000/2000. The absolute value of the signal is not
relevant, only absolute changes are used.

Absolute Heat Flow: used by Q1000/2000. Dividing
the signal by the measured heating rate converts the
heat flow signal into a heat capacity signal

DSC Training Course

DSC Heat Flow

dH
= DSC heat flow signal
dt

Cp = Sample Heat Capacity

= Sample Specific Heat x Sample Weight

dH
dT
= Cp
+ f (T, t)
dt
dt
dT
= Heating Rate
dt

f (T, t) = Heat flow that is function of time

at an absolute temperature (kinetic)

DSC Training Course

Agenda

What does a DSC measure?

How does a DSC make that measurement?
How is a Tzero DSC different?
Tzero Results
Advanced Tzero

DSC Training Course

How does a DSC Measure Heat Flow?

DSC comprises two nominally identical calorimeters in a

common enclosure that are assumed to be identical.
Advantages of a twin calorimeter:

Noise reduction by cancellation of common mode noise.

Simplified heat flow rate measurement.
Cancellation of calorimeter and pan heat capacities.
Cancellation of heat leakages.

DSC Training Course

Heat Flux DSC Cell Schematic

2900 Series DSC
Reference Pan

Sample Pan

Dynamic Sample Chamber

Lid

Thermoelectric Disc
(Constantan)

Gas Purge Inlet

Chromel
Disc

Chromel
Disc

Heating
Block
Chromel Wire
Alumel Wire

Thermocouple
Junction

DSC Training Course

Perfectly Symmetrical?

The heat flow rate of an empty perfectly symmetrical

twin calorimeter should be zero.
However, it almost never is because the DSC is rarely
symmetrical as assumed.
The asymmetry is the inevitable result of manufacturing
tolerances and is unavoidable.

For example, thermal resistance of the Tzero DSC cell is determined

by the wall thickness of the top hat which is .005 (0.13mm). To
achieve 1% thermal resistance imbalance would require
manufacturing tolerance of .00005 (.00127mm).

DSC Training Course

Conventional DSC Measurements

2900 Series

Heat Flow
Measurement Model

qs

Heat Balance Equations

qs =

qr

T fs Ts
Rs

qr =

T fr Tr
Rr

Ts

Tr

Conventional DSC Heat

Flow Rate Measurement

Rs

Rr

q = q s qr

q=
Tfs

Tfr

Tr Ts T
=
R
R

This model assumes that the sample and reference calorimeter thermal resistances
are identical, the temperature of the furnace at the sample and reference
calorimeters are equal and does not include other known heat flows.
DSC Training Course

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Conventional DSC - Assumptions

The resistance between the sample sensor and the

furnace equals the resistance between the reference
sensor and the furnace
Pan and calorimeter heat capacities are ignored
Measured temperature equals sample temperature
No heat exchange with the surroundings

DSC Training Course

Consequences of the Assumptions

Whenever the heating rate of the sample and reference

calorimeters is not identical, the measured heat flow is
not the actual sample heat flow rate. This occurs during
transitions in standard DSC and always during MDSC.
Resolution suffers.
Sensitivity suffers.
MDSC results are strongly period dependent, requiring
long periods and slow heating rates.
The heat flow baseline is usually curved and has large
slope and offset.

DSC Training Course

11

Violations of Assumptions
Pan and calorimeter heat capacities are ignored

Sample and reference heat capacities are assumed to be

the same and to heat at the same rate.
In general the sample and reference calorimeter heat
capacities do not match contributing to non-zero empty
DSC heat flow rate baseline.
During transitions and MDSC experiments the sample
and reference heating rates differ and the measured heat
flow rate is incorrect because the sample and reference
sensor and pan heat capacities store or release heat at
different rates.

DSC Training Course

Expanded Principle of Operation

Tfs

Rs

Rr
Ts
Cs

Q = Ts - Tr
R

Tfr

Tr

Thermal
Resistance
Imbalance

Cr

B
Thermal
Capacitance
Imbalance

Not Being
Measured w/
Conventional
DSC

C
Heating
Rate
Imbalance

DSC Training Course

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Agenda

What does a DSC measure?

How does a DSC make that measurement?
How is a Tzero DSC different?
Tzero Results
Advanced Tzero

DSC Training Course

Q-Series DSC Schematic

Sample & Reference Platforms

Tzero
Thermocouple

DSC Training Course

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Q-Series Heat Flow Measurement

Q-Series DSC

Tf

Rs

Rr

Ts

Tr

To

Cs

Cr

Sample Platform
Chromel Area Detector
Reference Platform
Constantan Body

Thin Wall Tube

Base Surface
Constantan Wire
Chromel Wire
Chromel Wire

DSC Training Course

Tzero Heat Flow Measurement

Heat Flow
Sensor Model

qs

Cs

Differential Temperatures
T = Ts Tr

qr

T0 = T0 Ts

Cr
Tr

Ts

Heat Flow Rate Equations

T

dT

0
R r qs = R Cs dt
s

Rs

qr =

T0

T0 + T
dT
Cr
Rr
dt

The sample and reference calorimeter thermal resistances and heat capacities
obtained from Tzero calibration are used in the heat flow rate measurements.

DSC Training Course

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Tzero Heat Flow Measurement (T4)

qT 4 = qs qr

qT 4 =

Thermal Resistance
Imbalance

Heating Rate
Difference

1
dT
dT
T
1
+ T0 + (Cr C s ) s Cr
Rr
d
d
Rs Rr

Principal DSC
Heat Flow

Heat Capacity
Imbalance

The four term Tzero heat flow rate measurement includes effects of the thermal
resistance and heat capacity imbalances as well as the difference in the heating
rates of the sample and reference calorimeters. When the assumptions of
conventional DSC are applied, only the first term remains and the conventional
heat flow rate measurement is obtained.
DSC Training Course

Tzero Heat Flow Equation

Heat Flow
Sensor Model
qr

qs
C

Tr

Ts
R

Besides the three

temperatures (Ts, Tr, T0);
what other values do we
need to calculate Heat
Flow?

Rr

T0

q=

1
T
1
dT
dT
+ T0 + (Cr Cs ) s Cr
Rr
d
d
Rs Rr

DSC Training Course

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Tzero Heat Flow Equation

Heat Flow
Sensor Model
qr

qs
C

Tr

Ts
R

Besides the three

temperatures (Ts, Tr, T0);
what other values do we
need to calculate Heat
Flow?

Rr

How do we calculate these?

T0

q=

1
T
1
dT
dT
+ T0 + (Cr Cs ) s Cr
Rr
d
d
Rs Rr

DSC Training Course

Measuring the Cs & Rs

Tzero Calibration calculates the Cs & Rs

Calibration is a misnomer, THIS IS NOT A
CALIBRATION, but rather a measurement of the
Capacitance (C) and Resistance (R) of each DSC cell
After determination of these values, they can be used in
the Four Term Heat Flow Equation (T4) shown previously

DSC Training Course

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A few words about the Cs and Rs

The curves should be smooth and continuous, without

evidence of noise or artifacts
Capacitance values should increase with temperature
(with a decreasing slope)
Resistance values should decrease with temperature
(also with a decreasing slope)
It is not unusual for there to be a difference between the
two sides, although often they are very close to identical

DSC Training Course

Good Tzero Calibration Run

17

Bad Tzero Calibration Run

Can see that it is bad during

Tzero cal run
DSC Training Course

Example of Typical Results

50

50

40

40

This cell is very well balanced. It is acceptable and usual

to have larger differences between sample and reference.
30
-200

-100

100

200

0.05

0.04

0.04

0.03

0.03

0.02

0.02

Sample Capacitance (Joule/C)

60

Reference Capacitance (Joule/C)

60

Reference Resistance (C/Watt)

Sample Resistance (C/Watt)

Characteristics
of the thermal resistances and heat capacities:
70
Both curves should be smooth, with no steps, spikes or inflection points.
Thermal resistances should always have negative slope that gradually decreases.
Heat capacities should always have positive slope that gradually decreases.

0.01
300

Temperature (C)

DSC Training Course

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Agenda

What does a DSC measure?

How does a DSC make that measurement?
How is a Tzero DSC different?
Tzero Results
Advanced Tzero

DSC Training Course

What does this do for us?

By measuring the capacitance and resistance, we are no

longer assuming the DSC cell is symmetrical
Using these values in the four term equation, we see
that nearly all aspects of DSC performance are improved
by Tzero DSC.

Empty DSC baselines are straighter and closer to zero.

Resolution is enhanced.
Sensitivity is enhanced.
Frequency dependence of MDSC is greatly reduced.

DSC Training Course

19

Tzero vs Conventional Baseline

0.6

Conventional Baseline
T zero Baseline

Heat Flow (mW)

0.4

0.2

0.0

-0.2

-0.4
-100

100

200

300

400

Temperature (C)

DSC Training Course

Q2000 Quantified Baseline Performance

100

Heat Flow (W)

50

4.94C
5.40W

-29.38C
31.23W

-50

-100
-50
Exo Up

50

100

150

200

250

300

350

Temperature (C)

DSC Training Course

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Agenda

What does a DSC measure?

How does a DSC make that measurement?
How is a Tzero DSC different?
Tzero Results
Advanced Tzero

DSC Training Course

Advanced Tzero Technology

During transitions and MDSC experiments, the heating

rates of the sample pan, sample calorimeter, reference
pan and reference calorimeter may be very different.
Sample pans have thermal resistance and heat capacity
and sample and reference pans rarely have the same
mass.
Advanced Tzero includes the heat capacity of the pans
and the heating rate differences between the sample and
reference calorimeters and pans.
Peaks are taller and sharper, hence both resolution and
sensitivity are dramatically improved.

DSC Training Course

21

Advanced Tzero Model

Advanced Tzero is a further refinement of the Tzero model and takes the
measurement up to the sample pan, one step closer to the actual sample
q sam

Advanced Tzero
model includes
the pans

Q2000

m pr c pan

m ps c pan
T ps
Rp

qs

Q200

Rp

qr

Ts

Tr
Cr

Cs

Tzero models the

Calorimeters

Cpan
Rp
Rs

T pr

Rs

Rr

T0

DSC Training Course

What is Pan Contact Resistance?

DSC Pan
Imperfect (non-intimate) contact
between pan and sensor causes lag
in heat flow which decreases resolution

Heat Flow
Heat Flow Sensor

DSC Training Course

22

Result of Pan Contact Resistance Factor

Without pan contact
resistance factor, temperature
is measured at the sensor

With pan contact resistance

factor, temperature
is measured at the bottom
of the pan, in intimate contact
with the sample

DSC Training Course

Indium with Q-Series Heat Flow Signals

Q1000

Q100

Q10

DSC Training Course

23

Indium with Q-Series Heat Flow Signals

Theoretical
Melting of
Indium

Q1000

Q100

Q10

DSC Training Course

Indium as a Measure of Sensitivity & Resolution

0

-5

Peak

Height Increases
Peak Width Decreases
Height/Width Increases

Height

Heat flow (mW)

-10

-15

-20

Width at Half-Height

-25

-30
140

145

150

155

160

165

170

175

180

Temperature (C)

DSC Training Course

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Improved Sensitivity/Resolution-Q2000
2

Heat Flow (mW)

-2

-4

Q2000
Tzero Pan
(Tzero pan)

-6

Standard Pan

Q1000

-8

-10

-12
154

155

Exo Up

156

157

158

159

160

Temperature (C)

DSC Training Course

Q-Series DSC Performance Comparison

Q10/20

Q100/200

Q1000/2000

1st Generation
Q-Series

7.50.4

20.82.1

36.34.4

2nd Generation
Q-Series

8.40.4

303.4

608

Improvement

12%

44%

65%

DSC Training Course

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Definitions

Amorphous Phase - The portion of material whose

molecules are randomly oriented in space. Liquids and
glassy or rubbery solids. Thermosets and some
thermoplastics

Crystalline Phase - The portion of material whose

molecules are regularly arranged into well defined structures
consisting of repeat units. Very few polymers are 100%
crystalline

Semi-crystalline Polymers - Polymers whose solid

phases are partially amorphous and partially crystalline.
Most common thermoplastics are semi-crystalline

DSC Training Course

Definitions (cont.)

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)

DSC Training Course

26

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.

DSC Training Course

Definitions (cont.)

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
Enthalpy of Melting/Crystallization - The heat
energy required for melting or released upon crystallization.
This is calculated by integrating the area of the DSC peak
on a time basis.

DSC Training Course

27

Typical DSC Transitions

Oxidation
Or
Decomposition

Heat Flow -> exothermic

Crystallization

Melting
Glass
Transition

Cross-Linking
(Cure)

Composite graph
Temperature

DSC Training Course

Experimental Design

Available Method Segments

Method Design Rules

Typical Methods (Examples)

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28

Methods vs. Procedures

The logic of the instrument control software is based upon
the concepts of methods and procedures.

METHODS are the actual steps that the DSC executes
during a run. The software provides custom templates
built around types of experiments.

PROCEDURES include, along with the method, all other
options that the user sets in creating a run. For
example, the data sampling interval, method end
conditions, etc.

DSC Training Course

Q-Series DSC Segment List

DSC Training Course

29

Method Design Rules

Start Temperature

Generally, the baseline should have two (2) minutes to

completely stabilize prior to the transition of interest.
Therefore, at 10C/min., start at least 20C below the
transition onset temperature

End Temperature

Allow a two (2) minute baseline after the transition of interest

in order to correctly select integration or analysis limits
Dont Decompose sample in DSC Cell

DSC Training Course

Why have 2 min of baseline?

0.0

Heat Flow (W/g)

-0.5

-1.0

-1.5

Wax 10C/min
-2.0

-2.5
20
Exo Up

40

60

80

100

Temperature (C)

120

140

160
Universal V3.9A TA Instruments

DSC Training Course

30

Heating/Cooling Methods
Typical Heating Method
1) Equilibrate at 0C
2) Ramp 10C/min. to 300C

Typical Cooling Method

1) Equilibrate at 300C
2) Ramp 10C/min. to 25C

DSC Training Course

Heat-Cool-Reheat Method
Typical Heat-Cool-Heat Method
1)
2)
3)
4)
5)
6)
7)

Equilibrate @ 25C
Ramp 10C/min. to 300C
Mark cycle end 0
Ramp 10C/min. to 25C
Mark cycle end 0
Ramp 10C/min. to 300C
Mark cycle end 0

DSC Training Course

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Oxidative Stability (OIT) Method

OIT Method
1)
2)
3)
4)
5)
6)
7)

Equilibrate at 60C
Isothermal for 5.00 min.
Ramp 20C/min. to 200C
Isothermal for 5.00 min.
Select gas: 2
Abort next seg. if W/g > 1.0
Isothermal for 200.00 min.

DSC Training Course

Modulated DSC Method

Typical MDSC Methods
1)
2)
3)
4)
5)
6)

Data storage: off

Equilibrate at -20C
Modulate 1C every 60 seconds
Isothermal for 5.00 min.
Data storage: on
Ramp 3C/min. to 300C

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32

DSC General Method Recommendations

Determine decomposition temp

Stay below that temperature

Run Heat-Cool-Heat @ 10C/min

Use specific segments as needed, i.e. gas switch, abort,
etc.
Modify heating rate based on what youre looking for

DSC Training Course

Calibration & Sample Preparation

Instrument Calibration

Q200 & Q2000

Q20 & 2900s

Cell Constant & Temperature

Baseline

Cell Constant & Temperature

Miscellaneous

Purge Gas
Cooling Accessories
Environment

Sample Preparation
Selecting Experimental Conditions

DSC Training Course

33

General Calibration Issues

Calibration

Use Calibration Mode

Calibrate upon installation
Re-calibrate every ????

Verification

Determine how often to verify data

Run a standard as a sample (std mode)
Compare results vs. known
If results are within your tolerance system checks out and doesnt reneed calibration
If results are out of tolerance, then re-calibrate

DSC Training Course

Heat Flow Calibration

Differential Heat Flow (ASTM E968)

Heat of fusion (melting) standards
Heat capacity (no transition)

Miscellaneous

Use specific purge gas at specified rate

Calibrate w/cooling accessory functioning if it will be used to run
samples
Single point used for heat of fusion
Calibration should not change w/heating rate

DSC Training Course

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Heat Flow Calibration

Prepare a 1-3mg sample of indium and

premelt prior to first use

Premelt

Verify at least once a month

Typical values for cell constant:

1.0 to 1.2 (in N2)

DSC Training Course

Calorimetric Calibration
5

Heat Flow (mW)

157.44C

-5

Sample: Indium, 5.95 mg.

CALIBRATION MODE; 10C/MIN
CALIBRATION BASED ON 28.42J/g

-10
Cell Const.: 1.0766
Onset Slope: -20.82 mW/C

-15
150

155

160
Temperature (C)

165

170

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Temperature Calibration

ASTM Method E967

Pure metals (indium, lead, etc.) typically used

Extrapolated onset is used as melting temperature
Sample is fully melted at the peak

DSC Training Course

Temperature Calibration

0
Heat Flow (W/g)

50

Extrapolated Onset
156.61C
28.36J/g

40

-1
30
-2
20
-3
HEATING RATE

10

-4

157.09C
PEAK

-5
150

152

154

156
158
160
Temperature (C)

Deriv. Temperature (C/min)

0
162

164

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36

Temperature Calibration

Verify at least once a month

Maximum of five points

Use tin, lead, and zinc one time only

DSC Training Course

Recommended Temperature & Enthalpy Standards

Enthalpy
(cell constant)

Temperature

Benzoic acid (147.3 J/g) Tm = 123C

Urea (241.8 J/g) Tm = 133C
Indium (28.45 J/g) Tm = 156.6C
Anthracene (161.9 J/g) Tm = 216C

Cyclopentane* -150.77C
Cyclopentane* -135.09C
Cyclopentane* -93.43C
Cyclohexane# -83C
Water# 0C
Gallium# 29.76C
Phenyl Ether# 30C
p-NitrotolueneE 51.45C
NaphthaleneE 80.25C
Indium# 156.60C
Tin# 231.95C
Lead* 327.46C
Zinc# 419.53C

* GEFTA recommended
Thermochim. Acta, 219 (1993) 333.
# ITS 90 Fixed Point
E Zone refined organic compound
(sublimes)

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37

To begin calibration start

DSC Calibration Wizard

DSC Training Course

Select Heat Flow signal

& type of cooler
Q2000/1000 = T4P
Q200/100

= T4

Q20/10

= T1

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38

T4P & T4
Calibration

Select which
calibration to perform
Tzero Calibration

DSC Training Course

T4P & T4
Calibration

Enter parameters for

first run (empty cell)

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39

T4P & T4
Calibration

Start experiment
DSC Training Course

T4P & T4
Calibration

Enter weight of sapphire samples

DSC Training Course

40

T4P & T4
Calibration

When run is completed, capacitance &

resistance are plotted and saved
DSC Training Course

T4P & T4
Calibration

Always run Indium for

Cell Constant

Enter parameters for Indium sample

DSC Training Course

41

T4P & T4
Calibration

Enter temperatures for Indium run

DSC Training Course

T4P & T4
Calibration

Start experiment
DSC Training Course

42

T4P & T4
Calibration

Data is analyzed
automatically

DSC Training Course

T4P & T4
Calibration

DSC Training Course

43

Baseline Calibration

Slope

Q20 & 2900s Only

Calibration should provide flat baseline with empty cell

Polymers should always have an endothermic slope due to increasing
heat capacity with increasing temperature

Curvature

Not normally part of calibration procedure

Can be eliminated if necessary with baseline subtraction
Curvature can cause errors in analyses

DSC Training Course

Baseline Slope due to Heat Capacity

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44

Baseline Curvature
0.6

Conventional Baseline
T zero Baseline

Heat Flow (mW)

0.4

0.2

0.0

-0.2

-0.4
-100

100

200

300

400

Temperature (C)

DSC Training Course

To begin calibration start

DSC Calibration Wizard

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45

T1 Calibration

DSC Training Course

T1 Calibration

Select type of
calibration to run

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46

T1 Baseline Cal

Enter parameters

Step 1 of 11

DSC Training Course

T1 Baseline Cal

Review summary

Step 2 of 11

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47

T1 Baseline Cal

Enter sample
information

Step 3 of 11

DSC Training Course

T1 Baseline Cal

Finish entering
sample information

Step 4 of 11

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T1 Baseline Cal

Review checklist

Step 5 of 11

DSC Training Course

T1 Baseline Cal

Baseline calibration running

Step 6 of 11

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49

T1 Baseline Cal

Start calibration analysis

Step 7 of 11

DSC Training Course

T1 Baseline Cal

File is opened
automatically

Step 8 of 11

DSC Training Course

50

T1 Baseline Cal

Select limits then click on

Limits Ok button
Step 9 of 11

DSC Training Course

T1 Baseline Cal

Click on Accept
to save calibration

Step 10 of 11

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51

T1 Baseline Cal

Once the file is analyzed and the

results are saved, a checkmark
appears next to the filename

Step 11 of 11

DSC Training Course

T1 Calibration

Select type of
calibration to run

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52

T1 Temperature Cal

Enter parameters

Step 1 of 7

DSC Training Course

T1 Temperature Cal

Review summary

Step 2 of 7

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53

T1 Temperature Cal

Enter sample
information

Step 3 of 7

DSC Training Course

T1 Temperature Cal

Finish entering
sample information

Step 4 of 7

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T1 Temperature Cal

Review checklist

Step 5 of 7

DSC Training Course

T1 Temperature Cal

Start calibration analysis

Step 6 of 7

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55

T1 Temperature Cal

File is opened and analyzed

automatically. Click Analyze
to change limits or Accept to
complete the calibration.

Step 7 of 7

DSC Training Course

Traceable Calibration Materials

NIST DSC calibration materials:

SRM 2232
SRM 2220
SRM 2222
SRM 2225

Indium
Tin
Biphenyl
Mercury

Tm = 156.5985C
Tm = 231.95C
Tm = 69.41C
Tm = -38.70C

NIST: Gaithersburg, MD 20899-0001

Phone: 301-975-6776
Fax: 301-948-3730
Email: [email protected]
Website: http://ts.nist.gov/srm

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56

Traceable Calibration Materials

LGC DSC Calibration Materials:

LGC2601: Indium (TA p/n: 915060-901)

LGC2608: Lead
LGC2609: Tin
LGC2611: Zinc

Laboratory of the Government Chemist, UK

Phone: 44 (0) 181 943 7565

Fax: 44 (0) 181 943 7554
Email: [email protected]

DSC Training Course

Traceable Calibration Materials

Certified materials used to establish traceability of
instrument calibration
ISO/GLP certification often requires third party
calibration of instruments:



Service provided by TA Instruments service representative

using certified materials
Certificate of Calibration issued showing traceability of
calibration to a national laboratory

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57

Verifying Baseline

After completion of calibration routine, run baseline

Standard mode
Empty cell, -90C-400C (w/ RCS)
Plot mW vs. temperature on a 1mW scale

Measure bow,drift & zero

Should look fairly flat on this scale

Bow <50 W
Drift <50 W
Should be around zero

To verify performance in the future re-run

DSC Training Course

Verifying Baseline
0 .4

Heat Flow (mW)

0 .2

0 .0

-0 .2

-0 .4

-1 0 0

100

200

300

400

Tem perature (C )

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58

Verifying Baseline
0 .5

0 .4

0 .3

1 7 6 .6 6 C
0 .0 2 1 3 8 m W

0 .2

2 1 m ic ro W b o w
4 2 m ic ro W d r ift

Heat Flow (mW)

0 .1

0 .0

-0 .0 0 3 2 5 2 m W

-0 .1

-0 .0 4 5 6 2 m W

-0 .2

-0 .3

-0 .4

-0 .5
-1 0 0

100

200

300

400

T e m p e ra tu re (C )

DSC Training Course

Verifying Baseline
0.4

Heat Flow (mW)

0.2

Initial B aseline after calibration

0.0

B aseline check - still good

-0.2

-0.4

-100

100

200

300

400

Tem perature (C )

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59

Verifying Baseline
0.4

B aseline check - needs recalibrating

Heat Flow (mW)

0.2

Initial B aseline after calibration

0.0

B aseline check - still good

-0.2

-0.4

-100

100

200

300

400

Tem perature (C )

DSC Training Course

Verifying Heat Flow & Temperature

Run Indium as a sample (i.e. in std mode not cal mode)

Analyze melt and record melt onset & heat of fusion
Compare to known values

Melting of In 156.6C
Heat of Fusion 28.71J/g

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60

Verifying Heat Flow & Temperature

5

1 5 6 .6 4 C
-2 8 .6 0 J /g
0

Heat Flow (mW)

-5

Temp is within
0.04C

-1 0

Heat of fusion is
within 0.11J/g

-1 5

-2 0

1 5 7 .0 6 C
-2 5
140

145

150

155

160

165

170

175

180

Te m pe ra ture (C )

DSC Training Course

Q-Series Platinum Software

Platinum features are designed to assist you in ensuring

that your instrument is in proper working condition,
calibrated, and has the latest software available.

Automatic Calibration Routines

Auto Diagnostics
Event Scheduler
Email/Messaging Notification
Live Software Updates

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61

Platinum Software
DSC

DSC Training Course

Automatic Calibration Routines

DSC Automatic Calibration Routines

Baseline Calibration (T1)

Cell/Cooler Conditioning (T4 or T4P)
Baseline Conditioning (T4 or T4P)
Tzero Calibration (T4 or T4P)
Cell Constant/Temperature Calibration
Cell Constant/Temperature Verification

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62

Calibration Sequence Generator

Select Auto Calibration through Platinum options to initiate the

Calibration Sequence Generator. Creates a calibration sequence
based on your selections.

DSC Training Course

DSC Diagnostics Routine

Perform a
diagnostic check of
the instrument
List based on
options (e.g.,
Autosampler, MFC,
Cooler Type)

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63

Event Scheduler

Sequences, Auto-calibration, Auto-Verification and Diagnostics Events

can be Scheduled via Platinum Software

DSC Training Course

SDT Q600 (2960) Calibration

DTA Baseline & TGA Weight Calibration

2 runs empty beams & then calibration weights

 Temperature Calibration

Up to 5 temperature standards

 DSC Heat Flow Calibration

2 runs empty pans then sapphire

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64

SDT Q600 (2960) DSC Heat Flow Calibration

 Two scans from ambient to 1500C at 20 oC/min

empty alumina pans

sapphire in alumina sample pan

 Use Software to analyze

 E-curve will be calculated and transferred to the module
when the user accepts the results

DSC Training Course

Instrument Preparation
 Purge Gas

Type of purge gas and flow rate affect calibration and therefore
should be controlled
Nitrogen is preferred because it is inert and calibration is least
affected by changes in flow rate

 Cooling Accessories

 If used, they should be operating and equilibrated prior to

calibration or sample runs

 Warm-up Time/Environment

Electronics should be given at least one hour to stabilize for

important samples if the instrument has been turned OFF
Electronics are effected by ambient temperature. Avoid areas
such as hoods or near an air conditioner

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65

Recommended Purge Gas Flow Rates

Module

Purge Port

All TA DSCs

50(N2) or 25(He)
(Purge in ml/min)

If you have a 2900s DSC, purge the vacuum port with 50ml/min
if using a RCS or LNCA.
If purge gas is too slow - possible moisture accumulation &
early aging of the cell
If purge gas is too fast excessive noise
DSC Training Course

Purge gas ports on Q-Series DSC

Dry N2 @ 20 psi

Purge gas @ 20 psi

20 psig not 20 psig max

Dry air @ 15-120 psi for Finned air cooler

Dry N2 @ 15-120 psi for RCS or LNCS
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66

This is used to specify the type

of gas connected to Gas #1
& Gas #2 inlets
DSC Training Course

This is used to select which

gas is going to the DSC cell
and the flow rate for that gas.

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67

Autolid II: Improved Purge Gas Exhaust

DSC Training Course

Selecting Optimum Experimental Conditions

"Always" run a TGA experiment before beginning DSC

tests on new materials
Heat approximately 10mg sample in the TGA at
10C/min to determine:

Volatile content

Unbound water or solvent is usually lost over a broader temperature

range and a lower temperature than a hydrate/solvate

Decomposition temperature

DSC results are of little value once the sample has lost 5% weight due
to decomposition (not desolvation)
Decomposition is a kinetic process (time + temperature dependent).
The measured decomposition temperature will shift to lower
temperatures at lower heat rates

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68

Selecting Optimum Experimental Conditions

Use TGA data to help select DSC experimental conditions

Crimped vs. Hermetic (sealed) Pan

Maximum Temperature

Use hermetic pan if sample loses approximately 0.5% or more

Excessive decomposition will contaminate DSC cell between runs

When comparing samples, always use the same experimental

conditions

DSC Training Course

Optimization of DSC Conditions

Sample Preparation

Keep thin; cut rather than crush

Weight of 10-15mg for polymers; 3-5mg for metal or chemical melting
Goal is to achieve a change of 0.1-10mW heat flow in going through
the transition (see Figure #1)
If sample contains volatiles, put 5-10 pinholes in the lid of the pan
before crimping in order to permit a continuous evaporation process

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69

Heat Flow Change During a Transition

Figure #1
1.0
161.17C
1.593mW

Heat Flow (mW)

0.5
0.0
-0.5

69.41C
73.37C(H)
+ 0.4881mW

-1.0

143.70C
34.95J/g

-1.5
-2.0
40

60

80

100

120

140

Temperature

160

180

200

220

(oC)

DSC Training Course

Selecting Optimum Experimental Conditions

Sample Pan: Crimped vs. Hermetically Sealed

Crimped pans are lighter ( 23mg) and provide better

sensitivity and resolution
Hermetic aluminum pans are heavier ( 55mg) but can be
sealed to prevent loss of volatiles
Hermetic stainless steel pans ( 250mg) permit use of
large samples (100mg) and higher temperatures/pressures
(2000 psig = 1.4 MPa)
Care should be taken to keep the bottom of all pans flat to
improve heat transfer/resolution

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70

Optimization of DSC Conditions

Experimental Conditions (cont.)

 Select an end-temperature which does not cause

decomposition of the sample to occur in the DSC.
 Decomposition products can condense in the cell and cause
either corrosion of the cell or baseline problems

Use sealed glass ampoules or stainless steel pans, which can take
high pressure (>1000psi), in order to study decomposition by DSC

DSC Training Course

Sample Pans

Type of pan depends on:

Sample form
Volatilization
Temperature range

Use lightest, flattest pan possible

Always use reference pan of the same type as sample
pan

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71

Standard DSC Pans (Crimped)

Pan & lid weighs ~23mg, bottom of pan is flat

Used for solid non-volatile samples
Always use lid (see exceptions)

Lid improves thermal contact

Keeps sample from moving

Exceptions to using a lid

Running oxidative experiment

Running PCA experiment

DSC Training Course

Standard DSC Pans (Crimped)

Crimped pans are available in:

Aluminum:
Copper:
Gold:

up to 600C
up to 725C (in N2)
up to 725C

Standard Pans without lids

Graphite:
Platinum:

up to 725C (in N2)

up to 725C

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72

Hermetic Pans (Sealed)

Pan & Lid weigh ~55mg, bottom of pan is not as flat as

std pans
Used for liquid samples and samples with volatiles
Always use lid (same exceptions as before)
After sealing pans, the lid should form a dome

DSC Training Course

Hermetic Pans (Sealed)

Hermetic Pans are available in:

Aluminum: <600C; <3 atm (300 kPa gage)

Alodined Aluminum: <600C; <3 atm (300 kPa gage)

(For aqueous samples)

Gold: <725C; <6 atm (600 kPa gage)

Specialized Sealed Pans

High Volume: 100L; <250C; 600 psig(4.1 MPa)

High Pressure: 35L; <300C; 1450 psig(10 MPa)

Note: 3 atm is approximately 44 psig

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73

New Tzero Sample Press & Pans

Completely Redesigned Press

Two New Sample Pans
Compatible with existing sample
pans
No tooling required
Color-coordination between pan
boxes and dies
Improved hermetic sealing
Improved DSC Performance

DSC Training Course

Factors Affecting Sensitivity/Resolution

Sensitivity

Thermocouple Output
Magnitude of T
Signal/Noise
Baseline Quality

Resolution

Time Constant of Transducer

Pan Contact Resistance
The flatness of the bottom of the DSC pan in critical to optimizing resolution

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74

New TA Instruments Tzero Pans

Tzero Pan

Tzero Low-Mass Pan

The Tzero pan has been engineered to

have a perfectly flat bottom and not to
deform during crimping. This ensures
the optimal contact between pan and
sensor, minimizing the contact
resistance and improving resolution.
The Tzero Pan can be configured for
crimped or hermetic use.
The Tzero Low-Mass Pan is designed
for the highest sensitivity when sample
mass is limited.

DSC Training Course

Tzero Press Kit Configurations

Standard Pan

Standard Lid

Small samples
High Sensitivity

Tzero
Hermetic Lid

Tzero Lid

Larger Samples
High Performance
Tzero
Low-Mass Pan

Hermetic seals

Tzero Pan

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75

It Does Matter What Pan You Use

Monohydrate
Pharmaceutical
sample

DSC Training Course

TGA of Monohydrate Pharmaceutical Drug

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76

Sample Shape

Keep sample thin

Cover as much as the bottom of pan as possible

DSC Training Course

Sample Shape

Cut sample to make thin, dont crush

If pellet, cut cross section

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77

Sample Shape

Cut sample to make thin, dont crush

If pellet, cut cross section

If powder, spread evenly over the bottom of the pan

DSC Training Course

Keeping the DSC Cell Clean

One of the first steps to ensuring good data is to keep

the DSC cell clean
How do DSC cells get dirty?

Decomposing samples during DSC runs

Samples spilling out of the pan
Transfer from bottom of pan to sensor

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78

How do we keep DSC cells clean?

DO NOT DECOMPOSE SAMPLES IN THE

DSC CELL!!!
Run TGA to determine the decomposition temperature

Stay below that temperature!

Make sure bottom of pans stay clean

Use lids
Use hermetic pans if necessary

DSC Training Course

TGA Gives Decomposition Temperature

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79

Cleaning Cell (Q-Series Only)

Use solvent slightly damp swab with an appropriate

solvent

Heat cell to 200C for 10 min to drive off any remaining solvent
Solvents are Last Resort for 2900 Series

If the cell is still dirty

DSC Training Course

Cleaning Cell (Q-Series and 2900 Series)

If the cell is still dirty

Clean w/ brush

Brush gently both sensors and cell if necessary

Be careful with the Tzero thermocouple
Blow out any remaining particles

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80

Q-Series Cell Before Cleaning

DSC Training Course

Brushing the Sample Sensor

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81

After Cleaning Sample Sensor

Fibers in
cell from
cleaning
brush
need to be
removed

DSC Training Course

Cleaning Cell (Q-Series and 2900 Series)

Bake out (Use as a last resort in Q-Series cell)

Air purge
Open lid
Heat @ 20C/min to appropriate temp (max of 550C) No
Isothermal @ the upper temperature
Cool back to room temp & brush cell again

Check for improved baseline performance

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82

Cleaning Cell (2900 Series)

LAST RESORT for 2900 Series

Use solvent slightly damp swab with appropriate solvent

Keep solvent away from holes in base of cell

Heat cell to 200C for 10 min to drive off any remaining solvent

DSC Training Course

What if I need help?

On-site training & e-Training courses - see Website

Call the TA Instruments Hotline

Call the TA Instruments Service Hotline

302-427-4070 M-F 8-4:30 Eastern Time

mailto:[email protected]
302-427-4050 M-F 8-4:30 Eastern Time

Check out our Website

http://www.tainstruments.com/

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83

Interpretation of Undesirable
Events in DSC Data

2009 TA Instruments

Topics

Event 1: Large Endothermic Shift in the Baseline

at the Beginning of the Experiment

Event 2: Baseline Slope After Baseline Calibration

Event 3: Unexpected Transitions Near 0C
Event 4: Shifts in the Baseline and Apparent Melting
at the Glass Transition
Events 5 and 6: Exothermic Peaks in the Data Between the Glass
Transition and Melting Temperature
Event 7: Changes in the Melting Transition Due to Thermal
History
Event 8: Decomposition
[See Figure 5]
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Figure 5

DSC Training Course

Event 3: Unexpected Transitions Near 0C

Event 3 in Figure 5 is caused by water. The
transition is also much larger than normally seen
in order to more easily illustrate it.
Water in the DSC Cell

It is possible to get condensation of water within the

DSC cell if the purge gas is not sufficiently dry or if the
cell is opened to room atmosphere when its temperature
is below the freezing point of water, 0C.
The transitions caused by water in the cell can cover a
wide temperature range from 10C to more than 50C
and are highly undesirable.

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85

Event 3 (cont.)
 When water condenses in the cell, it can condense on the sample

pan, reference pan, sensors, and furnace. Water on the sample

pan or inside it typically melts very sharply at 0C as seen in the
endothermic spike at 0C in Figure 5.
Water on the reference pan would look similar except that it
would appear as an exothermic spike in the data. In this data, the
melting peak is endothermic because most, if not all, of the water
was on the sample. To get this undesirable transition for
illustration purposes, the sample pan was removed from the DSC
when its temperature was 50C. Water from the room air
condensed on the pan, plus some of it probably condensed in
other parts of the cell.

DSC Training Course

Event 3 (cont.)

The broader endothermic peak between 0C and 25C

is due to the endothermic evaporation of the water on
the DSC pan. As can be seen in the data, the baseline
does not stabilize until almost 50C when all of the
water in contact with the pan and sensor has finally
evaporated.
To avoid artifacts in the data due to water, it is best to
have a drying tube in the purge gas line between the
source of the gas and the purge gas inlet on the DSC
cell base. In addition, never open the cell to the
atmosphere or load a sample when the cell temperature
is below 0C.

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86

Event 3 (cont.)
Water in the Sample

Many samples contain water and, therefore, can
undergo a transition near 0C due to this water.

However, just because the sample contains water does
not mean it will have a melting transition near 0C.

Water that is physically or chemically associated with
sample material generally will not freeze and, therefore,
cannot melt.

Unassociated water or free water in the sample has
the same properties as bulk water. However, the actual
melting point is often lower than 0C due to impurities
dissolved in the water.
DSC Training Course

Figure 5

DSC Training Course

87

Event 4: Shifts in the Baseline

Shifts in the Baseline

The most common baseline shift is due to the increase
in heat capacity that occurs upon heating through the
glass transition temperature. The size of the
endothermic shift is a measure of the amount of
amorphous material in the sample. The more
amorphous the sample, the larger the baseline shift.

Heat capacity is a measure of molecular mobility within
the sample. Since there is a step-increase in molecular
mobility within the sample as it is heated through its
glass transition temperature, there is also a stepincrease in the amount of heat required to continue
heating the sample at the same rate above its Tg.
DSC Training Course

Event 4 (cont.)
 An exothermic shift (less endothermic) in the baseline while
heating results in the baseline moving back closer to zero (0
mW) heat flow. This type of shift is much less common and in
order for this to occur while heating, there must either be a
reduction in molecular mobility or a reduction in sample mass.
Most of the time, this type of positive shift is due to evaporation
of some component within the sample.

Apparent Melting in the Glass Transition

 The endothermic shift in the baseline at the transition in Figure 5
is due to the glass transition of the amorphous PET polymer.

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88

Event 4 (cont.)
 Depending on the thermal history of amorphous (glassy)

polymers, the glass transition can appear as a simple step in the

baseline or one that has a substantial endothermic peak that can
be misinterpreted as a melting peak.
Figure 6 shows the results from two experiments on the same
sample; the only difference is the thermal history. The sample
with the endothermic peak was stored for over ten years at a
temperature just below its glass transition temperature. As it
aged, the enthalpy of the sample decreased towards equilibrium,
and it became denser and more brittle.

DSC Training Course

Event 4 (cont.)
 By heating a sample above the glass transition temperature and

then cooling it back to room temperature, the previous thermal

history is erased. This is the data marked as the Second Heat in
Figure 6.
The term for the endothermic peak that develops in the glass
transition with aging at temperatures below the glass transition
temperature is enthalpic relaxation. It is due to the fact that
amorphous materials are not in thermodynamic equilibrium but,
with time, do relax and move towards equilibrium.

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89

Figure 6

DSC Training Course

Aging of Amorphous Structure (Storage Stability)

Background Information

At temperatures above Tg, there is high molecular
mobility and the sample is in thermal equilibrium

At temperatures well below Tg (Tg-40C), molecular
mobility is low and the existing amorphous structure is
relatively stable

At temperatures just below Tg (Tg-10C), there is
enough molecular mobility that the existing amorphous
structure is not stable and will change with time as the
amorphous material seeks a lower energy state
(amorphous equilibrium or crystalline)
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90

Aging of Amorphous Structure (Storage Stability)

Cooling at relatively high rates from temperatures above

Tg to temperatures below Tg creates a meta-stable
glass which ages towards equilibrium over time. The rate
of change is a function of the storage temperature and
molecular structure
DSC/MDSC can be used to evaluate the stability of the
meta-stable glass and compare the structural state of the
amorphous phase

DSC Training Course

Some Definitions

Enthalpic Relaxation

The process of a meta-stable glass relaxing towards

equilibrium at a temperature below Tg
Occurs as the sample is being cooled to temperatures below Tg
Occurs as the sample is being stored at temperatures below Tg

Enthalpic Recovery

The recovery of energy (J/g) lost during Enthalpic Relaxation.

It (peak in DSC data @ Tg) occurs as the sample is heated to
a temperature above Tg

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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

Decreases

Enthalpy

Decreases

Entropy

Decreases

Max Tg
V

Storage
time
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

DSC Training Course

Effect of Cooling Rate on Shape of Tg

Sample cooled @ 40, 20,
10, 5, 2, & 1C/min

Cooled @ 40C/min

PMMA
6.36mg
Heating @ 20C/min

Cooled @ 1C/min

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Figure 7

DSC Training Course

Enthalpy/Volume Diagrams

ui
liq

Enthalpy or Volume

Tg

Above Tg, the

sample is
mobile, so it
doesnt matter
what cooling
rate we use. The
sample will be in
equilibrium

s
du

Equilibrium Conditions

Temperature
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93

Enthalpy or Volume

Enthalpy/Volume Diagrams
Below Tg, there
is very little
molecular
mobility, so the
cooling rate will
determine
whether the
sample stays in
equilibrium

Tg
ui
liq

s
du

Equilibrium
Conditions

Temperature
DSC Training Course

For Example

Enthalpy or Volume

Tg
ui
liq

s
du

Non-equilibrium
states

1C/year
s
solidu

Equilibrium Conditions

Temperature
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94

Enthalpy/Volume Diagrams

Enthalpy or Volume

Tg

Non-equilibrium states

Temperature
DSC Training Course

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.

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95

Figure 5

DSC Training Course

Events 5 and 6
Exothermic Peaks in the Data between the Tg and Melting Temperatures

Events 5 and 6 in Figure 1 are the result of crystallization

and crystal perfection processes that occur as the sample
is heated.
To understand what might be happening, so that the data
is interpreted correctly, there are three factors that need
to be considered:
1.
2.

3.

What is the thermal history of the sample?

Does the material crystallize and, if so, how fast or slow
(kinetics) does it crystallize as a function of time and
temperature?
How fast was the sample heated or cooled in the DSC
experiment?

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Events 5 and 6 (cont.)

Thermal History

When referring to Thermal History, we are identifying the

temperature versus time profile that the sample has been
subjected to in the past.

DSC Training Course

Events 5 and 6 (cont.)

As temperature is increased above Tg, molecular mobility

increases rapidly. This permits the molecules to align with their
neighbors and crystallize as seen in the exothermic peak
centered near 130C for the First Heat.
Although the baseline appears to stabilize between 150 and
225C, there is an ongoing process of crystallization and crystal
perfection over that temperature range as will be discussed later.
The term crystal perfection is used to describe the process
where small, less perfect crystals melt and then recrystallize into
larger, more perfect crystals that will melt again at a higher
temperature.

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Events 5 and 6 (cont.)

Crystallization Kinetics

Crystallization is a kinetic process, which means that the

rate of crystallization is a function of both time and
temperature. The fact that the peak of the crystallization
process occurs near 130C in Figure 8 is the result of the
selected experimental conditions.
Figure 9 shows how the cold crystallization peak
broadens and shifts to a higher temperature as the
heating rate is increased from 2 to 16C/min. This shift
is much larger than seen in the glass transition and
melting processes, which have relatively minor kinetic
contributions.

DSC Training Course

Figure 8

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98

Figure 9

DSC Training Course

Figure 5

DSC Training Course

99

Event 7: The Melting Transition

The melting transition can be the least complicated

transition measured by DSC. However, it can also be the
most complicated transition for some materials,
especially semi-crystalline polymers.
When measuring the melting transition, it is normal to
measure the temperature range over which it occurs as
well as the enthalpy of melting (Hm) which is
proportional to the crystalline content of the sample.

DSC Training Course

Event 7 (cont.)

The complication occurs with semi-crystalline materials because of

the fact that the sample can increase in crystallinity as it is being
heated in the DSC. If this occurs and is not considered in
calculating the crystallinity of the sample, an artificially large value
will result.
Figure 10 shows the data from an MDSC experiment. The Total
signal is qualitatively and quantitatively equivalent to traditional
DSC. From just the Total signal, it is possible and quite common to
calculate a crystallinity value which has an error in excess of 100%.

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100

Figure 10

DSC Training Course

Event 7 (cont.)

The question is: How can DSC provide such a wrong answer?
The answer is that it does not.
The error is due to the integration limits selected by the
operator.
Total signal of DSC is often misleading because it measures
only the sum of all exothermic and endothermic processes.
Figure 11 shows that slower heating rates provide more
exothermic (crystal perfection) activity in the temperature
region between 150 and 220C.
The increased crystal perfection that occurs at slower heating
rates causes the melting point to increase to higher
temperatures.

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Figure 11

DSC Training Course

Event 7 (cont.)

The shape of the melting peak is also affected by

crystal perfection processes that occur over the same

temperature range as bulk melting. This often gives
the appearance of two melting peaks rather than what
actually is an exothermic crystallization peak
superimposed on an endothermic melting peak.

Figure 12 compares the shape of the melting process

on the same sample of PET after it had been cooled at

different rates from above its melting point. This is
different from Figure 11 where all samples had the
same thermal history (quench cooled) but were heated
at different rates.
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102

Figure 12

DSC Training Course

Figure 5

DSC Training Course

103

Event 8: Decomposition

Beginning at about 310C in Figure 1, the sample of PET begins

to decompose.

Depending on the chemistry of the sample and type of sample
pan used, decomposition can either be endothermic or
exothermic.

Decomposition usually involves a release of some volatiles. The
process of off-gasing is usually erratic, and the data can become
noisy and nonreproducible.

Decomposing samples in a DSC will adversely affect the baseline
and may corrode the DSC cell.

DSC Training Course

Applications

Thermoplastics
Thermosets
Pharmaceuticals
Heat Capacity
Glass Transition
Melting and Crystallization
Additional Applications Examples

DSC Training Course

104

Thermoplastic Polymers
Semi-Crystalline or Amorphous
Crystalline Phase
melting temperature Tm
(endothermic peak)
Amorphous Phase
glass transition
temperature (Tg)
(causing Cp)

Tg < Tm
Crystallizable polymer can crystallize
on cooling from the melt at Tc
(Tg < Tc < Tm)
DSC Training Course

DSC of Thermoplastic Polymers

Tg
Melting
Crystallization
Oxidative Induction Time (OIT)

General Recommendations

10-15mg in crimped pan

H-C-H @ 10C/min

DSC Training Course

105

Selecting Experimental Conditions

Thermoplastic Polymers

Perform a Heat-Cool-Heat Experiment at 10C/min.

First heat data is a function of the material and an unknown
thermal history
Cooling segment data provides information on the
crystallization properties of the polymer and gives the sample a
known thermal history
Second heat data is a function of the material with a known
thermal history

DSC Training Course

Heat/Cool/Heat
1.5

1.0

Cool

Heat Flow (W/g)

0.5

Second Heat

0.0

First Heat

-0.5

-1.0

-1.5

20

60

100

140

180

220

260

Temperature (C)

DSC Training Course

106

Selecting Experimental Conditions

Thermoplastic Polymers (con't)

Interpreting Heat-Cool-Heat Results:

One of the primary benefits of doing Heat-Cool-Heat is
for the comparison of two or more samples which can
differ in material, thermal history or both

If the materials are different then there will be differences in

the Cool and Second Heat results
If the materials are the same and they have had the same
thermal history then all three (H-C-H) segments will be similar
If the materials are the same but they have had different
thermal histories then the Cool and Second Heat segments are
similar but the First Heats are different

DSC Training Course

Selecting Experimental Conditions

During first heat the maximum temperature must be

higher than the melting peak end; eventually an
isothermal period must be introduced

Too high temperature/time:

Too low temperature/time:

decomposition could occur

possibly subsequent memory effect because of the fact that crystalline
order is not completely destroyed

For non-crystallizable (amorphous) thermoplastics the

maximum temperature should be slightly above Tg
(removal of relaxation effects, avoid decomposition)

DSC Training Course

107

Thermosetting Polymers
A+B

Thermosetting polymers react (cross-link) irreversibly. A+B will

give out heat (exothermic) when they cross-link (cure). After
cooling and reheating C will have only a glass transition Tg.

GLUE

DSC Training Course

DSC of Thermosetting Polymers

Tg
Curing
Residual Cure

General Recommendations

10-15 mg in crimped pan if solid; hermetic pan if liquid

H-C-H @ 10C/min

DSC Training Course

108

Selecting Experimental Conditions

Thermosetting Polymers

Anneal the sample(if needed), then Heat-Cool-Heat at
10C/min.

Anneal approximately 25C above Tg onset for 1 minute to

eliminate enthalpic relaxation from Tg (if needed)
First Heat is used to measure Tg and residual cure
(unreacted resin). Stop at a temperature below the onset of
decomposition
Cooling segment gives the sample a known thermal history
Second Heat is used to measure the Tg of the fully cured
sample.

The greater the temperature difference between the Tg of the First and
Second Heats the lower the degree of cure of the sample as received

DSC Training Course

Comparison of First and Second Heating Runs

-0.04

Heat Flow (W/g)

-0.08

First

155.93C

Tg
Residual Cure

-0.12
-0.16

Second

Tg

102.64C
20.38J/g

-0.20
-0.24
0

50

100
150
200
Temperature (C)

250

300

DSC Training Course

109

Characterization of Epoxy Prepreg

2nd heat shows

increased Tg, due to
additional curing during
1st heat

Note: Small exotherm due to residual cure

DSC Training Course

Determination of % Cure
2.0

DSC Conditions:
Heating Rate = 10C/min.
Temperature Range = -50C to 250C
N2 Purge = 50mL/min.

1.5

Heat Flow (W/g)

145.4J/g
54.55 % cured
1.0

Under-cured Sample

-12.61C(H)

0.5

79.33J/g
75.21 % cured

-5.27C(H)
0.0

Optimally-cured Sample

NOTE: Curves rescaled and shifted for readability

-0.5
-50
Exo Up

50

100

Temperature (C)

150

200

250
Universal V2.4F TA Instruments

DSC Training Course

110

Pharmaceuticals

Tg
Melting

Purity

Polymorphs
General Recommendations

Use TGA to determine pan type

Use 1-5 mg samples (use 1mg for purity)
Initial H-C-H @ 10C/min (1C/min for purity)
If polymorphs present heat faster to inhibit polymorphic
transformations

DSC Training Course

Tg of Sucrose Varies with Moisture Content

Std DSC @ 20C/min
Vented Pans

DSC Training Course

111

Structure Changes With Time

Sucrose
13.98mg
Annealed @ 55C

10 min @ 55C

100 min

1000 min

DSC Training Course

Melting is Not Heating Rate Dependent

Phenacetin

Onset of melting shifts by 0.3C

over heating rate range of 120C/min for sample that has a
true melt

Hermetic Pan
Approx 1.5mg

DSC Training Course

112

Ciprofloxacin Hydrochloride Decomposes

Decomposition is kinetic (heating rate dependent)
Onset differs
by almost 30C

DSC Training Course

TGA of Ciprofloxacin Hydrochloride

100

1.0

Decomposition
0.5
60

Deriv. Weight (%/C)

Weight (%)

80

40

0.0

20
0

50

100

150

200

250

300

350

400

Temperature (C)

DSC Training Course

113

Sulfanilimide
Comparison of 1 & 10C/min Heating Rates on
Melting of three Polymorphs for Sulfanilimide

DSC Training Course

Specific Heat Capacity

What is it?

How is it observed and measured?

Methods for calculating specific heat capacity

What affects the specific heat capacity of a polymer?

DSC Training Course

114

What is Heat Capacity?

Heat capacity is the amount of heat required to raise or

lower the temperature of a material.
Specific heat capacity refers to a specific mass and
temperature change for the material (J/gC)

DSC Training Course

Why is Heat Capacity Important?

Thermodynamic property of material (vs. heat flow)

Measure of molecular mobility

Provides useful information about physical properties of

the material as a function of temperature

DSC Training Course

115

Heat Flow Due to Heat Capacity

10.04 mg PMMA

DSC Training Course

Measuring Heat Capacity

In a DSC experiment, heat capacity is measured as the

absolute value of the heat flow, divided by the heating
rate, and multiplied by a calibration constant.
dH/dt = Cp (dT/dt)
or

Cp = [(dH/dt)/(dT/dt)] x K
K = calibration constant

DSC Training Course

116

Conventional DSC Cp Measurement

Cp = K x

HFS HFMT
Heat Rate x wt

HFMT

HF

Where:
K
= Calibration constant
HFS

= Differential heat flow

with sample


endo

Temp.

HFMT = Differential heat flow

with empty pans
wt

HFS

= weight of sample

DSC Training Course

Alternative DSC Cp Measurement

Cp = K x

HFHR2 HFHR1
(HR2 HR1) wt

Where:
K
= Calibration constant
HFHR1 = Differential heat flow of
sample at HR1
HFHR2 = Differential heat flow of
sample at HR2
HR2 = Heating rate 2
HR1 = Heating rate 1
wt
= weight of sample

0
HFHR1
HF


HFHR2

endo
Temp.

DSC Training Course

117

Direct CP Measurement on Q2000/1000

Unlike any other DSC, the heat flow signal of the
Q2000/1000 is an absolute signal:

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 1-2% with just
single run measurements

DSC Training Course

Q1000 Direct Heat Capacity

1.5

97.00C
0.9111J/g/C

Heat Capacity (J/g/C)

1.0

97.00C
0.8758J/g/C
0.5

Average Value of 8 Runs at 20C/min in

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

0.0

-0.5

50

100
Temperature (C)

150

200
Universal V3.1B TA Instruments

DSC Training Course

118

What Affects the Specific Heat Capacity?

Amorphous Content
Aging
Side Chains
Polymer Backbone
Copolymer Composition
Anything that effects the mobility of the molecules,
affects the Heat Capacity

DSC Training Course

Effect of Amorphous Content on Cp

Amorphous Cp is greater than Crystalline Cp

Amorphous Content increases Specific Heat Capacity

Crystalline polymers contain more order and thus

fewer degrees of molecular motion. Less
molecular motion results in lower specific heat
capacity.

DSC Training Course

119

Heat Capacity Summary

Anything that effects the mobility of the molecules,

affects the Heat Capacity
The Q2000/1000 provides direct Cp measurement with
one run(pan weights required)

DSC Training Course

Glass Transitions (Tg)

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)

DSC Training Course

120

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

DSC Training Course

Heat Flow & Heat Capacity at the Tg

-0.3

Polystyrene
2.0

-0.4

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

[ ] Heat Flow (mW)

Heat Capacity (J/g/C)

-0.5

-0.8

-0.9

0.5

-1.0
70

Exo Up

90

110

Temperature (C)

Universal V3.8A TA Instruments

DSC Training Course

121

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)

DSC Training Course

Glass Transition Analysis

Polystyrene
9.67mg
10C/min

DSC Training Course

122

Glass Transition Analysis

Polystyrene
9.67mg
10C/min

DSC Training Course

Step Change in Cp at the Glass Transition

PET
9.43mg

% Amorphous = 0.145/0.353= 41%

DSC Training Course

123

A Glass Transition is Reversible

DSC Training Course

What Affects the Glass Transition?

Heating Rate
Heating & Cooling
Aging
Molecular Weight
Plasticizer
Filler

Crystalline Content
Copolymers
Side Chains
Polymer Backbone
Hydrogen Bonding

Anything that effects the

mobility of the molecules,
affects the Heat Capacity and,
in turn, the Glass Transition
DSC Training Course

124

Suggestions for Finding Weak Tgs

Know your empty-pan baseline

Get as much material in the amorphous state

Cool rapidly to reduce or eliminate crystallization

Use MDSC
Or use Quasi-Isothermal MDSC

DSC Training Course

Effect of Heating Rate on the Tg

10.04mg PMMA

DSC Training Course

125

Effect of Heating Rate on the Tg

Heating Rate
(C/min)

Heat Flow @
80C

Tg
Onset (C)

Tg
Midpoint (C)

Width of
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

DSC Training Course

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

DSC Training Course

126

Melting

In a DSC, a melt peak shows up as an endotherm during

the conversion of Crystalline structure to Amorphous
structure
If a material is 100% Amorphous, we will not see a
melting peak by DSC
We integrate this endothermic peak, on a time basis to
determine the Heat of Fusion

DSC Training Course

Melting of Indium
0

Heat Flow (mW)

-5

Extrapolated
Onset
Temperature

156.60C
28.50J/g

Indium
5.7mg
10C/min

Heat of
Fusion

-10

For pure, low molecular

weight materials
(mw<500 g/mol) use
Extrapolated Onset as
Melting Temperature

-15

-20

Peak Temperature
157.01C
-25
150
Exo Up

155

160

Temperature (C)

165
Universal V4.0B TA Instruments

DSC Training Course

127

Melting of PET
-1

For polymers, use Peak as Melting Temperature

-2

Extrapolated
Onset
Temperature

Heat Flow (mW)

-3

236.15C
52.19J/g

-4

Heat of
Fusion

-5

PET
6.79mg
10C/min

-6

Peak Temperature
-7
200

210

220

230

Exo Up

240

249.70C
250

260

270
Universal V4.0B TA Instruments

Temperature (C)

DSC Training Course

Comparison of Melting
0

Heat Flow (mW)

-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

160

Exo Up

180

200

220

Temperature (C)

240

260

280
Universal V4.0B TA Instruments

DSC Training Course

128

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

DSC Training Course

Baseline Due to Cp

DSC Training Course

129

Baseline Type

DSC Training Course

DSC of Polymer Blend

Where is the
Cp baseline?

DSC Training Course

130

DSC of Polymer Blend

Is it here?

Where is the
Cp baseline?

DSC Training Course

DSC of Polymer Blend

Is it here?

Where is the
Cp baseline?

DSC Training Course

131

MDSC Aids Interpretation

Xenoy 13.44 mg
MDSC Heat-Only

DSC Training Course

Is this Melting?

Phenacetin
Hermetic Pan

Onset of melting shifts by 0.3C

over heating rate range of 120C/min for sample that has a
true melt

Approx 1.5mg

DSC Training Course

132

Is this Melting?
Onset differs by
almost 30C

DSC Training Course

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

DSC Training Course

133

Effect of Heating Rate on Polymorph

DSC at 1C/min

DSC at 1C/min

DSC at 10C/min

DSC at 50C/min

DSC Training Course

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

100% Pure

96.0% Pure
95.0% Pure

NBS 1514
Thermal Analysis
Purity Set
Approx. 1mg
Crimped Al Pans
2C/min

DSC Training Course

134

Van't Hoff Purity Calculation

-0.8

135.0
125.20C

137.75C



-1.2



Heat Flow (W/g)

 
 
 







-1.4



-1.8

-2.0

Purity: 99.53mol %
Melting Point: 134.92C (determ ined)
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

134.0

 






-1.6

134.5












 



Temperature (C)

-1.0

133.5


Total Area / Partial Area

-2.2
122

-2

10

124

126

128

130

132

134

136

Exo Up

133.0
138

Temperature (C)

DSC Training Course

Calculation of % Crystallinity

Sample must be pure material, not copolymer or filled

Must know enthalpy of melting for 100% crystalline
material (Hlit)
You can use a standard Hlit for relative crystallinity

For standard samples:

% crystallinity = 100* Hm / Hlit
For samples with cold crystallization:
% crystallinity = 100* (
Hm - Hc)/ Hlit

DSC Training Course

135

ATHAS Databank

The ATHAS Databank is

a source for the Hf for
common polymers

DSC Training Course

ATHAS Summary Page for PET

Hf in kJ/mol

DSC Training Course

136

PET Data from ATHAS

Calculate g/mole from

molecular structure which
equals 192 g/mole for PET

DSC Training Course

ATHAS Summary Page for PET

Hf in kJ/mol

26.9kJ / mol
1000 = 140 J / g
192 g / mol

DSC Training Course

137

PET Initial Crystallinity

1.0

134.62C

0.5

Heat Flow (W/g)

Initial Crystallinity = 74.71 53.39

0.0

75.43C
242.91C
74.71J/g

78.99C(I)
-0.5

80.62C

127.72C
53.39J/g

-1.0

74.71 53.39 = 21.32

-1.5

50

100

256.24C

150

200

250

300

Temperature (C)

DSC Training Course

PET
1.0

134.62C

100

Heat Flow (W/g)

0.5

0.0

(74.71 53.39) = 15%

140

75.43C
242.91C
74.71J/g

78.99C(I)
-0.5

-1.0

80.62C

127.72C
53.39J/g

% crystallinity = 100* (
Hm - Hc)/ Hlit
256.24C

-1.5

50

100

150

200

250

300

Temperature (C)

DSC Training Course

138

PET % Crystallinity

21J/g Initial Crystallinity or 15% Crystalline

Does that sound right?

DSC Training Course

PET % Crystallinity

21J/g Initial Crystallinity or 15% Crystalline

Does that sound right?

The sample is quenched cooled PET

We know that quenched cooled PET is 100% amorphous
Why does DSC give us the wrong answer?

DSC Training Course

139

Change in Crystallinity While Heating

Heat Flow (W/g)

0.5

60

0.0

40

-0.5

20

Integral (J/g)

Quenched PET
9.56mg
10C/min

1.0

134.63C

105.00C

275.00C

127.68C
0.6877J/g
-1.0

230.06C
71.96J/g

230.06C

-1.5
-50

Exo Up

50

100

150

Temperature (C)

200

250

300

350

Universal V4.0B TA Instrum ents

DSC Training Course

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 enduse properties as well as processing conditions
Isothermal crystallization is the most sensitive way to
identify differences in crystallization rates

DSC Training Course

140

Crystallization

Crystallization is a two step process:

Nucleation
Growth

The onset temperature is the nucleation (Tn)

The peak maximum is the crystallization
temperature (Tc)

DSC Training Course

Crystallization

A temperature shift is seen in the cooling data on the

next slide. In this example, the samples were cooled
from 285C to room temperature at 2 to 16C/min. The
higher rates of temperature change broaden the
crystallization process and shift it further in temperature
from the starting point.

DSC Training Course

141

Effect of Cooling Rate on Crystallization

Sample: PET
Weight: 10.66mg

DSC Training Course

Effect of Nucleating Agents

2.0

crystallization

POLYPROPYLENE
WITHOUT
NUCLEATING AGENTS

POLYPROPYLENE
WITH NUCLEATING
AGENTS

Heat Flow (W/g)

1.5

0.0

Heat Flow (W/g)

1.0
-0.5

-1.0

melting
0.5
-1.5

60

80

Exo Up

0.0

40

50

Exo Up

100

120

140

160

180

200

Temperature (C)

60

70

80

90

100

110

120

130

140

150

160

Temperature (C)

DSC Training Course

142

What is Isothermal Crystallization?

A Time-To-Event Experiment
Annealing Temperature

Temperature

Melt Temperature
Isothermal Crystallization
Temperature
Zero Time
Time

DSC Training Course

Isothermal Crystallization
5
117.4 oC

Polypropylene

Heat Flow (mW)

117.8 oC

118.3 oC

118.8 oC
119.3 oC
119.8 oC

120.3 oC

-1

Time (min)

DSC Training Course

143

Supercooling of Water
250
-4.36C
+

Heat Flow (mW)

200
150
100
50
+

-15.55C

-50
-30

-25

-20

-15

-10

-5

10

Temperature (C)

DSC Training Course

144