Coupling to Fourier Transform Infrared Spectrometers

FT-IR
Concepts, Instruments and Applications from (10°C) RT to 2000°C
Thermal Analysis Plus FT-IR
 More Than Just the Sum of Its Parts

FT-IR
Coupling

Perfect Combination Bridges the Analytical Gap and Facilitates Finterprint Analysis

Thermal Analysis provides ideal tools for the characterization of all kinds of organic and inorganic
solids and liquids. Thermodynamic transitions, thermal stability, decomposition and chemical
reactions can be detected and quantified with high accuracy over a broad temperature range.

In some cases, however, information about the type of gases evolved is needed in order to gain a
detailed understanding of the chemistry behind the processes. The combination of thermal
analysis with the powerful infrared spectroscopy for gas analysis bridges this analytical gap. It
allows for deeper insight into the material’s behavior and may provide a fingerprint of the
analyzed material.

The Proteus® software for thermal analysis and the OPUS software for the FT-IR are integrated
with one another to support the Thermal Analysis-to-FT-IR coupling. The relationship to temper-
ature and time of all information produced by the running experiment is meticulously
maintained.

2
 Harmonized Instrument Combinations with Fully Integrated Software
from the Specialists in Thermal Analysis and IR Spectroscopy

Optimized Vacuum capability

low-volume gas cells for oxygen removal, elimination
without mirrors inside of carryover, and lowering of
boiling points

01 02 03 04
Parallel operation for
regular FT-IR experiments
or for hyphenated tests without
modification and disassembling High resolution and
(by use of an external gas cell) high sensitivity

Great Variety of Configurations to Meet all Needs

Tranfer line – Tranfer line – FT-IR- PERSEUS®

Coupling type FT-IR-MS
external gas cell internal gas cell GC-MS Coupling
TG 209 F1 Libra®     
TG 209 F3 Tarsus®  
STA 449 F1/F3/F5 Jupiter®      (F1, F3)
STA 2500 Regulus®    
DSC 204 F1 Phoenix®    
DSC 404 F1/F3 Pegasus®    
TMA 402 F1/F3 Hyperion®    
DIL 402 Expedis
   
Select/Supreme

3
 Optimized TGA/STA/DSC – FT-IR Coupling

Infrared spectroscopy is a
10-13
m 10 m
4 classical technique which depends
Wave length on the interaction of infrared
radiation with the vibrating dipole
moments of molecules. It provides
Gamma X rays UV Visible Infrared Micro- Radio a characteristic spectrum for each
rays waves waves
substance, with the exception of
homonuclear diatomic molecules
or noble gases. Examples of
homonuclear diatomic molecules
are N2 and O2.

Functional Principle of an FT-IR Fixed

Spectrometer mirror

A light beam, shown in the

diagram as emanating from the
light source on the right side, is
divided into two single beams Moving Q Light
mirror source
by means of a beam splitter. One
beam is focused on a fixed mirror
and reflected; the other one Beam splitter
encounters a moving mirror and is
reflected as well. Sample

Afterwards, the two beams are D

Interferogram:
merged once again and interfere Detector
– depending on the frequencies
contained in the beam and the
distance covered by the mirror.

The result is an interferogram

characterized by a center burst
and comparatively flat wings.
The center burst represents the
point at which the two mirrors Spectrum:
are equidistant from the beam
splitter (this means all frequencies
interfere additively). Subsequently,
the interferogram is transformed
into a spectrum using Fourier
Transformation.

4
 Sophisticated Gas Cell Design

To ensure highly sensitive

detection of the gases evolved, it is
necessary to have a gas cell with a
long path length and low volume.
The longer the path length, the
more molecules are passing
through at any given moment. On
the other hand, the gas concen-
tration is also influenced by the
volume of the gas cell. The lower
the volume, the higher the
concentration of the gases
evolved.

Developed in a collaboration
between NETZSCH Analyzing &
Testing and Bruker Optics, the
beam-conforming metal gas cells
with their optimized gas flows Characteristics of available gas cell types:
perfectly combine these
requirements. Type Path length Volume

An additional advantage to this Gas cell for, among others,

123 mm 8.7 ml
design is that the absence of an TENSOR II* (internal or external)
internal mirror prevents particle
Gas cell for PERSEUS® coupling
condensation, thus also preventing 70 mm 5.8 ml
(only internal)
any influence to the detection
sensitivity by a polluted mirror
surface.

Outstanding Window Concept Reduced Pressure Capabilities

* TENSOR II is the follow-up model of TENSOR 27

The gas cell of the PERSEUS® The spectrometers used for

coupling is equipped with ZnSe coupling typically work in the
windows. The gas cell of the mid infrared range (MIR) and are
TENSOR II* uses a dual window operated under normal pressure.
technique with KBr windows on But for special tasks, a reduced
the outer face and ZnSe windows pressure is also possible.
on the inner face. For cleaning
Windows of the external gas cell for
TENSOR II* with screw thread; double
purposes, all different window
window technique for safe cleaning types can be easily removed and
and removal reused.

5
TGA/STA-FT-IR Coupling for Maximum Flexibility
All NETZSCH thermobalances (TGAs) and simultaneous Three modes of connecting FT-IR to a thermal
thermal analyzers (STAs) are characterized by their analyzer:

∙∙
vertical, top-loading design. This not only guarantees
easy operation and sample loading, but is also in Coupling to an external gas cell via
accordance with the natural gas flow path inside the transfer line for highest FT-IR system flexibility

∙∙
furnace (warm gases have the tendency to rise) and
protects the balance in an optimal way. Coupling to an internal gas cell via transfer line
using the FT-IR sample chamber

∙∙
Because of this natural gas flow path, top-loading
thermobalances are ideally suited for coupling to Direct PERSEUS® coupling without transfer line
evolved gas analyzers such as FT-IR spectrometers,
mass spectrometers and/or GC-MS systems (gas
chromatograph-mass spectrometers) – and for most
instruments, this can also be combined with an Defined Gas Atmosphere
automatic sample changer (ASC).
Fourier Transform Infrared Spectroscopy is extremely
sensitive to water and carbon dioxide. It is therefore
important to establish a pure inert gas atmosphere
at the sample and to minimize the H2O and CO2
background in the FT-IR spectra.

In order to achieve this requirement, all TGA/DSC/

STA-FT-IR systems are vacuum-tight or gas-tight.

6
 Schematic of a TGA 209 F1-FT-IR coupling using
an external gass cell and a heated transfer line

Prerequisite for Effective Coupling

An adapter together with a short transfer line should connect the gas outlet of the TGA, DSC or STA furnace to
the gas cell of the FT-IR spectrometer. The evolved gases are transferred using a carrier gas (usually nitrogen).

To prevent cold spots and thus condensation of the gases evolved, the entire gas path should be heated. The
temperatures are up to 300°C for the adapter and max. 230°C for the gas cell and transfer line.

The Right Detector for Any Application

Built-in DLaTGS (deuterated triglycine sulfate,

additionally doped with L-alanine), detectors
are standard for Bruker TENSOR II* and ALPHA
systems. They do not require any additional
cooling and are therefore particularly well-
suited for TGA/DSC/STA test runs with an
* TENSOR II is the follow-up model of TENSOR 27

automatic sample changer (ASC) or for measure-

ments of longer duration.

The external gas cells are equipped with MCT

detectors (Mercury-Cadmium-Telluride) by
default. They provide a significantly higher
signal-to-noise ratio (compared to DLaTGS) and
require liquid nitrogen cooling.

STA 2500 Regulus® with transfer line for STA-FT-IR coupling

7
 Coupling Via Transfer Line
 Low-Volume Gas Path Ensures Fast Response Times

TG 209 F1 Libra®

Bruker TENSOR 27 with external gas cell

TGA-FT-IR – Smart Gas Transfer

Depending on the application High Concentrations and Short

range, one may select from among Gas Transfer Paths for Direct FT-IR connection
the following available coupling Correlation with Mass Loss for the TG 209 F3
Tarsus®
possibilities:

∙∙
The gas transfer line is charac-
TG 209 F1 Libra® coupled to terized by a low volume and
an FT-IR, to FT-IR and MS (mass a short capillary length, thus
spectrometer), or to FT-IR and minimizing dilution effects and
GC-MS together, via a heated guaranteeing fast response

∙∙
adapter times.
PERSEUS® coupling for the TG
209 F1 Libra® (see following The interface is optimized for

∙∙
pages) Bruker FT-IR spectrometers, but
TG 209 F3 Tarsus® connected is not limited to them. Please ask
to an FT-IR transfer line directly your NETZSCH representative for
from the furnace lid. This type more information.
of adaption is specially designed
for manually operated TGA
systems.

Sophisticated heated adapter system for

coupling of an FT-IR (plus MS or GC-MS)
to the TG 209 F1 Libra®

8
STA-FT-IR – Sensitive Evolved Gas Analysis

The combination of evolved gas A heated adapter is the interface

analysis (EGA) with simultaneous between the gas outlet of the
thermal analysis (STA) provides STA furnace and the heated
also information on changes in transfer line to the Bruker FT-IR
the heat flow of the sample (DSC spectrometer. Also here, it is
signal), thus allowing for an even possible to connect one thermal
deeper understanding of the analysis instrument with two gas
chemical and physical processes analyzers, such as FT-IR and QMS
under investigation. or FT-IR and GC-MS.

Classical hyphenation of STA The heated adapter itself can

systems (STA 449 F1/F3/F5 be mounted on both sides of
Jupiter®, STA 2500 Regulus®) a double hoisting device. The
is carried out similarly to the temperature of the adapter is up
coupling of a TGA 209 F1 Libra® to 300°C, the temperature of the
with a free-standing FT-IR system transfer line is max. 230°C.
(for details see previous page). The
same is also valid for thermome- An external gas cell allows the
chanical analysis systems such as operator access to a great deal of
TMA or dilatometers. the FT-IR spectrometer’s flexibility Schematic of the gas path of a
and makes it possible to add on capillary-coupled STA system
accessories such as an ATR unit
(for parallel use) or a microscope.

Heated adapter for capillary coupling to

an STA 449 F1/F3/F5 Jupiter® or STA 2500
Regulus®

9 9
 PERSEUS®
 Perfect Coupling of Thermal Analysis and FT-IR

PERSEUS® TG 209 F1 – No Separate Transfer Line

PERSEUS® is the name given to the unique alliance

between a NETZSCH thermobalance (or STA system)
and a tiny but efficient FT-IR spectrometer by Bruker
Optics. Its revolutionary layout sets a benchmark for
state-of-the-art hyphenation.

The PERSEUS® coupling interface excels in both

design and ease of handling. No separate transfer
line is necessary. The built-in heated gas cell is directly
connected to the gas outlet of the furnace via a
heated tube. The low volume of the short gas path
guarantees fast response and is quite advantageous
in cases where condensable evolved gases are
present. Additionally, the PERSEUS® features an
PERSEUS® TG 209 F1 extremely small footprint.

An STA 449 F1 Jupiter® system

connected to a TENSOR 27
spectrometer in a side-in-side
comparison with the compact
PERSEUS® coupling

Bruker TENSOR 27 with external gas cell STA 449 F1 Jupiter®

10
Space-Saving PERSEUS® STA 449 F1/F3

The powerful and cost-effective PERSEUS® STA 449 F1/F3 features a

compact 2-in-1 design which saves over 50% of the bench top space
required for a capillary-coupled system. The short gas path with low
volume provides an excellent correlation between mass losses and the
gases detected.

To gain further information about the evolved gases, the PERSEUS® STA
can additionally be coupled to a GC-MS system.

In order to minimize the risk of condensation, the PERSEUS® coupling

interface is heated using a constant voltage. Optionally, a temperature
control system is available (recommended for condensable gases). The
maximum temperature of the entire gas path is set to 200°C.

Any existing STA 449 F1/F3 system can be upgraded to the PERSEUS®
configuration. Various furnaces for the temperature range from RT to Schematic of the gas path of a
2000°C are available for this kind of coupling. PERSEUS® STA system

PERSEUS® No Need for Liquid Nitrogen

Coupling The DLaTGS detector (DLaTGS

= L-alanine doped deuterated
PERSEUS® STA 449 F1
triglycine sulfate) employed in the
spectrometer works without any
cooling. The PERSEUS® system is
thus perfectly suited for tests with
an automatic sample changer (for
64 samples in the TG 209 F1 or
20 in the STA 449 F1/F3).

The photos, depicting the instrument

configuration in scale, clearly demonstrate
the space-saving design of the
unprecedented PERSEUS® system

11
 DSC-FT-IR Coupling

The primary objective of TGA-FT-IR

experiments is to study decompo-
sition processes. In contrast with
that, the temperature profiles
of DSC-FT-IR measurements
are designed to avoid thermal
degradation of the sample or
to stay maximally at processing
temperature of e.g., polymers.
The main focus of DSC investiga-
tions is to analyze phase transi-
tions such as melting and crystal-
lization or structural changes.
But even in investigations such as
these, gaseous substances such
as moisture or adsorbed solvents
sometimes evolve. These can then
be characterized using FT-IR, MS or
GC-MS.

A DSC-FT-IR measurement on
DSC 204 F1 Phoenix® with automatic sample changer (ASC)
citric acid monohydrate (C6H8O7
x H2O) serves here as an example.
Between 30°C and 100°C, two
superimposed DSC effects are
visible (red curve). According to
literature, the melting of citric acid
monohydrate is accompanied by
dehydration – and indeed, a library
156°C
search reveals the presence of
crystal water. 0.3

DSC curve
Absorbance Units

In the temperature range from

130°C to 250°C, two additional 0.2

superimposed effects occur. The

endothermic one at 156°C is
0.1
associated with the melting of the
water-free citric acid, immediately
followed by decomposition. This 4000 0.0
is reflected by a sharp increase in 3000 200
150
the intensity of the IR absorbance 2000 100
Temperature
bands detected. Wavenumber cm-1 1000 50

Measurement of 7.7 mg of citric acid monohydrate at a heating rate of

5 K/min in a nitrogen atmosphere; 3-dimensional presentation of the
measured FT-IR spectra including the corresponding DSC curve in red

12
PulseTA® – A Clever Tool for Calibration,
Quantification and Catalysis Studies
injected gas
The idea behind the unique
PulseTA® technique is to inject a
defined amount of gas into the
purge gas flow of a thermo-
balance (TGA) or simultaneous carrier gas
thermal analyzer (STA) and then
TA MS/FT-IR
monitor the corresponding
changes in the sample mass,
enthalpy or evolved gases. by the special
pulse device TGA, TGA-DSC/DTA gas detection

PulseTA® clearly expands the scope of measurement. It can be used

for three types of thermoanalytical experiments:

01 Injection of a gas which 02 Injection of a gas which 03 Injection of an inert gas

adsorbs at the sample chemically reacts with the
surface sample As the amount of the
injected gas is known,
This mode offers the means to This mode provides the this mode can be used for
study adsorption/desorption opportunity to investigate all calibration of the coupled
phenomena at atmospheric types of solid-gas reactions at TGA/DSC/STA-FT-IR instru-
pressure and at a specific incremental reaction extents ments for quantification
temperature. (e.g., stepwise control of purposes.
catalytic processes by pulsed
supply of the reactive gas).

0.3

TGA curve
Absorbance Units

0.2

0.1

4000
3000
3-D plot for CO2 calibration pulses and CaCO3 decomposition;
2000
0.0 suitable pulses for quantification need to be repeatable and
800
Wavenumber cm-1 1000 400
600 temperature-independent, and they should show a linear
200
Temperature relationship to the injected gas concentration

13
 Comprehensive Software
 One Package for Thermal Analysis and FT-IR

Bruker OPUS and NETZSCH Proteus® – Unrivaled Combination

The alliance between the NETZSCH Proteus® software and the OPUS FT-IR software is
based on effective data exchange and serves to unify the coupled system functionally.

Measurements are controlled via the NETZSCH Proteus® software. The user only needs
to input the command for data acquisition and for the start of measurement once, and
both the OPUS and Proteus® software will be readied with parameter inputs. Online data
collection is simultaneous and synchronized to guarantee precise time and temperature
correlation between all signals from the two coupled instruments during evaluation.

The user operates the two software packages from a single computer and has access to
the full range of possibilities for data evaluation and results display in either package at
any time.

Screenshot of the OPUS software during evaluation of a straw pyrolysis test:

Multi-window presentation containing a 3-dimensional diagram (x-y-z view, including TGA curve and
temperature information from the thermal analysis system), a 2-dimensional plot (topview on the 3-D cube) and
a spectrum window, representing the spectrum at the position of the red line within the 3-D diagram

14
Convenient Software Setup for Maximum Ease of Use

∙∙ Full software integration – online data exchange

between the two instrument software packages
∙∙ Conjoint presentation of the Gram-Schmidt plot
plus up to four pre-selected traces together with
during the running experiment thermal analysis curves in Proteus® software during

∙∙
the experiment

∙∙
Simultaneous instrument control and data storage
on the same computer Online evaluation (SNAP SHOT) of TGA/STA/DSC

∙∙
measurements already including FT-IR data

∙∙
Segmental activation or deactivation of the FT-IR
coupling with just a few mouse clicks Trace calculations with evaluation of characteristic

∙∙
temperatures and peak areas together with TGA
Automatic saving of data sets with identical file and DSC curves

∙∙
names (but different extensions) in the same
directories Combined analysis graphics of thermal analysis and
FT-IR signals

Screenshot of the Proteus® software during evaluation of the same straw experiment as displayed before:
Temperature-scaled presentation of the TGA and DTGA curves together with the Gram-Schmidt plot and the
calculated traces of methane, water and carbon monoxide. A trace represents the course of the absorption intensity of
a specific band as a function of time or temperature.

15
 Advanced Materials Characterization

Fourier Transform Infrared Spectroscopy is a well-known technique in

analytics. Since FT-IR spectrometers can be found in so many laboratories,
it is often both convenient and logical to couple these to thermal analysis
systems in order to gain a deeper understanding of the decomposition
or evaporation processes under investigation. Tailored libraries support
evaluation and offer quick and easy spectrum interpretation.

TGA/STA-FT-IR coupling is best suited for detecting permanent inorganic

gases such as HF, CO2 or H2O at reasonable concentrations as well as
organic molecules released from polymers, pharmaceuticals, etc.

Areas of Application

∙∙∙∙
Decomposition
Dehydration
∙∙∙∙
Compositional analysis
Binder burn-out
∙∙∙∙
Residual solvent content
Pyrolysis
∙∙∙∙
Coal analysis
Polymer content
∙∙
∙∙∙∙
Ash content

∙∙
Solid-gas reactions
Combustion Evaporation, outgassing
∙∙∙∙
Oxidation
Corrosion
∙∙
Catalysis

16
Decomposition Behavior of Ethylene Vinyl Acetate (EVA)

EVA is a semi-crystalline thermo-

plastic which is often used in the
production of sport-shoe soles but is
0.20
also applied in the textile industry, in
agriculture and horticulture, and as
0.15
a hot melt adhesive.
TGA

Intensity / a.u.
0.10
When heated in a nitrogen atmos-
phere at 10 K/min, EVA is stable up
0.05
to approx. 300°C and decomposes
afterwards in two steps.
0.00
4000 500
400
3000 300
2000 200
1000 100 Temperature
Wavenumber cm-1

To identify the decomposition TG /% Gram Schmidt AC CH

25
products, 2-dimensional spectra 0.350
100 50
can be extracted from the 3-D
cube shown above and subjected 0.300 20
to a library search. In the present 80
-28.9 %
40
0.250
case, analysis of the FT-IR
349.6 °C -71.1 % 15
absorption intensities shows the 60 0.200 30
351.4 °C
release of acetic acid and various
hydrocarbons. 40
351.5 °C
468.4 °C
0.150 10
20
469.5 °C
0.100
Correlation with the corre- 469.4 °C
20 5
sponding TGA and DTGA curves 0.050 10
(lower plot) reveals that acetic acid
0
evolves solely in the 1st mass-loss 0
0
0
step (at approx. 350°C), whereas
100 200 300 400 500
the polymer backbone – illustrated Temperature /°C
by C-H vibrations – collapses
within the 2nd mass-loss step
(DTGA peak at 468°C) after the PERSEUS® TGA: Combined presentation in the Proteus® software of TGA (black solid) and
acetic acid has all been fully DTGA (black dashed) curves in correlation with the Gram-Schmidt curve (blue) as well as
released. with the individual absorption intensities of acetic acid (red) and CH (green), respectively.

17
 Decomposition Behavior of a Medical Drug Product: Aspirin®

TG /% Gram Schmidt *10 -2 DTG /(%/min) Stability, shelf life and residual
0
solvents are important character-
DTG
150
istics to study in drug substances,
8 excipients and drug products.
-5
175.9 °C
348.1 °C Acetylsalicylic acid, the active
100
6 ingredient in Aspirin®, is respon-
-10
-39.3 % sible for its analgesic and
antipyretic properties. Unfortu-
50
4 nately, the acetyl group of this
177.2 °C -15
-54.8 %
compound is very sensitive to
353.5 °C TG hydrolysis and even reacts with
0 2 humidity. Adding excipients and
-20
coating the tablets with paraffin
Gram-Schmidt are possible measures to suppress
-50 0 this reaction.
-25
100 200 300 400 500
Temperature /°C For the TGA-FT-IR investigation
shown here, a piece of an Aspirin®
TGA-FT-IR experiment on Aspirin®; sample mass: 9.14 mg, Al2O3 crucible, heating tablet was heated up to complete
rate: 10 K/min, N2 atmosphere; combined presentation of TGA curve (blue solid),
DTGA curve (blue dashed) and Gram-Schmidt plot (green)
decomposition, leading to two
main mass-loss steps (according to
the TGA and DTGA profiles). The
FT-IR analysis of the gas phase
above the sample yields acetic
acid, salicylic acid, phenol and
0.25 TGA curve
carbon dioxide as key compo-
nents. This result corresponds well
0.20 with the reaction and decompo-
sition scheme of acetylsalicylic acid
Absorbance Units

0.15
O OH which can be found in literature.
0.10 O CH3 The high boiling components are
efficiently transferred through the
0.05
O heated transfer line to the gas cell
0.00 500 and clearly detected by FT-IR.
4000 400
3000 300
200
Wavenumber cm-1
2000
1000
100
Temperature
The boiling point of salicylic acid
is specified as 211°C and that
of phenol as 181°C, both at a
TGA-FT-IR experiment, 3-dimensional presentation of surrounding pressure of
the measured FT-IR spectra and the TGA curve (red) 1013 mbar.

18
 Differentiation between Diesel Fuel and Biodiesel

TG /% DTG /(%/min) For some years, fuel has been

0 mixed with a certain amount of
bio fuel. This also applies to diesel.
In Europe, biodiesel is mostly
150
rapeseed methyl ester; in the US,
-10
the source is almost exclusively
soybean oil.
177.0 °C 187.2 °C
100 178.2 °C -20 Various norms define the chemical
243.0 °C composition, inorganic content,
density and stability, etc. In order
Biodiesel -30 to investigate the decomposition
50
Diesel fuel
behavior and thermal stability,
Diesel fuel + 10% biodiesel
pure diesel fuel, pure biodiesel and
Diesel fuel + 30% biodiesel -40
two mixtures (10% and 30%
biodiesel) were measured here
0 using TGA-FT-IR.

-50
There is a clear difference in the
50 100 150 200 250 300
Temperature /°C thermal stability between the
vaporization temperatures of pure
TGA comparison of various diesel fuel/biodiesel mixtures; sample masses: biodiesel (green) and pure diesel
10 to 11.5 mg, Al2O3 crucibles, heating rate: 10 K/min, N2 atmosphere
fuel (red) as discovered by TGA,
but there is no apparent system-
atic relationship with regard to the
Absorbance Units
mixtures. The comparison of the
0.12
corresponding IR spectra, however,
reveals a band at 1759 cm-1 which
1759 cm-1
is specific for biodiesel. It is most
0.10
probably related to the ester
group. The intensity of this band
0.08
even shows a relationship with the
biodiesel proportion: it increases
0.06 with increasing biodiesel content.
Biodiesel
Diesel fuel
0.04
Diesel fuel + 10% biodiesel
Diesel fuel + 30% biodiesel
0.02

0.00
2100 2000 1900 1800 1700 1600
Wavenumber cm-1

Comparison of the IR spectra of all measured samples. Zoom in the region

between 1500 and 2200 cm-1.

19
 Simulation of Application and
Curing of Water-Based Paint
Solvent-based products typically
0.12
contain high levels of “Volatile
0.10 Organic Compounds” (VOCs),

Absorbance Units
0.08
associated with relatively long
drying times and a strong smell.
0.06
Water-based products usually
0.04
have much lower VOC levels.
0.02 However, volatile components in
0.00
water-based paints can still be an
500
400
2000
1000 environmental issue – e.g., during
300
Temperature
200
100 4000
3000
Wavenumber cm-1 application if by-products of the
curing reaction evolve.

TGA-FT-IR experiment on a hydro clear coat; 3-dimensional 31.9 mg of a two-component

presentation of the measured FT-IR spectra and TGA curve hydro clear coat were analyzed
(brown) spectra
with the TGA-FT-IR coupling. The
sample was heated to 300°C at a
rate of 5 K/min in a nitrogen flow
of 45 ml/min.

As the measurement graphs show,

one of the main weight-loss
occurrences prior to 250°C is
TG /% water alcohol DTG /(%/min)
clearly attributed to water, but a
0 significant contribution also comes
140 DTG 1.0 from hydrocarbons such as alkyl
154.2 °C -2 acetates and aliphatic alcohols.
120 4.0
The maximum evolution rate for
-4
-4.4 % 94.7 °C
0.8 these latter components is shown
100
-6
by the peaks in the traces (temper-
-26.3 %
3.0
ature-dependent intensities) at
80
0.6
-8 157°C. This means that no
60
-6.7 %
indication of harmful or toxic
2.0
-13.2 %
TG
-10 volatiles is found during drying of
40
157.4 °C 0.4
this clear coat.
-12
101.0 °C 1.0
20
Alcohol 0.2 -14

Acetate solvent
0
0 -16
Water
0
50 100 150 200 250 300
Temperature /°C

Drying and curing of a water-based clear coat; sample mass: 31.9 mg, Al2O3 crucibles;
combined presentation of TGA curve (blue solid), DTGA curve (blue dashed) and traces
of water (red), alcohol (black) and alkyl acetates (green)

20
Manufacturing Conditions
Firing of Clay
DSC /(mW/mg) TG /%
To save energy in buildings, wall ↓ exo
1299.1 °C
constructions should have low 123.8 °C
578.3 °C
720.6 °C
thermal conductivity. One way to 0.0
110.0
37.15 J/g
achieve this is to use highly porous 11.49 J/g 2.55 J/g
9.74 J/g 929.3 °C
building bricks. Various organic DSC
-17.26 J/g
products capable of generating -0.5 105.0
a high volume of voids are mixed -775.08 J/g
into the clay to form cavities -1.0
350.0 °C
-0.9 %
during firing. -0.3 % 100.0

In this example, 107.6 mg of a clay -1.5 -3.2 %

green body was heated at a rate of -1.4 % 95.0

TG
10 K/min in Pt/Rh crucibles in -2.0
flowing air (50 ml/min). The -3.0 %
-0.6 %
predominant effect during heating -0.7 %
90.0
is the burnout of the organics -2.5

between 200°C and 550°C, which

200.0 400.0 600.0 800.0 1000.0 1200.0
is accompanied by a high energy Temperature /°C
release (775 J/g).
Mass changes and energetic changes of a clay for porous bricks;
The main volatiles emerging presentation of the TGA curve (blue) and the corresponding DSC
during this process are water and curve (red)
carbon dioxide, but the FT-IR also
clearly detects the evolution of
HF (around 4000 cm-1) and SO2
(around 1300 to 1400 cm-1) from
the clay (red circles).

Identification of such emissions

allows for optimization of the 0.4

firing process from both

economical and ecological
Absorbance Units

0.3

standpoints.
TGA curve 0.2

0.1

0.00
4000
1200
3000 1000
800
2000 600
400
Wavenumber cm-1 1000 200 Temperature

STA-FT-IR experiment on a clay, 3-dimensional

presentation of the measured FT-IR spectra, including
TGA curves from the STA

21
 Process Optimization
TG /%

Manufacturing of Silicones
Sample 1
100 -1.1 %
TGA-FT-IR coupling can be of great
Sample 2 help in detecting causes of failure
95 during polymer processing. Here,
two control samples of silicones
were tested – one of them (sample
90
2) revealed manufacturing
-25.1 % problems.
85 The TGA curves exhibit signifi-
cantly different thermal behavior.
Sample 2 loses approx. 25% of its
80 weight whereas the mass loss for
sample 1 is only about 1% up to
75
250°C.

To identify the gases evolved, a

70 single spectrum was extracted at
50 100 150 200 250 300
Temperature /°C
the point of maximum IR intensity
and maximum mass-loss rate
Comparison of the TGA results of two TGA-FT-IR experiments; sample masses: 24.5 mg (about 126°C; DTGA curve not
and 26.3 mg, Al2O3 crucibles, heating rate: 10 K/min, N2 atmosphere
demonstrated here). Library
comparison suggests cyclo-
Absorbance Units
octamethyltetrasiloxane with a
2.0
perfect agreement in band pattern
with the experimental spectrum.
O Si
1.5 The polymerization mechanism for
Si O
the generation of silicones often
O Si proceeds via cyclosiloxanes as
intermediate products (presented
1.0 Si O
below in a simplified manner).
Organochlorosilanes such as
dimethylchlorosilane (CH3)2SiCl2
0.5 are hydrolyzed and form silanoles
which react at higher tempera-
tures and in the presence of
catalysts to become the desired
0.0
end product. In the present case,
4000 3500 3000 2500 2000 1500 1000 neither water nor the educt
Wavenumber cm-1
dimethylchlorosilane contributes
Comparison of the measured spectrum extracted at 126°C and the results of the library to the observed mass loss. This
search (cyclooctamethyltetrasiloxane) leads to the conclusion that in the
case of sample 2, the reaction was
partially halted at the intermediate
CH3 CH3 product.
n Cl Sl Cl + m H2O HO Sl O H +
(Me2SiO)y
x
CH3 CH3

22
 Technical Specification
Characteristic Data for All Available FT-IR Coupling Systems

TG 209 F1 PERSEUS®
DSC 404 F1/F3; TMA 402 F1/F3;
Libra®; STA 449 F1/F3; DSC 204 F1
Coupling system STA 2500 Regulus®; DIL 402 Expedis
TG 209 F3 PERSEUS® Phoenix®
STA 449 F1/F3/F5 Select/Supreme
Tarsus® TG 209 F1

RT-1600°C
RT-1000°C (F3)
(Regulus®, F5) RT-2000°C (STA) RT-1550°C (TMA)
Temperature range 4
10°C(RT)-1100°C RT-700°C
-150°C-2000°C RT-1100°C (TGA) RT-2000°C (DIL)
(F1)
(F1/F3)

Measurements under
No, atmospheric
reduced pressure (for Yes (F1) Yes Yes Yes
pressure only
solvent separation)

Vacuum-tightness of
Yes (F1) Yes Yes Yes No
the complete system

Additional automatic Yes (DSC 404,

sample changer Yes (F1) STA 449) Yes No Yes
operation1 No (Regulus®)

Possible Bruker FT-IR

TENSOR, VERTEX TENSOR, VERTEX ALPHA TENSOR, VERTEX TENSOR, VERTEX
spectrometer types2

Stand-alone operation
Yes Yes No Yes Yes
of the FT-IR

Additional analytical
MS or GC-MS
instruments to be MS or GC-MS MS or GC-MS MS or GC-MS MS or GC-MS
(F1)
coupled

Tmax transfer line,

transfer tube/ 230°C/300°C 230°C/300°C 200°C 230°C/300°C 230°C/300°C
adapter head

Internal or Internal or Internal or Internal or

Set-up gas cell Internal
external external external external

Nickel-coated
Material gas cell Stainless steel Stainless steel Stainless steel Stainless steel
aluminum

Gas cell – path length 123 mm 123 mm 70 mm 123 mm 123 mm

Gas cell – volume 8.7 ml 8.7 ml 5.8 ml 7.8 ml 8.7 ml

DLaTGS (internal) DLaTGS (internal) DLaTGS (internal) DLaTGS (internal)

Detector3 DLaTGS (internal)
or MCT (external) or MCT (external) or MCT (external) or MCT (external)

1 Larger Dewar recommended for MCT detector

2 For coupling with FT-IR spectrometers from other suppliers, please ask your NETZSCH representative
3 MCT detector requires LN2 cooling
4 For most instruments, variable furnaces are required to cover the stated temperature range

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
3,000 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 · FT-IR Spectrometers – FT-IR · EN · 1000 · 0615 · LH · 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