Thermal Analysis:

methods, principles,
application
S.K.Date
Department of Physics ,University of Pune.
(Saturday 21/12/2013)
Common Definition of Thermal
Analysis
A branch of materials science where the properties of materials
are studied as they change with temperature.

Techniques:
 Differential Scanning Calorimetry
 Dynamic Mechanical Analysis
 Thermomechanical Analysis
 Thermogravimetric Analysis
 Differential Thermal Analysis
 Dilatometry
 Optical Dilatometry
 Dielectric Thermal Analysis
 Evolved Gas Analysis
 Thermo-Optical Analysis
 Production Thermal Analysis of Metals
 Thermal Analysis of Foods
Concepts of Thermal Analysis
Temperature
mV 2 3
A measure of kinetic energy of molecular motion Ek   kT
2 2

Temperature Scales:

 Newton (1701): freezing point of water 0, human body 12

 Fahrenheit (1714): freezing point of water mixed with NaCl 0, human

body 96, freezing point of water 32, boiling point of water 212

 Celsius (1742): freezing point of water 0, boiling point of water 100

 Kelvin (1848): absolute zero is the temperature at which molecular

energy is a minimum and it corresponds to a temperature of -273.15°C
Temperature Scales

P. Atkins, Four Laws that drive the Universe, Oxford Univ. Press, 2007
Maxwell-Boltzmann Distribution

P. Atkins, Four Laws that drive the Universe, Oxford Univ. Press, 2007
Some Important Temperatures
 Absolute zero (precisely by definition): 0 K or −273.15 °C
 Coldest measured temperature: 450 pK or –273.14999999955 °C
 Water’s triple point (precisely by definition): 273.16 K or 0.01 °C
 Water’s boiling point: 373.1339 K or 99.9839 °C
 Incandescent lamp: ~2500 K or ~2200 °C
 Melting point of tungsten: 3695 K or 3422 °C
 Melting point of carbon: 3773.15 K or 3500 °C
 Sun’s visible surface 5778 K or 5505 °C
 Lightning bolt’s channel 28,000 K or 28,000 °C
 Sun’s core 16 MK or 16M°C
 Thermonuclear weapon (peak temperature) 350 MK or 350M°C
 CERN’s proton vs. nucleus collisions 10 TK or 10 trillion °C
 Universe 5.391×10−44 s after the Big Bang 1.417×1032 K 1.417×1032 °C
Concepts of Thermal Analysis
Heat
A form of energy produced by the motion of atoms and molecules

Heat Units: J (Joule) [m2 kg s-2], Cal (Calorie) 1 cal = 4.184 J

 Heat is related to internal energy of a system and work done on or by a system

through the First Law of Thermodynamics:
dU  Q  A  Q  pdV  TdS  pdV U  f S ,V 
U – internal energy, Q – heat, A – work, T – temperature, V – volume, S - Entropy

 Enthalpy
H  U  PV dH  Q  Vdp  TdS  VdP H  f S , p 
 Heat Capacity

dQ  H 
Cp   
dT  T  p
 Basic Principles and Terminology
Principle of combined thermocouple
Registration the temperature of the object and temperature difference
between sample and reference

Consequence
Depending on the engineering design, measuring cell construction on
and the way of data representation on, variety of methods has been
arisen: DTG, DTA, DSC, STA etc.
 Basic Principles and Terminology DSC-TG

DSC ‐ (Differen5al Scanning Calorimetry):

Voltage to keep ΔT = TS‐TR= 0 vs. T

RDTA (Reverse Diff. Thermal Analysis)

dt/dT vs. T
TG
TA – (Thermal analysis )
TS vs. t

In AC TG – (Thermogravimetric analysis)
ThermoLab Δm vs. T
DTA-TG
DTA ‐ (Differen5al Thermal Analysis)
ΔT = TS‐TR vs. T

DDTA ‐ (Derivative DTA)

dΔT/dt vs. T

Calvet-DSC

STA – Simultaneous Thermal Analysis: TG – DSC ; EVA – Evolved gas analysis: MS, FTIR, GC

Hyphenated techniques
 DSC TG

Pb(S) → Pb(L), ΔH°298= 5 kJ/mol CuO(S)+H2(g)→ CuO(s)+H2O(g) ,

ΔH°298= -86 kJ/mol
 1. Experimental DTA curve
2. DTA curve corrected to heat transfer
conditions
3. True baseline of DTA curve
4. Interpolated baseline;
5. Experimental baseline;
6. Experimental baseline alter process,
shifted because of
thermal capacity changes.
Thermogravimetric Analysis (TGA)

 A technique that
permits the
continuous
weighing of a
sample as a
function of
temperature and/or
as a function of
time at a desired
temperature
TGA Applications: Inorganics

 Hydrates decomposition, drying phenomena

 Carbonates and other salts decomposition
 Kinetics and mechanisms of oxidation, and other solid-gas reactions
 Analysis of magnetic materials
 Etc.
TGA Applications: Organics

 Identification of polymers and pharmaceutical agents

 Thermal stability of synthetic and natural polymers and other organics
 Analysis of polymer-matrix composites
 Kinetics and mechanism of solid organics – gas reactions
 Residual solvent determinations
 TGA Applications: Oxidation of SWCNT
C+O2=CO2
Oxidation of amorphous
carbon Oxidation of catalyst

http://www.msel.nist.gov/Nanotube2/
TGA+Spectroscopy/Chromatography
Combination

Gases, vapors
TGA IR or MS or GC
Kinetic studies
The kinetic reaction mechanism can be determined from the
Arrhenius equation,
K=A exp (-Ea/RT),
where Ea is the activation energy; R is the universal gas
constant; A is the pre-exponential factor; T is the absolute
temperature; and K is the reaction rate constant.
The above equation upon log transformation can be rewritten
as
lnK= lnA - Ea/RT
The activation energy can be determined from the slope of the
above plot, and the intercept value would yield the pre-
exponential factor.
 Arrhenius plot

Determination of kinetic mechanism for volatilization of triacetin, diethyl phthalate,

and glycerin from Arrhenius plots.
The Ea values are 66.45, 65.12, and 67.54 kJ/mol
 Differential Thermal Analysis (DTA)

Can be conducted at
the same time with
TGA

 DTA measures temperature difference between a sample and

an inert reference (usually Al2O3) while heat flow to the
reference and the sample remains the same
Differential Scanning Calorimetry (DSC)

Exothermal dQ/dT
Temperature

 DSC measures differences in the amount of heat required to

increase the temperature of a sample and a reference as a
function of temperature
Differential Scanning Calorimeter
 Differential Scanning Calorimetry
(DSC)
 To heat a sample and a reference with the same heating rate requires
different amount of heat for the sample and the reference. Why?
 On the X-axis we plot the temperature, on the Y-axis we plot difference in
heat output of the two heaters at a given temperature.
Heat flow

Heat flow Q t Q
Heat Q     Cp
 Temperature rate t T T
Time t
Heat Flow

Temperature
Major difference between TGA and
DTA (DSC)
 TGA reveals changes of a sample due to weight, whereas DTA and
DSC reveal changes not related to the weight (mainly due to phase
transitions)
 Types of Phase Transitions
 First order transitions, where first and second derivatives of
thermodynamic potentials by temperature are not 0
 G    2 G 
   S  0,   0
2 
 T  p  T  p
 Examples: crystallization and melting

 Second order transitions where the first derivatives of

thermodynamic potentials by temperature are 0 and the second
derivatives are not 0
 G    2 G 
   S  0,   0
2 
 T  p  T  p
 Examples: ferromagnetic – diamagnetic transition
 Differential Scanning Calorimeter

Parts:
 Isolated box with 2
pans
 Heatingelement and
thermocouple
 Liquid nitrogen
 Nitrogen gas
 Aluminum pan
Differential Scanning Calorimeter
 Differential Scanning Calorimeter
Perkin Elmer DSC 7

Platinum sensors  Temperature range 110 –

1000 K
 Heating rate 0.1 – 500 K/min
(normally 0.5 – 50 K/min)
 Noise ± 4 mW
Sample heater Reference heater  Sample volume up to 75 mm3
An Example of Phase Transitions
Studied by DSC
Melting and freezing of water in ordered
mesoporous silica materials.

Pore size increases from 4.4 to 9.4 nm in

the series SBA-15/1 to SBA 15/8

A.Schreiber et al. Phys.Chem.Chem.Phys.,2001,3,1185-1195

An Example of Phase Transition in
DSC: Martensite/Austenite
Transition in Cu-Al-Ni Alloy
DSC in Polymer Analysis

Main transitions which can be studied by DSC:

 Melting
 Freezing
 Glass transition
 Polymers in Condensed State
Lamellar crystals
and Clusters
Crystallinity
concept
the molecules are
much larger than the
crystals
Chain folded
1. Fold length 5 -50 nm
2. Best grown from dilute
solution
3. Metastable lamellae
because of the large fold
surface area
Extended chain: presents
equilibrium crystals.
1. Produced by annealing:
e.g. polyethylene
polytetrafluoroethylene
polychlorotrifluoroethylene
2. Produced by crystallization
during polymerization:
e.g. polyoxymethylene
polyphosphates, selenium
Glassy amorphous
1. Random copolymers
2. Atatic stereoisomers
e.g. PS, PMMA, PP
3.Quenched slow
crystallizing
molecules
e.g. PET, PC
and others.
 Glass Transition
 The glass transition temperature,
Tg, is the temperature at which an
amorphous solid, such as glass or
a polymer, becomes brittle on
cooling, or soft on heating.
 More specifically, it defines a
pseudo second order phase
transition in which a supercooled
melt yields, on cooling, a glassy
structure and properties similar to
those of cristalline materials e.g. of
an isotropic solid material.
 Exothermal How to observe Tg

Exothermal
Temperature

Experimental curves on heating after cooling at 0.0084 K/min (1), 0.2 K/min (2)
0.52 K/min (3), 1.1 K/min (4), 2.5 K/min (5), 5 K/min (6), and 30 K/min (7).
Typical DSC Curve of a
Thermoplastic Polymer
Sample: PET80PC20_MM1 1min
DSC
Size: 23.4300 mg
Method: standard dsc heat
-cool-heat
File: C:...\DSC\Melt Mixed1\PET80PC20_MM1.001
Operator: SAC
Run Date: 05-Apr-2006 15:34
Comment: 5/4/06
1.5
Tm
Instrument: DSC Q1000 V9.4 Build 287

245.24°C

1.0 Tc
Tg
Heat Flow(W/g)

137.58°C
20.30J/g 228.80°C
22.48J/g
79.70°C(I) 81.80°C
0.5
75.41°C

Cycle 1

144.72°C
0.0

-0.5
0 50 100 150 200 250 300
Exo Down Temperature(°C) Universal V4.2E TA Instruments
Typical DSC Curve of a
Thermosetting Polymer

Oxidation
Heat Flow -> exothermic

Crystallisation Cross-Linking
(Cure)

Glass
Transition

Melting

Temperature
Differential Scanning Calorimetry
PET
2
Melting
1.5
ENDOTHERMIC
1 Glass Transition
Heat Flow (W/gm)

0.5

0
0 50 100 150 200 250 300 350
-0.5

-1

EXOTHERMIC Crystallization
-1.5
Temperature (C)

Sample: Polyethylene terephthalate (PET)

Temperature increase rate: 20°C/min
Temperature range: 30°C - 300°C
DSC Artifacts
 The properties of the system «sample‐sensor» strongly influence the
experimental TA curves

Features of TA Setup Characteristics of the sample

a) Reaction Atmosphere
b) Size and shape of the oven
c) Sample holder material
d) Sample holder geometry
e) Heating rate
f) Thermocouple (wire diameter)
g) Thermocouple loca5on
h) Response 5me
a) Particle size
b) Thermal conductivity
c) Thermal capacity
d) Packing density of particles (powder,
pill, tablet)
e) Sample expansion and shrinking
f) Sample mass
g) Inert filler
h) Degree of Crystallinity
Influence of external atmosphere
Influence of external atmosphere
Influence of heating rate

La(OH)3→LaOOH+H2O
LaOOH→La2O3+H2O
 Influence of the pan material

Pyrolisis of Fluoropolymer: TFE‐VDF, ‐{C2F4}n ‐ {C2H2F2}m , F42 – in Al an

Au pans
Measurement in inert. Is the system oxygen
free?
Measurement in inert. Is the system oxygen free?

DSC‐TG sample holder,

Al2O3 pan, Ar 100ml/min
Sample: Ni/MgAl2O4
Weight: 14.1mg
Skimmer coupling system
The First law (Conservation of Energy)
We define Internal Energy, U, by:
dU = q - w
Can we measure the absolute value of the Internal Energy?
How is it stored?
 Specific heat - increased atomic vibration
 Making or breaking of atomic bonds
 Latent heat
 Chemical Reaction Heat - breaking and remaking chemical bonds
2Mg + O2 -> 2 MgO

Statement of First Law:

Internal Energy is a State Function:
U = f (T,P,…)
The same amount of work, however it is performed (motion, electrical current,
friction, etc.) brings about the same change of the system (means, change of
state is path independent)
Thank you