Characterization of Inorganic Materials:

Thermal and Thermodynamic Methods

270153 VO, 2 lecture hours, 3 ECTS credits
Klaus Richter

1. Common Basics for High Temperature Techniques

2. Dynamic Methods
3. Selected Isothermal Methods for Combination
4. Measurement of Thermodynamic Properties
5. Estimation and Tabulation of Thermodynamic
Properties
6. Thermodynamic Modeling

1 Common Basics
 Temperature Scales

0. Law of Thermodynamics:
temperature ⇔ thermal equilibrium

Primary Temperature Scale:

Kelvin scale uses the triple point of water
T = 273.16 K

Secondary Temperature Scale:

ITS90 – International Temperature Scale of 1990
The temperature is defined by a number of secondary fixed
temperatures.
Important for the calibration of all kind of thermometers!

2 Common Basics
 Fixed Points of the ITS 90

ITS Methods:

• 3.0 - 24.5561K:
He – gas thermometer
• 13.8033 - 1234.93K:
Pt – resistance
thermometer
• more than 1234.93K:
Monochromatic pyrometer

Important Calibration Substances!

3 Common Basics
 Temperature measurement: Thermocouples
Type T max / °C

Thermoelectric effect: Fe-CuNi (Typ J) 1150

“Seebeck effect” Ni-CrNi (Typ K) 1350

Pt-PtPh (Typ S) 1650

Material A Pt-EL18 (Typ B) 1800

W-WRe (Typ C) 2300
ΔE

T1 Material B T2 A

Thermoelectric Voltage ΔE Tm B
T0
Cu
dependent on T1, T2 and the
Thermocouple Measurement
“Seebeck coefficient” α
Arrangement

4 Common Basics
 Temperature Measurement: Resistance Thermometer

Metals: Semiconductors:
Pt, Ni, Cu, ….. Fe3O4, MgAl2O4, …..
e.g. “Pt100”

B
R = R0 + Rth (T ) R = R∞ ⋅ e (T + Θ )

PTC Materials NTC Materials

The temperature-dependence Strong non-linear temperature

of R is almost linear dependence of R

ρ ~ 10-5-10-6 Ωcm ρ ~ 10-2-109 Ωcm

Attention: Ceramic PTC Materials (BaTiO3) have no linear behavior!

5 Common Basics
 Temperature Measurement: Pyrometry
Black Body Radiation

∫ λ λ = σ 4
1. Stefan – Boltzmann: I (T , )d T
0

2. Wien: λMax .T = const .

1
3. Planck: I (T , λ ) = c1λ −5

e c 2 / λT − 1 IR Pyrometer
Monochromatic Pyrometer
Two color Pyrometer
Measurement correction by surface
emissivity or use of hollow body radiation

6 Common Basics
 Furnace Construction

Resistance Heating
(Induction Heating)
(Fast Pulse Heating)
Important Construction Principles
for Commercial Instruments:
Materials for Heating elements:
• Kanthal Steel (up to 1350°C)
• SiC (up to 1550°C)
• MoSi2 (up to 1700°C)
• Mo wire (up to 1800°C)
• Graphite, W (more than 1800°C)

• Axial Symmetric Tube Furnace Materials for Isolation and

• T-constant zone Shielding:
• Small heat capacity • Al2O3 ceramics
• Radiation shielding • refractory metals
• Cooling unit (air or water) • Graphite
• Separate T-measurement for
controller

7 Common Basics
 Vacuum and inert gas atmosphere
Measurements in air at high temperatures ⇒ Reaction with oxygen
⇒ Use vacuum or inert gas atmosphere

> 1 mbar Low vacuum

Sliding vane pump
10-3-1 mbar Medium vacuum
10-7-10-3 mbar High vacuum
Turbo-molecular pump
< 10-7 mbar Ultra high
Oil diffusion pump
(fore-vacuum required)

Inert gas: Ar (N2, He): e.g. Ar 5.0 (= 99.999 % Ar)

• Subsequent cleaning systems (e.g. Oxisorb®)
• Flushing
• Dynamic flow or static atmosphere

8 Common Basics
 Pumping Systems

Sliding vane pump Turbo molecular pump

9 Common Basics
 Crucible Materials
The selection of a proper crucible material is essential for every high-
temperature measurement!

Criteria:
thermal stability ♦ reactivity with the sample ♦ thermal conductivity
♦ permeability for gases ♦ thermal shock resistance

High temperature Materials:

• quartz glass (silica) ~ 1250 °C
• sintered Al2O3 (alumina) ~ 1900 °C
• sintered MgO (magnesia) ~ 2300 °C
• BN ~ 1600 °C
• graphite ~ 3000 °C
• Ta ~ 2500 °C

10 Common Basics