RESEARCH / DEVELOPMENT
POLYMERS
INSULATIONS
PHARMACY / CHEMISTRY
VEHICLE CONSTRUCTION
OnSet
ELECTRONICS / METALS
CERAMICS / GLASS
10
News, Facts and Professional Solutions for Thermal Analysis
In this edition:
Page 5
Characterization of the Cooling
Behavior of Sealing Materials by
Means of TMA
The New FT-IR Coupling
Perseus STA 449 F1/F3
Dr. Alexander Schindler, NGB Research & Development
Page 6
Protective Anti-Oxidation Coatings
for Hot Gas Piping Systems and
Their Characterization by Means
of a High-Speed Furnace
Fig. 1. STA-FT-IR coupling Perseus STA 449
F1/F3 with automatic sample changer ASC
(optional). Gas path portrayed partially
transparent and in blue.
Page 10
Large Sample Surface – Excellent
Atmospheric Access for Oxidation
and Corrosion Studies
Page 11
Accessories for DSC/DTA, TGA,
STA, DIL/TMA and LFA
Page 12
NETZSCH-Gerätebau Celebrates
its 50th Anniversary
Page 13
NETZSCH Japan K.K. – A New
Daugher Company is Born in the
Far East
Seite 14
PRECISE PRACTICE – Factors Influencing the TGA Test Result, Part 2
Page 16
Events
It is no coincidence that the brand
new NETZSCH STA-FT-IR coupling
bears the name Perseus. Just like the
brave hero from Greek mythology
who craftily mastered many difficult
tasks, the clever Perseus STA 449
F1/F3 coupling is equipped to deliver
solutions to a great variety of problems in the field of thermal analysis.
EDITORIAL
Editorial
Dear Reader:
We are happy to present you
today with the latest edition
of our customer magazine,
OnSet. The year 2012 has been
a special one for us. We are
celebrating our 50th anniversary
as an independent business unit
of the NETZSCH Group – so
we have dedicated one short
article to the development of
NETZSCH-Gerätebau during the
past decades.
Additionally this year, we were
able to improve our positioning
on the world market; as of
September, we have our own
daughter company in Japan,
one of the most important
national markets for thermal
analysis. We are looking forward
to being able to serve our customers in Japan better than ever
before with our new team there
(see page 13).
In this edition of OnSet, our
main focus is on thermogravimetry. Along with tips on
factors influencing the TGA test
result, we will present newly
developed test configurations
2
for oxidation studies. New
evaluation routines in thermomechanical analysis are the
topic of yet another article.
We would also like to draw
your attention to some interesting contributions: Our main
article will introduce you to our
new Perseus STA 449 F1/F3.
This system allows, for the first
time, an STA (combination of
a TGA and a DSC) to be coupled
directly to an FT-IR. Have a
browse through the great variety of possibilities that this new
system offers.
We are particularly pleased to
present the article contributed
by our customers Thomas
Hutsch, Dr. Ralf Hauser and
Prof. Dr. Bernd Kieback of the
Fraunhofer IFAM in Dresden.
They are reporting about using
a high-speed furnace to investigate the oxidation behavior of
hot gas piping systems.
Please also have a look at our
calendar of events. The many
exhibitions, conferences and
seminars will offer you the
opportunity to discuss with our
experts any questions or problems you may have in the field
of the thermal materials characterization.
Enjoy this edition of our OnSet.
Dr. Jürgen Blumm
Managing Director Sales,
Applications & Marketing
perseus STA 449 F1/F3
Continued from Page 1
In general, systems which connect
thermoanalytical instruments such as
TGA or STA (simultaneous TGA-DSC)
with the corresponding gas analyzers, such as FT-IR or MS couplings,
provide considerably more information than TGA or STA alone. This is
because analysis of the evolved gases
(EGA) produces direct data about the
reaction processes and thus about the
chemical composition of a sample.
Gas analysis by means of FT-IR
(Fourier Transform Infrared) is particularly well suited for organic molecules or samples, but also for ceramic
or composite samples which release
primarily infrared active permanent
gases during decomposition, such as
CO2 or SO2.
Until now, it had been state-of-theart to connect an STA and FT-IR to
each other by means of a heated
transfer line; i.e., they were spatially
separated. The Perseus STA 449
F1/F3 takes a completely new and
better approach. As can be seen in
figure 1, the compact “alpha” FT-IR
spectrometer [1] is directly coupled
to the furnace outlet of the STA 449
F1 or F3 Jupiter® – without a transfer line – thus creating an STA-FT-IR
coupling system which is fully integrated with regard to hardware. The
software also meets all corresponding
expectations, by simultaneously carrying out measurement and evaluation
of STA and FT-IR.
STA 449 F1/F3 features a
very attractive price-performance
ratio.
Perseus
Perseus STA 449 F1/F3 allows
for an excellent correlation of
the mass losses and the gases
detected. This applies in particular
to highly condensable gases [2].
The
the Perseus STA 449 F1/F3, no
liquid nitrogen is required for the
infrared detector, since the DTGS
detector built into the spectrometer does not need to be cooled.
For
Perseus also benefits from the outstanding features of the well-proven
STA 449 F1 or F3 Jupiter®. The STA
449 F1 or F3 Jupiter® is well designed
for coupling purposes; its vertical
arrangement takes full advantage
of the natural upward flow of hot
gases, while vacuum-tightness is a
prerequisite for a clean and defined
gas atmosphere during the measurement. A variety of exchangeable
furnaces and sample carriers allow
for TGA-DSC-cp, TGA-DTA or just
TGA measurements in a wide temperature range from -150°C to 2400°C
(Perseus: to 2000°C). The maximum
sample weight and dynamic measuring range amount to 35 grams. To
increase efficiency, a double-hoist
for two furnaces and an automatic
sample changer (ASC) are available.
The Perseus coupling is well suited
for many applications [2, 3]. As an
example, figure 2 shows the TGADSC results for a PTFE graphite
compound, together with the GramSchmidt curve. The Gram-Schmidt
curve portrays the entire IR absorption detected. At approx. 349°C
(peak temperature), the DSC signal
shows an endothermal effect which
is due to melting of the PTFE portion.
Between approx. 480°C and 620°C,
The new FT-IR coupling Perseus STA
449 F1/F3 thus features four main
advantages:
The
very compact arrangement reduces space requirements by more
than 50% over coupling systems
with a transfer line.
Fig. 2. Mass changes (TGA), heat flow (DSC) and Gram-Schmidt signal (GS) of the des
PTFE/graphite compound as a function of temperature
perseus STA 449 F1/F3
simultaneous recording of TGA and
DSC and, at the same time, detection
of the gases evolved by means of
FT-IR. Initially unidentified gases can
also often be identified by means of a
database search [2, 3].
All in all, the new Perseus STA 449
F1/F3 is a high-performance, direct
STA-FT-IR coupling that sets itself
apart particularly by virtue of its compactness.
Fig. 3. IR absorption as a function of temperature and wave number together with the
TGA curve (reddish brown)
a mass-loss step of 97.4% occurs,
together with an endothermal DSC
effect and a peak in the GramSchmidt signal. In this range, pyrolytic
decomposition of the PTFE portion
takes place. Above approx. 870°C,
the gas atmosphere was switched
from inert (argon) to oxidative
(synthetic air), leading to exothermal
burn-up of the graphite portion of
approx. 2.1%. The residual mass of
approx. 0.6% is most probably due to
a ceramic filler.
The “3-D cube” presented in figure 3
again shows the IR absorption as a
function of wave number and temperature, together with the TGA
curve. During the first mass-loss step,
the well-known absorption bands of
tetrafluoroethylene, C2F4, can primarily be identified, in the range from
1100 cm-1 to 1400 cm-1 (as well as
traces of HF in the range from
4000 cm-1 to 4200 cm-1). The bands
detected during the second massloss step, primarily in the range
4
from 2200 cm-1 to 2400 cm-1, can
be attributed to CO2 formed during
combustion. Finally, figure 4 shows
the characteristic integration traces
for C2F4 and CO2 as a function of
temperature.
Literature
[1] BRUKER Optik GmbH, RudolfPlank-Straße 27, 76275 Ettlingen,
Deutschland
[2] A. Schindler, G. Neumann, A.
Rager, E. Füglein, J. Blumm und T.
Denner, published in Journal of
Thermal Analysis and Calorimetry.
[3] Perseus STA 449 F1/F3, product
brochure
The application example above
demonstrates that Perseus allows for
Fig. 4. Mass changes (TGA) and FT-IR integration traces for C2F4 and CO2 as a function of
temperature
TMA
Characterization of the Cooling Behavior of
Sealing Materials by Means of TMA
Dr. Gabriele Kaiser, Technical and Scientific Communications
ture behavior, especially for dynamic
applications.
Fig. 1. NETZSCH TMA 402 F1 Hyperion®
Be it in the aircraft or aerospace
industries, in refrigeration or air-conditioning technologies, the chemical
industry, hydraulic plants or the automotive industry – sealings that must
withstand low temperatures without
losing their flexibility are employed
everywhere.
As temperature declines, the thermal
expansion properties of the elastomer
causes a decrease in the dimension
of the seal (thermal shrinkage) – but
this can be compensated for in the
early stages by decompression of the
previously applied deformation. Only
once the glass transition range is
reached does the mobility of the elastomer molecules become so severely
restricted that elastic recovery of
the seal becomes almost impossible.
Any further decrease in temperature
can therefore cause a crack to form
between the seal and its partner. The
seal effect is no longer assured.
A variety of test methods, such as
differential scanning calorimetry
(DSC), are available for characterizing
the behavior at low temperatures of
sealing materials. From a technical
applications point of view, the TR 10
value is often the most meaningful
indicator with regard to low-tempera-
What Does TR 10 Mean?
For classical determination of the TR
10 value (TR = temperature retraction) in accordance with both ASTM
D1329 and ISO 2921, a sample is
frozen while in its extended state and
then reheated. The TR 10 value in
°C is the temperature at which the
sealing material has undergone 10%
of the reformation to its original
state. Literature also contains references to TR 30, TR 50 or even TR 70
values, which correspond to a 30%,
50% or 70% recovery.
As per ASTM D1329, typical samples
are in the shape of a tension rod with
a thickness of 2 mm and a bar length
of 25 mm, 38 mm or 51 mm. In
literature, O-rings with a cross-section
diameter of up to 3.5 mm and an
inside diameter of at least approx.
15 mm are also mentined.
Determination of TR 10 by Means
of TMA
For investigating smaller samples,
thermomechanical analysis (TMA;
see figure 1) is a suitable alternate
method. On the basis of the procedure described above, this method
allows for samples to be cooled under
a load and for the applied force to
again be decreased prior to the start
of the heating process.
Figure 2 shows the result of a TMA
measurement on a piece of an
O-ring 1.9 mm in height. Initially,
the elastomer was subjected to controlled cooling to -70°C under a load
of 200 mN and then – after a 15minute isothermal phase – it was
heated again at a rate of 2.5 K/min
under a reduced load of 10 mN. In
the evaluation part of the Proteus®
software, the “temperature retraction” function shows the TR 10 value
in just a few mouse clicks. The TR 20
or TR 30 values can also be calculated
if desired.
This evaluation function further
complements the broad array of
application possibilities provided by
combining the NETZSCH TMA 402
Hyperion® with Proteus® software in
the field of elastomers.
Fig. 2. TR 10 test on an FKM O-ring. Comparative determination of the TR 10 value with
conventional methods also resulted in a temperature of -13°C.
high-speed furnace
Protective Anti-Oxidation Coatings for Hot
Gas Piping Systems and Their Characterization
by Means of a High-Speed Furnace
Thomas Hutsch, Dr. rer. nat. Ralf Hauser and Prof. Dr.-Ing. Bernd Kieback, Dresden Branch Lab of Fraunhofer IFAM
anti-oxidation systems include a
prolonged service life for components
and equipment, the possibility of
increasing operating temperatures
without increasing the amounts of
material used, and the possibility of
using less oxidation-resistant (and
thus less expensive) steels under
identical operating conditions.
Fig. 1. Speciality fields at the Dresden Branch Lab of the Fraunhofer IFAM
Introduction
The Dresden Branch Lab of the Fraunhofer Institute for Manufacturing
Technology and Applied Materials
Research (IFAM) is active in the field
of powder metallurgy and has
specialized in sintered and composite
materials, gradient and functional
materials, and highly porous metals.
At the Dresden site, 58 employees
work in the specialty fields summarized in figure 1. Their work encompasses domestic and international
projects, from cooperative efforts
with both academic and nonacademic research institutes to direct
industrial orders.
In dealing with this broad variety of
topics, a certain question arises again
and again: What level of oxidation
resistance do the different materials
exhibit when in use? The application
range of a pure material in particular
is limited by its ability to resist corrosive and oxidative attack. Figure 2
depicts typical corrosion damage on
6
heating tubes and hot gas channels.
Such damage leads to financial loss,
long downtime or maintenance
periods, and high costs for the supply
of spare parts.
One solution to this problem is to
develop protective coating systems
which can be applied to the metal.
Polymer-derived ceramic (PDC) materials in SiOC, Si(B)CN and SiC systems
exhibit a high resistance to both
temperature and corrosion [1; 2].
The advantages of such protective
a)
Source materials for the coatings are
commercially available inorganic
polymers such as polysiloxanes,
polysilazanes or polycarbosilanes
which are transformed into inorganic
solids by means of a thermal process.
These polymer-derived ceramics have
a glass-like structure or a nanostructure. A liquid phase process such
as dip or spray coating is used. This
forms a polymer film on the surface
of the component which thermally
decomposes by means of thermal
treatment under a protective gas or
air and is thus transformed into the
polymer ceramic. The use of fillers
can increase the maximum producible layer thicknesses for single-layer
coatings, as well as allow for targeted
modification of the coating properties. The technological process for
producing polymer-derived ceramic
coatings is presented in figure 3.
b)
Fig. 2. Typical corrosion damage to industrial equipment
a) Damaged heating tubes and unused tubes (www.met-tech.com);
b) Oxidized hot gas channel (www.pacifictesting.com.au)
high-speed furnace
Fig. 5. Pierced DTA crucible
Fig. 3. Technological process for the production of polymerderived ceramic coatings
Experimental
Sample Material
Measuring Instrument
The samples were ST 37 structural
steels onto which coatings of polysilazane HTA 1500 rc by Clariant
Advanced Materials had been
applied. Added as primary fillers were
Al2O3 (Aeroxide® Alu C, Evonik), SiO2
(Spheriglass 5000, Potters) or ZrO2
(high charms). The filler content was
approx. 30% by volume. Ceramization occurred at 800°C in air. In the
following, the applied coatings will
be referred to using a combination
of the terms for the SiCN material
system and the corresponding main
filler; e.g., SiCN (Al2O3).
The NETZSCH STA 449 F3 Jupiter®
was employed as the measuring
instrument, in the DTA/TG measurement configuration. The high-speed
furnace was used for the investigations using synthetic air as the
atmospheric gas, with the special
objective of being able to record
isothermal and cyclic temperature
loads (figure 4). The heating and
cooling rates of the rectangular test
pieces (length: 7 mm, width: 4 mm,
height: 2 mm) were at 200 K/min
each. To determine a comparable
time, the documented durations of
a)
b)
Fig. 4. Temperature-time regime for characterization of the oxidation behavior under
a) isothermal and b) cyclic temperature load
the heating and isothermal segments
were added, and the duration at an
increased temperature thus obtained.
Additionally, a pierced Al2O3 crucible
was used, which – in contrast with
the conventional type – allows the
gas atmosphere to freely access the
sample (figure 5).
Coating
The structural steel sheets were pretreated by means of sandblasting,
and then coated with a layer between 12 and 25 µm thick. They are
impermeable, crack- and pore-free,
and conform well to the surface of
the substrate. An example showing
an Al2O3-filled coating on a structural
steel substrate can be seen in
figure 6.
For the coated ST 37 sheets, the test
was carried out in synthetic air in
the temperature range from 300°C
to 800°C, in accordance with the
temperature-time regimes in figure
4. In order to be able to assess the
influences of the selected setup on
the results, parameters such as
crucible type, substrate pre-treatment
and flow rate were varied on the
pure substrate.
high-speed furnace
Results of the STA Oxidation Tests
Uncoated Substrate
Fig. 6. Al2O3-filled coating on a structural steel substrate. Left: substrate after pyrolysis; right:
cross-section micrograph (x 200), layer thickness approx. 25 µm; the upper nickel coating serves
for mechanical stabilization during the metallographic presentation
a)
Under otherwise identical test
conditions, a significantly higher
mass increase in the substrate in the
isothermal T-t regime (figure 7a) was
exhibited with pierced crucibles than
with conventional closed crucibles.
This is due to the direct perfusion of
the crucible resulting from the
apertures (compare figure 5).
Simultaneously, when carrying out
isothermal tests, faster formation
of a plateau can be observed; this
can be attributed to the increase in
b)
Fig. 7. Uncoated substrate: Variation in the crucible geometry alters interaction between the atmosphere and sample under
a) isothermal and b) cyclic test conditions
b)
Fig. 8. Coated substrate: Characterization of the applied protective anti-oxidation coatings with their primary fillers by means of
a) isothermal and b) cyclic tests
8
high-speed-furnace
the thickness of the oxide layer. This
prevents oxygen from accessing the
metal‘s surface. In contrast, a cyclic
temperature load can be applied to
the oxide layer as it forms by using a
high-speed furnace. Due to the
associated tension in the layer,
constant chipping occurs.
For the following investigations, only
a pierced crucible was used, since this
best corresponds with real-life
operating conditions for hot gas
piping systems. The following
measurement configuration requirements for characterizing protective
anti-oxidation coatings were thus
derived:
Use of pierced crucibles
Pre-treatment of the substrate
by
sandblasting
Same flow rate for all tests
Consistent sample geometry
Cyclic investigation is preferable
Coated Substrate
For characterizing the applied SiCNbased protective anti-oxidation
coatings with SiO2, Al2O3 and ZrO2 as
the primary fillers, the isothermal and
cyclic T-t regime was employed. The
recorded mass increases are summarized in figure 8. It can clearly be seen
that the protective anti-oxidation
coatings serve to greatly lessen oxidation. Upon closer inspection, it can be
determined that cyclic testing enables
the individual coatings to be differentiated after much shorter times and
at a higher temperature than isothermal investigation would allow.
The basic ranking of the coatings
remains unchanged. SiCN(ZrO2) is the
most stable to corrosive attack,
followed by SiCN(Al2O3) and
SiCN(SiO2).
Summary
The polysilazane-based coating
systems developed in cooperation
with Clariant (Advanced Materials)
at the Dresden Branch Lab of the
Fraunhofer IFAM reduced the oxidation rate for ST 37 structural steel by
twenty-fold in both static and cyclic
tests at 800°C in air. The applied
coatings are suitable as protective
anti-oxidation coatings as well as for
passivation of protective anticorrosion coatings. The SiCN(ZrO2)
coating systems exhibits the best
protection against oxidation. For
testing the oxidation stability, a cyclic
measurement method allowing for
high heating and cooling rates is
preferable. This reduces the amount
of time needed for characterization.
The Authors
Thomas Hutsch is responsible for Thermal Analysis at the
Dresden Branch Lab of the
Fraunhofer IFAM. His research
work centers on sintered and
composite materials, particularly
metal-carbon composites.
In order to foster direct interaction
between the sample and atmospheric gas, it is recommended to use
a pierced crucible. These requirements can be fully met with the
high-speed furnace.
Literature
[1] R. Riedel, G. Mera, R. Hauser and
A. Klonczynski, „Silicon based
polymer-derived ceramics: synthesis,
properties and applications – a
review”, J. Ceram. Soc. Japan, 2006,
(114(6)), 425 - 444
[2] Ralf Hauser, Saifun Nahar-Borchard, Ralf Riedel, Yumi H. Ikuhara
and Yuji Iwamoto, „Polymer-Derived
SiBCN Ceramic and their Potential
Application for High Temperature
Membranes”, Ceram. Soc. Japan,
2006, (114(6)), 524 - 528
Dr. rer. nat. Ralf Hauser
is on the scientific staff at
the Dresden Branch Lab of
the Fraunhofer IFAM in the
areas of chemistry and surface
technolgy, primarily focusing
on “high-temperature protection“.
Prof. Dr.-Ing. Bernd Kieback is
Director of the Dresden Branch
Lab of the Fraunhofer IFAM.
new sensors
Large Sample Surface – Excellent Atmospheric
Access for Oxidation and Corrosion Studies
Dr. Elisabeth Kapsch, Technical and Scientific Communications
Advantages of the Sensors for
Suspended Samples
Sample can be hung down directly
Bendable thermocouple type S
Improved contact between the
sample and purge gas
slow mass increase detectable
(µg/h range)
Long-term signal stability, typcial
drift less than 0.1 µg/h
Various atmospheres are possible:
- Oxygen
- Corrosive gases, with silica tubes
- Controlled humidity when working under humid atmospheres
(using a humidity generator)
Very
Platinum cage
TGA-DTA sensor for
hanging samples
Lately, the demand for special crucibles has been increasing for oxidation and corrosion studies. For these
investigations, it is preferable to have
a large sample surface in order to
maximize the gas access. Of course,
measurements can only be carried
out when the right sensor for these
special crucibles is available. In the
high-temperature range, specific TGA
and DTA crucibles, slip-on plates,
meshes and baskets are available to
accommodate several sample dimensions and densities.
TGA sample carrier
for hanging samples
The particular TGA and TGA-DTA
sensors for hanging or suspended
samples allow perfect access to all
sample surfaces by the atmosphere.
These Al2O3 sample carriers and
sensors with Al2O3 frame are available
for the STA 449 F1/F3 Jupiter®
systems. The sample carrier is easy
to handle and allows selection of
the hanging wires according to the
sample properties.
TGA Measurement of a Hanging
Coated Sample
In figure 1, two sheets of a coated
glass were pierced and fixed into
the special TGA sample holder for
suspended samples. The total sample
mass amounted to 274.99 mg. The
two sheets were heated up to 600°C
in synthetic air at a heating rate of
5 K/min.
The improved contact between the
sample surface and purge gas resulted in the detection of very weak
mass-loss steps at 316°C (0.087%)
and 398°C (0.036%).
Steel Corrosion
The TGA measurement in figure 2
shows several heating cycles on a
hanging steel sample. The steel sheet
was heated at a rate of 5 K/min in
a nitrogen atmosphere with 16%
oxygen. The visible mass gain decreases with each subsequent heating
cycle. At the beginning of the test,
oxidation of the sheet surface takes
place. This can be observed in the
Fig 1. Mass-loss behavior of coated glass sheets
10
accessories
early onset and rapid mass increase
for the first heating (green curve).
After a couple of heating cycles, inner
oxidation occurs, which is indicated
by a slower, diffusion-dependent
mass increase.
TG /%
[1.3]
100,10
Steel corrosion in oxidative atmosphere
1.9 g, 5 K/min, 16 % O2 in N2, 110 ml/min
100,08
Mass Change: 0,150%
100,06
100,04
Mass Change: 0,082%
100,02
Hanging the sample in the special
holder maximizes the accessible
sample surface and therefore improves oxygen access to all sample
sides.
100,00
1st heating
99,98
3rd heating
Mass Change: 0,066%
99,96
5th heating
200
400
600
Temperature /°C
800
1000
1200
Fig 2. Steel corrosion in an oxidative atmosphere
Analyzing & Testing
Analyzing & Testing
Analyzing & Testing
Accessories for DSC/DTA, TGA, STA, DIL/TMA
and LFA
Dr. Elisabeth
Kapsch,
Technical
and
Accessories
for Differential
Scanning
Calorimeters
and Thermobalances
Scientific
Communications
Accessories for Laser Flash Analysis
Crucibles, Sensors, Sample Carriers, Calibration Kits for DSC, TGA and STA Systems
Sample Holders, Accessories and Reference Materials for LFA 447 NanoFlash®,
LFA 457 MicroFlash® and LFA 427
Accessories for Thermomechanical Analysis
Sample Holders, Spare Parts and Calibration Materials for DIL and TMA Systems
Crucibles, Sensors, Sample Carriers, Calibration
Kits for DSC, TGA and STA SystemsLeading Thermal Analysis
Sample Holders, Accessories and Reference
Materials for LFA 447 NanoFlash®, Leading Thermal Analysis
LFA 457 MicroFlash® and LFA 427
Sample Holders, Spare Parts and Calibration
Materials for DIL and TMA SystemsLeading Thermal Analysis
To attain proper results, proficient
state-of-the-art instruments are
required, featuring optimum technical
attributes such as high sensitivity and
resolution in the required temperature
range. In recent years, a rise in the
development of new materials for
emerging applications has been presenting an ongoing challenge for the
thermal analysis industry in keeping
pace with rapidly evolving market
needs. In order to arrive at determinations regarding the thermoanalytical
and thermophysical properties of such
materials, special sample preparation,
measurement set-up and accessories
are often needed.
NETZSCH accessories can open up a
world of possibilities for your thermoanalytical and thermophysical properties (TPP) needs. Three topic-specific
catalogues summarize the accessories
for all DTA/DSC/STA, TMA/DIL and
LFA instruments. It is our hope that
these new catalogues will serve to
acquaint you with these.
Accessories in contact with the
sample or in close proximity to it
require special attention. Potential
reactions between the sample material and instrument parts must be
prevented while ensuring that the
test results remain reliable and accurate. For these reasons, one of our
primary areas of focus is crucibles and
sensors for DTA/ DSC, TGA and STA
and sample holders and supports for
DIL/TMA and LFA instruments.
Please contact us or your local sales
representative if you are interested in
obtaining one of these catalogues.
50 Years ngb
NETZSCH-Gerätebau GmbH Celebrates its
50th anniversary
Dr. Thomas Denner, Managing Director A&T Business Unit
Milestones at NGB
1952 Foundation as a department of
Gebrüder NETZSCH-Maschinenfabrik; first measurement instrument
deliverd
1954 Delivery of the first dilatometer
1959 Delivery of the first thermobalance
1962 Foundation of NETZSCHGerätebau GmbH
1970 Delivery of the first
Simultaneous Thermal Analysis
instrument, the STA (TGA-DSC)
Expansions strategy since 1962
1975 First STA-MS orifice coupling
worldwide
It has been 50 years since NETZSCHGerätebau GmbH was spun off from
Gebrüder NETZSCH-Maschinenfabrik
and became its own company. Our
beginnings can be traced back to the
emergence of the ceramic industry
here in Selb in 1890 and the associated rising demand for specialized
quality assurance machines.
In close cooperation with our customers, we pressed forward with
developments in this area and, in the
process, came to understand how a
successful business relationship rests
upon the exchange of ideas and
the readiness to address customers’
wishes.
In looking back over these last five
decades and scrutinizing the experience and expertise that our company has gathered during this time,
it becomes clear that one thing has
not changed over the course of these
years: Our most valuable asset has
always been – and continues to be –
12
our relationship with our customers.
This is what motivates us and inspires
us; it is the driving force behind our
new developments and new ideas.
As a result, our customers can expect
a product that is precise, diligently
engineered, and easy to use. They
demand reliability and consistent high
quality – requirements which we are
happy to fulfill.
After 50 years of ceaseless innovation
and a vast number of developments
achieved, our family-owned company
has become one of the market leaders in the fields of thermal analysis
and thermophysical properties measurement, with subsidiaries all around
the world. We are proud of our past
and confident in our future.
This year, we celebrate our 50th
anniversary – and want to thank you
all for your trust and your loyalty over
the years. We could not have done it
without you.
1985 First STA-MS Skimmer
coupling worldwide
1986 Development of the hightemperature DSC 404
1992 Introduction of the Laser Flash
Appartaus (LFA) as core product of
the “Thermophysical Properties“
instrument series
1993 Coupling of TGA and STA
with FT-IR
2009 Diversification of the product
portfolio by introduction of
Accelerating Rate and Multiple
Module Calorimeters
2011 Introduction of unique
TGA/STA-GC-MS coupling solution
with event- or temperature-controlled
GC-MS triggering
2012 Acquisition of Bruker AXS‘s
Thermal Analysis Instruments
Business in Japan
NETZSCH Japan K.K.
NETZSCH Japan K.K. – A New Daughter
Company is Born in the Far East!
Yoshio Shinoda, President NETZSCH Japan K.K.
The team at NETZSCH Japan K.K.; Yoshio Shinoda (front row, second from right) and Dr. Jürgen Blumm, NGB Managing Director
(front row, on the right)
2012 is the 50th anniversary of
NETZSCH Analyzing & Testing.
Celebrating this memorial year, it
was announced that a new daughter
company of NETZSCH A&T, NETZSCH
Japan K.K., was founded in Japan,
and 30 new people joined the
NETZSCH family.
After acquiring Bruker’s Thermal
Analysis instruments business in
Japan, it is estimated that NETZSCH
Japan K.K. has a market share of
20%. Their business bases are
located in Yokohama (near Tokyo)
and Osaka.
The sales activity of NGB products in
Japan was initiated by the foundation
of the Tokyo Representative Office in
1995 by Mr. Matsui, who successfully
developed the sales of products for
Thermophysical Properties in principal
research institutes.
Meanwhile, the business partnership between Bruker and NETZSCH
started in the early 1990s for the
development of the TGA-FT-IR coupling
system. Aiming at further business
development in Japan, Bruker AXS
has been an exclusive agent of
NETZSCH A&T since 2004, and has
expanded its sales and service
organization as well as setting up a
new application laboratory in
Yokohama. This synergy between
Bruker and NETZSCH led to
tremendous business success in
Japan. More than 100 LFA instru-
ments have been sold in Japan so far.
Even after the huge earthquake in
Fukushima and the succeeding
nuclear accident, this Thermal
Analysis team did not give up.
Immediately after the accident, they
confirmed that all NETZSCH users
were safe and helped investigate the
instruments free of charge.
Now NETZSCH Japan K.K. has been
founded for further improvement of
our outstanding reputation as the
performance leader in Thermal
Analysis instrumentation. We are
convinced that this will boost the
success NETZSCH has had in recent
years in the Asia-Pacific region.
precise practice
pRecise practice
Factors Influencing the TGA Test Result (Part 2)
Dr. Stefan Schmölzer, NGB Applications Laboratory
In OnSet8, we presented the ways in
which the atmosphere and sample
shape affect the TGA test result,
using detailed examples from the
field of thermoplastic elastomers.
In addition to the purge gas type
(e.g., inert or oxidative), another
factor influencing the test result is
the purge gas rate. Figure 1 shows
the TGA curves for a polymer additive
formulation at two different purge
gas rates. The solid sample was
heated under nitrogen to 230°C
and the temperature was then held
constant. During heating, the sample
melted at 75°C and then remained in
the liquid state.
For both measurements, a sample
weight of 10.50 mg and a heating
rate of 20 K/min were used. The mass
loss observed here is highly correlated
with the purge gas rate employed.
For the purge gas rate of 40 ml/min
(green TGA curve), a mass loss of
23.6% can be observed; for the
reduced purge gas rate of 20 ml/min
(blue TGA curve), the mass loss
amounted to only 22.8% after the
Fig. 1. Influece of the purge gas rate on the TGA test result
same amount of time. The massloss step in this example cannot be
attributed to decomposition of the
sample, but rather to the evaporation
of volatiles. The evaporation process
can thus be accelerated by means of
high purge gas rates.
Fig. 2. Influence of the crucible diamater on the TGA test result
14
Similarly, the choice of crucible also
affects the TGA test result. Figure 2
shows the test results for the same
sample shown in figure 1.
All measurement parameters – temperature program, sample weight,
atmosphere and flow rate – were set
identically. The only difference was
the crucible geometry. For the test
yielding the blue TGA curve, the
crucible had a smaller diameter than
for the one yielding the green curve.
Also, a clear difference in the massloss step can be seen in the TGA test
result here. With the larger crucible,
a mass loss of 23.6% was observed;
for the smaller crucible, the mass
loss amounted to only 21.2% under
otherwise identical measurement
conditions.
As already discussed in OnSet8, the
ratio of surface to sample mass
always plays a decisive role in the
reproducibility of thermogravimetric
test results.
precise practice
Besides the crucible geometry,
another important consideration
when comparing results is whether
a pierced lid was employed for the
measurement. Generally, TGA
measurements are carried out
without a lid, but sometimes a lid is
used to prevent sample material in a
liquid state from spilling out of the
crucible.
Figure 3 depicts the difference in
decomposition behavior of an HDPE
sample as measured in an Al2O3
crucible without a lid versus in a
crucible with a pierced lid. The
sample weight for both measurements was 10 mg and the heating
rate amounted to 10 K/min. The
measurement was carried out under a
synthetic air atmosphere.
Under these measurement conditions,
it can be assumed that the polyolefin
is undergoing thermo-oxidative decomposition. The oxygen contained
in the purge gas (synthetic air) is
simultaneously a reaction partner
for the sample. The concentration
of oxygen at the sample thus has a
direct influence on the decomposition
Sample holder and radiation shield for
corrosive media (TG 209 F1 Libra®)
Fig. 3. Decomposition behavior of an HDPE sample; measurement in an Al2O3 crucible without lid
and in a crucible with pierced lid
itself and/or the beginning of decomposition. This can be evaluated using
the extrapolated onset temperatures
in figure 3.
In the measurement without a lid, decomposition starts already at 384°C;
in the measurement with a pierced
lid, on the other hand, decomposition
does not occur until 419°C. In the
measurement with a pierced lid, the
sample does not come into contact
with oxygen until a later point in
time, so oxidation is not observed
until a higher temperature is reached.
The residual mass, however, is unaffected by this and is identical in the
two measurements.
general
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The End of an Era ...
Erwin Kaisersberger
A widely respected expert who has
earned himself an outstanding
reputation in the world of thermal
analysis has just retired from
service: NETZSCH’s very own Mr.
Erwin Kaisersberger. On September
28th, 2012, shortly after his 70th
birthday, Mr. Kaisersberger celebrated his launch into retirement
with a little ceremony here at NGB.
After an impressive 39 years of
work, Mr. Kaisersberger has now
decided to devote more time to his
family and his garden.
It was 1973 when the young
physicist Erwin Kaisersberger
initially joined NGB, responsible for
sales and applications in Germany
and abroad. He then progressed
through a number of other positions during the course of his many
years here, including Head of the
Lab, Head of Technical Sales and
“Senior Scientist“ for the global
NETZSCH Service & Applications
Support Team. NETZSCH was very
pleased in 2007 when, after first
considering retirement, Mr.
Kaisersberger decided to accept
our offer to continue working for
us in a consultancy relationship.
Over these last five years, he has
dedicated the majority of his
professional efforts to our TGAGC-MS coupling system.
In a farewell speech to Mr.
Kaisersberger, NGB Managing
Director Dr. Jürgen Blumm thanked
him for the long and fruitful
working relationship, conferring
special accolades upon his rich
pool of knowledge and experience.
Numerous lectures at seminars
and conferences both at home
and abroad, as well as countless
publications and an abundance of
work groups for thermal analysis,
had all made Mr. Kaisersberger to
a globally renowned expert in our
field
We bid a heartfelt “farewell” to
Mr. Erwin Kaisersberger – a very
well-liked colleague who was
always ready to lend a helping
hand and who always had the
right answer to almost any question. We wish him the very best for
this new era in his life, and hope
that he will continue to find great
joy in his new freedom for many,
many years to come.
Editor:
NETZSCH-Gerätebau GmbH
Wittelsbacherstraße 42
95100 Selb, Germany
Tel.: +49 9287 881-0
Fax: +49 9287 881-505
[email protected]
www.netzsch.com
16
Editorial Staff:
Dr. Gabriele Kaiser, Dr. Jürgen Blumm, Dr. Ekkehard
Füglein, Dr. Elisabeth Kapsch, Rolf Preuß, Doris Steidl
Translation:
Doris Steidl, Nicole Huss
Copyright:
NETZSCH-Gerätebau GmbH, 11/12
Print:
NETZSCH Werbe- und Service GmbH
Gebrüder-Netzsch-Straße 19
95100 Selb
Germany
Tel.: +49 9287 75-160
Fax: +49 9287 75-166
[email protected]
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