Materials Characterization

Methods
Thermal properties of
Materials

1. MIcheal E Brown (Ed), Introduction to Thermal Analysis, Techniques and applications, Chapman and Hall, NY, 1988.
2. J. Rak, P. Skurski, M. Gutowski and J. Btazejowski; J. Thermal analysis 43, 239-246, 1995
3. NPTEL lectures on Introduction to polymer science (Week 7 and 8), by IIT KGP
4. https://www.youtube.com/watch?v=wH3J4DDQWnc&ab_channel=LaboratorySolutionsfromMETTLERTOLEDO
5. N.W. Hurst, S.J. Gentry, A. Jones, B.D. McNicol, Temperature Programmed Reduction, Catal. Rev. 24, 233–309, 1982
 Thermal Property Measurements
Thermal properties - Response of materials to application of heat
o Heat capacity, specific heat capacity and molar heat capacity
o Latent Heat Thermal Analysis - Study of change of properties of material as
o Thermal Conductivity a function of temperature
o Thermal Expansion etc • Thermogravimetric Analysis (TGA): Mass change
• Differential thermal analysis (DTA): Temperature difference
• Differential scanning calorimetry (DSC): Heat flow difference
Reactivity: TPR
• Thermal expansion measurements (Dilatometry)
• Dynamic mechanical analysis (DMA): Mechanical stiffness
and damping
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 Thermal expansion measurements (Dilatometry)
Micheal E Brown (Ed), Introduction to Thermal Analysis, Techniques and applications,
Chapman and Hall, NY, 1988

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 Thermal expansion
o Thermal expansion is the tendency of matter to change its shape, area, volume, and
density in response to a change in temperature, usually not including phase
transitions.

Drinking glass with fracture due

to uneven thermal expansion
after pouring of hot liquid into
the otherwise cool glass
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Opening a glass jar with metal lid
Dilatometry - Measures the
expansion as a function of T
Expansion joint in a road
bridge used to avoid damage
from thermal expansion.
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 Some Basics about Thermal Expansion
o Changes in length compared to original length (∆ℓ/ℓ0) called linear expansion. Changes in
area compared to original area (∆A/A0) called areal expansion or superficial expansion.
Changes in volume compared to original volume (∆V/V0) called volumetric expansion or
cubical expansion.
o Isotropic and anisotropic expansion
o Co-efficient of thermal expansion - fractional change in size per degree change in
temperature at a constant pressure (unit K-1). In the general case of a gas, liquid, or solid,

the volumetric coefficient of thermal expansion is given by

o Linear thermal Expansion Coefficient

Negative and positive a
 Some Basics about Thermal Expansion

Energy

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 Thermal expansion measurements
Methods of Measurement Applications
o Push-rod Dilatometers o Selection of suitable material for various
(Mechanical) applications
o X-ray diffraction o Determination of compatibility of materials
o Twin - telemicroscope Method o Determination of glass transition temperature
o Interferometers o Study of kinetics of sintering
o Capacitance dilatometer o Study of defects in non-stoichiometric oxides
o Optical dilatometer o Study of the effect of additives on shrinkage of
o Strain gauge cellular concretes etc.

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 Push-rod Dilatometer Linear variable
differential transformer

Absolute measurement Differential measurement

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 Optoelectronic Transducer Dilatometer
o A stabilized light source illuminates two photodetectors through a screen with rectangular
holes.
o This screen is attached to the push-rods - when expansion/contraction occurs light
illumination changes.
o Dimensional variations 10-2 mm can be
measured
o Speed of response ten times of that of
LVDT

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 Laser Dilatometer
o Based on Michelson interferometry
o The laser beam is split into two after 90o
reflection
o Two beams are directed at the reflectors
attached at the end of sample and
reference.
o After complete reflection, beams are recombined to obtain interference patterns.
o Patterns are examined using photodetectors and converted into expansion/shrinkage.
o Accurate to one-quarter of the wavelength of the laser, no mechanical parts, rapid,
wider temperature range
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 Temperature-programmed reduction
N.W. Hurst, S.J. Gentry, A. Jones, B.D. McNicol, Temperature Programmed Reduction, Catal. Rev. 24,
233–309, 1982

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 Temperature-programmed reduction
o Temperature-programmed reduction (TPR) is a technique for the characterization of
solid materials and is often used in the field of heterogeneous catalysis to find the
most efficient reduction conditions,
o An oxidized catalyst precursor is submitted to a programmed temperature rise while
a reducing gas mixture is flowed over it. Typically measured with 10% H2 in N2.
o It can give information of presence of different oxidation states, etc.

o Area under the peak gives amount of hydrogen used. MO(s) + H2(g)  M(s) + H2O(g)

o Oxidation, sulfidation, and desorption may also be measured.

 Oxygen storage capacity
o Oxygen Storage Capacity is a measure of how much Oxygen a material can store and release

CeO2 Fluorite
a : Oxygen vacancy
structure
defect
b : Self interstitials
c,d : Interstitial
impurities
e,f : Edge dislocations

o The presence of Cerium, which can exist in +4 and +3 oxidation states results in oxygen
vacancies in the structure.
o As the number of vacancies increases, ease at which oxygen can move around increases
allowing ceria to get reduced/ oxidized easily.
 Oxygen storage capacity
o Catalytic activity of Ceria is directly related to Oxygen vacancies in the Crystal.
o Oxygen vacancies can be increased by the presence of impurities/dopants.
o Doping of Cerium oxide by Zirconium increases Oxygen vacancies and also Thermal
stability.
o Zirconium, Yttrium promotes oxygen vacancies creation
o At the high temperatures that can be reached under driving conditions, “thermal
deactivation” of the ceria begins to occur and it will diminish the OSC of the particle
o With the help of TPR, the characterization of heterogeneous catalyst to find the most
efficient reduction conditions - reducibility of oxide’s surface – can be achieved.
TPR Set-up
 Temperature-programmed reduction

o A simple container is filled with a solid or catalyst. This sample vessel is positioned in a
furnace with temperature control equipment. A thermocouple is placed in the solid for
temperature measurement. A reducing gas (H2) flows over the sample and temperature
is increased.
o At the beginning of a TPR experiment, gas flows over a fixed amount of solid at a
temperature low enough to prevent reaction. The temperature of the solid is then
increased at a linear rate, b K/min, and the rate of the reaction is monitored. This can
be achieved by measuring concentration or pressure changes in the gas phase
(reactants or products) or weight changes of the solid.
 Temperature Programmed Reduction (TPR)
o Depending upon the temperature, Oxygen is Thermal conductivity
cell: H2 has a high
released, reducing gas is consumed, which will be electrical conductivity,
detected by measuring thermal conductivity of so a decrease in H2 is
marked by a decrease in
the gas stream by a Thermal conductivity conductivity.

detector (TCD). The TCD signal is then converted

to concentration of active gas using a level
calibration.
o In a TPR spectrum, peak maximum indicates the
temperature that corresponds to the maximum
rate of reduction.
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