CHARACTERIZATION METHODS PART 2

Basics of Thermal Analysis

Introduction to Thermal Analysis

• Definition (ICTAC):
Thermal analysis (TA) is a group of techniques in
which changes of physical or chemical properties of
the sample are monitored against time or
temperature, while the temperature of the sample is
programmed.

The temperature program may involve heating or

cooling at a fixed rate, holding the temperature
constant (isothermal), or any sequence of these.
 Methods of Thermal Analysis (TA)

Differential Thermogravimetry Thermomechanical

Scanning (TG) Analysis
Calorimetry (TMA)
(DSC, DTA) Dilatometry (DIL)
Dynamic-Mechanical
Analysis (DMA)

Physical and chemical Mass changes due to Dimensional changes,

processes related to evaporation, deformations,
thermal effects can be decomposition and viscoelastic
characterized interaction with the properties,
atmosphere transitions, density

Evolved Gas Analysis (EGA)

Thermal analysis for the characterization
of solids

Solids
Crystalline Amorphous

Glass transition
Polymorphism
Cp, L
H
L Phase transition Crystallization
Softening
H, Cp H L
L L
Decomposition
Decomposition
m H
m H L
L Liquid Crystal Glass-ceramics, polymers
Thermodynamics
Thermodynamics
Thermodynamics
Heat Conduction
Conduction is heat transfer by means of molecular agitation
within a material without any motion of the material as a whole. If
one end of a metal rod is at a higher temperature, then energy
will be transferred down the rod toward the colder end because
the higher speed particles will collide with the slower ones with a
net transfer of energy to the slower ones. For heat transfer
between two plane surfaces, such as heat loss through the wall
of a house, the rate of conduction heat transfer is:
Thermodynamics
Heat Convection
Convection is heat transfer by mass motion of a fluid such as air or
water when the heated fluid is caused to move away from the source
of heat, carrying energy with it. Convection above a hot surface
occurs because hot air expands, becomes less dense, and rises.
Hot water is likewise less dense than cold water and rises, causing
convection currents which transport energy.
Thermodynamics
Heat Radiation
Radiation is heat transfer by the emission of electromagnetic waves
which carry energy away from the emitting object. For ordinary
temperatures (less than “red hot"), the radiation is in the infrared
region of the electromagnetic spectrum. The relationship governing
radiation from hot objects is called the Stefan Boltzmann law:
Introduction to Thermal Analysis

• Differential Thermal Analysis (DTA)

A technique in which the temperature difference
between the sample and a reference material (inert
material) is monitored during the temperature
program
• Differential Scanning Calorimetry (DSC)
A technique in which the heat flow rate to the sample
is monitored. In practice, the difference in heat flow
rate to the sample compared to a reference material
is monitored
– Heat flux DSC: the temperature difference caused by the
difference in heat flow to sample and reference is measured
– Power compensation DSC: the electric heating power to
compensate the difference in heat flow is measured
Introduction to Thermal Analysis

• Thermomechanical Analysis (TMA)

A technique in which the deformation of a sample
under non oscillating stress (load) is monitored during
the temperature program
• Thermodilatometry (DIL)
A technique in which the dimensional changes of the
sample under negligible load are monitored
• Dynamic Mechanical Analysis (DMA)
A technique in which the elastic response and the
damping behavior of the sample under oscillating
load with defined frequency are are monitored
Introduction to Thermal Analysis

• Thermogravimetry (TG, TGA)

A technique in which the mass of the sample is
monitored during the temperature program
• Thermodilatometry (DIL)
A technique in which the dimensional changes of the
sample under negligible load are monitored
• Dynamic Mechanical Analysis (DMA)
A technique in which the elastic response and the
damping behavior of the sample under oscillating
load with defined frequency are monitored
Introduction to Thermal Analysis

• Evolved Gas Analysis (EGA)

A technique in which the amount and/or nature of gas
or vapor evolved from the sample is monitored during
the temperature program
This technique is normally combined with other
thermoanalytical techniques via coupling interfaces
General concept of instruments
Temperature measurement: Thermocouples

Thermocouple - a pair of dissimilar electrical conductors joined at

one end (the measuring junction). When the other ends of the
thermocouple are maintained at a known reference temperature, the
thermoelectric voltage produced by the thermocouple is a repeatable
function of the temperature of the measuring junction.

Electromotive force, thermoelectric voltage - synonymous terms

that describe the net value of electrochemical potential that is
generated by a thermocouple with reference junctions at 0 °C and
measuring junctions at the indicated temperature. The
electromotive force is abbreviated "emf" and is denoted by the
symbol E.
Temperature measurement: Thermocouples
The NIST ITS-90 thermocouple database
NIST Standard Reference Database 60, Version 2.0 (Web Version)
http://srdata.nist.gov/its90/main/

THERMOCOUPLES
Type Composition Temperature range, °C
B Pt-30% Rh versus Pt-6% Rh 0 to 1820
E Ni-Cr alloy versus a Cu-Ni alloy -270 to 1000
J Fe versus a Cu-Ni alloy -210 to 1200
K Ni-Cr alloy versus Ni-Al alloy -270 to 1372
N Ni-Cr-Si alloy versus Ni-Si-Mg alloy -270 to 1300
R Pt-13% Rh versus Pt -50 to 1768
S Pt-10% Rh versus Pt -50 to 1768
T Cu versus a Cu-Ni alloy -270 to 400

Types normally used by NGB

Measurement terms: accuracy - precision
Temperature measurement: Thermocouples

The right position of the thermocouple in the temperature field to be

measured is extremely important. If the temperature gradient along
the thermocouple is too high, heat is conducted away from the
welding point and the temperature at the virtual point (V) is indi-
cated (748 °C) instead of the true value of 778 °C.
Temperature program and signal creation
Temperature program and STC function

STC influence
Furnaces: characteristics of heaters
Nickel-Chromium Alloys
Nickel-chromium alloys are the most
common class of resistance heater
materials. Various formulations,
which can include iron, aluminum and
silicon, show useable element
temperatures up to some 1400 °C.
Change in resistance from room
temperature over the working range
is only some 4 to 6%. It also changes
very little during service life.

Silicon Carbide
This class of materials has a
permissible element temperature
close to 1600 °C. The control system
has to cope with resistance changes
of up to about 3:1 over the working
temperature range and some 4:1
over the useful life of the element
Furnaces: characteristics of heaters

Molybdenum Disilicide
Heaters. In the figure you can
see there is a resistance change
of some 14:1 over the working
temperature range -- much more
than silicon carbide but subject
to only small changes with
service life.
Tungsten Heaters. The
resistance change over the
working range is about 17:1.
Aging effects are negligible.
Current limiting is inherent in the
resistance attained at working
temperature.
DSC signal (first order transition)
DTA

Point contacts between

thermocouples and crucibles
DSC

Area contacts between

thermocouples and crucibles
Noise in DSC signal, 0.036 mg Indium, 10 K/min

DSC /(mW/mg)

 exo 156 .84 °C

[2] Indium5.sdd 2-2/5 - DSC
16
DSC /(mW/mg)
 exo
8.100
14 8.000
7.900
7.800
7.700
7.600
7.500
7.400
12 7.300
7.200
151.5 152.0 152.5 153.0
Temperature /°C

10
156 .61 °C

29 .3 J/g

150 152 154 156 158 160

Temperature /°C
Noise in DSC signal, 0.036 mg Indium, 10 K/min
 DSC 404C Pegasus DSC-Sample holders

Influence of type of thermocouple on sensitivity and resolution

 DSC 404C Pegasus Sample holders

Influence of type of sample holder on sensitivity and resolution

Dilatometry

Horizontal pushrod dilatometer

Dilatometry: LVDT

Linear variable displacement transformer,

consisting of a primary coil and two secondary
coils
DIL 402C: sample holders
-180 ... 2000°C
Calibration of relative expansion
measurements
DIL: Sample arrangements

cylinder
sample piston

pushrod sample

Sample container (various materials)

for pastes and powders

spacers
supports

pushrod sample
Sample Supporting Kit
(fused silica or Al2 O3 )
for samples: Ø 4mm, 6 mm and 8 mm Spacers (Al2 O3 )
prevent the sticking of samples
Principle of thermogravimetry (TG)
Basics of online coupling-gas flow profile

• Gas flow in vertical,

toploading systems

Vertical+toploading:
• controlled convection
• controlled chimney-
effect
STA 449C Jupiter -120 ... 1650°C
Thermogravimetry: Buoyancy effect

Equal Volumes Feel Equal Buoyant Forces

Suppose you had equal sized balls of cork, aluminum and lead, with
respective specific gravities of 0.2, 2.7, and 11.3. If the volume of
each is 10 cubic cm then their masses are 2, 27, and 113 g.

Each would displace 10 grams of water, yielding apparent masses of

-8 (the cork would accelerate upward, swim), 17 and 103 g
respectively.
Thermogravimetry: Buoyancy effect

Buoyant Force

Buoyant force is also present in gases, but much smaller

compared to liquids (density difference)