USER COM

Information for users of December 1995

2
METTLER TOLEDO thermal analysis systems

Dear customer
Many thanks for the confidence
you have shown in us this year. It
is a pleasure for us to be in regular
contact with you as this continual-
ly leads to new improvements in
our products. Once again, we can
inform you of new products in
addition to interesting application
examples.
May we also urge you to use User
Com as a platform for the ex-
change of experiences with other
persons interested in thermal
analysis.
To ensure we can give even
greater consideration to your
wishes, please let us know your
opinion of User Com.
Selection of
the heating rate
TA-TIP
With the selection of the heating rate you can facilitate or complicate the
interpretation of the measurement.
1. Temperature difference between sample and temperature sensor
As the temperature sensor does not measure the temperature directly in
the sample, but only in the vicinity of the sample, a temperature difference
between sample and temperature sensor appears with every thermal
analysis measuring cell. This depends on the heating rate and the
temperature. If it can not be calibrated, the temperature results must be
corrected by hand when the heating rate differs from the calibration.
With Mettler you can calibrate this heating rate dependence (tau lag
calibration). In accord with the physics, the onset values become practi-
cally identical even with different heating rates (Fig. 1: Indium melting
peaks).

Indium with different heating rates 18.12.1995 07:30:53

Contents
TA-TIP:
– Selection of the heating rate
NEW in sales program
– New DSC821e module
– New cooling option (intra cooler)
– Automatic crucible opening before
the measurement
Applications
– New possibilities with ADSC cp
– Measurement with TGA/SDTA
– Curing behavior of adhesives METTLER TOLEDO TA 8000

Fig. 1: Indium melting peaks at different heating rates

USER COM December 95 1

You thus save yourself the manual result corrections with their associated 3. Improvement in the resolution
errors. If you wish to use your module over a wide temperature range, we with decreasing heating rate
advise you to perform the tau lag calibration with several different sub- For the peak separation, a low heat-
stances so that the system can also take the temperature dependence of this ing rate and a low signal time con-
correction function into account. stant is necessary. With the ceramic
In the case of chemical reactions, the onset temperature is naturally not con- sensor you have a rapidly reacting
stant at different heating rates (however, the difference between the onset sensor available (signal time con-
temperatures would be even greater if the tau lag calibration were wrong or stant approx. 3 s with the standard
if it were not carried out). aluminum crucible). To separate
effects cleanly, the time between
2. Increase in the sensitivity with increasing heating rate them should be approx. 5 time con-
As you have certainly already discovered, melting peaks, for example, stants. The deflection drops back to
become larger with increasing heating rate. You can thus amplify minor 1% of the original baseline.
effects very simply by selecting a higher heating rate (Fig. 2: Glass If, for example, your effects are
transition). separated by around 5°C, you can
calculate the maximum heating rate
at a signal time constant of 3 s as
follows:
5°C/5 * 3 s) * 60 s/min
= 20°C/min
(Fig. 3: Peak separation)

4. Blank value correction

The shape of the blank curve also
depends on the heating rate. With the
TSW870, the database automatically
searches for the latest blank curve
measured with an identical heating
rate and performs an online correc-
tion during the measurement.

Fig. 2: Glass transition

However, if you have a substance which exhibits two effects which lie close
together, these peaks will merge to a single peak at a high heating rate.
Smectic transformations of a ferroelectric
liquid crystal measured at 2 and 5 K/min.
The first 3 phases have a narrow stability
range of only approx. 1°C. As the trans-
formations are not really clearly defined,
the baseline is not reached completely even
with 2°C/min. The resolution of the lower
curve with 5°C/min is clearly poorer. Always
remember that the peak areas of DSC curves
plotted against the temperature do not
correspond to the heat effect (the enthalpy
change is the integral of the DSC curve with
respect to time).

Fig. 3: Peak separation of a liquid crystal

2 USER COM December 95

The new DSC module DSC821e
The DSC821e was introduced in
January as a successor to the
DSC820 module and is based on
leading edge technology. The
module is available in two tempera-
ture versions. The modular concept
of the DSC820 has been extended
further so that we can now give even
better consideration to your specific
wishes. Countless system combi-
nations are possible with the old and
the new options.
We are convinced that we can now
offer you exactly the right solution.
You pay only for what you actually
need.
But the future is still open to you.
The properties of the DSC821e module at a glance:
You can expand your instrument at
any time with additional options to • Large measurement range ±350 mW at RT
meet your needs. • High resolution 0.7 µW at RT
• Wide temperature range -150°C – max. 500/700°C
• High temperature accuracy ±0.2°C
• Excellent peak separation low signal time constant (3 s)
• Modular construction open for the future
• Automatable with sample changer 34 samples
• Further options Automatic sample chamber opening
Gas controller
Control of peripherals
Power output switched by software
Local module operation
Liquid nitrogen (-150°C)
• Cooling systems Intra cooler (-65°C),
cryostat (-50°C) and
air cooling (standard)

Intra Cooler
You now have an intra cooler (Lab
Plant or Haake) available as a new
cooling option for the DSC820/821e.
In addition to the air cooling, the
cryostat or water cooling and the
liquid nitrogen cooling, you can now
equip your existing system with
the intra cooler. The cold finger is
cooled directly with the coolant,
the intermediate circulation system
found with the cryostat is no longer
used.
You can thus perform low temperatu-
re measurements down to the
region of -65°C very quickly and at
a very favorable price. You will
METTLER TOLEDO TA 8000
find the cooling times in Figure 4.
Fig. 4: Cooling curve with intra cooler

USER COM December 95 3

Automatic crucible opening before the measurement
With the DSC820/821e and the
TGA850, the sample changers can
now be equipped with an accessory
that automatically opens the crucible
shortly before the measurement. A
mechanism attached to the gripper
punctures the crucible on the sample
turntable.
During the wait time on the sample
turntable, the sample thus exchanges
no moisture with the surroundings.
This is a great advantage especially
with the readily volatile sample frac-
tions found in the pharmaceutical,
paint and food industries.
TGA850 specific heat from
the SDTA curve?
G. Widmann
Several users have asked us whether
at least a semiquantitative measure-
ment of the specific heat from the
SDTA signal is possible.
As the temperature function of the
calorimetric sensitivity is not (yet)
known, only the sapphire crucible
method can be used. As the cp
temperature function of sapphire is
known, use is made of a standard-
ization employing a sapphire
measurement corrected by the
blank curve. The software used the
rule of three to calculate the
specific heat from the sample
measurement corrected by the
blank curve:
cp = cpSap • mSap • SDTAProbe /
(mProbe • SDTASap)
The following Figure (Fig. 5) shows
how this is achieved.
In the superimposed coordinate
system you can see the sapphire and
the sample SDTA curves (both cor-
rected by the blank curve). The
4 USER COM December 95
At present two types of crucibles
suited to this type of measurement
are available:
The present standard aluminum cru-
cible 40 µl (DSC) and the new
aluminum 100 µl crucible (DSC and
TGA). The following new crucible
sets are available:
• Standard aluminum crucible 40 µl,
set of 160 without lid
• Standard lid, set of 160
• Membrane lid, set of 160 (for the
automatic opening)
Existing customers of a DSC820 or
TGA850 module have the following
upgrade possibilities:
Abb. 5 cp Messung mit TGA 850
sample used was a quartz with its
solid-solid transition at around
570°C. The calculated cp curve of
quartz is shown in the large coordi- software version will also include
nate system.
Enthalpy changes
As you know, enthalpy changes with mination with the sapphire method
DSC curves are calculated by inte-
gration of the heat flow with time.
By analogy, heat effects can be
determined by integration of the spe- measurements, when possible with
cific heat with respect to tempera-
ture. However, version 3.01 of our
software always integrates with re-
spect to time. The result obtained in
Conversion kit for the (DSC) sample
changer
• Calibration crucible
• Needles (3 types)
• Drive shaft
• Crucible holding-down ring
Conversion kit for the (TGA) sample
changer
• Calibration crucible
• Needles (3 types)
• Drive shaft
• Crucible holding-down ring
– Sample turntable type 1 (7.8 mm)
– Gripper type 1 (7.8 mm)
– Crucible holder
(weighing pan plus deflector)
the unit Js/gK must therefore be
divided by the heating rate in K/s to
obtain the result in J/g (the next
integration with respect to the
abscissa).
The circuitous route via the cp deter-
thus allows at least semiquantitative
calorimetric measurements. You
should use the Pt crucible for such
lid.
Alternating differential scanning calorimetry, ADSC, opens up new possibilities
Fig. 6: Section from an ADSC measurement. The top part shows the alternating temperature program.
The corresponding startup deflections are shown on the associated ADSC curve. After approx. 20 min.,
a heat effect starts to shift both envelope curves upward.
Dr. B. Benzler, G. Widmann
In DSC, the heat flow of the sample
under investigation is usually
measured at a constant heating or
cooling rate. High heating and cool-
ing rates – 10 K/min and higher –
have the advantage of high measure-
ment sensitivity (large peak), how-
ever, this is associated with low
resolution relative to the tempera-
ture axis. At low rates, on the
other hand, the conditions are the
opposite: virtually invisibly small
peaks which are often very well
separated.
ADSC with its periodic temperature
program combines the advantages of
both measurement modes:
– High sensitivity thanks to high
instantaneous heating rate
– High temperature resolution thanks
to low average heating rate
The temperature program of ADSC
comprises a periodic succession of
short, linear heating and cooling pha-
ses. The heating or cooling rates lie
between 2 and 5 K/min. For a hea-
ting measurement the final tempera-
ture of the cooling phase is higher
that the start temperature of the
USER COM December 95
The other part is called the latent
heat flow.
After the stabilization time, the
ADSC measurement signal of each
segment is proportional to the
heat capacity of the sample. The
software connects the points of the
measured curve at the end of each
heating segment to the lower en-
velope curve and those at the end of
the cooling segments to the upper
envelope curve. Half of the dif-
ference between the two envelope
curves corresponds to the sensible
heat flow.
Cp changes appear with the follow-
ing effects:
• Glass transition of amorphous sub-
stances
• Cold crystallization
previous heating phase by a small • Chemical reactions (the reactants
amount thus leading to the low, aver- do not have the same heat capacity
age rate: as the products formed).
The measured heat flow comprises
fractions which arise from the The additional latent heat flow
heat capacity Cp and those due to appears with heat effects in both the
physical transformations or chemical heating and cooling phase. The mean
reactions. The Cp part is thus also value of the two envelope curves
called sensible heat (specific heat thus corresponds to the latent heat
is synonymous with sensible heat). flow.
Fig. 7: ADSC curve of 20.425 mg PET in the temperature range 40 to 140°C. Each heating segment
increases the temperature by 4°C with an instantaneous rate of 3°C/min. The subsequent cooling
segment lowers it at the same rate by 3°C. A period thus lasts 2 min. and 20 s. The mean heating rate is
1°C/2.33 min = 0.43°C/min. The two envelope curves needed to calculate the curves in Fig. 8 are also
shown.
5
This allows separation of certain
latent effects from cp changes:
• Enthalpy relaxation peak during
glass transition
• Cold crystallisation in the heating
of supercooled melts
• Crystallization of melts during cooling
• Chemical reactions
• Vaporization of volatile substances
(drying)
Such effects are also called nonre-
versing. More problematic are rever-
sible transformations such as melting
and crystallization; the crystals
which have just started to melt on
attainment of the melting point
would immediately crystallize in the
following cooling segment.
To prevent this, in such cases iso-
thermal holding times are pro-
grammed instead of cooling phases.
The separation of the ADSC heating
curve into the sensible and latent
heat flow is shown in Figure 8 using
the example of polyethylene tereph-
thalate, PET. The usual DSC heating
curve would falsify the glass transi-
tion owing to the simultaneous re-
laxation peak. Moreover, the cp
change of the cold crystallization
would scarcely be visible (Fig. 9).
The separated curves can be evalu-
ated with the software in exactly the
same manner as measured curves.
The separation can also be achieved
by the optional Fourier analysis.
(In this case, the phase shift appears
as a curve.)

Summary

Compared with classical DSC, the

ADSC measurement technique in
combination with the TSW870 TA
software offers the following advan-
tages:
• High resolution of the processes
associated with heat effects thanks
to low average heating rate. The
Fig. 8: Two endothermic peaks (enthalpy relaxation) during the glass transition at 70°C as well as the
exothermic crystallisation peak at 110°C appear on the curve of the latent heat (mean value of the en- measured temperatures are near the
velope curves). The curve of the sensible heat (half the difference between the envelope curves) shows equilibrium values.
the corresponding Cp changes. • High sensitivity of the measure-
ment signal through relative high
instantaneous heating and cooling
rate.
• Separate representation of sensible
and latent heat flow.

However, there are also a few dis-

advantages:
• Additional parameters in the
method development widen the
range of selection possibilities.
• Longer measurement times owing
to the low average heating rate.
• Standard methods require constant
heating rates.

Fig. 9: Comparison of the usual, dynamic DSC curve at a constant heating rate of 0.43 °C/min with the
two separated DSC curves from the ADSC measurement. If the curve of the latent heat and the curve of
the sensible heat divided by the heating rate factor are added, the classical DSC curve is obtained. The
heating rate factor is the ratio of the instantaneous rate to the mean rate: 3/0.43 = 7.

6 USER COM December 95

Model-free kinetics
Dr. J. de Buhr

The launch of the new software

version also saw the introduction
of the model-free kinetics in the last
issue of User Com. As numerous
measurements have shown, in
most cases these new model-free
kinetics allow a considerably more
accurate prediction than the traditio-
nal model concepts, even in the
case of complex or multi-stage reac-
tions.

Only three or more dynamic measu-

red curves (recorded using DSC or
TGA) are needed to analyse the
dynamic or isothermal behavior
of a reaction. The activation energy
E(α) is calculated as a function
of the conversion α.
With simple reactions, this E(α) is
comparable with the classical
activation energy Ea, but its profile
allows additional information on
the complexity of a reaction to be
gained.
Fig. 10: Curing of a 2-component resin
The DSC analysis of a special adhesive from the automobile branch shows
the rapid setting-in of curing, which is manifested in a very steep reaction
peak (1. DSC curves measured). The complexity of this reaction also be-
comes apparent in the analysis of the activation energy E(α), which assumes
very high values at the start of the reaction (2. Activation energy calculated).
Even with this complex reaction, the model-free kinetics allow simulation of
the dynamic curing at different heating rates as the comparison between the
simulated and measured curves shows (3. Simulated curves). The relation
between conversion, time and temperature can also be shown in tabular form
and/or graphically (4. Iso-Conversion).

The curing of a 2-component resin

was recorded at heating rates of
2, 5, 10 and 20 K/min (1. Dynamic
curing measured). The associated
activation energy E(aα) is calculated
automatically (3. Activation energy
calculated). For comparison, the
kinetic model of the nth order was
used, with the following parameters
resulting for a heating rate of
5 K/min:
ln (ko) = 88, Ea = 267 kJ/mol and n
= 1.76.
These two kinetic data records were
used to simulate the isothermal
curing at 60°C and compare it with
the curve actually measured.
(4. Isothermal conversion at 60°C). It
is clear that the model-free kinetics Fig. 11: Curing of a special adhesive
can describe the behavior very
much better than the nth order
kinetics.

USER COM December 95 7

Exhibitions/conferences
Pittsburgh Conference March 4 – 7, ’96 Chicago (USA)
Forum Laboratoire April 1 – 5, ’96 Paris (F)
Analytica (hall 18/stand B14) April 23 – 26, ’96 München (D)
Instrurama June 2 – 7, ’96 Brussels (B)
ICTAC August 12 – 16, ’96 Philadelphia (USA)
Het Instrument October 7 – 10, ’96 Utrecht (NL)
GEFTA/AFCAT/STK Sept. 23 – 26, ’96 Freiburg im Brsg. (D)
Ilmac 96 Nov. 19 – 22, ’96 Basle (CH)

TA customer courses and seminars (CH)

For further information, please contact Mettler-Toledo AG, Analytical
Phone ++41 1 806 72 74
Fax ++41 1 806 72 40
TA customer course (French) May 7 – 9, ’96 Greifensee (CH)
TA customer course (German) May 21 – 23, ’96 Greifensee (CH)
TA customer course (English) May 29 – 31, ’96 Greifensee (CH)
TA customer course (German) Nov. 12 – 14, ’96 Greifensee (CH)
TA customer course (English) Nov. 19 – 21, ’96 Greifensee (CH)

Lab Talk advance notices ’96 (CH)

Interested parties requiring further information should contact
Mettler-Toledo (Switzerland) AG (phone 01/944 45 45, fax 01/944 46 60)
TA8000 user seminar April Greifensee (CH)
TA8000 user seminar May Greifensee (CH)
2nd specialized seminar on
control of inspection, measuring
and test equipment in Q systems May Basle (CH)

TA information days and training courses (USA)

Please contact your local instrument specialists or R. Truttman
Phone 1 800 METTLER (63 88 537) 88 21 or fax 1 609 448 47 77

If you have any questions concerning other meetings, the products or appli-
cations, please contact your local METTLER TOLEDO dealer.

Internet: http://www.mt.com

Editorial office
Mettler-Toledo AG, Analytical
Sonnenbergstrasse 74
CH-8603 Schwerzenbach, Switzerland
Phone ++41 1 806 73 87
Fax ++41 1 806 72 60
E-mail: joerimann@ana-ta.mtg.mt.com

U. Jörimann, Dr. B. Benzler, Dr. J. de Buhr, Dr. R. Riesen, J. Widmann

Layout and production:
MCG – MarCom Greifensee
ME – 51 709 521