2. Dr.Anand, MME, NITK 2
2/7/2023
Differential Scanning Calorimetry
(DSC)
Principle
DSC measures the differences in heat flow into
a substance and a reference as a function of
sample temperature while both are subjected to
a controlled temperature program
DSC provides access to accurate
thermodynamic data as well as information
regarding reactivity and phase
transformations
3. -0.4
-0.3
-0.2
-0.1
0.0
0.1
Heat
Flow
(W/g)
0 25 50 75 100 125 150
Temperature (°C)
Exo Up
Endothermic Heat Flow
Heat flows into the sample as a result of either
Heat capacity (heating)
Glass Transition (Tg)
Melting
Evaporation
Other endothermic processes
Endothermic
4. -0.1
0.0
0.1
Heat
Flow
(W/g)
0 20 40 60 80 100 120 140 160
Temperature (°C)
Exo Up
Exothermic Heat Flow
Heat flows out of the sample as a result of either
Heat capacity (cooling)
Crystallization
Curing
Oxidation
Other exothermic processes
Exothermic
6. Dr.Anand, MME, NITK 6
2/7/2023
DSC is the most sophisticated and
advanced of the thermal methods.
There are two principal types:
power compensated DSC
heat-flux DSC
DSC - types
7. Dr.Anand, MME, NITK 7
2/7/2023
Power Compensated DSC-
principles
Temperature difference is maintained
zero, i.e., ΔT = 0, by supplying heat into
the sample or reference according to heat
emission or absorption
Electrical power is proportional to heat
change in the sample
i.e., P = I2.R
8. Dr.Anand, MME, NITK 8
2/7/2023
Power Compensated DSC-
principles
Rate of change of power input is plotted
against average S & R temperature
x-axis (abscissa) is temperature and the y-
axis (ordinate) is difference in power input
(which is proportional to the heat change
i.e., enthalpy)
11. Dr.Anand, MME, NITK 11
2/7/2023
Small, flat samples are contained in shallow
pans, with the aim of making a good
thermal contact between sample, pan and
heat flux plate.
Symmetrical heating of the cell, and
therefore S and R, is achieved by
constructing the furnace from a metal of
high thermal conductivity – for example,
silver
How does it work?
12. Dr.Anand, MME, NITK 12
2/7/2023
How does it work?
Sample and reference material are heated
by separate heaters in two independent
furnaces
The furnaces are imbedded in a large
temperature-controlled heat sink
Sample holders are above the furnaces
Pt resistance thermometers are imbedded
in the furnaces to monitor the
temperatures of sample and reference
continuously
13. Dr.Anand, MME, NITK 13
2/7/2023
How does it work?
There is provision for establishing gas
flow through the cell, to sweep away
volatiles, provide the required atmosphere,
and to assist in heat transfer.
Control of the furnace, signal acquisition,
and data storage and analysis are
handled by a computer.
14. Dr.Anand, MME, NITK 14
2/7/2023
How does it work?
Two control circuits are used to obtain
differential thermograms
One for average temperature control
One for ΔT control
S and R temp. signals are fed into a
differential amplifier via a comparator circuit
that determines which is greater
The amplifier output then adjusts the power
input to the two furnaces in such a way that
their temperatures are kept identical
15. Dr.Anand, MME, NITK 15
2/7/2023
How does it work?
Throughout the experiment, S and R are
isothermal
A signal proportional to difference in power
input to the S and R furnaces is
transmitted to the data acquisition system
The power differences are plotted as a
function of the sample temperature and its
unit is milli Watts (mW)
16. Dr.Anand, MME, NITK 16
2/7/2023
Heat flux DSC
Constantan disk
Chromel disk
Chromel wire
Alumel wire
17. Dr.Anand, MME, NITK 17
2/7/2023
How does it work?
S and R are heated by a single heater
Differential heat flow into the S and R pans is
monitored by chromel disk/constantan
thermocouple
Differential heat flow in to S and R pans is
directly proportional to the difference in output
of the two thermocouple junctions
Sample temp. is estimated by chromel/alumel
junction under the sample disk
18. Dr.Anand, MME, NITK 18
2/7/2023
Purge gases
Typical purge gases are air/N2
He is useful for efficient heat transfer and
removal of volatiles.
Ar is preferred as an inert purge when
examining samples that can react with
nitrogen.
The experiment can also be carried out
under a vacuum or under high pressure.
19. Dr.Anand, MME, NITK 19
2/7/2023
Crucibles
Choice of crucible is critical.
• Thermal properties of crucible.
• Reactive properties with samples.
• Catalytic behaviour with samples.
Aluminum: inexpensive, low temp
Copper: used as catalyst (testing polymers)
Gold: higher temp, expensive
Platinum: still higher temp, expensive.
Alumina (Al2O3): very high temp
Sapphire: crystalline alumina, more
chemically resistant than amorphous Al2O3.
20. Dr.Anand, MME, NITK 20
2/7/2023
DSC thermograms
S – glass transition
Ex – exothermic reaction
En – endothermic reaction
Exo
Endo
DSC thermogram of poly(ethylene terephthalate)
21. Dr.Anand, MME, NITK 21
2/7/2023
Enthalpy changes
The DSC curve may show an exothermic or
endothermic peak
The enthalpy changes associated with the events
occurring are given by the area under the peaks.
Peaks may be characterized by:
Position (i.e., start, end, extrapolated onset and peak
temperatures)
Size (related to the amount of material and energy of
the reaction)
Shape (which can be related to the kinetics of the
process)
26. Dr.Anand, MME, NITK 26
2/7/2023
Calibration of DSC
Temperature calibration is carried out by
running standard materials, usually very
pure metals with accurately known
melting points.
Energy calibration may be carried out by
using either known heats of fusion for
metals, commonly indium, or known heat
capacities.
31. Dr.Anand, MME, NITK 31
2/7/2023
Effect of heating rate
Exo
Endo
Temperature (0 C)
Heat
flow
(mW)
32. Dr.Anand, MME, NITK 32
2/7/2023
Effect of heating rate
Slower heating rates will more accurately
depict the onset temperature of
transformation
Two transformations which are very close
in temperature range may be more
distinctly seen as separate peaks, whereas
they may be mistaken for a single
transformation under a rapid heating rate
33.
34. Comparison of First and Second Heating Runs
0 5
0 1
0
0 1
5
0 2
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0 3
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35. Method Design Rules
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 to correctly select integration or analysis
limits
Don’t Decompose sample in DSC Cell
36. Selecting Optimum Experimental Conditions
"Always" 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 lower heat rates
38. Dr.Anand, MME, NITK 38
2/7/2023
Here is the DSC curve for a polymeric material such
as high density polyethylene (HDPE). We see
three phase transition temperatures: glass
transition temperature (Tg), crystallization
temperature (Tc), and the melting temperature (Tm)
Tg
Tc
Tm
Polymer characterization
40. 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
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)
41. Measuring/Reporting Glass Transitions
The glass transition is always a temperature range
The molecular motion associated with the glass transition is
time dependent. Therefore, Tg increases when heating
rate increases or test frequency (MDSC®, DMA, DEA, etc.)
increases.
When reporting Tg, it is necessary to state the test method
(DSC, DMA, etc.), experimental conditions (heating rate,
sample size, etc.) and how Tg was determined
Midpoint based on ½ Cp or inflection (peak in derivative)
43. Step Change in Cp at the Glass Transition
% Amorphous = 0.145/0.353= 41%
PET
9.43mg
44. 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 affects the
mobility of the molecules,
affects the Heat Capacity and,
in turn, the Glass Transition
45. Dr.Anand, MME, NITK 45
2/7/2023
Polymer characterization
Tg may be used to identify polymers
The amount or effectiveness of a plasticizer may
be judged by how much it reduces Tg or affects
the shape of the transition.
Examination of the transitions in polymer blends
gives information as to their compatibility.
Curing reactions result in an increase in Tg and
measurements can be used to monitor the extent
of cure.
46. Dr.Anand, MME, NITK 46
2/7/2023
It is well known that Tg increases with increasing molecular weight, M. This is
expressed by the Fox and Flory equation: Tg = Tg() - Kg/M
where Tg() is the limiting Tg at a very high molecular weight and
Kg is a constant.
48. Dr.Anand, MME, NITK 48
2/7/2023
Polymer characterization
Thermogram of the blend shows two distinct Tg.
Therefore, the components of this blend are
immiscible in each other
exo
endo
Polymer A
Polymer B
Blend of A+B
49. Dr.Anand, MME, NITK 49
2/7/2023
Polymer characterization
Tg also varies with chain length for a related
group of polymers.
Additional features occurring in the glass
transition region, often a superimposed
endothermic peak, are related to the aging
undergone by the material in the glassy state,
and can sometimes obscure the transition,
making precise temperature measurement
difficult.
51. Dr.Anand, MME, NITK 51
2/7/2023
Analysis of explosives
Ammonium perchlorate is an important
component of high explosives. The
stability of this material is critical to their
safe handling. Mechanism of
decomposition was investigated.
52. Dr.Anand, MME, NITK 52
2/7/2023
solid-solid phase transition
to the cubic phase
decomposition
Literature values for Ea 37 - 260 kJ/mol with different
mechanisms proposed. This work clarified the mechanism
and identified the activation energy as 115 kJ/mol.
53. Dr.Anand, MME, NITK 53
2/7/2023
Analysis of lubricants
An important test in the automotive
industry is to determine the stability of
lubricating oils at elevated temperatures
and pressures. This will impact its utility
as a lubricant in motors. In this case, the
oil is brought to a high operating
temperature and held there under an
oxygen atmosphere.
54. Dr.Anand, MME, NITK 54
2/7/2023
At some point, the oil begins to oxidize and then
quickly decomposes exothermically. Note how the
synthetic oil has a much longer oxidation induction
time (OIT) than does the mineral oil.
55. Guidelines for interpreting data
Dr.Anand, MME, NITK 55
2/7/2023
It is better to have some idea of what transitions to look for and why.
For example:
1. What type of sample is it?
2. What type of transitions can it undergo?
3. What would any changes appear as?
4. What is the temperature range of interest?
5. What data are available from complimentary techniques, e.g. TGA?
6. Has there been any previous analysis?
Then examine the data:
1. Is the event an endotherm or exotherm?
2. Is the event repeatable on a fresh sample or on a reheat?
3. What happens on cooling?
4. Is the event the same in a sealed and unsealed pan?
5. Is the transition sharp or gradual, large or small?
6. Does the event look real? Thermal events are not normally excessively sharp.
56. Dr.Anand, MME, NITK 56
2/7/2023
Text book
D. A. Skoog et al., Principles of
instrumental analysis, fifth edition,
Harcourt Publishers, 2001.
R. F. Speyer, Thermal analysis of
materials, Marcel Dekker, 1994.
Reference