Lehrstuhl für Werkstoffanwendungen im Maschinenbau Nizzaallee 32

Univ.- Prof. Dr.-Ing. C. Broeckmann 52072 Aachen

Report No. AU10172

Number of pages 13

Date 4.01.2011

Determination of thermo physical

Subject properties of Certec P-35

Content:

Analysis of Certec P-35

• Thermal diffusivity under argon

• Thermal diffusivity under vacuum

• Heat capacity under the influence of air

• Density and pore-size distribution

• Evaluation of thermal conductivity

• Thermal expansion with evaluation of technical and physical alpha

• Microstructure analysis via REM/EDX

Commissioned by ACCESS, Aachen (Dr. Hediger)

Address Intzestr. 5, 52072 Aachen

Scientist responsible Dr.-Ing. Ewald Pfaff

Tel.: +49 241 8096704

e-mail: [email protected]

Signature

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Contents

1. Objectives ............................................................................................................................... 3

2. Samples .................................................................................................................................. 3

3. Measurements .........................................................................................................................

3.1. Density ........................................................................................................................... 7

3.2. Thermal diffusivity .......................................................................................................... 8

3.3. Heat capacity ................................................................................................................ 9

3.4. Coefficient of thermal expansion ................................................................................. 10

3.5. Evaluation of thermal conductivity ................................................................................ 11

4. Description of methods of investigation ...............................................................................

4.1. Laser Flash Analysis (LFA) .......................................................................................... 12

4.2. Differential Scanning Calorimetry (DSC) .................................................................... 12

4.3. Dilatometry ................................................................................................................... 13

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1. Objectives
The goal of the analysis was determination of the thermo physical properties of Certec P-35. It includes
the measurement of thermal expansion by dilatometry, of thermal diffusivity a by laser flash analysis
(LFA), of specific heat capacity cp by Differential Scanning Calorimetry (DSC) and density ρ. From the
measured values the values of thermal conductivity λ at RT, 200, 400, 600, 800, 1000 and 1200°C were
calculated according to the equation λ = a · cp ·ρ.

Firstly, the microstructure was examined from ground samples using SEM (scanning electron
microscope). For sample specification, density and pore distribution are measured via Mercury Intrusion
Porosimetry (MIP).

2. Samples
Parts of samples of Certec P-35 were delivered by Access on 29. Nov. 2010. Samples for each analysis
were prepared by dry diamond cutting and grinding. Subsequent structural analysis showed a
microstructure mainly consisting of two phases. The main phase exhibits the elements Si and O and is
characterized as SiO2. The secondary phase has a high Zr, Si and O content. The corresponding phase
should be ZrSiO4. Element analysis also revealed C and Cl, arising from the embedding resin and the
coating.

Fig. 1: Light microscopy picture of a polished cross-section of sample „Certec P-35“

Samples for subsequent analysis were prepared as follows:

REM: Parts of approx. 1 cm3 of each sample are cut, embedded in resin, grinded and
C-coated.
LFA: A core of 10.0 x 10.0 mm is bored out. Disks of a thickness of approx. 4 mm are
cut. Plane parallelism is achieved by manual sanding. Subsequently, a fine
coating of platinum is sputtered on and the graphite sprayed on.
DSC measurement: A core of Ø=5 mm is bored out. Disks with thickness of approx. 1 mm were cut.
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Hg-Porosimetry: Several pieces of undefined geometry were cut.
Dilatometry: Separation of rods of dimensions of approx. 20 x 4 x 4 mm3. Plane parallelism
was achieved by manual sanding.

Fig. 2: Polished cross-section of sample „Certec P-35“ (SEM, SE).

Fig. 3: Polished cross-section of sample „Certec P-35“ (SEM, BE).

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Fig. 4: Polished cross-section used for EDS analysis (SEM, BE).

Fig. 5: Element analysis at point a (SEM, BE picture No.22957abc).

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Fig. 6: Element analysis at point b (SEM, BE picture No. 22957abc).

Fig. 7: Element analysis at point c (SEM, BE picture No.22957abc) shows C and Cl of resin embedding
material as well as SiO2.

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3. Measurements
3.1 Density
Density was measured using MIP. The dependency of density on temperature is estimated by equation ρ
(T) = ρ0 / (1 + α∆T)3; in which α is the expansion coefficient between RT and Tx determined by dilatometry
(Table 2).

Table 1: Density
Name of sample Certec P-35
Density [g/ccm] 1.553
Porosity (open) [%] 30.33

Fig. 2: Graph for Density as function of temperature (sintering above 1200 °C)

Tab. 2: Dependency of density on temperature of Certec P-35.

T α ρ(T)
[°C] [10 K-1]
-6
[g/cm3]

25 --- 1.553
200 3.95 1.550
400 2.64 1.548
600 2.31 1.547
800 2.07 1.546
1000 1.70 1.546
1200 1.33 1.546
1400 1.20 1.546
*)
Sintering

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3.2 Thermal Diffusivity
Thermal diffusivity was determined by the Laser Pulse Method (see annex).

Tab. 3: Test overview

Sample Run Date Thickness
[mm]
Certec P-35 argon 10510 15.12.2010 3.987

Certec P-35 vacuum 10610 17.12.2010 3.993

Tab. 4: Thermal diffusivity a (mean and standard deviation).

a [mm²/s] Deviation a [mm²/s] Deviation
T
Certec P-35 [%] Certec P-35 [%]
[°C]
(10510 - Argon) (10610 - Vacuum)
20 0.481 ± 0.014 2.9 0.451 ± 0.002
200 0.415 ± 0.001 <1 0.393 ± 0.002
400 0.409 ± 0.003 <1 0.387 ± 0.001
600 0.402 ± 0.025 6.2 0.385 ± 0.003
800 0.419 ± 0.021 5.0 0.393 ± 0.004
1000 0.445 ± 0.022 4.9 0.421 ± 0.028
1200 0.488 ± 0.028

Fig. 3: Thermal Diffusivity measured and corrected as f(T) under Argon and Vacuum (± 5 %).

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3.3 Specific Heat Capacity

Determination of specific heat capacity was carried out using DSC equipment (Netzsch, DSC 404
Pegasus F/SO) by application of the relation method with calibration on sapphire under air.

Tab. 5: Abstract
Sample Run Date Mass
[mg]
Certec P-35 p38-10 14.12.10 27.5

Tab. 6: Heat capacity cp

Cp
T
Certec P-35
[°C]
[J/(K*g)]
20 0.7601)
200 0.877
400 0.981
600 1.044
800 1.064
1000 1.120
1200 1.408
1400 1.494
1) 2)
extrapolated apparent cp

Fig. 4: Measured specific heat capacity as function of temperature of Certec P-35.

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3.4 Coefficient of Thermal Expansion
Thermal expansion dl/l0 was measured in air as a function of temperature in a high temperature
dilatometer DIL 402C (Netzsch Gerätebau GmbH, Selb). The coefficient of expansion α was calculated
therefrom.

Tab. 7: Test overview

Sample Run Date Length
[mm]
Certec P-35 p36-10 22.12.10 20.120

Tab. 8: Coefficient of thermal expansion

T α techn. α phys. dL/L0
-6 -1 -6 -1
[°C] [10 K ] [10 K ] [10-3]
25 --- --- 0
200 3.95 3.03 0.62
400 2.64 1.66 0.98
600 2.31 1.99 1.33
800 2.07 0.55 1.61
1000 1.70 -0.17 1.69
1200 1.33 -2.39 1.61
1400 1.20 1.25 1.70
*)
contraction by sintering

Fig. 5: Graph of thermal expansion (± 5 %); method limited values < 100°C cannot be evaluated

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3.5 Determination of Heat Conductivity
Heat conductivity λ was calculated from data measured for thermal diffusivity a, specific heat capacity cp
and density ρ in relation λ = a . cp . ρ.

Tab. 9: Heat conductivity λ

λ 10510 λ 10610
T
Certec P-35(Argon) Certec P-35(Vacuum)
[°C]
[W/mK] [W/mK]
20 0.567 0.532
200 0.564 0.535
400 0.622 0.587
600 0.649 0.622
800 0.689 0.646
1000 0.771 0.728
1200 1.061

Fig. 6: Heat conductivity λ as function of temperature.

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4. Description of methods of investigation
4.1 Laser Flash Analysis (LFA)
Thermal Diffusivity a [mm2/s] as a function of temperature measured by the Laser Flash method

Specification EN 821/2
Test conditions
Equipment LFA 427 (NETSCH Gerätebau GmbH, Selb)
Nd:Cr:GGG-Laser of variable output (< 20 J/pulse) and
pulse length (0.2 – 1.2 ms), wavelength: 1.046 nm
In-Sb infrared detector (N2-cooled)
Temperature range: 20°C… 1600°C (thermocouple Type S)
Measurement range: 0.001… 10 cm2/s
Software with separate data evaluation models including finite pulse and
heat loss correction
Atmosphere: Argon 4.8 / vacuum ( 3*10-4 mbar )
Pulse width: 0.6 ms
Voltage: 400 V
Uncertainty of measurement: Thermal diffusivity < 5%
Sample carrier material: Al2O3 + SSiC cap
Coating of samples: Platinum & carbon spray (graphit 33, Kontakt Chemie, Iffezheim)
Analysis software: LFA Proteus Analysis
Correction: „Best Model“for each shot

4.2 Differential Scanning Calorimetry (DSC)

Specific heat capacity as function of temperature cp [J/gK]

Specification DIN EN 821/3

Equipment DSC Pegasus404/So (NETSCH Gerätebau GmbH, Selb)

Temperature range: 100°C… 1450°C (thermocouple Type S)
Atmosphere: Air
Sample dimensions: d ≅ 5 mm (accurate dimensions were not recorded since not relevant to
analysis)
Error of measurement: Temperature u(T) < 10 K
Uncertainty of measurement: Specific heat capacity u(cp) < 5%
Sample crucible material: Pt/Rh
Heating rate: 15 K/min (analysis of heating curve)

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4.3 Dilatometry
Technical and physical coefficient of expansion [10-6/K]

Specification DIN EN 821 – 1

Equipment DIL 402C (Netzsch Gerätebau GmbH, Selb)

Temperature range: 20°C… 1600°C (thermocouple Type S)
Measuring range for length: 5000 μm
Atmosphere: Air
Sample dimensions: Length l ≅ 25 mm (see results); edge length ≅ 8 x 8 mm
Error of measurement: Change in length u(∆I) < 1µm
Temperature u(∆T) < 2 K
u(T) < 10 K
Uncertainty of measurement: Relative change in length u(∆l/l0) < 5 %
Coefficient of expansion u(α) < 5 %
Sample holder: Al2O3 + thermocouple Type S
Standard: Al2O3
Force: 25 cN
Heating/cooling rate: 3K/min
TReference: 70°C

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