Principles of TG, DSC, STA and EGA

Ekkehard Post
NETZSCH Gerätebau GmbH
Wittelsbacherstrasse 42
D-95100 Selb, Germany

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 Thermal Analysis

Definition (ICTAC):
Thermal analysis (TA) is a group of techniques in
which changes of physical or chemical properties of
the sample are monitored against time or
temperature, while the temperature of the sample is
programmed.

The temperature program may involve heating or

cooling at a fixed rate, holding the temperature
constant (isothermal), or any sequence of these.

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 Methods of Thermal Analysis (TA)

Differential Thermogravimetry Thermomechanical

Scanning (TG) Analysis
Calorimetry (TMA)
(DSC, DTA) Dilatometry (DIL)
Dynamic-Mechanical
Analysis (DMA)

Physical and Mass changes due to Dimensional changes,

chemical processes evaporation, deformations,
related to thermal decomposition and viscoelastic
effects can be interaction with the properties,
characterized atmosphere transitions, density

Evolved Gas Analysis (EGA)

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 Thermal analysis for the characterization
of solids

Solids
Crystalline Amorphous

Glass transition
Polymorphism
∆Cp, ∆L
∆H
∆L Phase transition Crystallization
Softening
∆H, ∆Cp ∆H ∆L
∆L ∆L
Decomposition
Decomposition
∆m ∆H
∆m ∆H ∆L
∆L Liquid Crystal Glass-ceramics, polymers
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 Principle of thermogravimetry (TG)

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 Thermogravimetry

Mass change versus temperature and/or time

Thermobalance types

horizontal
Top loading Hang down
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 TG Curve - Principle

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 DTG Curve - Principle

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 Thermogravimetry: Buoyancy effect

Equal Volumes Feel Equal Buoyant Forces

Suppose you had equal sized balls of cork, aluminum and lead, with
respective specific gravities of 0.2, 2.7, and 11.3. If the volume of
each is 10 cubic cm then their masses are 2, 27, and 113 g.

Each would displace 10 grams of water, yielding apparent masses of

-8 (the cork would accelerate upward, swim), 17 and 103 g
respectively.
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 Thermogravimetry: Buoyancy effect

Buoyant Force

Buoyant force is also present in gases, but much smaller

compared to liquids (density difference)
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 STA 409PC Luxx

The sample holder

„swims“ in the
atmosphere. The
buoyancy force
(Archimedes‘ prin-
ciple) is reduced
with increasing
temperature, the
balance shows an
apparent weight
increase. This
depends also on
density of the gas.
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 STA 449 F1: Buouancy Reproducibility

TG /mg

0.5

0.4 Two Baselines

0.3

0.2

0.1

-> microgram accuracy!

Difference of the two baselines
0.0
0.000 mg

-0.1

100 200 300 400 500 600 700 800 900

Temperatur /°C

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 TG of Calcium Oxalate Monohydrate

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 Bouyancy and Convection

Dependent on
Fa = g • ρ • VK

Atmosphere

Type of sample carrier ∆Fa = g • VK • (ρ1- ρ2)

Heating rate

Crucible size

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 Bouyancy and Convection

Dependent on

Atmosphere

Type of sample carrier

Heating rate

Crucible size

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 Bouyancy and Convection

Dependent on

Atmosphere

Type of sample carrier
TG /mg

0.40

Heating rate

Crucible size
0.30

0.20

20 K/min
0.10

-0.0
10 K/min 2.5 K/min
-0.10

-0.20

-0.30
100 200 300 400 500 600 700 800 900
Temperature /°C

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 Heating Rate – Atmosphere generated

TG /%

100
861.9 °C

95 701.8 °C
783.7 °C
90

85

100 K/min
80

75 Dolomite 20 K/min
2 K/min
70 in nitrogen

65

60

55
550 600 650 700 750 800 850 900 950
Temperature /°C
Main 2008-09-03 10:21 User: Ekkehard.Post dolomit-heizraten.ngb
[#] Instrument File Date Identity Sample Mass/mg Segment Range Atmosphere Corr.
[1] TG 209 F3 xxx-3-08-06.dt6 2008-08-30 xxx-3-08-06 dolomit 41.092 1/1 20/100.0(K/min)/990 N2, 20.0ml/min / N2, 20.0ml/min 420
[2] TG 209 F3 xxx-0-08-4.dt6 2008-08-30 xxx-0-08-4 dolomit 2 K 39.129 1/1 20/2.0(K/min)/990 N2, 20.0ml/min / N2, 20.0ml/min 420
[3] TG 209 F3 xxx-3-08-5.dt6 2008-08-30 xxx-3-08-5 dolomit 37.307 1/1 20/20.0(K/min)/990 N2, 20.0ml/min / N2, 20.0ml/min 420

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 Application – Ferromagnetic Metals
Measurements in a Static Magnetic Field

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 Amorphous Metal: Ironboride (II)
TG /% DSC /(mW/mg)
↓ exo
5
550.0 °C 741.4 °C
101
421.0 °C 4

100 magnetic reentrance 1153.2 °C

due to crystallization! 3

99 melting
280 J/g!
Sample: Ironboride Measurement in magnetic 1066.5 °C 3.285 %
1188.0 °C 100.000 %
2

98 field gradient!
1
97 Curie-transition
1051.1 °C
421.2 °C 660.9 °C
-151 J/g 0
1.6 J/g
96
STA 449 Jupiter
Sample: Ironboride
-1
95
crystallization mass: 17.74 mg
crucible: Pt+Al2O3 lin.
atm.: Ar
flow rate: 70 -2
ml/min
94 554.6 °C
heating rate: 20 K/min

-3
200 400 600 800 1000 1200
Temperature /°C

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 Differential Thermal Analysis (DTA)

Differential Scanning Calorimetry (DSC)

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 Temperature Measurement

Temperature is one of the most frequently measured quantities.

Measurement with thermocouples or resistance thermometers.
Thermocouples for measuring temperature differences according to the Seebeck effect:

If an electric conductor is
Metal A exposed to a temperature
gradient, an electron flow is
soldering
generated inside the conductor,
EMF which causes an electromagnetic
joint
force (EMF, thermocouple
voltage).
Metal B

EMF = resulting voltage, S – Seebeck Coefficient.; t1 – temperature at the soldering

joint, t2 – reference temperature

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 Thermocouples according to
ITS 90 and IEC 584-1

Thermocouple (+) (-) Generated emf change approx. working Notes

type Leg Leg in µV/°C temperature range
(reference junction at 0°C)

at at at
100°C 500°C 1000°C
K Ni-Cr Ni-Al 42 43 39 0 …1100°C most suited for oxidising
(Chromel) (Alumel) atmospheres
T Cu CuNi 46 - - -185 … 300°C excellent for low
(Constantan) temperatures
J Fe CuNi 54 56 59 20 … 700°C used in reducing
atmospheres as an
unprotected thermocouple
N NiCrSi NiSi 30 38 39 0 … 1100°C very stable output signal
(Nicrosil) at high temperatures

E NiCr CuNi 68 81 - -200 … 800°C highest thermal emf

per °C
R Pt13Rh Platinum 8 11 13 0 … 1600°C high resistance to
Platin- oxidation and corrosion
13%Rhodium
S Pt10Rh Platinum 8 9 11 0 … 1550°C similar characteristics to
Platin- type R
10%Rhodium
B Pt30Rh Pt6Rh 1 5 9 0 ... 1600° similar characteristics to
Platin- Platinum- type R and S
30%Rhodium 6%Rhodium

Thermocouple type E usually used for low temperature DSC instruments

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 DTA and DSC Principle

Difference of heat flow

Furnace
Sample Refer. rate between sample and
.
Q PR reference

∆T

During a phase transition

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

Melting of a metal
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 Transformation Energetics of a Slag

The DSC 404 C Pegasus® allows examination of nearly all transformation energetics
over a wide temperature range. Glass transitions, crystallization and melting effects
can easily be studied.

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Dehydration of Al(OH)3, Crystallization of
Al2O3 and Melting

DSC /(uV/mg)

6 ↓ exo
Al(OH)3
348 °C
5

4 dehydration
2057 °C

3 αγ
1136 °C
2

melting
1 Al(OH)3Al2O3
gamma Al2O3 1378 °C alpha Al2O3

0
1259 °C
crystallization
-1
500 1000 1500 2000
Temperature /°C

Al(OH)3 42.4 mg, tungsten crucible, 75 K/min, helium static

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 Application of DSC

Melting temperatures
Transition enthalpies
Phase transformations, Phase diagrams
Crystallization temperatures
Degree of crystallinity
Glass transition temperatures
Decomposition effects
Reaction kinetics
Purity determinations
SPECIFIC HEAT

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 Calculation of Specific Heat

signal difference ( sample − baseline )

Cp =
sample mass • heating rate • sensitivit y

The specific heat of a material can be calculated from 3 measurements

(baseline, sapphire and sample).

The sensitivity is determined from the sapphire measurement

signal difference ( sapphire − baseline )

sensitivit y =
mass ( sapphire ) • heating rate • theoret . Cp ( sapphire )

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 Calculation of the specific heat (Ratio Method)

Isothermal segment of about 5-10 min. to obtain stable start conditions.

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 Calculation of specific heat

• All 3 measurements have to be performed with the same crucibles

and the same conditions

• Only sample crucible will be filled, reference crucible stays empty

• The crucibles should have during the 3 measurements the same

positions (for example mark with the tweezers).

• Switch off the STC.

• Cp values are only valid when no weight loss occurs.

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 Calculation of specific heat

sample
sapphire

Specific heat

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 Specific Heat Capacity of Sapphire
DSC /(mW/mg) Temp. /°C
↓ exo
0.20
150
0.15

0.10 dynamic
100
0.05

0.00 50

-0.05

0
-0.10 isothermal isothermal

10 20 30 40 50
Time /min

ASTM E 1269 : Test method for determining specific heat capacity by differential
scanning calorimetry
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 Specific Heat Capacity of Sapphire

DSC /(mW/mg) Cp /(J/(g*K))

↓ exo
2.0
0.16

0.14
DSC signal sapphire 1 1.5
0.12 DSC signal sapphire 2

0.10 literature values of the temperature dependent change

of the specific heat capacity of sapphire
1.0
0.08

0.06
measured values of the temperature dependent change
0.04 of the specific heat capacity of sapphire 0.5

0.02

0.00 0.0
0 20 40 60 80 100 120 140 160
Temperature /°C

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 Specific Heat of stab. Zirconia

Cp /(J/(g*K))

1.0000

Sample: Stab. Zirconia

0.9000
Sample weight: 127.07 mg
Crucibles Pt + lids
Heating rate: 20 K/min
0.8000 Atmosphere: Argon
Sensor: DSC-cp type S

0.7000

0.6000

0.5000

0.4000

0.3000

200.0 400.0 600.0 800.0 1000.0 1200.0 1400.0

Temperature /°C

Stab. zirconia is a ceramic material often used for industrial applications such as
thermal barrier coating or electrolyte material. The specific heat measured with the
DSC is close (less than 3% ) to the literature values for such materials.

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 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.

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 Advantages of STA

TG and DSC are applied simultaneously to the same sample!

Time effective! Also (expensive) sample

material can be saved.
Direct comparison of TG and DSC possible
(same measurement conditions on exactly
the same sample)

Exact determination of enthalpy changes

(sample mass continuously monitored)

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 Exchangable Furnaces Automatic Sample Changer (ASC)

Double furnace hoist

Exchangable Sample
Carriers (TG, TG-DSC, ...)
Various Crucibles
and Accessories
Flexible Temperature
Program (-150...2000°C)

Different Gas
Atmospheres Coupling with
MS and/or FTIR

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 Various Crucibles (I)

Various Crucibles for TG,

TG-DTA, TG-DSC (STA)
(also TG-plate, TG-basket)

Volumes: 40µl … 3.4 ml

Materials: Al2O3, Pt/Rh, Pt/Ir, Al

Au, Ag, ZrO2, graphite,
Cu, Ni, steel

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 STA Interchangeable Sensors

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 Schematics (A)

Toploading design!
(easy handling, robust)

Chimney effect!
(sensor contamination
avoided, less purge gas
required which is good
for EGA)

Vacuum tight for

defined atmospheres!

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 Inorganic Application: MnO2

TG /% DSC /(mW/mg)
STA 449 Jupiter ↓ exo
102 Sample: MnO2
evaporation of humidity mass: 32.14 mg
crucible: Pt
6
-0.23 % MnO2 -> Mn2O3 atm.: Synth. air
100 flow rate: 70 ml/min
heating rate: 20 K/min
619.1 °C
98 4
Solid state phase transition
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
Mn2O3 -> Mn3O4 -71.83 J/g

90
1147.8 °C -2
-3.07 %

88 cooling
-4

86
200 400 600 800 1000 1200 1400
Temperatur /°C

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 STA measurement of Fe2O3

3Fe2O32Fe3O4+1/2O2

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 A very short excourse about
the influence of measurement
parameters

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 Hexatriacontane

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Gas atmosphere - Calciumoxalat Monohydrate

Instrument: TG 209 Iris DTG /(%/min)

TG /% Sample mass: 10.12 mg c-DTA /K Gram Schmidt
Cruciblel: Al2O3
↓ exo
Atmosphere: syn. air, 30 ml/min 3.0
Heating rate: 10 K/min 0.20
100 1.0
-12.05 %
2.0
90 0
0.15
80 1.0 -1.0
-18.81 %
70 -2.0 0.10
0
60 -3.0
-29.48 % -1.0
0.05
50 -4.0

-2.0 -5.0
40
0
30 -3.0 -6.0
100 200 300 400 500 600 700 800 900
Temperature /°C

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Gas atmosphere - Calciumoxalat Monohydrate

TG /%

100 -12.32 %
-12.01 %
90
Stickstoff
Synthetic air
80 synthetische Luft
-18.96 %
-18.78 %
Nitrogen
70

60
-30.06 %
-29.47 %
50

40

30
100 200 300 400 500 600 700 800 900
Temperature /°C

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Gas atmosphere - Calciumoxalat Monohydrate

Instrument: TG 209 Iris

DTG /(%/min)
Sample mass: 9.84 mg
TG /% Crucible: Al2O3
c-DTA /K Gram Schmidt
Atmosphere: N2, 30 ml/min ↓ exo
Heating rate: 10 K/min
1.0 0.10
100
-12.32 % 3.0
0
90 0.08

2.0 -1.0
80 -19.02 % 0.06

70 -2.0
1.0
0.04
60
-30.02 % -3.0
0 0.02
50
-4.0
40 -1.0 0

100 200 300 400 500 600 700 800 900

Temperature /°C

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Gas atmosphere - Calciumoxalat Monohydrate

CaC 2 O 4 ∗ H 2 O ≈
150° C
→ CaC 2 O 4 + H 2 O

CaC 2 O 4 ≈
500° C
→ CaCO 3 + CO

≈ 500° C
CO + 1
2 O 2  → CO 2

CaCO 3 ≈
750° C
→ CaO + CO 2

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 Gypsum (CaSO4 - Dihydrate) - Pt-Crucibles

Sample: CaSO104
Sample mass: 38.68 mg
Crucibles: Pt+lids
Heating rate: 20 K/min
Atmosphere: Air
Sensor: TG/DSC type S

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 Gypsum (CaSO4 - Mixture) - Al-Crucibles (with 50
micron hole)

Sample: CaSO4
Sample mass: ≈ 12 mg
Crucibles: Closed Al
Heating rate: 30 K/min
Atmosphere: Air
Sensor: TG/DSC type S

Self-generated water vapor

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 Coupling with MS and/or FTIR

STA-MS-FTIR

STA-FTIR

STA-MS

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 Fe(OH)SO4
DSC /(mW/mg)
TG /% Ion Current *10-9 /A
↓ exo
100 -2.46 %
4.50
STA 449 Jupiter -4.31 % 6
750.3 °C
Sample: Fe(OH)SO4
90 mass: 30.58 mg 4.00
crucible: Pt
atm.: N2
flow rate: 70 ml/min 3.50 4
80 heating rate: 20 K/min

Probe: Fe(OH)SO4 3.00

562.9 °C -45.48 %
70 2
Ferrofluid
2.50

60 2.00
246 J/g 1170 J/g 0
1.50
50
567.9 °C

amu 18 H2O 1.00

This material is a possible amu 32 O2 -2
40 precursor for the production amu 64 SO2
of iron oxide particles. 759.7 °C
0.50

30
0 -4
100 200 300 400 500 600 700 800 900 1000
Temperature /°C

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 EGA methods combined with TGA

MS Mass Spectrometry
FTIR Fourier Transform Infrared
Spectroscopy
GC-MS Gas Chromatography with
MS
GC-FTIR GC with FTIR

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 Mass Spectrometer Couplings

Most common mass spectrometer types which are

used for TGA coupling are Quadrupol Mass
Spectrometer

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 Quadrupol Mass Spectrometer (QMS)

+
- -

electrons

cathode

evolved gas inlet

ion source detector

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Principle of Function
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 Ionization (II)

Molecule fragments
ABC + e- ABC+ + 2e-
AB+C+ + 2e-
AB+ + C + 2e-
A + BC+ + 2e-
A+ + BC + 2e-
AC+ + B + 2e-
AC + B+ + 2e-

red = ionized
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blue = neutral
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 Ionization (III)

CO2 spectra of the 11 most intense Natural

fragments Abundancies

18O = 0.2%

13C = 1.1%

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 Gas flow in the STA furnace

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 Hydromagnesite
(STA-MS Capillary)

mass 25.98 mg
temp. 25 ... 960°C
HR 10 K/min
Air, 80 ml/min

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 STA 409 C/5 Skimmer

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RT....2000° C (1550° C)
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 Skimmer Pressure Reduction Steps

divergent
nozzle

Sample
chamber
molecule
cloud

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 Skimmer Coupling

Quadrupol analyzer
-5
10 mbar Ion source

10-1 mbar

Skimmer
Orifice
Sample
1013 mbar

Heater

Sample carrier

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 STA-MS Skimmer: CuGaSe2

mass 333.08 mg
temp. 10 ... 1170°C
HR 10 K/min
He, 75 ml/min

I2

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Impurities: Selenium excess, Iodine
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 STA – FTIR Coupling

BRUKER TensorTM 27

STA 449 C Jupiter®

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 TG-FTIR Coupling

IR spectra
Wave lengths 2.5 to approx. 15 micron
Wave numbers 4000 to 600 cm-1
Change in Dipolmoment
Nonsymmetrical Molecules

Bending Streching
Change of Bonding Length Change of Bonding Angle
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 FTIR Principle

Fixed Mirror
Michelson
Interferometer Beamsplitter
Principle
Movable Mirror

Globar
Sample
Interfero-
Detector gram

Spectra

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 FTIR Coupling System

Thermocouple Thermo-
Adapter couple

Transferline (230°C)
Thermocouple
Microfurnace
Sample
Sample carrier
Outlet
TG

FTIR gas cell (230°C)

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 Pyrolysis of PVC

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 HCl emission during PVC pyrolysis

0.5
0.4
Absorbance Units
0.2 0.3
0.1
0.0

4000 3500 3000 2500 2000 1500 1000

Wavenumber cm-1

Y:\Commissions\823-xxx-06\006-3-06-TG209F1-FTIR-MS\006-3-06-12_PVC\006-3-06-12_PVC_308.0 PVC 10.060 | NETZSCH TG 209 F1 | Z:\Commissions\823-xxx-06\006-3-06-TG209F1-FTIR-MS\006-3-06-12_PVC\006-3-

P:\measurement\0_libspectra\HCl.0

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 Thank you for your attention

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