Leading Thermal Analysis

Thermomechanical Analysis TMA

Method, Technique, Applications
Analyzing & Testing
TMA 402 F1/F3
22
Thermomechanical Analysis TMA
Thermomechanical analysis (TMA)
determines dimensional changes of
solids, liquids or pasty materials as a
function of temperature and/or time
under a dened mechanical force (DIN
51 005, ASTM E 831, ASTM D 696,
ASTM D 3386, ISO 11359 Parts 1 to
3). It is closely related to dilatometry,
which determines the length change of
samples under negligible load (DIN
51 045).
Many materials undergo changes of
their thermomechanical properties
during heating or cooling. For example,
phase changes, sintering steps or
softening can occur in addition to
thermal expansion. TMA analyses can
hereby provide valuable insight into the
composition, structure, production
conditions or application possibilities for
various materials.
The application range of instruments
for thermomechanical analysis extends
from quality control to research and
development. Typical domains include
plastics and elastomers, paints and dyes,
composite materials, adhesives, lms
and bers, ceramics, glass and metals.

Operating Principle
Irrespective of the selected type of
deformation (expansion, compression,
penetration, tension or bending),
every length change in the sample is
communicated to a highly sensitive
inductive displacement transducer
(LVDT) via a push rod and transformed
into a digital signal. The push rod and
corresponding sample holders of fused
silica or aluminum oxide can be quickly
and easily interchanged to optimize the
system to the respective application.
furnace
sample
push rod
sample carrier
height setting
displacement
transducer
actuator
(static or modulating)
force sensor
TMA: Operating principle
3
Results and Accuracy
The linear thermal expansion is an
important variable for assessing the
behavior of a material.
This chart shows the thermal expansion
(dL/L
0
in %) and the resulting curve of
the coefcient of thermal expansion
(CTE in 1/K) of sapphire compared to
literature values (circles). The results
demonstrate the high accuracy which
can be achieved using the TMA 402
Hyperion

.
TMA 402 F1 Hyperion

with
double furnace hoist
At a Glance
What sets the new
TMA 402 F1/F3 Hyperion

apart:
A modular concept of
interchangeable furnaces
covering the temperature range
from -150C to 1550C, which
are also compatible with other
NETZSCH instruments
The large number of sample
holder types and adjustment
possibilities
The broad range of force,
without added weight, digitally
programmable from -3 N to 3 N
44
TMA 402 Hyperion

Trend-Setting Technology
The Heart of the TMA 402 Hyperion

is a Highly Precise Inductive
Displacement Transducer (LVDT)
This technology has stood the test of
time; it is also used for dilatometers and
allows measurement of even the smallest
of length changes, into the nanometer
range (digital resolution of 0.125 nm).
Vacuum-tight Thermostatic
Measuring System
The entire TMA 402 Hyperion

measuring system is thermally stabilized
via water-cooling. This ensures that the
measurement will not be inuenced by
heat from the furnace or by temperature
uctuations in the local environment.
All joints have a vacuum-tight design
to allow measurements in a highly pure
atmosphere or under vacuum. Pressures
of less than 10
-4
mbar can be achieved
with the use of a turbomolecular pump.
In combination with the integrated mass
ow controllers (MFC) for purge
and protective gases (optional in the
TMA 402 F3), measurements in highly
pure inert gas or in oxidizing
atmospheres can be optimally
controlled.
Further Information
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5
Simultaneous Measurement of Force
and Displacement Signal
The force operating on the sample is
generated electromagnetically in the
TMA 402 Hyperion

. This guarantees
a quick response time for experiments
with a changing load, e.g. tests on
creep behavior. A highly sensitive force
sensor (digital resolution < 0.01 mN)
continuously measures the force
exerted via the push rod and readjusts
it automatically. This sets the TMA 402
Hyperion

apart from other instruments,

which use only preset values.
Precise Force Control
The electronic control system for the
TMA 402 Hyperion

allows forces to
be set in the mN-range. This enables
testing even on sensitive materials such
as thin bers or lms. The force
operating on the sample can be altered
via the software in a stepwise or linear
fashion. This makes it particularly simple
to carry out such analyses as creep or
stress sweep tests. The premium version
of the Hyperion

, the TMA 402 F1,

provides even more capabilities. From
single pulse in rectangular or ramp
form to continuous modulation with a
customizable frequency (up to 1 Hz),
every possibility is covered. This model is
particularly well-suited for determining
visco-elastic material properties such as
elasticity and creep modulus.
Technical Data TMA 402 F1/F3
Max. sample length 30 mm
Measuring Range 5000 m (total) / 500 m
Dig. resolution (length) 1.25 nm / 0.125 nm
Force range
Dig. resolution (force) < 0.01 mN
Modulated force Up to 1 Hz (only F1)
Final vacuum pressure < 10
-4
mbar
Gas connections
MFC Standard (F3 optional)
furnace
sample carrier
system
thermostatic
controlled support
force sensor displacement transducer
loading cell
vacuum-tight
housing
TMA 402 Hyperion

:

Sectional Drawing
5
0.001 N to 3 N in steps of 0.2 mN (tension or pressure)
Protective gas, 2 purge gases
66
Common System Congurations by Temperature Range
-150C to 1000C
Steel furnace with LN
2
cooling, sample holder system
of fused silica, Type K thermocouple
RT to 1550C
SiC furnace, sample holder system of Al
2
O
3
,
Type S thermocouple
Other congurations can easily be realized due to the modular concept.
Highest Precision Maximum Flexibility
Interchangeable Furnaces
The furnaces can be easily interchanged
among various high-temperature series
thermal analysis instruments (STA 449
Jupiter

, DSC 404 Pegasus

). The
selection of available furnace models is
continuously being expanded. The TMA
402 Hyperion

can thus cover the entire

temperature range from -150C to
1550C and is prepared for temperature
extensions.
Sample Holder Systems Tailored to
the Task
Depending upon the question at hand
and the geometry of the sample, the
operator has a variety of sample holders
to choose from. Holding devices for
expansion, penetration, and tension
measurements are available, as well as
push rods and supports for analyses
in 3-point bending. Accessories for
the temperature range up to 1000C
are made of fused silica. For the high-
temperature range, aluminum oxide
varieties are available.
In the TMA 402 Hyperion

, the
thermocouple can be changed quickly
and easily. Besides type K, the S and E
varieties are also available. The system
electronics recognizes the installed
sensor automatically.
Special Sample Holders
With the help of special sample
containers, the expansion behavior of
powders, pastes and liquids can be
analyzed, as can metals all the way
to the melting point. Accessories for
experiments on swelling behavior upon
immersion are also available.
Coupling with MS / FT-IR
To analyze gases evolving upon heating
(EGA), the TMA 402 Hyperion

can be
coupled to a mass spectrometer and/or
FT-IR spectrometer.
The Modular Design of the TMA 402
Hyperion

Makes it Unique among

the Competition
To adjust the instrument for the
respective temperature ranges, all
that needs to be done is to exchange
the furnace. This can be done by the
operator. Due to the double furnace
hoist, switching to a second furnace
takes only moments.
Further Information
www.netzsch.com/n10830
77
Feature Advantage Benet
Modular concept
Furnaces are interchangeable and compat-
ible with other NETZSCH instruments
Synergies in procuring and operating, easy and
cost-effective expansion and retrotting
Gas ows controllable via
software
Programmable atmosphere change
Analysis of, for example, oxidation behavior
without manual valve operation
Digitally programmable
force control up to 3 N
Force alteration (linear/stepwise),
continuous force modulation (TMA 402 F1)
Determination of visco-elastic properties
A variety of accessories,
e.g. special sample hold-
ers, immersion baths
Extension of the application range
Measurement of powders, liquids, pastes or
metals (until melting), immersion measurements
Sample holder and push rods
(fused silica, aluminum oxide)
8 8
Proteus

Software for the TMA 402 F1/F3 Hyperion

The software includes everything

necessary for carrying out
measurements and evaluating the
results. Simple menu navigation and
automated routines make the
software easy to operate while allowing
for complex analyses.
General Software Characteristics:
For Windows

XP and Windows

7
operating systems
Multi-tasking: Simultaneous
measurement and evaluation
Multi-moduling: Operation of several
pieces of equipment via a single PC
Combined analysis: Comparison and/
or evaluation of TMA, DMA, DEA,
DIL, DSC, TGA and STA
measurements in a single
presentation
Labeling: Text elements can be
entered and positioned freely
Calculation of the 1
st
and 2
nd

derivative
Export of graphics and data
Selectable colors and line types
Saving and recovery of the analysis
status
Macro-recorder (optional)
Context-based help system
Temperature calibration
Software developed by ISO-certied
enterprise of the NETZSCH Group
99
Features Specic to TMA:
Various correction possibilities for
taking the expansion behavior of the
system itself into account, as well as
offset and sample length correction
Automatic adjustment of sign for
force and displacement signal to the
measurement conguration being
used
Routines for the determination of
characteristic temperatures such as
onset, peak and nal temperatures
Evaluation of glass transitions and
softening points in accordance with
DIN
Automatic shut-off at softening point
Expansion coefcients: Calculation
and presentation of the technical and
physical expansion coefcients
Automatic sintering step evaluation
Measurements with variable force:
Determination of visco-elastic
properties
Extensions
c-DTA

function: Evaluation of the

temperature signal for endothermic
or exothermic effects
Thermokinetics:
Extensive characterization and
optimization of sintering processes
Density Software: Determination of
changes in volume and density until
the liquid state
Peak Separation:
The separation of overlapping effects
Rate-Controlled Sintering (RCS)
Software: Sintering with a constant
shrinkage rate (optional)
10 10
Meaningful Material Characterization
in the Low-Temperature Fields
Tension Test on a Polymer Film
Orientation effects, stretch conditions
and shrinkage are measured under load
for lms.
In this example, the expansion and
contraction behavior of a 40-m thick
polycarbonate lm was tested under
tensile load. The results varied
considerably depending on the load.
Under low amounts of force (5 mN), the
lm contracted at higher temperatures;
however, it expanded if greater force
(50 mN) was applied.
Application Examples
11 11
Meaningful Material Characterization
in the Low-Temperature Fields
Visco-Elastic Properties of
Polytetrauoroethylene
The combination of a 3-point bending
sample holder and a modulated sample
force allows the visco-elastic properties
of a material to be determined.
A PTFE bar was measured between
-150C and 150C under (rectangular)
modulated force (xed static force
of 0.2 N and three different dynamic
forces). Based on the expansion data
and the sample geometry, the storage
modulus E can be calculated as a
function of temperature.
The three typical PTFE transformations
are clearly visible at around -100C
( transition), between 0C and 50C
(crystal to condis-crystal transformation)
and above 100C (glass transition).
Behavior of Polymers under Pressure
The extent to which the elastic
properties of a seal remain intact after
being subjected to a constant load of
longer duration is very important.
To test this, an elastomer seal was
loaded with a force of 3 N and then
relieved to 5 mN. Following a 40-hour
load time, 21% compression was
observed. After a 30-minute relief
period, the compression had reversed
by 16.2%; after 60 min, by 16.8%. The
visco-elastic properties of the elastomer
were such that the sample did not
return to its original length even after
30 hours.
12 12
Meaningful Material Characterization
in the High-Temperature Fields
Refractory Materials
The life span and efciency of any
technical furnace can be greatly
improved with an appropriate
conguration, along with a high-quality
interior lining made of refractory
materials. An important criterion in
assessing such materials is thermal
expansion.
Shown in the example is the thermal
behavior of a typical coarse-grained
refractory material. At the beginning of
the measurement, the -
transformation of the tridymite is rst
observed, followed by the -
transformation of the free quartz
between 548C and 580C. After
another transformation between
1233C and 1299C, the material
begins to soften at 1450C.
Sintering of Aluminum Titanate
One use of aluminum titanate is as a
carrier material for catalytic converters in
the automobile industry.
Shown here is the measurement of an
aluminum titanate green body in the
temperature range from RT to 1450C
with a subsequent isothermal line at
1450C of 7 hours. During heating, a
shrinkage of 12.7% is observed.
Sintering takes place in two steps with a
maximum sintering rate of 0.31%/min.
In the subsequent isothermal phase,
further shrinkage of 0.6% occurs.
To optimize the sintering process, an
RCS measurement (rate-controlled
sintering; optionally available) can
additionally be carried out.
Application Examples
13 13
Measurement with EGA
(Evolved Gas Analysis)
A clay sample (powder) was tested in
air using a TMA-MS (Aolos

) coupling
in the temperature range from RT to
800C.
At the beginning of the measurement,
the adsorptively bound water and the
interlayer water are released (shrinkage
of 0.01%). Above 300C, the samples
organic constituents burn up (release of
water, m18, and CO
2
, m44). There is no
visible inuence on the expansion curve
here, due to the very low proportion.
Between 487C and 536C, dehydro-
xylation of the samples clay mineral
content takes place.
Associated with that is a sample
shrinkage of 0.05%.
14 14
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Our Expertise Service
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after sale. Our qualied personnel
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application departments are always
available for consultation.
In special training programs tailored
for you and your employees, you will
learn to tap the full potential of your
instrument.
To maintain and protect your
investment, you will be accompanied
by our experienced service team over
the entire life span of your instrument.
Summary of Our Services
Installation and commissioning
Hotline service
Preventive maintenance
Calibration service
IQ / OQ / PQ
On-site repairs with emergency
service for NETZSCH components
Moving / exchange service
Technical information service
Spare parts assistance
15
Our Expertise Applications Laboratories
The NETZSCH Thermal Analysis
applications laboratories are a
procient partner for nearly any
Thermal Analysis issue. Our
involvement in your projects begins
with proper sample preparation and
continues through meticulous
examination and interpretation of the
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Within the realm of thermal analysis
and the measurement of thermo-
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diverse analysis techniques for
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powders and liquids).
Measurements can be carried out on
samples of the most varied of geome-
tries and congurations. You will
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This will enable you to precisely
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Wittelsbacherstrae 42
95100 Selb
Germany
Tel.: +49 9287 881-0
Fax: +49 9287 881 505
at@netzsch.com
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