Thermal Analysis: Differential

Scanning Calorimetry (DSC)

Professor Maria L. Auad
E-mail: auad@auburn.edu
Phone: 334 844-5459
Office: 103 Textile Building
2
Introduction
Any measurement of a change in properties as the
temperature changes qualifies as a thermal analysis technique.

When performing thermal analysis procedures, usually a
controlled temperature program heats or cools a sample at a
certain rate, and physical or chemical property changes are
monitored as a function of temperature.

Some of the measured properties include mass, temperature,
heat flow, size, malleability, sound transmission, magnetic
characteristics, optical characteristics, electrical conductivity,
and tensile strength.

Thermal analysis techniques give useful information about
polymers, inorganic compounds, alloys, drugs, and other
organic materials.
3
Techniques in this category include

TG or TGA: thermal gravimetric analysis or thermogravimetry. Measures
the mass change of the sample with a thermobalance. A variation on this
is DTG, or derivative thermogravimetry, which measures the slope or
derivative of the mass change with temperature, dm/dt.
EGD: evolved gas detection. Measures and usually further analyzes
evolved gas as the sample decomposes.
DRS: dynamic reflectance spectroscopy. Measures the amount of light
reflected from the sample as the temperature changes.
TMA: thermo-mechanical analysis measures the expansion or
contraction of a sample as the temperature changes.
DSC and DTA: differential scanning calorimetry, and a related technique,
differential thermal analysis. DSC measures the amount of heat flowing
into the sample (endothermic, +dH/dt) or out of the sample (exothermic, -
dH/dt), and DTA (the older technique) measures small differences in
temperature between a sample and reference as the same amount of
heat energy is applied to both.
Differential Scanning Calorimetry - DSC
Differential Scanning Calorimetry (DSC) is concerned with the
measurement of energy changes in materials. It is thus the most generally
applicable of all thermal analysis methods, since every physical or
chemical change involves a change in energy.
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.
Note the provision for establishing a gas flow through the cell, to sweep away
volatiles, provide the required atmosphere, and to assist in heat transfer.
Traditional Heat Flux DSC: Cell Schematic Diagram
Dynamic Sample Chamber
Reference Pan
Sample Pan
Lid
Gas Purge Inlet
Chromel
Disc
Heating
Block
Chromel
Disc
Alumel Wire
Chromel Wire
Thermocouple
J unction
Thermoelectric Disc
(Constantan)
DSC working range: typically up to 700C, and down to -140C with
a liquid nitrogen cooling system.

-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. -
DSC: operational details

A variety of sample pans can be used for different purposes.
The best quantitative results for polymers are obtained from thin samples
crimped flat between the pan and a lid.

Hermetically-sealed pans capable of holding a few atmospheres pressure
are used for liquids, or when it is necessary to retain volatiles.
Very high-pressure seals can be achieved using O-ring or screw-
threaded seals.
For materials that react with aluminium, or for higher temperatures, pans
may be made from stainless steel, inconel, gold, alumina, graphite, silica
or platinum.

Typical purge gases are air and nitrogen, though helium is useful for
efficient heat transfer and removal of volatiles. Argon is preferred as an
inert purge when examining samples that can react with nitrogen. The
experiment can also be carried out under vacuum or under high
pressure using instruments of the appropriate design.
Differential Scanning Calorimetry (DSC) measures
the temperatures and heat flows associated with
transitions in materials as a function of time and
temperature in a controlled atmosphere.

These measurements provide quantitative and
qualitative information about physical and chemical
changes that involve endothermic or exothermic
processes, or changes in heat capacity.
DSC: The Technique
DSC: What DSC Can Tell You?
Glass Transitions
Melting and Boiling Points
Crystallization time and
temperature
Percent Crystallinity
Heats of Fusion and Reactions
Specific Heat / Heat Capacity
Oxidative/Thermal Stability
Rate and Degree of Cure
Reaction Kinetics
Purity
Typical DSC Transitions
Temperature




















H
e
a
t

F
l
o
w

Glass
Transition
Crystallization
Melting
Cross-Linking
(Cure)
Oxidation
or
Decomposition
Exothermic:
Understanding DSC Signals
Heat Flow




Where:
= measured heat flow rate

Cp = sample heat capacity
= specific heat (J /gC) x mass (g)

= measured heating rate

f (T,t) = heat flow due to kinetic processes
(evaporation, crystallization, etc.)
dt
dH
dt
dT
Calibration of Differential Scanning Calorimeters Differential Scanning
Calorimeters are almost universally calibrated for temperature and enthalpy
using the melting temperatures of highly pure metals.
Recommended values for the melting temperature (Tm) and heat of fusion (Hf)
are given below. Many of these substances will react with standard aluminum
crucibles. This may be overcomes by annealing the empty crucible (and lid) air
above 400C in order to build up a protective layer of aluminum oxide.
Calibration of Differential Scanning Calorimeters
Material
Tm (C)

Hf (J/g)

Mercury -38.8344 11.469
Gallium 29.7646 79.88
Indium 156.5985 28.62
Tin 231.298 7.170
Bismuth 271.40 53.83
Lead 327.462 23.00
Zinc 419.527 108.6
Aluminum 660.323 398.1
Melting of Indium
157.01C
156.60C
28.50J /g
Indium
5.7mg
10C/min
-25
-20
-15
-10
-5
0
H
e
a
t

F
l
o
w

(
m
W
)
150 155 160 165
Temperature (C)

Exo Up Universal V4.0B TA Instruments
Peak Temperature
Extrapolated
Onset
Temperature
Heat of
Fusion
For pure, low
molecular weight
materials (mw<500
g/mol) use
Extrapolated Onset as
Melting Temperature
Indium Melt, 5.7mg at 10C/min
Second Order Transitions: Tg
The DSC curve may show a step change, as at S in the curve, reflecting a
change in heat capacity not accompanied by a discrete enthalpy change.
The most common example, and a major application area of DSC, is the
glass transition (Tg) seen in amorphous polymers. This important region, in
which the material changes from a rigid glassy state to a rubber, or very
viscous liquid state, may be analyzed to give a wealth of information about
the material.
Temperature




















H
e
a
t

F
l
o
w

Glass
Transition
Crystallization
Melting
Cross-
Linking
(Cure)
Oxidation
or
Decomposition
Exo up
15
Examples:
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.

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.

The temperature Tg may be used to identify polymers, as it
varies over a wide range for commonly used materials.

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)
Enthalpy Changes (first order transition)
The DSC/DTA curve may show an exothermic or endothermic peak,.
The enthalpy changes associated with the events occurring are given
by the area under the peaks.

In general, the heat capacity will also change over the region, and
problems may arise in the correct assignment of the baseline. In many
cases the change is small, and techniques have been developed for
reproducible measurements in specific systems.
Process
Exothermic Endothermic
Solid-solid transition
* *
Crystallization
*
Melting
*
Vaporization
*
Sublimation
*
Adsorption
*
Desorption
*
Desolvation (drying)
*
Decomposition
* *
Solid-solid reaction
* *
Solid-liquid reaction
* *
Solid-gas reaction
* *
Curing
*
Polymerization
*
Catalytic reactions
*
Applications
Thermoplastics
Thermosets
Heat Capacity
Glass Transition
Melting and Crystallization
Additional Applications

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 of Thermoplastic Polymers
Tg
Melting
Crystallization
Oxidative Induction Time
General Recommendations
10-15mg in crimped pan
@ 10C/min


Thermoplastic: Heat/Cool/Heat
0 20 40 60 80
-0.8
-0.6
-0.4
-0.2
0.0
0.2
0.4
0
50
100
150
200
250
300
Time (min)
H
e
a
t

F
l
o
w

(
W
/
g
)

[












]

T
e
m
p
e
r
a
t
u
r
e

(

C
)

First Heat
Cooling
Second
Heat
Thermoplastic: Heat Flow vs.
Temperature for Heat/Cool/Heat
Second Heat
First Heat
Cool
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
H
e
a
t

F
l
o
w

(
W
/
g
)
20 60 100 140 180 220 260
Temperature (C)
The Glass Transition (Tg)
The glass transition is a step change in molecular mobility (in the
amorphous phase of a sample) that results in the change of many
physical properties

The material is rigid below the glass transition temperature and
rubbery above it.

Amorphous materials flow, they do not melt

The change in heat capacity at Tg is a measure of the amount of
amorphous phase in the sample.

Enthalpic recovery at Tg 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

Advantages of DSC Techniques
Differential Scanning Calorimetry
Most common technique for Tg
Small sample size
Faster analysis (fast heating, automation)

Modulated - DSC (MDSC

)
Can separate kinetic and heat capacity
events
Typical Polymer Tg by DSC
92.87C(H)
0.2638mW
-2.0
-1.5
-1.0
-0.5
0.0
H
e
a
t

F
l
o
w

(
m
W
)
20 40 60 80 100 120 140 160
Temperature (C)
Sample: PMMA Size:
10.47mg Heating Rate:
10C/min
Effect of Plasticizer on Tg
Plasticizers are generally low molecular weight organic
additives which are used to soften rigid polymers
Plasticizers are typically added to a polymer for two
reasons:
1. To lower the glass transition to make a rigid
polymer become soft and rubbery.
2. To make the polymer easier to process.
Plasticizers make it easier for a polymer to change
molecular conformation.
Therefore plasticizers will have the effect lowering and
broadening the glass transition.
Crystallization
Crystallization is a kinetic process which can be
studied either while cooling, heating or
isothermally

Differences in crystallization temperature or
time (at a specific temperature) between
samples can affect end-use properties as well
as processing conditions

Isothermal crystallization is the most sensitive
way to identify differences in crystallization
rates

Crystallization
Crystallization is a two step process:
Nucleation
Growth

The onset temperature is the nucleation (T
n
)

The peak maximum is the crystallization
temperature (T
c
)
Effect of Cooling Rate on 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.
0.0
0.5
1.0
1.5
2.0
H
e
a
t

F
l
o
w

(
W
/
g
)
40 50 60 70 80 90 100 110 120 130 140 150 160
Temperature (C)
Exo Up
POLYPROPYLENE
WITH NUCLEATING
AGENTS
POLYPROPYLENE
WITHOUT
NUCLEATING AGENTS
-1.5
-1.0
-0.5
0.0
H
e
a
t

F
l
o
w

(
W
/
g
)
60 80 100 120 140 160 180 200
Temperature (C)
ExoUp
crystallization
melting
Effect of Nucleating Agents
Sample must be pure material, not copolymer or
filled
Must know enthalpy of melting for 100% crystalline
material (H
literature
)
You can use a standard H
literature
for relative
crystallinity
Calculation of % Crystallinity
For standard samples:

% crystallinity = 100* H
m
/ H
literature


For samples with cold crystallization:

% crystallinity = 100* (H
m
- H
c
)/ H
lit

Crystallinity Calculation
78.99C(I)
75.43C
80.62C
134.62C
127.72C
53.39J /g
256.24C
242.91C
74.71J /g
-1.5
-1.0
-0.5
0.0
0.5
1.0
H
e
a
t

F
l
o
w

(
W
/
g
)
50 100 150 200 250 300
Temperature (C)

( )
% 15
140
39 . 53 71 . 74
100 =

% crystallinity = 100* (H
m
- H
c
)/ H
lit
Melting Definitions
Melting the process of converting crystalline
structure to a liquid amorphous structure
Thermodynamic Melting Temperature the
temperature where a crystal would melt if it had
a perfect structure (large crystal with no
defects)
Metastable Crystals Crystals that melt at
lower temperature due to small size (high
surface area) and poor quality (large number of
defects)

Melting of Indium
157.01C
156.60C
28.50J /g
Indium
5.7mg
10C/min
-25
-20
-15
-10
-5
0
H
e
a
t

F
l
o
w

(
m
W
)
150 155 160 165
Temperature (C)

Exo Up Universal V4.0B TA Instruments
Peak Temperature
Extrapolated
Onset
Temperature
Heat of
Fusion
For pure, low
molecular weight
materials (mw<500
g/mol) use
Extrapolated Onset as
Melting Temperature
Melting of PET
249.70C
236.15C
52.19J /g
PET
6.79mg
10C/min
-7
-6
-5
-4
-3
-2
-1
H
e
a
t

F
l
o
w

(
m
W
)
200 210 220 230 240 250 260 270
Temperature (C)

Exo Up Universal V4.0B TA Instruments
Extrapolated
Onset
Temperature
Peak Temperature
Heat of
Fusion
For polymers, use Peak as Melting Temperature
Comparison of Melting
249.70C
236.15C
52.19J /g
157.01C
156.60C
28.50J /g
Indium
5.7mg
10C/min
PET
6.79mg
10C/min
-25
-20
-15
-10
-5
0
H
e
a
t

F
l
o
w

(
m
W
)
140 160 180 200 220 240 260 280
Temperature (C)
Exo Up Universal V4.0B TA Instruments
Thermosetting Polymers: polymerization Rxn
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.
A +B C
GLUE
DSC Thermoset Cure: First and Second Heat
0 50 100 150 200 250 300
-0.24
-0.20
-0.16
-0.12
-0.08
-0.04
Temperature (C)
H
e
a
t

F
l
o
w

(
W
/
g
)
Tg
Tg
155.93C
102.64C
20.38J /g
Residual Cure
First
Second

General Recommendations
10-15 mg in crimped pan if solid; hermetic pan if liquid
@ 10C/min
Determination of % Cure
79.33J /g
75.21 % cured
NOTE: Curves rescaled and shifted for readability
145.4J /g
54.55 % cured
Under-cured Sample
Optimally-cured Sample
-5.27C(H)
DSC Conditions:
Heating Rate =10C/min.
Temperature Range =-50C to 250C
N2 Purge =50mL/min.
-12.61C(H)
-0.5
0.0
0.5
1.0
1.5
2.0
H
e
a
t

F
l
o
w

(
W
/
g
)
-50 0 50 100 150 200 250
Temperature (C)
Exo Up Universal V2.4F TA
245.22C
125.54C
-20
-10
0
10
20
H
e
a
t

F
l
o
w

(
m
W
)
50 100 150 200 250 300
Temperature (C)
Polyethylene Oxidation Onset Temperature
Oxidation
Another type of thermal stability is that of stability to combustion. By heating a
hydrocarbon sample in air or oxygen, the temperature at which the sample begins to
burn is an indicator of the thermal stability of the material.
OXIDATION INDUCTION TIME EFFECT OF PRESSURE


Increased pressure of O2 decreases oxidation time
Modulated
Differential Scanning Calorimetry
(MDSC

)

What its all about & how to get better results
What Does MDSC

Measure?
MDSC separates the Total heat flow of
DSC into two parts based on the heat flow
that does and does not respond to a
changing heating rate
MDSC applies a changing heating rate on
top of a linear heating rate in order
measure the heat flow that responds to the
changing heating rate
In general, only heat capacity and melting
respond to the changing heating rate.


Note that temperature is not decreasing during
Modulation i.e. no cooling
Modulate +/- 0.42 C every 40 seconds
Ramp 4.00 C/min to 290.00 C
52
54
56
58
60
62
M
o
d
u
l
a
t
e
d

T
e
m
p
e
r
a
t
u
r
e

(

C
)
52
54
56
58
60
62
T
e
m
p
e
r
a
t
u
r
e

(

C
)
13.0 13.5 14.0 14.5 15.0
Time (min)
Average & Modulated
Temperature
Modulated Temperature
Average Temperature
(Heat-Iso)
Modulated DSC

Theory
MDSC

uses two simultaneous heating

rates
Average Heating Rate
This gives Total Heat Flow data which is
equivalent to standard DSC @ same average
heating rate
Modulated Heating Rate
Purpose is to obtain heat capacity information
at the same time as heat flow
MDSC

of Quench-Cooled PET
Nonreversing
Reversing
Total
-0.4
-0.2
0.0
N
o
n
r
e
v

H
e
a
t

F
l
o
w

(
W
/
g
)
-0.4
-0.2
0.0
0.2
0.4
R
e
v

H
e
a
t

F
l
o
w

(
W
/
g
)
-0.4
-0.2
0.0
0.2
H
e
a
t

F
l
o
w

(
W
/
g
)
0 50 100 150 200 250 300
Temperature (C)
Exo Up
H total = H rev. + H nonrev.
When & Why to Run MDSC

Always run a standard DSC @ 10C/min
first

If youre looking for a glass transition --
If the glass transition is detectable and can be
routinely analyzed, then you dont need to use
MDSC
However, if the Tg is hard to detect, or has an
enthalpic recovery, then run MDSC
When & Why to Run MDSC

If looking at melting and crystallization
If the melting process looks normal (single
endothermic peak) and there is no apparent
crystallization of the sample as it is heated,
then there is no need to use MDSC
However, if melt is not straightforward, or it is
difficult to determine if crystallization is
occurring as the sample is heated, use MDSC


Wheres the Tg?
Tablet Binder, 44%RH
3.08mg
MDSC

1/60/5
Vented pan
Heres the Tg!
MDSC

Aids Interpretation
Xenoy 13.44 mg
MDSC .318602
DSC of Amorphous PET/PC MixtureWhere
is the PC Tg ?
120.00C
170.00C
30.74J /g
215.00C
270.00C
42.95J /g
120.00C 270.00C
13.31J /g
Standard DSC @ 10C/min
57% PET; 43% PC
DSC Heat Flow Analyzed
Two Different Ways
-16
-12
-8
-4
0
4
[

]

H
e
a
t

F
l
o
w

(
m
W
)
-22
-18
-14
-10
-6
-2
H
e
a
t

F
l
o
w

(
m
W
)
50 100 150 200 250
Temperature (C)





Exo Up Universal V3.8A TA Instruments
It is often difficult to accurately measure the crystallinity of polymers by DSC because the
crystallinity increases as the sample is being heated in the DSC cell.
To measure the correct crystallinity requires the ability to:
determine the true heat capacity (no transitions) baseline
quantitatively measure how much crystallinity developed during the heating
process
MDSC

Shows Two Tgs in Polymer Mixture

Decrease in Heat Capacity
Due to Cold Crystallization
Glass Transition
of Polycarbonate
True Onset
of Melting
Cold Crystallization Peak
Seen Only in Total Signal
Total
Heat Flow
Reversing
Heat Flow
-3.2
-3.0
-2.8
-2.6
-2.4
-2.2
-2.0
[

]

R
e
v

H
e
a
t

F
l
o
w

(
m
W
)
-3.2
-3.0
-2.8
-2.6
-2.4
-2.2
-2.0
H
e
a
t

F
l
o
w

(
m
W
)
50 100 150 200 250
Temperature (C)





Exo Up Universal V3.8A TA Instruments
MDSC

.318/40/3
MDSC

Gives Correct Crystallinity of Zero