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