Differential Scanning Calorimetry

(DSC)

Q-series
Discovery
DSC2500
DSC250
DSC25

TAINSTRUMENTS.COM
 Agenda for the course

Understanding heat flow

measurements on a DSC

Calibrations and Verification

Experimental design and

method development

Applications

2 TAINSTRUMENTS.COM
 TA Instruments DSC Models

DSC 25
DSC 250
DSC 2500

Q2000
3 AutoQ20 Discovery DSC TAINSTRUMENTS.COM
 What is a Differential Scanning Calorimetry

• A DSC measures the difference in Heat Flow Rate

between a sample and inert reference as a function of
time and temperature

4 TAINSTRUMENTS.COM
 Simple Heat Flux DSC Cell Schematic

Sample

Reference Sensor Sample Sensor

An empty pan on the Heat absorbed by the

reference sensor should sample gives an
react similarly to the pan endothermic response
on the sample sensor, thus
canceling out any pan Heat released by the
contribution sample gives an
exothermic response

5 TAINSTRUMENTS.COM
 Endothermic Heat Flow – Heat Absorbed by
Sample
4
Endothermic Events
• Glass transition
2
• Melting
0
• Evaporation/
volatilization
Heat Flow (Normalized) (W/g)

-2 • Enthalpic recovery
• Polymorphic
-4
transitions
• Some
-6
decompositions
-8

-10
25 50 75 100 125 150 175
Exo Up Temperature (°C)

6 TAINSTRUMENTS.COM
 Exothermic Heat Flow – Heat Released by
Sample
4

Exothermic Events
2
• Crystallization
• Cure reactions
0
• Polymorphic transitions
• Oxidation
Heat Flow (Normalized) (W/g)

-2
• Decomposition

-4

-6

-8

-10
25 50 75 100 125 150 175
Exo Up Temperature (°C)

7 TAINSTRUMENTS.COM
 DSC Heat Flow

dH Cp  Sample Heat Capacity

 DSC heat flow signal
dt  Sample Specific Heat x Sample Weight
mJ
(mW or )
s

dH dT
 Cp  f (T, t)
dt dt
dT f (T, t)  Heat flow that is function of time
 Heating Rate (C/min)
dt at an absolute temperature (kinetic)

TAINSTRUMENTS.COM
DSC Heat Flow

dH dT
 Cp  f (T, t)
dt dt
Heat
Kinetic
Capacity
Crystallization
Some melting
Glass
Transition Cure reactions
Some Melting Volatilization
Decomposition
Denaturation

TAINSTRUMENTS.COM
 DSC heat flow modes – T1 vs T4 vs T4P mode

10 TAINSTRUMENTS.COM
 Measurement of Temperature
• What temperature is being measured and displayed by the DSC?
 Sample Sensor Temperature
 Used by most DSCs
 Measured at the sample platform with a thermocouple,
thermopile or PRT
• The actual temperature of the sample is never measured by DSC
 There is no thermocouple in direct contact with the sample

11 TAINSTRUMENTS.COM
 Conventional DSC Measurements, T1 Heat Flow
Heat Balance Equations
Heat Flow
Measurement Model
T fs  Ts T fr  Tr
qs  qr 
qs qr Rs Rr
Conventional DSC Heat
Ts Tr Flow Rate Measurement

Rs Rr q  q s  qr
Tr  Ts  T
q 
R R
Tfs Tfr

This model assumes that the sample and reference calorimeter thermal resistances are identical and that
the furnace temperature is uniform throughout the cell.

12 TAINSTRUMENTS.COM
 Conventional DSC - Assumptions

• The heat flow rate of an empty, perfectly symmetrical twin

calorimeter should be zero
 The heat flow is almost never zero because the DSC is
rarely perfectly symmetrical as assumed due to the
inevitable result of manufacturing tolerances and is
unavoidable
 To achieve a 1% thermal resistance imbalance
between the sample and reference sensors would
require a manufacturing tolerance of 0.00005”
(0.00127mm)
• The thermal resistances between the sample sensor and the
furnace is the same as the resistance between the reference
sensor and the furnace
• The pan and sensor heat capacities are ignored
• The measured temperature equals sample temperature
• No heat exchange with the surroundings
13 TAINSTRUMENTS.COM
 Consequences of the Assumptions

• The heat flow baseline is usually curved and has large slope
and offset. Loss of sensitivity as a result of curvature in the
baseline.
• The heating rate of the sample and reference calorimeters are
not identical, resulting in reduced resolution.

Typical baseline of a DSC Q20

14 TAINSTRUMENTS.COM
 Expanded Principles of DSC Operation
Accounting for Imbalances

Tfs Rs Rr Tfr
Ts Tr

Cs Cr
Not being
measured with
Conventional
DSC

Q = Ts - Tr + A + B + C
R
Thermal Thermal Heating
Resistance Capacitance Rate
Imbalance Imbalance Imbalance

15 TAINSTRUMENTS.COM
 What is Tzero Technology? (T4/T4P Heat Flow)

Tf

Rs Rr
Ts To Tr
Cs Cr

16 TAINSTRUMENTS.COM
 Tzero™ Heat Flow Measurement

Heat Flow Differential Temperatures

Sensor Model
T  Ts  Tr T0  T0  Ts
qs qr
Cs Cr
Ts Tr Heat Flow Rate Equations

T0 dT
Rs Rr qs   Cs
Rs dt

T0  T dT
T0 qr   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.

17 TAINSTRUMENTS.COM
 Tzero Heat Flow Equation
Heat Flow Besides the three temperatures
Sensor Model (Ts, Tr, T0);
qs qr What other values do we need
C s C r to calculate Heat Flow?
Ts Tr

R s R r

How do we calculate these?

T0

T  1 1  dTs dT
q  T0     Cr  Cs   Cr
Rr  Rs Rr  d d

18 TAINSTRUMENTS.COM
 Measuring the Sensor C’s and R’s

• The Tzero measurements are used to determine the C’s

and R’s using two experiments
 A temperature ramp of an empty cell
 A temperature ramp with two sapphire disks placed directly on
the DSC sensors

• On determination of the capacitance and resistance of the

reference and sample side of the cell, these values are
inputted into the expanded heat flow equation
corresponding to T4 heat flow

19 TAINSTRUMENTS.COM
 Tzero Heat Flow Equation

Thermal Resistance Heating Rate

Imbalance Difference

T  1 1  dTs d T
qT 4   T0     Cr  C s   Cr
Rr  Rs Rr  d d

Principal DSC Heat Capacity

Heat Flow Imbalance

20 TAINSTRUMENTS.COM
 Benefit of the Tzero heat flow measurements

• 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.

21 TAINSTRUMENTS.COM
 Empty cell baseline using the TzeroTM heat flow
equation

Discovery DSC, DSC 250, DSC 2500

100

50

DSC Q2000
Heat Flow (µW)

4.94°C
5.40µW

0
-29.38°C
31.23µW

-50

-100
22 -50 0 50 100 150 200 250 300 350
TAINSTRUMENTS.COM
Exo Up Temperature (°C)
 Tzero Benefit: Improved Peak Resolution

T  1 1  dTs d T
qT 4   T0     Cr  C s   Cr
Rr  Rs Rr  d d
1

-1

-2
Heat Flow (W/g)

-3

-4

-5

-6
Heat Flow T1
-7 Heat Flow T4

-8
150 152 154 156 158 160 162 164
Temperature (°C)

23 TAINSTRUMENTS.COM
 Advanced Tzero Technology (T4P)

• 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;
sample and reference pans rarely have the same mass.
• Advanced Tzero includes the capacitance and resistance
of the pans so that the heating rate differences between
the sample and reference calorimeters and pans can be
corrected for.
• As a result peaks are taller and sharper; both resolution
and sensitivity are dramatically improved.

24 TAINSTRUMENTS.COM
 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 m ps c pan m pr c pan Cpan
model includes
T ps T pr Rp
the pans
Rs

qs Rp Rp qr
T4P

T4 Ts Tr
Cs Cr
Tzero models the Rs Rr
Calorimeters

T0
25 TAINSTRUMENTS.COM
 Indium with T1, T4 and T4P Heat Flow Signals
Improvements to Sensitivity and Resolution

Theoretical
Melting of
Indium
T4P heat flow

T4 Heat flow

T1 heat flow

26 TAINSTRUMENTS.COM
Modulated DSC® Theory
(MDSC®)

TAINSTRUMENTS.COM
What is MDSC?

• MDSC separates the Total heat flow of DSC into two parts
based on the response of the system to a changing heating
rate. The changing heating rate is effected by ‘superimposing’ a
sinusoidal heating rate on a linear heating rate.
• In general, only heat capacity and melting respond to the
changing heating rate resulting in an increase in signal. Kinetic
events tend to occur at different temperatures as a function of
heating rate. For example, increasing the heating rate can shift
decomposition to a higher temperature.
• The Reversing and Nonreversing signals of MDSC are not
necessarily a measure of reversible and nonreversible
properties.

28
TAINSTRUMENTS.COM
MDSC® Theory: Heat Flow Signals

dQ dT
 Cp  f (T, t)
dt dt
Total Heat Reversing Heat Non-Reversing Heat
Flow Flow Flow
•Heat Capacity
•All Transitions •Glass Transition •Enthalpic Recovery
•Melting •Evaporation
•Crystallization
•Thermoset Cure
•Denaturation
•Decomposition
•Some Melting
•Chemical Reactions
29
TAINSTRUMENTS.COM
Isothermal @ 25°C

Isothermal @ 25°C

Exo Up

30
TAINSTRUMENTS.COM
MDSC - Quasi-Isothermal @ 25°C

Quasi-Isothermal @ 25°C
Modulate ±1°C every 60 sec

Exo Up

31
TAINSTRUMENTS.COM
 MDSC – 1°C amplitude, every 60 sec, @
2°C/min

Modulate ±1°C every 60 sec

Ramp @ 2°C/min

Exo Up

32
TAINSTRUMENTS.COM
MDSC® Theory: Calculation of MDSC® Signals

• All MDSC signals are calculated from three measured

signals.
 Time
 Modulated Temperature and by implication Modulated
Heating Rate
 Modulated Heat Flow
• During the setup of the MDSC experiment, the user enters
the following parameters:
 Average (or underlying) heating rate (°C/min)
 Temperature modulation period (seconds)
 Temperature modulation amplitude (°C)

33
TAINSTRUMENTS.COM
MDSC® Raw Data Signals

Polylactic Acid
Heating Rate: 1 °C / min
Period: 60s
Amplitude: +/- 0.159 °C

34
TAINSTRUMENTS.COM
MDSC Theory: Calculation of MDSC® Signals – Simple
Deconvolution

• Raw data is averaged over a period of 1 oscillation and

the average is subtracted from the raw data.
• Modulation is analyzed using a Fourier Transform which
yields the amplitude of the heat flow response at the
modulation frequency.
• This results in the following:
 <dQ/dt> = average heat flow; Q = heat
 AHF= Amplitude of heat flow modulation
 AHR = Amplitude of modulated heating rate

35
TAINSTRUMENTS.COM
MDSC® Raw Data Signals: Modulated Heat Flow and Modulated
Heating Rate with Calculated Total (or Average) Heat Flow and
Average Heating Rate

Polylactic Acid
Heating Rate: 1 °C / min
Total Heat Flow Period: 60s
Amplitude: +/- 0.159 °C

Average Heating Rate

36
TAINSTRUMENTS.COM
 MDSC Theory: Heat Flow Signals

dQ / dt  Average Heat Flow

CpRe v   Reversing Heat Flow
dQ / dt  CpRe v   Non - Reversing Heat Flow

37
TAINSTRUMENTS.COM
MDSC® Theory: Calculation of MDSC® Reversing Heat
Flow and Reversing Cp

Reversing Cp

Modulated Reversing
Heat Flow Heat Flow

38
TAINSTRUMENTS.COM
MDSC® Theory: Calculated MDSC® Heat Flow Signals
Summary

Non-Reversing Heat Flow

Modulated Heat Flow

Reversing Total Heat

Heat Flow Flow

39
TAINSTRUMENTS.COM
Calibration &
Verification

TAINSTRUMENTS.COM
 The DSC Heat Flow Rate Equation

• A DSC measures the difference in Heat Flow Rate

between a sample and inert reference as a function of
time and temperature.

dH dT
 Cp  f (T, t)
dt dt

• A DSC is calibrated for the heat flow enthalpy and

temperature. Baseline calibrations are performed per
manufacturers recommendations.

41 TAINSTRUMENTS.COM
 International Standards pertaining to DSC
calibrations

• American Society of Testing and Materials, ASTM

 www.astm.org

• International Organization of Standards, ISO

 www.iso.org

• Deutsches Institut für Normung/German Institute for

Standardization, DIN
 www.din.de/en

42 TAINSTRUMENTS.COM
 ASTM Standards for DSC Heat Flow,
Temperature and Enthalpy Calibration

• ASTM E 967 - Standard Test Method for Temperature

Calibration of Differential Scanning Calorimeters and
Differential Thermal Analyzers

• ASTM E 968 - Standard Practice for Heat Flow

Calibration of Differential Scanning Calorimeters

43 TAINSTRUMENTS.COM
 Calibration of specific instrument models

Tzero Baseline
calibration Cell constant
Measurement of
Rs and Cs Measurement of and temperature
slope and offset

DSC2500 All DSCs

DSC 25
DSC250
Q20
Q2000
Q200

44 TAINSTRUMENTS.COM
Calibration Setup in Trios

45
TAINSTRUMENTS.COM
 General calibration and verification guidelines

• Calibration
 Use Calibration Mode
 Calibrate upon installation
 Re-calibrate if does not pass verification or if instrument setup is
modified (see previous slide)

• Verification
 Determine how often to verify data
 Run a reference material as a sample (in standard mode)
 Compare results vs literature values
 If results are within your tolerance – system checks out and
does not need re-calibration
 If results are out of tolerance, then re-calibrate

46 TAINSTRUMENTS.COM
 Requirements Prior to Calibration

• DSC cell must be free of contaminants

• An inert purge gas, such as nitrogen, where the flow rate

is controlled to 10-50 ml/min +/- 5 ml/min

• A balance to weigh specimens and containers to at least

+/- 0.1 mg. The balance should have a capacity greater
than 20 mg.

• High purity reference materials (>99.99%) for calibration

47 TAINSTRUMENTS.COM
 ASTM E 967 - Standard Test Method for
Temperature Calibration of DSC’s

• For transition temperature, calibration is required with known reference

standards.
 Pure metals (indium, lead, etc.) typically used
 Extrapolated onset is used as melting temperature
 Sample is fully melted at the peak

• This test method consists of heating the calibration materials at a

controlled rate in a controlled atmosphere through a region of known
thermal transition. The heat flow into the calibration material or the
difference of temperature between the calibration material and a
reference is monitored and continuously recorded. A transition is marked
by the absorption of energy by the specimen resulting in a corresponding
endothermic peak in the heating curve.

48 TAINSTRUMENTS.COM
 Instrument setup factors affecting calibration

• Purge Gas
 Re-calibrate baseline/Tzero, temperature and cell constant
 Thermal conductivity of helium ≠ Thermal conductivity of
nitrogen/air/oxygen ≠ Thermal conductivity of argon

• Cooling Accessories
 Re-calibrate baseline/Tzero, temperature and cell constant
 The position of the cooling head around the cell will affect the
calibration of the instrument. Uninstallation and reinstallation of a
cooling accessory or changing the cooling accessory warrants a
complete re-calibration

• Pan selection
 Re-calibrate temperature and cell constant
 It will not impact the baseline/Tzero calibration

49 TAINSTRUMENTS.COM
 ASTM E 967 - Temperature Calibration of DSC’s

Indium (156.6°C)
Can be re-used, can pre-melt

Tin (231.9°C)
Has multiple crystalline forms,
use once – no pre-melt

Zinc (419.5°C)
Can easily oxidize and alloy with
container, use once – no pre-melt

50 TAINSTRUMENTS.COM
 Temperature and Cell Constant Calibration

• Prepare a 3-5 mg sample of indium and “pre-melt” prior to first

use

Premelt

• Verify at least once a month

• Typical values for cell constant:

 0.9 to 1.2 (in N2)
 Helium will typically give higher values for the cell constant

51 TAINSTRUMENTS.COM
 Verifying Cell Constant & Temperature

• Run Indium as a sample (i.e. in standard mode not

calibration mode)
• Analyze melt and record melt onset & heat of fusion
• Compare to known values
 Melting of In 156.6°C
 Heat of Fusion 28.71J/g

52 TAINSTRUMENTS.COM
Calorimetric and Temperature Calibration
(Un-calibrated Data – No Correction Factors Applied)

53 TAINSTRUMENTS.COM
 Verifying Cell Constant & Temperature
5

1 5 6 .6 4 ° C
-2 8 .6 0 J /g
0

-5
Temp is within 0.04°C
Heat Flow (mW)

Heat of fusion is within 0.11J/g

-1 0

-1 5

-2 0

1 5 7 .0 6 °C

-2 5
140 145 150 155 160 165 170 175 180
T e m pera ture (°C )

54 TAINSTRUMENTS.COM
 Temperature Calibration of DSC’s

• Enthalpy (cell constant) • Temperature

 Benzoic acid (147.3 J/g)  Cyclopentane* -150.77°C
Tm = 123°C  Cyclopentane* -135.09°C
 Urea (241.8 J/g)  Cyclopentane* -93.43°C
Tm = 133°C  Cyclohexane # -83°C
 Indium (28.71 J/g)  Water # 0°C
Tm = 156.6°C
 Gallium # 29.76°C
 Anthracene (161.9 J/g)
Tm = 216°C  Phenyl Ether # 30°C
 p-Nitrotoluene E 51.45°C
* GEFTA recommended
Thermochim. Acta, 219 (1993) 333.
 Naphthalene E 80.25°C
 Indium # 156.60°C
# ITS 90 Fixed Point
 Tin # 231.95°C
E Zone refined organic compound  Lead* 327.46°C
(sublimes)
 Zinc # 419.53°C
55 TAINSTRUMENTS.COM
 A note on certified and 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

56 TAINSTRUMENTS.COM
 Verifying Baseline

• Run Empty cell (no pans), -90°C to 400°C (w/ RCS) at

20°C/min
 Experiment is run in the standard mode
 Plot mW vs. temperature on a 1mW scale
 Should look fairly flat on this scale
 Should be around zero heat flow
 Measure bow, drift and compare to instrument
specifications.
 Verify performance periodically

57 TAINSTRUMENTS.COM
 Verifying Baseline

• Importance of a flat baseline

 Detecting very weak transitions
 Accurate integration of enthalpy
Kinetics, partial area analysis, extent of reactions
Initial crystallinity

58 TAINSTRUMENTS.COM
 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 rif t
0 .1
Heat Flow (mW)

0 .0

-0 .1 - 0 .0 0 3 2 5 2 m W
-0 .0 4 5 6 2 m W

-0 .2

-0 .3

-0 .4

-0 .5
-1 0 0 0 100 200 300 400
T e m p e ra tu re (°C )

59 TAINSTRUMENTS.COM
 Verifying Baseline

0 .4

0 .2
Heat Flow (mW)

In itia l B a s e lin e a fte r c a lib ra tio n

0 .0

B a s e lin e c h e c k - s till g o o d
-0 .2

-0 .4

-1 0 0 0 100 200 300 400

T e m p e ra ture (°C )
60 TAINSTRUMENTS.COM
 Empty Cell Baseline at 20 deg/min – DSC2500

20

15

10

5
(µW)

0
Heat Flow

-5

-10

-15

-20
-100 -50 0 50 100 150 200 250 300 350 400
Temperature (°C)

TAINSTRUMENTS.COM
MDSC Calibration – Discovery Series

• Calibrate your DSC as normal

 Tzero™
 Cell Constant
 Temperature
• Cp Calibration is Optional
• If measuring absolute quantitative Cp then…
• Need to calibrate Reversing Heat Capacity or Direct
Heat Capacity (DSC2500 only)

62
TAINSTRUMENTS.COM
Cp Calibration in Trios

T4P
only

63
TAINSTRUMENTS.COM
MDSC Cp calibration using TRIOS

KCp is determined as a continuous function of temperature in the Discovery DSC.

64
TAINSTRUMENTS.COM
MDSC Cp verification using TRIOS

65
TAINSTRUMENTS.COM
Experimental Design:
Instrument Set Up

TAINSTRUMENTS.COM
 Instrument Hardware and Gas Selection
Considerations
Temperature Range Dependent On The Cooling System
•Finned Air Cooling System (FACS): Ambient to 725°C
•Quench Cooling Accessory (QCA): -180°C to 400°C
•Liquid Nitrogen Cooling System (LN2P): -180°C to 550°C
•RCS120: -120°C to 400°C
•RCS90: -90°C to 550°C
•RCS40: -40°C to 400°C

Purge Gas Selection

• Nitrogen
• inert, inexpensive and readily available
• flow rate of 50ml/min
• Helium
• a high thermal conductivity gas which improves response time and cooling capabilities
• the recommended purge gas when using the LN2 accessory at temperatures below -100°C
• flow rates of 10-25ml/min are typically used; cell constant affected by flow rate
• Air/Oxygen
• used when studying oxidative stability of materials

Sample Press and Pan Selection

•Aluminum: max. temperature of 600°C
•Gold
•Copper
•Graphite, Alumina
•Platinum
•Stainless Steel

67 TAINSTRUMENTS.COM
 Cooling Accessories

• Finned Air Cooling System (FACS): Ambient to 725°C

• Quench Cooling Accessory (QCA): -180°C to 550°C *
• Liquid Nitrogen Cooling System (LNCS): -180°C to 550°C
• RCS120: -120 °C to 400 °C
• RCS90: -90°C to 550°C
• RCS40: -40°C to 400°C

68 TAINSTRUMENTS.COM
 Performance of the cooling accessories

69 TAINSTRUMENTS.COM
 Selecting the cooler – Discovery DSC

This is used to select the cooler type

70 TAINSTRUMENTS.COM
 Selecting the purge gas – Discovery DSC

This is used to specify the type of gas

This isconnected
used to specify
to Gasthe
#1type
and of
Gasgas#2 inlets
connected to Gas #1 and Gas #2 inlets

71 TAINSTRUMENTS.COM
Setting the purge gas flow rate – Discovery DSC

This is used to select which gas is

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

72 TAINSTRUMENTS.COM
 Recommended Purge Gas Flow Rates

Module Purge Port

All TA DSC’s 50 ml/min (N2) or 25 ml/min (He)

• If purge gas is too slow - possible moisture accumulation &

early aging of the cell

• If purge gas is too fast – excessive noise

73 TAINSTRUMENTS.COM
 Experimental design:
Sample Preparation and Considerations

TAINSTRUMENTS.COM
 TGA for DSC Experimental Design

• Thermogravimetric Analysis (TGA)

measures weight loss or gain as a
function of temperature, time and
atmosphere.

• General applications of TGA include:

 thermal stability
 residual solvent, out gassing, moisture
sorption/desorption
 filler/fiber content
 weight loss on cure

• TGA measurements are extremely

useful in selecting experimental
conditions for DSC experiments and for
interpreting results.

75 TAINSTRUMENTS.COM
 Selecting Optimum Experimental Conditions

• If possible, run a TGA experiment before beginning DSC tests on

new materials
• Heat approximately 10mg sample in the TGA at 10°C/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 slower heat rates

76 TAINSTRUMENTS.COM
 Typical TGA data: TGA of Drug A Monohydrate
105 6

4.946%
(0.7505mg) Decomposition

100
4

Deriv. Weight (%/min)

95
Weight (%)

Water weight loss 2

90

0
85
Sample: Drug A Monohydrate
Size: 15.1740mg
Heating Rate: 10°C/min
80 -2
0 50 100 150 200 250 300
Temperature (°C) Universal V3.4C TA Instruments

77 TAINSTRUMENTS.COM
 Selecting Optimum Experimental Conditions

• Use TGA data to help select DSC experimental conditions

 Standard (non-hermetic) vs. Hermetic (sealed) pans
 Use hermetic pan if sample loses approximately 0.5%
weight or more.
 Use hermetic pan with pin hole lids if sample loses volatiles
such as water
 Maximum Temperature
 Excessive decomposition will contaminate the DSC cell
between runs
 When comparing samples, always use the same
experimental conditions

78 TAINSTRUMENTS.COM
 DSC Pan Selection

• High thermal conductivity – aluminum, gold, copper,

platinum
• Inert - alodined aluminum, ceramic, graphite
• Flatness of the pan for optimal thermal contact
• Standard, non-hermetic vs. hermetic sealing
• Capacity/sample volume
• Temperature range

79 TAINSTRUMENTS.COM
 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

80 TAINSTRUMENTS.COM
 TA Instruments Tzero Pans

Tzero 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

non-hermetic or hermetic use. P/N
Tzero Low-Mass Pan 901683.901 Tzero Pans (pkg. of 100)

• The Tzero Low-Mass Pan is designed

for the highest sensitivity when sample
mass is limited. P/N 901670.901 Tzero
Low-Mass Pans (pkg. of 100). Can only
be used with the non-hermetic Tzero lid.

81 TAINSTRUMENTS.COM
 Tzero Press (P/N 901600.901)

Tzero Press kit includes die sets for:

1. Tzero Pans / Tzero Lids and Tzero

Low-Mass Pans / Tzero Lids
(Black)
2. Tzero Pans / Tzero Hermetic Lids
(Blue)
3. Standard Aluminum Pans / Lids
(Green)
4. Standard Hermetic Pans / Lids
(White)

The kit also includes one box each of

Tzero Pans (100) and Tzero Lids
(100).

82 TAINSTRUMENTS.COM
 TA Instruments Tzero Pans

Tzero Lid
• Tzero Lid (P/N: 901671.901) -
Lightweight aluminum lids for use in
sample encapsulation with the Tzero
Pans and the Tzero Low-Mass Pans.
The seal is not hermetic.

Tzero Hermetic Lid

• Tzero Hermetic Lid (P/N: 901684.901
Tzero Hermetic Lids (pkg. of 100) and
P/N: 901685.901 Tzero Hermetic
Pinhole Lid (75 micron diameter pinhole)
(pkg. of 50). Used only with the Tzero
pan, not the low mass Tzero pan

83 TAINSTRUMENTS.COM
 Standard Series DSC Pans (Crimped lid)

• Part numbers for the pans and lid

- 900760.901 Classic Aluminum Pans (pkg. of 200) (higher sidewall
compared to the standard aluminum sample pans to accommodate
larger samples)
- 900786.901 Aluminum Sample Pans (pkg. of 200)
- 900779.901 Aluminum Lids (pkg. of 200)
• 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

84 TAINSTRUMENTS.COM
 Sample Shape

• Keep sample thin

• Cover as much as the bottom of pan as possible

85 TAINSTRUMENTS.COM
 Hermetic DSC Pans

135 °C 165 °C

Aluminum
Hermetic
Heat Flow (Normalized) (W/g)

Experimental conditions:
3 atm
20 mg of water
Tzero Aluminum pan with hermetic lid, 40 ul internal volume
Heating rate of 10C/min

Endothermic peak is a result of delamination of the hermetic seal and

rapid depressurization of the pan.

Sample:
1. Liquid
Exo Up 2. Solid with
volatile
content
High Volume Gold
Stainless
Steel Hermetic
40 atm 6 atm

86 TAINSTRUMENTS.COM
 Hermetic Pans (Sealed)
• Hermetic Pans are available in:
 Aluminum: <600°C; <3 atm (300 kPa gage)
 Alodined Aluminum: <200°C; <3 atm (300 kPa gage)
 Gold: <725°C; <6 atm (600 kPa gage)

• Specialized Sealed Pans

 High Volume: 100µL; <250°C; 600 psig
 P/N 900825.901

 High Pressure: 35µL; <300°C; 1450 psig

 P/N 900808.901

Note: 3 atm is approximately 44 psig

87 TAINSTRUMENTS.COM
 It Can Matter What Pan You Use

Monohydrate
Pharmaceutical
sample

88 TAINSTRUMENTS.COM
 What if Sample Spills out of the Pan?
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

89 TAINSTRUMENTS.COM
 Cleaning the cell

• Use solvent – slightly damp swab with an appropriate solvent

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

• If the cell is still dirty

 Clean w/ brush
 Be careful with the Tzero™ thermocouple
 Fibers in cell from cleaning brush need to be removed

90 TAINSTRUMENTS.COM
 Cleaning Cell: Bakeout procedure

• Bake out
 Should be used as a last resort if none of the previous steps are
effective
 Involves Air purge and/or an open lid
 Heat @ 20°C/min to appropriate temp (max of 550°C on Q series,
max. 400°C in Discovery)
 Do NOT hold Isothermal @ the upper temperature
 Cool back to room temp & brush cell again

• Irrespective of the cleaning method used, always verify the baseline

at the end of the cleaning procedure, and recalibrate the DSC if
required

• Check out the TA Tech tip video on cleaning the DSC cell:
https://www.youtube.com/watch?v=cclJXrbUICA

91 TAINSTRUMENTS.COM
 Sample preparation: Optimization of Sample
Mass

• Sample Preparation
 Weight of 5-10 mg for polymers; 10-15 mg for cross-linked
thermosets; 3-5 mg for metal or chemical melting
 Goal is to achieve a change of 0.1-10mW heat flow in
going through the transition

dH dT
 Cp  f (T, t)
dt dt

92 TAINSTRUMENTS.COM
 Heat Flow Change During a Transition

93 TAINSTRUMENTS.COM
Method development

TAINSTRUMENTS.COM
 Method Design: DSC • The Ramp segment heats or cools
Segment List the sample at a fixed rate until it
reaches the specified temperature,
producing a linear plot of temperature
versus time

• The Equilibrate segment heats or

cools the furnace to the defined
temperature, stabilizes the furnace at
that temperature, then continues to
the next segment.

• The Select Gas segment controls the

switching of gas between Gas 1 and
Gas 2 for an instrument with a gas
delivery module. This segment is
used to synchronize gas switching at
a specific time or temperature in an
experiment.

95 TAINSTRUMENTS.COM
 DSC General Method Recommendations

• Run a Heat-Cool-Heat @ 10-20 °C/min

• Use specific segments as needed, i.e. gas switch, abort,
etc.
• Ensure that the starting temperature of the experiment is
chosen to encompass the entire transition (see next slide)
• Modify heating rate based on what you’re looking for

96 TAINSTRUMENTS.COM
 Why have 2 minutes of baseline?

• Start Temperature
 Generally, the baseline should have two (2) minutes to completely
stabilize prior to the transition of interest. Therefore, at 10°C/min.,
start at least 20°C below the transition onset temperature
• End Temperature
 Allow a two (2) minute baseline after the transition of interest in order
97
to correctly select integration or analysis limits TAINSTRUMENTS.COM
 Heating/Cooling Methods

• Typical Heating Method

1) Equilibrate at -90°C
2) Ramp 10°C/min. to 300°C

• Typical Cooling Method

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

98 TAINSTRUMENTS.COM
 Method Development

A Heat Cool Ramp Method

1) Ramp 10°C/min to -90°C or Equilibrate to -90°C
2) Ramp 10°C/min to 200°C
3) Ramp 10°C/min to -90°C
4) Ramp 10°C/min to 200°C

99 TAINSTRUMENTS.COM
 Heat Cool Heat Cycles of High Density
Polyethylene (HDPE)
4

3
Heat Flow (Normalized) (W/g)

Cool Cycle
2

-1

Second Heat Cycle

-2

First Heat Cycle

-3

-4
-100 -50 0 50 100 150 200
Exo Up Temperature (°C)
100 TAINSTRUMENTS.COM
 Oxidative Stability (OIT) Method

An OIT Method

1) Isothermal for 5.00 minutes in Nitrogen

2) Ramp 20°C/min. to 200°C
3) Isothermal for 5.00 minutes
4) Select gas: 2 (air or oxygen)
5) Isothermal for 100.00 minutes (hold to a time where the
exotherm reaches a peak to get accurate OIT)

101 TAINSTRUMENTS.COM
 Oxidative Induction Time of Polyolefin Film

102 TAINSTRUMENTS.COM
 Modulated® DSC Method

An MDSC Method

1) Equilibrate at 25°C
2) Modulate ± 0.318°C every 60 seconds
3) Isothermal for 5.00 minutes
4) Data storage: On
5) Ramp 2°C/min. to -90°C
6) Ramp 2°C/min. to 25°C

103 TAINSTRUMENTS.COM
 MDSC of a Process Oil
Separation of a Tg from Crystallization

104 TAINSTRUMENTS.COM
Applications

TAINSTRUMENTS.COM
 Typical DSC Transitions

Oxidation
Or
Crystallization Decomposition
Heat Flow -> exothermic

Melting
Glass
Transition Cross-Linking
(Cure)

Composite graph

Temperature

106 TAINSTRUMENTS.COM
The Glass Transition Temperature (Tg)

TAINSTRUMENTS.COM
 The Glass Transition (Tg)

• The glass transition is a change in the free volume and molecular

mobility in the amorphous phase of a material that results in a step
change in heat capacity.

Below Tg Above Tg
Tg Transition
• Rigid, Glassy • Rubbery Flow
• Immobile, no long 2nd Order • Increased Mobility
range molecular Transition • Disordered Solid
movement
• Disordered Solid

108 TAINSTRUMENTS.COM
 Heat Flow & Heat Capacity at the Tg
-0.3

Polystyrene
2.0 -0.4

-0.5

[ ––––– · ] Heat Flow (mW)

Heat Capacity (J/g/°C)

1.5 Glass Transition is Detectable by DSC -0.6

Heat Capacity Because of a Step-Change in Heat Capacity

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

0.5 -1.0
70 90 110
Exo Up Temperature (°C) Universal V3.8A TA Instruments

109 TAINSTRUMENTS.COM
 What Affects the Glass Transition?

• Heating Rate • Crystalline Content

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

Anything that effects the

mobility of the molecules,
affects the Heat Capacity and,
in turn, the Glass Transition
110 TAINSTRUMENTS.COM
 DSC Tg Analysis – Half-Height
0.0

Selected Start
-0.1
Extrapolated Onset

ΔCp(or Heat Flow) Used

13.73°C to Calculate % Amorphous
21.27°C
Heat Flow (W/g)

-0.2

23.00°C(H)
0.5853J/(g·°C)
Midpoint at ½ Cp or
-0.3
Heat Flow Change
34.18°C
25.02°C

-0.4 Selected End

Extrapolated End

5 10 15 20 25 30 35 40 45
Exo Up Temperature (°C) Universal V4.7A TA Instruments

111 TAINSTRUMENTS.COM
 Step Change in Cp at the Glass Transition

PET
9.43mg

% Amorphous = 0.145/0.353= 41%

112 TAINSTRUMENTS.COM
 A Glass Transition is Reversible

113 TAINSTRUMENTS.COM
 10mg PMMA Sample at Different Heating Rates

114 TAINSTRUMENTS.COM
 Glass transition measurements using other
techniques

• The Tg can also be measured by other techniques apart

from the standard DSC
 Using a Modulated DSC (MDSC)
 Dynamic Mechanical Analysis (DMA)

• Sensitivity of the technique to detect a glass transition:-

 Standard DSC < MDSC < DMA

115 TAINSTRUMENTS.COM
 The measured value of Tg will depend on the
experimental technique as well as the setup…
• The molecular motion associated with the glass transition
is time dependent. Therefore,
 it takes place over a temperature range
 is dependent on the test frequency (in case Modulated
DSC®, DMA, etc.).

• When reporting Tg, it is necessary to state the test

method (DSC, MDSC, DMA, etc.), experimental
conditions (heating rate, sample size, etc.) and how Tg
was determined

116 TAINSTRUMENTS.COM
 MDSC: Effect of Frequency on Tg

117 TAINSTRUMENTS.COM
 DMA: Effect of Frequency on Tg

118 TAINSTRUMENTS.COM
 Aged Epoxy: The Tg On The First Heat Cycle

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.
119 TAINSTRUMENTS.COM
 Enthalpic Recovery

• By heating a sample above the glass transition

temperature and then cooling it back to room
temperature, the previous thermal history is erased.
 The second heat typically shows the true properties of the
material rather than the material properties with some
processing effects
• 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.

120 TAINSTRUMENTS.COM
 Enthalpic Relaxation and Recovery

• 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

121 TAINSTRUMENTS.COM
 Effect of Annealing on the Tg

122 TAINSTRUMENTS.COM
 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.

123 TAINSTRUMENTS.COM
 Glass Transition Summary

• The glass transition is due to the amorphosity of the

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

124 TAINSTRUMENTS.COM
Thermosets

TAINSTRUMENTS.COM
Thermosetting Polymers

A “thermoset” is a cross-linked polymer formed by an

irreversible exothermic chemical reaction
Thermosetting polymers react (cross-link) irreversibly. A+B
will give out heat (exothermic) when they cross-link (cure).

A+B C

TAINSTRUMENTS.COM
 Commonly used thermoset materials

• Commonly used thermosets

 Epoxies (a 2 part epoxy adhesive)
 Phenolics
 Urea-formaldehyde/Melamine formaldehyde
 Polyurethanes
 Bismaleimides
 Cyanate esters
 Acrylates

127 TAINSTRUMENTS.COM
 Typical properties of crosslinking reactions

• Crosslinking reactions are generally • Crosslinking reactions are generally

exothermic. As the chemical reaction accompanied by a sharp change in the
takes place, it is almost always material’s mechanical properties.
accompanied by a release of heat.
• Increase in modulus that may be
• The reactions can be easily monitored accompanied by shrinkage.
using a DSC.
 Heat of reaction • The reactions can thus be monitored
 Residual cure using a Thermo-mechanical Analyzer
 Glass transition (TMA)/Dynamic Mechanical Analyzer
 Heat capacity (DMA)/Rheometer.
 Viscosity
 Modulus
 Glass transition
 Dimension change (shrinkage)

These techniques give useful information about the impact of the polymerization
conditions on the end product’s thermo-mechanical properties.

TAINSTRUMENTS.COM
DSC: General considerations for selecting
optimum experimental Conditions

• Sample weight: 10–15 mg

• Pan types:
 Solids – Standard aluminum pan/lid
 Liquids – Hermetic aluminum pan/lid
• General protocol for studying thermosets:
 Determine decomposition temperature using TGA
 Heat-Cool-reheat at 10°C/min
 First Heat is used to measure Tg of starting material, heat of
reaction and presence of any reactive functional groups.
 Second Heat is used to measure the Tg of the fully cured
sample and any residual cure from the first heat.

TAINSTRUMENTS.COM
DSC: General considerations for selecting
optimum experimental Conditions

• Sample weight: 10–15 mg

• Pan types:
 Solids – Standard aluminum pan/lid
 Liquids – Hermetic aluminum pan/lid
• General protocol for studying thermosets:
 Determine decomposition temperature using TGA
 Heat-Cool-reheat at 10°C/min
 First Heat is used to measure Tg of starting material, heat of
reaction and presence of any reactive functional groups.
 Second Heat is used to measure the Tg of the fully cured
sample and any residual cure from the first heat.

TAINSTRUMENTS.COM
DSC: General considerations for selecting
optimum experimental Conditions

• Sample weight: 10–15 mg

• Pan types:
 Solids – Standard aluminum pan/lid
 Liquids – Hermetic aluminum pan/lid
• General protocol for studying thermosets:
 Determine decomposition temperature using TGA
 Heat-Cool-reheat at 10°C/min
 First Heat is used to measure Tg of starting material, heat of
reaction and presence of any reactive functional groups.
 Second Heat is used to measure the Tg of the fully cured
sample and any residual cure from the first heat.

TAINSTRUMENTS.COM
 Comparison of First and Second Heats

132 TAINSTRUMENTS.COM
 Epoxy Cured 48 Hours: Heat Cool Heat
4
1st Heat @ 10°C/min
Cool @ 10°C/min
2nd Heat @ 10°C/min

2
Heat Flow (mW)

-2

-4
5 Min Epoxy - 9.85mg
Cured 2 nights @ RT

-50 0 50 100 150 200

Exo Up Temperature (°C) Universal V4.3A TA Instruments

133 TAINSTRUMENTS.COM
 Percent Cure Calculation by DSC

• Need Heat of Reaction (Enthalpy) of unreacted material

curing
 Typically run uncured material in DSC
• Run cured or partially cured sample in DSC
% Cure = 1 - (H Residual Cure / H Full Cure) * 100
% Uncured = (H Residual Cure / H Full Cure) * 100

134 TAINSTRUMENTS.COM
 Calculation of % Cure: An Epoxy

% Cure = (410.6 - 82.7) / 410.6 S a m p le ra m p e d @ 1 0 °C /m in

% Cure = 79.86%
6 .5

7 9 .1 7 °C
4 1 0 .6 J /g
Heat Flow (mW)

1 .5

9 1 .4 2 °C
8 2 .6 9 J /g
7 9 .8 6 % c u re d
3 3 .6 5 ° C (H )
-3 .5
S a m p le c u re d fo r 1 7 h o u rs a t R T ;
th e n ra m p e d a t 1 0 °C /m in .
-1 0 0 -5 0 0 50 100 150 200 250
E xo U p Tem pera ture (°C ) U n iversa l V 4 .4 A T A In stru m en ts

135 TAINSTRUMENTS.COM
 Thank You

The World Leader in Thermal Analysis,

Rheology, and Microcalorimetry

TAINSTRUMENTS.COM