Thermal Analysis

Mass Spectrometer Coupling

Evolved Gas Analysis
Method, Techniques and Applications
Thermal Analysis
 and Evolved Gas Analysis
Thermoanalytical Techniques
Thermoanalytical techniques are universal tools for characterizing solids and liquids
with respect to their thermal behavior. Especially Thermogravimetry and Simultaneous
Thermal Analysis (STA, TGA-DTA/DSC) find broad application in testing the weight
changes of a sample during a programmed heat treatment. This yields a multitude of
information on material properties, composition and stability.

However, chemical and analytical information about the products causing the weight
changes to the sample is often lacking. Evolved Gas Analysis (EGA) by such techniques
as quadrupole mass spectrometry can supply this additional information.

Application Fields
∙∙∙∙
Decomposition
Dehydration
for Thermal Analysis
∙∙∙∙
Stability
Coupled to Mass Residual solvent
Pyrolysis
Spectrometry

∙∙∙∙
Solid-Gas Reactions
Combustion

∙∙∙∙
Oxidation
Adsorption

∙∙
Desorption
Catalysis

∙∙∙∙
Compositional Analysis
Polymer content

∙∙∙∙
Proximate analysis
Binder burnout

∙∙
Dewaxing
Ash content

∙∙∙∙
Identification
Gas composition

∙∙∙∙
Fingerprint
Partial pressure

∙∙
Fragmentation
Solid-gas interactions

∙∙∙∙
Evaporation
Vapor pressure
QMS 403 D Aëolos® Sublimation

2
 Reasons to Couple a Thermal
Analyzer to a Mass Spectrometer
Ion Current Ion Current DTG
TG /% *10-10 /A *10-11 /(/A) /(%/min)

Complementary Information
3.0 3.0
439.2°C
100 0

m/z 104
Mass changes detected by 2.5 2.5 -10

thermal analysis can be explained 80

by gas analysis in the mass 2.0 2.0

-20

spectrometer; a workstation for 60 Magnified by -30

analytical chemistry is thus formed. factor of 10 for
mass no. 208 1.5 1.5
Evolved species are detected -40
down to the ppm level, which 40

exceeds the standard sensitivity 1.0 1.0 -50

of thermal analysis methods. The

20
coupling of thermal analysis with 0.5 0.5
-60

mass spectrometry therefore 445.5 °C

m/z 208 -70
results in high-class material 0
433.5°C

research and characterization. 0 0

100 200 300 400 500 600 700
Temperature /°C

104
100

Quadrupole Mass
Spectrometry (QMS) 51 78

50
MS spectrum at 439.2°C
The sensitive, selective, fast and
continuous functionality of a 39

quadrupole mass spectrometer 63

74
91
65 130 139 168 183 198
makes this system ideally suited 0
44 56 83
89 98 110
115
123 134 143 152 164 179 187 194 202 209

for evolved gas analysis in combi- 34 44 54 64 74 84 94 104 114 124 134 144 154 164 174 184 194 204

nation with thermal analyzers, 100

specifically Thermogravimetry 104

(TGA) and Simultaneous Thermal

Analysis (STA, TGA-DTA/DSC).

Optimum coupling with thermal 50

78
analyzers is provided thanks to the
small dimensions of the quadrupole 51

mass filter, the efficient and repro- 39 63 74

ducible ionization of gases in the 0
41 65 84 89 98

electron impact ion source, and 34 44 54 64 74 84 94 104 114 124 134 144 154 164 174 184 194 204

the resolution in the detection of

Upper plot: TGA-QMS Aëolos® measurement on an unknown polymer shows one
molecules, atoms and fragments. mass-loss step between 400°C and 460°C.
Lower plot: NIST library search of the spectrum measured at 22.4 min clearly indicates
styrene. Also the dimer of styrene is detected, see mass number 208 in the upper plot.

3
HYPHENATION OF THERMAL ANALYSIS
AND EVOLVED GAS ANALYSIS

STA 449 F1 Jupiter® coupled to QMS 403 D Aëolos®;

other thermal analyzers can also be coupled to MS, such as the TG 209 F1 Libra®

4
Withstanding the Test of Time –
Capillary and SKIMMER
Coupling Techniques

NETZSCH offers complete solutions for

Thermal Analysis coupled to Mass
Spectrometry in terms of both
hardware and software. Evaluation
and presentation of the results is
carried out with the well-proven
Proteus® software.
Gas flow conditions in all thermal
analyzers are ideal for coupling to a
mass spectrometer via capillary or a
double-orifice system known as the
SKIMMER coupling.

By measuring the mass numbers

(m/z), conclusions on the composition
of the evolved gases can be drawn.

While the capillary coupling is

well-suited for the investigation of
permanent gases, the SKIMMER
coupling is advantageous for metallic
ions and inorganics where conden-
sation can be expected at higher
temperature.

STA 409 CD SKIMMER

5
 TA-QMS Coupling Techniques
Interface for Pressure Adjustment
Mass spectrometers, composed of a mass filter, an electron impact ion source and an ion detector, work only in
high vacuum. Therefore, an interface is required for the coupling of a thermobalance – which works with a purge
gas flow at atmospheric pressure – to the mass spectrometer. Different versions of pressure reduction interfaces
are realized, depending on instrumentation and applications.

QMS 403 D Aëolos® STA 409 CD SKIMMER

Single-Step Pressure Reduction
A capillary of small internal diameter connects the
gas outlet on the furnace of the thermobalance with
the gas inlet on the mass spectrometer. The pressure
drops from atmospheric pressure down to high
vacuum in one continuous step.
Double-Step Pressure Reduction
Different systems such as laminar flow capillary, nozzle,
and orifice are used to reduce the pressure in the first
step down to the range from 10-1 mbar to 10 mbar. A
membrane pump, rotary pump or the drag stage of
the turbo molecular pump is applied to achieve this
pressure reduction. The second step is either an orifice
or a skimmer as a molecular leak for the gas inlet into
the high-vacuum recipient of the mass spectrometer.

Pump
Step 1 Step 2

103 mbar 10-5 mbar Pump 103 mbar 10-5 mbar Pump
Interface Interface
Thermobalance Mass Spectrometer Thermobalance Mass Spectrometer

Capillary Coupling Double orifice SKIMMER coupling

6
Ideal Gas Flow Conditions Ensure Transport of All Relevant Gases
The aim of coupling is to have all relevant gases and vapors transported from the sample area into the ion source
of the mass spectrometer for precise qualitative and quantitative analysis. This is only achieved through perfect
gas flow conditions in the thermal analyzer, the coupling interface and the gas inlet of the mass spectrometer. As
only a small quantity of gas is required for the analysis, a bypass is used at the gas outlet on the thermobalance
for the excess purge gas flow; i.e., for the flow not passing through the coupling interface, which can be used for
a second gas analyzer such as FT-IR.

QMS 403 D Aëolos®

QMS transfer line

25°C to 300°C
Gas outlet and FT-IR
connection
25°C to 230°C Quadrupole 10-5 mbar
analyzer
Ion source

Coupling
10-1 mbar
adaptor
25°C to 300°C

Skimmer
Orifice
Capillary Sample
1013 mbar

Heater
Sample carrier

Gas overflow

Capillary coupling Double orifice SKIMMER coupling

Perfectly coupled for precise results.

7
Coupling TA-QMS 403 D Aëolos®
A fleshed-out design for capillary coupling to NETZSCH thermal analyzers (e.g.,
simultaneous TGA-DSC, STA) can be found in the QMS 403 D Aëolos® quadrupole
mass spectrometer. Volatile sample materials under a controlled temperature
treatment are directly transferred into the electron impact ion source of the MS
via a fused silica capillary.

The Capillary Coupling is Designed for Optimum Gas Flow

E Conditions and Flexibility
TOP-LIN
L A RY
CAPIL
COUPL
Overall
IN G

Heating
∙∙∙∙Minimization of cold spots in the transfer path
Minimized condensation losses due to overall temperature of 300°C across
le-Step the entire gas transfer system from the furnace outlet to the capillary to the
and Sing uction
∙∙
Red MS gas inlet.
Pressure Flexible, allowing standard thermoanalytical measurements and also

∙∙
simultaneous TGA, MS (GC-MS) and MS-FT-IR measurements.
Very robust and service-friendly while still maintaining high sensitivity

∙∙∙∙
(detectable mass loss in the μg-range).
Allows TGA-MS measurements under humid atmospheres.
Upgrade of existing thermal analyzers.

The QMS 403 D Aëolos® can also be independently employed for the analysis of
other gas sources.

TGA-DSC/DTA Systems TGA Systems

∙∙∙∙ ∙∙∙∙
STA 449 F1 Jupiter® TG 209 F1 Libra®
T-range: -150°C to 2000°C T-range: RT to 1100°C

∙∙ ∙∙
Weighing range: 5 g Weighing range: 2 g
TGA resolution: 0.025 μg TGA resolution: 0.1 μg

∙∙∙∙
STA 449 F3 Jupiter® Automatic sample changer for up
T-range: -150°C to 2400°C to 192 sample pans

∙∙
Weighing range: 35 g
TGA resolution: 0.1 μg

∙∙∙∙
STA 449 F5 Jupiter®
T-range: RT to 1600°C

∙∙
Weighing range: 35 g
TGA resolution: 0.1 μg

8
 Insulated inert quartz glass capillary with
controlled heating to 300°C for lossfree
gas transfer to the QMS

Heated chamber for easy handling and

precise adjustment of the capillary inlet
to the QMS

Natural vertical gas

flow through the STA
furnace to the heated
adapter with capillary
inlet and bypass

Quadrupole MS with cathode,

electron and ion lenses, mass filter and
Channeltron® detector

DSC/DTA Systems Dilatometer/Thermomechanical Analyzer

∙∙∙∙ ∙∙∙∙ ∙∙∙∙

DSC 404 F1/F3 Pegasus® DIL 402 Supreme TMA 402 F1/F3 Hyperion®
T-range: -150°C to 2000°C T-range: -180°C to 2000°C T-range: -150°C to 1550°C

∙∙
High-sensitivity and high- Measuring range: 5000 μm Measuring range:

∙∙
resolution sensors Δl resolution: 0.1 nm 500 μm/5000 μm
Δl resolution:

∙∙∙∙
DIL 402 Select
0.125 nm/1.25 nm
T-range: -180°C to 1600°C
Measuring
range:

∙∙
2000 μm
Δl resolution:
1 nm

9
 Continuous heating of the entire
gas transfer line reduces the risk of
condensation so that even larger
molecules can be detected.

Ion Current DTG Optimized Transfer Path Allows

TG /mg *10-9 /A /(mg/min)
270.1°C 50 for the Detection of Larger
0.000 0.0
Molecules – Heptadecane
Detection
40 -0.5
-1.000

-1.0 This measurement was carried out

-2.000 30 with the STA 449 F3 Jupiter®
-1.5
coupled to the QMS Aëolos®. The
-2.0 temperature adapter, transfer line
-3.000 20
and MS inlet were set to 300°C.
-2.5

-4.000
10 -3.0 Evaporation of this unbranched
isomer (CH3(CH2)15CH3; bp. 302°C)
-5.000 -3.5 starts at approx. 170°C (blue
264.3°C 0
curve). The maximum decompo-
50 100 150 200 250
Temperature /°C
300 350 400 450
sition rate is achieved at 264,3°C
(DTG peak, dotted line) when
using a heating rate of 20 K/min.
100
57
After a short delay (0.4 min), the
ion current achieves its maximum
at 270,1°C (dark blue curve). After
detection of heptadecane in the
50
71
MS, the ion current immediately
returns to the zero-level without
85
any tailing effect.
55

67 91
99
113 127 141 155 169 183 197
240 A comparison between the
45 77 210
0
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 detected MS spectrum for hepta-
100 57 decane and the corresponding
NIST library spectrum confirms
that even larger molecules (e.g.,
43 71 m/z 240) pass the adapter, transfer
50
NIST Spectrum line and MS inlet without
85
condensation.
41
55 99
113 127 141 240
45 77 91 105 119 133 145 155 169 183 197 211
0
40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250

10
 ACCESSORIES MAKE THE DIFFERENCE
Water-Vapor Furnace up to
High Water-Vapor Concentrations

Furnace

STA-MS Measurements under

Water-Vapor Atmosphere

In addition to a variety of other

furnaces for the STA systems, Sample chamber
NETZSCH also offers a water-
Heated transfer
vapor furnace which allows for line to Aëolos®
pure vapor atmospheres at the
sample between room tempe-
rature and 1250°C. The water-
vapor furnace can be connected Heated transfer line
from vapor generator
with a humidity or a water-
vapor generator. It provides
Water vapor
protection against flooding and
carrier gas
minimal dilution due to a special
gas flow design.
Outlet
protective gas
Heated Aëolos®
adaptor

Monitoring Reaction Steps During the Carbon Gasification Process

Ion Current Tem.
This plot shows a typical TG /% *10-10 /A /°C
switching to Ar+20% H2O
example of the configuration 8 800
with the water-vapor furnace: 120
carbon gasification: 700
Here, the water vapor – present 100
-2.5 % -10.8 % C + H2O ↔ CO + H2 6
in relatively high concentrations -6.8 %
-3.4 %
CO + H2O ↔ CO2 + H2 600
80
(20% H2O) – serves as a reactant 4
500
for the transition from coal to 60
400
hydrogen, and the STA with 40 2 300
coupled gas analysis shows both
20
the weight loss of the coal amu 28 (CO)
0
200
amu 44 (CO2)
sample and the products 0 decomposition of organics amu 2 (H2) 100
resulting from the reaction. -20
0 10 20 30 40 50 60 70 80 90
Time /min

11
 TA-QMS 403 D Aëolos®
Application

Measurement of an Unknown Polymer

This TGA-MS measurement of an unknown polymer (7.52 mg) was carried out in the temperature range between
room temperature and 250°C in a helium atmosphere. The 3-D plot above shows the TGA measurement together
with the MS results. The plot on the right correlates the TGA curve with various MS traces of m/z 35, 47, 48, 51,
77, 83, and 105.

By exporting the 2-dimensional scan-bargraph directly into the NIST database (see image below as an example
at 166°C), it becomes possible to interpret the individual mass-loss steps.

TG /% Ion Current *10-12 /A

Ion Current 100

*E-12 /A -9.04 %
90 -1.71 % 5.0
amu 35 -30.85 %
amu 44
4 80 amu 47
amu 48 4.0
3 amu 51 191.0 °C
70
amu 77
amu 81
2 60 amu 83 3.0
amu 105
247.5 °C
1 50
172.7 °C 2.0
241.8 °C
40
40 166.4 °C
50 189.7 °C
60 30 1.0
70
80 400
m/z 90 350 20
300 0
100 250
200
110 150 10
Temperature /°C
50 100
50 100 150 200 250
Temperature /°C

3-D plot of a TGA-MS measurement on an unknown Correlation of mass-loss steps and different gases detected and
polymer sample as a function of temperature identified in the MS; 35 amu most probably corresponds to HCl.

12
Direct export of the MS results at 166°C into the NIST
database for identification of the evolved gases

13
 SKIMMER DETECTIO
N OF
ules
e molec able

DOUBLE ORIFICE SOLUTION

 Larg ns
 High
ly conde
vap rs
o
(metal) ases
 Perm
anent g

FOR HIGH-BOILING MATERIALS

Vertical – Top-Loading STA System and SKIMMER on Top of the Furnace

The SKIMMER coupling (realized with the STA 409 CD) actualizes the shortest possible route for gas transfer from
the sample to the QMS. The SKIMMER collimates the molecules from the barrel-shaped jet expansion behind the
divergent nozzle towards the QMS ion source.

The pressure reduction of the purge gas flow from atmospheric pressure down to the high vacuum behind the
SKIMMER orifice is achieved in two steps along a distance of less than 20 mm. This drastically reduces the risk of
condensation and thus achieves high detection sensitivity. Even metal vapors are detected by this unrivaled
coupling system.

The nozzle and SKIMMER are precisely machined from either alumina or glassy carbon, allowing application
temperatures of 1450°C or 2000°C in the corresponding furnaces. The molecular beams are analyzed by a
quadrupole mass spectrometer up to high mass numbers of 512 u or optionally 1024 u.

DSC Ion Current

Detection of Metal Vapors TG /% /uV *10-11 /A
100 25 3.5
↓ exo
Lead chloride (7.92 mg) in an TG -97.10
argon flow of 150 ml/min 20 3.0
80 487.3°C 699.0°C
exhibits evaporation starting in %
the melting range (487°C). The 15 2.5
molecule ion (PbCl2 m/z 278)
60
and fragment ions caused by 10 2.0
dissociation and ionization 35 703.1°C
(PbCl m/z = 243, Pb m/z = 208, 40 5 1.5
Cl m/z 37, Cl m/z = 35) are DSC
clearly detected far below the 0 1.0
boiling temperature of the 20
37
starting material. 208 243 -5 0.5
MID
-2.90 %
0 278
-10 0
400 450 500 550 600 650 700 750 800 850
Temperature /°C

14
 Quadrupole MS

Intermediate
vaccuum

SKIMMER

Supersonic jet
expansion zone
Divergent nozzle
Sample
Furnace

Sample holder
Gas overflow capillary

Shortest possible
coupling solution via
unique supersonic
jet gas transfer

15
 SKIMMER Applications

Thermal Stability of the Thermoelectric PbTe Isotopes

Pb und Te Isotopes
Material PbTe (m/z)

332 u Pb + 125Te
207 206
Pb + 126Te
Knowledge about thermal stability properties, such as
phase change and evolving gases at elevated temper- 333 u Pb + 125Te
208 207
Pb + 126Te
atures, is crucial for the development of thermo-
electric materials. In this example, the thermal 334 u Pb + 126Te
208 206
Pb + 128Te
stability of PbTe was analyzed using the STA 409 CD
coupled to a mass spectrometer via the SKIMMER 335 u Pb + 128Te
207

system. The plots each show the TGA curve of the

PbTe sample, but with different mass spectrometer 336 u Pb + 128Te
208

results. PbTe starts decomposing at around 600°C.

337 u Pb + 130Te
207
The plotted mass numbers represent the combination
of the Pb and Te isotopes. The following gaseous 338 u Pb + 130Te
208
products were detected:

TG /mgTG /mg Ion Current

Ion Current
*10 -12 /A
*10 -12 /A TG /mgTG /mg Ion Current *10 -12 /A
Ion Current *10 -12 /A

0 /mgTG
TG 0 /mg Ion Current *10 -12 /A
Ion Current *10 -12 /A TG
0 /mgTG
0 /mg Ion Current *10 -121.0
Ion Current *10 -121.0
/A /A
1.2 1.2
-1 -1 -1 -1 0.8
1.0 0.8
1.0
0 0 332 332 1.0 1.0 0 0 335 335
1.2 1.2
-2 -2 -2 -2
-1 -1 PbTe PbTe 0.8 0.8 -1 -1 PbTe PbTe mg-6.43 mg 0.6
0.8 0.6
0.8
332 -6.43 mg-6.43 mg 1.0
332 1.0 335 -6.43
335
-3 -3 -3 -3
-2 -2 0.23455E-09A*s
0.23455E-09A*s 0.6 0.6 -2 -2 0.20489E-09A*s
0.20489E-09A*s
PbTe PbTe 333 -6.43
333
mg-6.43 mg
0.8 0.8 PbTe PbTe 337 -6.43 mg-6.43 mg 0.4
337 0.6 0.4
0.6
-4 -4 0.28191E-09A*s
0.28191E-09A*s -4 -4 0.19645E-09A*s
0.19645E-09A*s
-3 -3 0.4 0.4 -3 -3
0.23455E-09A*s
0.23455E-09A*s 0.6 0.6 0.20489E-09A*s
0.20489E-09A*s
-5 -5 0.28191E-09A*s
0.28191E-09A*s 333 333 -5 -5 0.19645E-09A*s
0.19645E-09A*s 337 337 0.2
0.4 0.2
0.4
-4 -4 0.2 0.2 -4 -4
0.4 0.4
-6 -6 -6 -6
-5 -5 0 0 -5 -5 0
0.2 0
0.2
0.2 0.2
-6 -6 200 200 400 400 600 600 800 800 1000 10001200 1200 -6 -6 200 200 400 400 600 600 800 800 1000 10001200 1200
Temperature
Temperature
/°C /°C 0 0 Temperature
Temperature
/°C /°C 0 0

200 200 400 400 600 600 800 800 1000 10001200 1200 200 200 400 400 600 600 800 800 1000 10001200 1200
Temperature
Temperature /°C /°C Temperature /°C
Temperature /°C

TG /mgTG /mg Ion Current

Ion Current *10 -12 /A
*10 -12 /A TG /mgTG /mg Ion Current
Ion Current *10 -12 *10
/A -12 /A

2.5 3.5 -123.5

TG
0 /mgTG
0 /mg Ion Current *10 -122.5
Ion Current /A
*10 -12 /A TG
0 /mgTG
0 /mg Ion Current
Ion Current
*10 -12 *10
/A /A
3.0 3.0
-1 -1 2.5
2.0 2.5
2.0 -1 -1 3.5 3.5
0 0 334 334 0 0 336 336
2.5 2.5
-2 -2 -2 -2 3.0 3.0
-1 -1 2.0 2.0
1.5 -1 -1
PbTe PbTe
334 -6.43 mg-6.43 mg 1.5
334
PbTe PbTe
336 2.0
-6.43 mg-6.43 mg
336 2.0
-3 -3 -3 -3 2.5 2.5
-2 -2 0.52077E-09A*s
0.52077E-09A*s -2 -2 0.71867E-09A*s
0.71867E-09A*s
1.5 1.5
PbTe PbTe
0.50302E-09A*s
0.50302E-09A*s 338 -6.43
338 1.5
mg-6.43 mg 1.0 1.5
1.0 PbTe PbTe
0.50572E-09A*s
0.50572E-09A*s 338 338 mg-6.43 2.0
-6.43 mg 2.0
-4 -4 -4 -4
-3 -3 0.52077E-09A*s
0.52077E-09A*s
-3 -3 0.71867E-09A*s
0.71867E-09A*s 1.0 1.0
-5 -5 1.5 1.5
-5 -5 0.50302E-09A*s
0.50302E-09A*s 338 338 1.0
0.5 1.0
0.5 0.50572E-09A*s
0.50572E-09A*s 338 338
-4 -4 -4 -4 0.5 0.5
1.0 1.0
-6 -6 -6 -6
-5 -5 0.5
0 0.5
0 -5 -5 0 0
0.5 0.5
-6 -6 200 200 400 400 600 600 800 800 1000 10001200 1200 -6 -6 200 200 400 400 600 600 800 800 1000 1000 1200 1200
Temperature
Temperature /°C /°C 0 0 Temperature /°C
Temperature /°C 0 0
200 200 400 400 600 600 800 800 1000 10001200 1200 200 200 400 400 600 600 800 800 1000 1000 1200 1200
Temperature
Temperature
/°C /°C Temperature
Temperature
/°C /°C

16
 Sophisticated applications require
ingenious analytical tools

Decomposition Products TG /% Ion Current *10-10 /A

TG
of Carbon Pitch 100
2.5

DTG -8.67 %
95
Carbon pitch is the primary 322.0°C 2.0

product from the distillation of

coal tar. It is used as a binding 90
-6.30 % 1.5
agent in the production of carbon 252
anodes for aluminum smelters and 85 202
graphite electrodes for electric arc 535.3°C -3.18 %
1.0
furnace steel producers.
80

228
Carbon pitch powder (55.2 mg) 0.5
75
decomposes in a nitrogen flow (50 276
302
ml/min) into aromatic compounds MID
of high molecular weight, mainly 70 0

below 600°C. Only a selection is 200 400 600 800 1000 1200
Temperature /°C
shown here with MID curves for
such substances as pyrenes (m/z =
202), triphenylenes m/z = 228),
benzo(a)pyrenes (m/z = 252),
benzo(ghi)perylenes (m/z = 276)
and dibenzopyrenes (m/z = 302).

ion of
Detect ounds of
p
tic com ht
aroma lecular weig
o
high m

17
 PulseTA®
Calibration/Quantification

The quantification of MS signals requires calibration of the whole coupled system with a known
type and amount of gas or solvent to control for the temperature-dependent flow properties.
PulseTA® is a perfect tool for achieving quantitative gas detection in separate calibration runs or
even online during a sample measurement. A known amount of gas is injected into the sample
gas stream and the registered signal of the resulting pulse is integrated. The application of
PulseTA® also allows for studying gas/solid reactions with stepwise control of the process via the
injection of a reactive gas, and simplifies adsorption/desorption experiments.

CO2
injected
Injectedgas
gas

Purge gas
carrier m/z = 44

TA
TA MS/FTIR
MS/FT-IR

TG
pulse deviceCO2
Pulse device
TGA-DSC Gas composition

H2

m/z = 44
Inert gas Reactive gas (gas-solid reaction) Reactive gas (adsorption)
CO2 pulses for calibration of a Reduction of metal oxide by NH3 adsorption by a zeolithe
carbonate decomposition H2 pulses sample

TG
CO2
TG

H2

m/z = 44 NH3

TG
18
TG
Quantification of Contaminations on an Mo Wire –
Separation of Overlapping Oxidation and Carbon Burn-Up

TG /% Ion Current *10-9 /A

In this analysis, a small mass loss
of 0.02% occurred below ~500°C,
101
1.5 followed by an increase in sample
mass of 0.85% due to oxidation of
100.8
the sample. At the same time,
1.0 carbon impurities on the wire’s
100.6 surface were burnt, which can be
seen from the MS signal for m/z
100.4 0.85% 0.5 44 due to the CO2 release (solid
473.0°C
560.6°C line). The carbon content was
100.2 amu 44 (CO2)
quantified at ~900 ppm by means
0 of the NETZSCH PulseTA® device as
-0.02% follows:
100.0
During an empty run, several CO2
-0.5 pulses of defined volumes (0.25 ml
99.8 and 1 ml) were injected into the
100 200 300 400 500 600 700 STA and detected by the MS
Temperature /°C
(dashed line). From the ratio of the
Heating of a molybdenum sample (4153.9 mg) in an Al2O3 beaker at a ion current peak areas of the
heating rate of 10 K/min in a synthetic air atmosphere. The sensitivity of
the QMS 403 D Aëolos® is linear and temperature-independent.
calibration pulses and the signal
from the sample, the amount of
CO2 evolved from the sample can
be calculated.

19
 Proteus® Software
 for TA-MS Coupling

The control of measurements with coupled TGA-QMS instruments is governed by the

Proteus® software. The user gives the command for data acquisition once both the QMS
and the Proteus® software are ready with parameter inputs as well as checked pressure and
ion source conditions. The online data collection is simultaneous and synchronized through
a triggered start to guarantee precise time and temperature correlation among all the
signals from the two systems during evaluation. The user works with the two software
packages on one computer and has access to the entire spectrum of possibilities for evalu-
ating data and displaying results in the Proteus® software according to preference. The
integration of the TA and QMS software based on effective data exchange from acquisition
to evaluation is what makes the coupled TGA-QMS to a true functional unit.

20
Key Software Features

∙∙
Direct import for MS data

∙∙
Evaluation of MS data within Proteus®

∙∙
Simultaneous start/stop of the coupled measurements
(trigger system)

∙∙
Evaluation of results precisely correlated in terms of
time and temperature

∙∙
Integration of MS peaks (MID and QMID peaks)

∙∙
Fast MID input of 8 mass numbers

∙∙
Several scan-bargraph ranges with fast mass range input

∙∙
Selection of up to 64 MID mass numbers

∙∙
Selection of analog scans in max. 64 channels

∙∙
Selection of scan-bargraphs or scan analog graphs with
optimized rate and sensitivity in 4 different channels

∙∙
Spectra export in NIST format for identification in the
NIST database

∙∙
TGA-DSC/DTA total ion current

∙∙
3-D presentation of spectra data together with
temperature, TGA and/or DSC curves, including peak
determination (see plot on the left)

∙∙
Navigator to enlarge, reduce or rotate the 3-D plot
(see plot on the left)

∙∙
Turbo pump and pressure displayed by software

∙∙
TGA-DSC/DTA-MID curves and scan-bargraph envelope
curves: characteristic temperatures, peak areas

21
 Various Ways of
Presenting Test Results
for Optimum Evaluation
1,0E-06
Comprehensive Information
via Scan-Bargraph

1,0E-08 A scan-bargraph is often the basis

for depicting comprehensive
Ion Current/A

information about all of a sample’s

evolved species; it allows for the
selection of all mass numbers or
1,0E-10
just individual ones of interest for
import into the Proteus® software
as continuous MID curves. Here,
one scan out of the repeated scans
1,0E-12
is shown for Nd2(SO4)3·5 H2O
10 15 20 25 30 35 40 45 50 55 60 65 70 measured in air at 950°C.
Mass/Charge

TG /% Ion Current *10-9 /A Direct Correlation Between

Mass Loss and Evolved Gas
100 4.00

-12.70%
90
3.50 via MID Curves
3.00
Nd2(SO4)3·4.7 H2O (29.53 mg) was
80 heated at a rate of 10 K/min up to
-23.61% 2.50
amu 18 (H2O) 1400°C in a nitrogen flow. The
70 2.00
MID curves, directly imported from
amu 64 (SO2)
the coupled Aëolos®, show the
1.50
well separated gas evolution for
60
-11.79 %
water, oxygen and sulfur dioxide
1.00 in perfect correlation with the
TGA steps.
50 amu 32 (O2)
0.50

40 0
200 400 600 800 1000 1200 1400
Temperature /°C

22
Key Technical Data
QMS 403 D Aëolos®

QMS mass range 300 u* Resolution >0.5 u* Scan, Scan-Bargraph, MID

Electron impact ionization Ionization energy: 25 eV to 100 eV Two iridium cathodes, Y2O3-coated

Channeltron® SEM Detection limit ≈ 1 ppm

Turbo molecular and membrane

Single-step pressure reduction 103 mbar to 10-5 mbar
pump systems (oil-free)

Quartz glass capillary Insulated; Ø 75 μm; length ≈ 2.5 m Entire transfer heated at 300°C

* u: unified atomic mass

STA 409 CD with SKIMMER QMS

∙∙ RT to 1450°C, QMS options ∙∙∙∙

1 to 512 u

∙∙
SiC furnace 1 to 1024 u
Temperature range
RT to 2000°C,
graphite furnace Analog scan, scan-
Measuring modes
bargraph, MID
Weighing range 15 g Electron impact ionization:
Energy up to 125 eV;
TGA resolution 2 μg Ion source
adjustable in
steps of 1 eV
Sensor types TGA, DSC, DTA

SKIMMER systems
∙∙∙∙ Alumina (up to 1450°C)
Glassy carbon
Cathodes
Tungsten; others on
request

(up to 2000°C) Detection limit < 10 ppb

23
 The NETZSCH Group is a mid-sized, family-owned German company
engaging in the manufacture of machinery and instrumentation with
worldwide production, sales, and service branches.

The three Business Units – Analyzing & Testing, Grinding & Dispersing and
Pumps & Systems – provide tailored solutions for highest-level needs. Over
3,400 employees at 210 sales and production centers in 35 countries across
the globe guarantee that expert service is never far from our customers.

When it comes to Thermal Analysis, Calorimetry (adiabatic & reaction) and

the determination of Thermophysical Properties, NETZSCH has it covered.
Our 50 years of applications experience, broad state-of-the-art product line
and comprehensive service offerings ensure that our solutions will not only
meet your every requirement but also exceed your every expectation.

NGB · Thermal Analysis – Mass Spectrometer Coupling · EN · 0517 · NWS · Technical specifications are subject to change.

NETZSCH-Gerätebau GmbH
Wittelsbacherstraße 42
95100 Selb
Germany
Tel.: +49 9287 881-0
Fax: +49 9287 881 505
at@netzsch.com