Im SWP L 002f

Analyzing & Testing
Business Unit
Thermal Analysis Methods (Part 1):

TG, DSC, STA, EGA
Practical Applications of Thermal Analysis Methods in Material Science

Krakow, 15 – 16 May, 2012
Ekkehard Post, NETZSCH Gerätebau, Wittelsbacher Str. 42, D-95100 Selb/Germany
Krakow 2012/ep www.netzsch.com

Thermal Analysis Techniques
Thermo- Thermophysical
Differential Thermo- mechanical Dielectric Properties
Scanning gravimetric Analysis (TMA) Analysis
Calorimetry Analysis Dilatometry (DEA) Laser Flash
(DIL) Analysis (LFA)
(DSC, DTA) (TGA) Heat Flow Meter
Dynamic-
Mechanical Guarded Hot
Analysis (DMA) Plate etc.
Thermal effects Dielectr. Thermal

Mass changes Dimensional
from physical constant Conductivity
due to changes,
and chemical (permittivity), Thermal
evaporation, deformations,
processes loss factor, Diffusivity
decomposition viscoelastic
(phase conductivity, Specific Heat
and interaction properties,
transitions, resisitivity Thermal
with the transitions,
reactions); (ion viscosity); Expansion
atmosphere density
specific heat cure index (degr.
of cross-linking)
Evolved Gas Analysis
(EGA – MS, FTIR, GC-MS)

Thermogravimetric Analysis
With this Instrument were

obtained the first TG-curves for
MnSO4• H20, CaCO3 and
CrCO3.
First thermobalance were built by Kotaro Honda in 1915, working at

Tohoku Imperial University.
Thermogravimetry (TG):
Measuring Principle
Background:
- law of mass conservation

- mass change by reaction
separation/absorption of
gaseous materials
 transition rate = f(m)
Electronic microbalance – the sample’s gravitational force is continually evened out by the
electromagnetic force.
The needed current for the equilibrium represents the measurand and is recorded.
ASTM E 473 – 85:
Thermogravimetry is a technique in which the mass of a substance is measured as a
function of temperature while the substance is subjected to a controlled-temperature
program.

Arrangements of Commercial TGAs

Schematic of a Top Loading Balance
gas outlet
cover support
sample
sample carrier cooling

gas inlet
vacuum purge
cooling
pressure sensor hoist

sample carrier
relief valve
balance
gas inlet
protective

TG curve
TG /%
100
-12.05 %
90
80
-18.81 %
70
60
-29.48 %
50
40
30
100 200 300 400 500 600 700 800 900
Temperature /°C

TG and DTG curves
TG /% DTG /(%/min)
100 1.0
-12.05 %
90 0
80 -1.0
-18.81 %
70 -2.0
60 -3.0
-29.48 %
50 -4.0
40 -5.0
30 -6.0
100 200 300 400 500 600 700 800 900
Temperature /°C

Stainless Steel in Humid Atmosphere
2 days isothermal at 900°C
Sample: Stainless Steel

Sample mass: ~ 500 mg
Crucible: Alumina Plate
Heating rate: 10/0 K/min
Atmosphere: Water vapor
Sensor: TG type S

Differential Scanning Calorimetry /
Differential Thermal Analysis
Furnace
Sample Refer.
.
Q PR
T
Differential Scanning Calorimetry (DSC) is a Thermal Analysis

technique in which the heat flow rate (power) to the sample is
monitored against time or temperature while the temperature of
the sample, in a specified atmosphere, is programmed
ICTA; For better Thermal Analysis and Calorimetry, Edition III
(1991)

DTA and DSC Principle
During a phase transition a temperature difference

(heat flux difference) between the sample and
reference can be measured by means of a
thermocouple.
Generation of the DSC/DTA Signal

Magnesium Alloy

Second Order Phase Transitions
- magnetic phase transition of iron (Lambda shape) -
DSC /(mW/mg) Sample: Iron disk

exo Sample mass: 129.68 mg
Crucible: Pt+liner+lid
7 Sample holder: DSC-cp
Heating rate: 20 K/min
6 Atmosphere: Argon at 50 ml/min
1559.7 °C
5
Sample: Iron
4
3 266.1 J/g
2
1399.3 °C
926.4 °C
1
770.2 °C 16 J/g 16.13 J/g
0 1534.0 °C
magnetic A3 A4
melting
-1
200 400 600 800 1000 1200 1400 1600
Temperature /°C

Phase diagrams - DSC

Phase diagram of NiAl

Phase diagram of NiAl

Heat Capacity of Molydenum
0.40
Mo: Literature
Mo: Measurement
0.35
Specific Heat /J/(g K)
0.30
0.25
0.20
0.15
-200 -100 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300
Temperature /°C

Simultaneous Thermal Analysis (STA)
Simultaneous Techniques
This refers to the application of two or more techniques to a (single)

sample at the same time. A hyphen is used to separate the
appreviations, e.g. simultaneous thermogravimetric analysis and
differential scanning calorimetry (TGA-DSC).
ICTA 1991
TG-DSC/DTA
Simultaneous mass change and energetic information on one and the same
sample under absolutely identical measurement conditions

Simultaneous Thermal Analysis (STA)
Furnace
Sample Refer.
.
Q PR
T
TG + DSC = STA
Thermogravimetry Differential Scanning
Calorimetry
TG, DSC applied simultaneously to the same sample.

TG – DSC Measurement of Fe2O3

Heating and Cooling of MnO2
TG /% DSC /(mW/mg)
exo
102
6
-0.23 %
100
619.1 °C
98 4
958.2 °C
96 Sample: MnO2 1200.7 °C
-9.20 % 2
71.45 J/g
94
432.1 J/g 179.7 J/g 0

92
-71.83 J/g
90
1147.8 °C -2
-3.07 %
88
-4
86
200 400 600 800 1000 1200 1400
Temperatur /°C

Different Furnaces for Different Applications

Sample Carriers
TG-DSC
TG-DTA
TG
TG-DSC- cp

Special STA furnaces increase
application range
2400°C
Furnace
Water Vapour
Furnace

Scheme of the Tungsten Furnace
Maximum temperature
at sample:
2400°C
Maximum heating and

cooling rate:
100 K/min
Atmospheres:
Helium, vacuum

Tungsten Furnace Guarantees very
clean Atmospheres
At 2400 °C, the vapor pressure of graphite is 10-3 torr, therefore no high vacuum can be
applied. The tungsten furnace of the STA 429 allows measurements in high vacuum
(10-5 torr) up to 2400 °C. This is essential for clean atmospheres and Knudsen cell tests
Melting and Crystallization of Vanadium
TG /% DTA /(µV/mg)
[1.2]
120 sample Vanadium, 20 K/min, He 7
exo
100
6
theoretical values: melting1890°C 38.47 µVs/mg
80
1887.1 °C
5
heating
60
4
40 cooling 1879.9 °C
Temperature program: RT to 1970°C to 1600°C

-38.74 µVs/mg 3
20 Heating rate: 20 K/min
Atmosphere: He
Crucible: ZrO2 „liner“ in W crucibles
0 2
1760 1780 1800 1820 1840 1860 1880 1900 1920 1940
Main 2009-07-03 08:08
Temperature /°C
Created with NETZSCH Proteus software

Sapphire
TG /% DTA /(µV/mg)
exo
100
Temperature range: RT to 2100°C 12
50 Heating rate: 75 K/min

Crucible: W with lid 11
0 Atmosphere: He
Sample weight: 12.34 mg 52.43 µVs/mg
-50 10
Melting of Sapphire
-100
9
2nd heating
-150
8
-200 2055.0 °C
7
-250
-300 6
2000 2020 2040 2060 2080 2100
Main 2009-07-03 12:01
Temperature /°C

EGA methods combined with TGA
 MS Mass Spectrometry
 FTIR Fourier Transform Infrared

Spectroscopy
 GC-MS Gas Chromatography with MS
 GC-FTIR GC with FTIR
www.netzsch.com Krakow 2012/ep

MS Capillary Coupling

Hydromagnesite
(STA-MS Capillary)
Mg5(CO3)4 (OH)2 * 4 H2O
mass 25.98 mg
temp. 25 ... 960°C
HR 10 K/min
Air, 80 ml/min

16th March 2011

Tools to Investigate such Events?

Zircaloy Zirc-4 BCR-276
DTG /(%/min)
TG /% Ion Current *10-9 /A
5.0 0.8
114
TG 0.7
112 BCR-276 4.0
0.6
110 in N2 and water vapor atmosphere
DTG
0.5
5 K/min 3.0
108 0.4
106 0.3
2.0
104 0.2
102 2 amu 1.0 0.1
100 0.0
0
500 600 700 800 900 1000
Temperature /°C

MS-Skimmer Coupling
Quadrupol analyzer
10-5 mbar Ion source
10-1 mbar
Skimmer
Orifice
Sample
1013 mbar Heater
Sample carrier
Gasoverflow

Melting behaviour of CuGaSe2
http://www.nrel.gov/docs/fy03osti/33997.pdf
NREL/SR-520-33997

CuGaSe2
I2
Impurities: Selenium excess, Iodine

STA – MS – FTIR Coupling

TG – FTIR Measurement of PVC

STA – GC – MS Coupling

Thank you for your attention

Im SWP L 002f

Încărcat de

Informații document

Titlu original

Drepturi de autor

Formate disponibile

Partajați acest document

Partajați sau inserați document

Opțiuni de partajare

Vi se pare util acest document?

Este necorespunzător acest conținut?

Drepturi de autor:

Formate disponibile

Im SWP L 002f

Încărcat de

Drepturi de autor:

Formate disponibile

Analyzing & Testing

Thermal Analysis Methods (Part 1):

Practical Applications of Thermal Analysis Methods in Material Science

Ekkehard Post, NETZSCH Gerätebau, Wittelsbacher Str. 42, D-95100 Selb/Germany

Krakow 2012/ep www.netzsch.com

Thermal effects Dielectr. Thermal

Krakow 2012/ep www.netzsch.com

With this Instrument were

First thermobalance were built by Kotaro Honda in 1915, working at

- law of mass conservation

Krakow 2012/ep www.netzsch.com

Krakow 2012/ep www.netzsch.com

sample carrier cooling

pressure sensor hoist

Krakow 2012/ep www.netzsch.com

Krakow 2012/ep www.netzsch.com

Krakow 2012/ep www.netzsch.com

2 days isothermal at 900°C

Sample: Stainless Steel

Krakow 2012/ep www.netzsch.com

Differential Scanning Calorimetry (DSC) is a Thermal Analysis

Krakow 2012/ep www.netzsch.com

During a phase transition a temperature difference

Krakow 2012/ep www.netzsch.com

Krakow 2012/ep www.netzsch.com

DSC /(mW/mg) Sample: Iron disk

Krakow 2012/ep www.netzsch.com

Krakow 2012/ep www.netzsch.com

Krakow 2012/ep www.netzsch.com

Krakow 2012/ep www.netzsch.com

Krakow 2012/ep www.netzsch.com

This refers to the application of two or more techniques to a (single)

Krakow 2012/ep www.netzsch.com

TG, DSC applied simultaneously to the same sample.

Krakow 2012/ep www.netzsch.com

Krakow 2012/ep www.netzsch.com

432.1 J/g 179.7 J/g 0

Krakow 2012/ep www.netzsch.com

Krakow 2012/ep www.netzsch.com

Krakow 2012/ep www.netzsch.com

Krakow 2012/ep www.netzsch.com

Maximum heating and

Krakow 2012/ep www.netzsch.com

Temperature program: RT to 1970°C to 1600°C

Created with NETZSCH Proteus software

50 Heating rate: 75 K/min

Krakow 2012/ep www.netzsch.com

 FTIR Fourier Transform Infrared

 GC-MS Gas Chromatography with MS

 GC-FTIR GC with FTIR

www.netzsch.com Krakow 2012/ep

Krakow 2012/ep www.netzsch.com

Mg5(CO3)4 (OH)2 * 4 H2O

www.netzsch.com Krakow 2012/ep

Krakow 2012/ep www.netzsch.com

Krakow 2012/ep www.netzsch.com

102 2 amu 1.0 0.1

Krakow 2012/ep www.netzsch.com

1013 mbar Heater

Krakow 2012/ep www.netzsch.com

Krakow 2012/ep www.netzsch.com

Impurities: Selenium excess, Iodine

Krakow 2012/ep www.netzsch.com