USER COM

Information for users of

METTLER TOLEDO thermal analysis systems
2/98

Dear customer
One of the most important aims of
UserCom is to make you aware of new
application possibilities. We would es-
pecially like to thank all our customers
who give us articles that we can pub-
lish.
We are also pleased to include any tips
that make your daily work easier.
Our application booklets inform you in
more detail on special topics (thermo-
plastics, pharmaceuticals and food).
Contents
TA-TIP
- Tips on model free kinetics
NEW in the sales program
- STARe SW V6.0
- New reference substances
- Crucible lid with a 50 µm hole
Applications
- Polymorphism using DSC
- Swelling measurements of thin polymer
films with TMA
- Vitrification in the isothermal curing of
epoxy resins by ADSC
- TGA measurements at reduced pressure
- Application of DSC to the investigation of
damaged plastic materials
Tips on model free
kinetics
What is model free kinetics used for?
8
TA TIP
The rate of a chemical reaction depends on the temperature and on the proportion of
unreacted substance (or the conversion of the reaction α). The Arrhenius equation (acti-
vation energy) is generally used for the temperature dependence. The effect of conversion
is, however, more difficult to describe. Nth order kinetics makes an attempt at a simple
model, whereby the initial rate of an isothermally performed reaction corresponds to the
rate constants at this temperature. The rate decreases uniformly towards zero during the
course of the reaction. The activation energy is considered to be constant.
In practice, the function of α is complex and the activation energy depends on the con-
version. This is especially the case with solid state reactions, heterogeneous reactions (e.g.
liberation of gas) or with parallel reactions.
Model free kinetics (mfk) is based on the realization that the function of α and the acti-
vation energy indeed depend on the reaction conversion, but that they are always the
same at a particular conversion (isoconversion method), independent of the heating rate
used. Because of this they can be calculated from several measurements at different heat-
ing rates.
The main application of kinetic investigations is for the accurate prediction of the reac-
tion conversion at (almost) any isothermal temperature or heating rate.
Reaction DSC TGA
Polymerization O
Polyaddition O
Polycondensation O o
Pyrolysis o O
Thermal decomposition o O
Oxidative degradation O o
Loss of water of crystallization O O

USER COM 2/98 1

Practical procedures Evaluations Assessment
Technical details Checks Now you have to assess the conversion
Most reactions are investigated with DSC. DSC: Check that the reaction enthalpies are curves:
Thermogravimetry can also be used if you constant to within ±10% at all heating • Are the curves uniformly shifted to the
expect a change of weight proportional to rates (reaction enthalpies are somewhat right with increasing heating rate? Do
the course of the reaction. temperature dependent). An outlier indi- they cross at anywhere? If a curve does
cates incorrect sample preparation. not “fit”, check the evaluation limits,
Preliminary experiment TGA: Determine the height of the steps and with the DSC the type of baseline. Is
In a preliminary experiment, the substance (horizontal steps). Are the percent values the conversion curve better? If not, repeat
of interest is measured at relatively high constant to within ±5%? Here also, an out- the measurement. If only one of the four
heating rates, e.g. 10 or 20 K/min in or- lier usually indicates incorrect sample curves is an outlier, then delete it.
der to quickly estimate the initial and preparation. • Zoom in on the first 10% of the conver-
final temperatures as well as the heating sion. Are there any crossovers in this re-
rates for the following measurements. Settings gion?
The sample, (or mixture for multicom- If you are interested in predictions of con- Afterwards check the uppermost 10% (i.e.
ponent systems), should be as homoge- versions below 10% or above 90%, we rec- 90% to 100%)!
neous as possible. ommend that you use more than the stan- If you are satisfied with the conversion
dard number of 100 data points for the curves, put the measurements curves in a
Sample and crucibles evaluation: Kinetics/Evaluation settings/ small coordinate system e.g. in the bottom
Check that the crucible has not been at- Number of points e.g. 500. left-hand corner of the window.
tacked by the sample. If necessary, use
other crucibles (e.g. stainless steel, gold). Evaluation of conversion Evaluation of kinetics
Does the sample remain in the crucible (no Open the curves as a function of the refer- Select all the conversion curves (depress
sputtering or foaming)? If necessary, use a ence temperature. the Ctrl key) and continue with Kinetic/
smaller sample or cover the sample with an Your own evaluation limits are often better Model free kinetics. The activation energy
inert powder (α-Al2O3). The automatic than those automatically selected (Set- curve appears after a few seconds. Double
blank curve correction is recommended for tings/Limits/Manual limits). click on the ordinate in order to judge the
weak measurement signals. With the thermogravimetric measurements order of magnitude. You can display the ac-
you often have more possibilities if you tivation energy in numbers with TA/Table:
Measurement technique evaluate the DTG curve as a DSC curve. In Enter a starting value and an increment of
DSC: Is the size of the peak (or peaks) at particular, by choosing suitable baselines, 10% and use Settings/Result mode/Abscissa
least 1 mW (ideally 5 mW)? Otherwise use a you can avoid the problem of any overlap- unit. The activation energy is usually in the
larger sample. If the crucible lid has to be ping of secondary reactions that are not of range of approx. 50 to 400 kJ/mol.
pierced, use a hole of uniform size. Smaller interest. In order to do this, you need the
holes shift certain reactions to higher tem- software option “DSC evaluation” and Applied kinetics
peratures. “Mathematics”,. Conversion plot and table:
TGA: Does the reaction result in a weight For each heating rate used, try to create a Click on Kinetic/Applied model free/Conver-
change of at least 100 µg (ideally 5 mg)? frame that includes the range of the chemi- sion Plot and Table. You obtain the conver-
Otherwise use a larger sample. cal reaction and click on DSC/Conversion sion plot with an abscissa scale that corre-
(for TGA curves TG/Conversion). With the sponds to the evaluation range of the slow-
Measurements calculation of the conversion from the DSC est reaction. The results for the five tem-
Prepare three or four crucibles each with curves, a small info-box opens which you peratures are shown uniformly distributed
the optimum sample amount determined can confirm with OK (mfk is, in general, over the evaluation range of the slowest re-
previously. Set up methods with (2), 5, 10, only used when the chemical reaction can action. In the table, only those reaction
20 K/min. Remember that low heating be measured from α = 0% to α = 100%). times are printed that lie within the ab-
rates require a lower temperature range Color the conversion curves the same color scissa range. You can now optimize the
(chemical reactions are shifted to higher as the measurement curves; this improves evaluation as desired:
temperatures with increasing heating the overall view. Put the conversion curves Kinetic/Conversion parameter settings,
rates). Never use, for example, heating in a small coordinate system, e.g. in the Maximum time 60 min, Temperatures
rates of 10, 11 and 12 K/min; the differ- bottom right-hand corner of the evaluation 120 °C, 140 °C and 160 °C, Conversion
ences are too small and the uncertainty of window (open the corresponding frame, select 50%, 90% and 95%. In order to change the
the results too large. the α ordinate, View/Coordinates in the temperature or the conversion delete the
frame). The conversion table can be deleted. standard values. The easiest way is to click

2 USER COM 2/98

 repeatedly on the button Delete. Don’t for-
get to delete the first conversion plot before
you begin a new evaluation. If you don’t
delete it, then the plots are superimposed.
In the same way, you can obtain the
isoconversion plot and the corresponding
table. In this case you should enter the de-
sired times for the table under Kinetic/Iso-
conversion.
Do not extrapolate more than about 50 °C
beyond the measured temperature range of
the reaction; predictions are more accurate
if you stay close to the measured range.
Ideally, you should check one of the predic-
tions with an isothermal measurement at
Fig. 1. On the left the DSC curves of the dehydration of CaSO4 hemihydrate (standard aluminum the temperature in question. An agreement
crucible, lid with a small hole of approx. 50 µm diameter) are shown recorded at various rates. to within 10% between the predicted reac-
The very small exothermic peak immediately following the dehydration peak is attributed to a tion time and the time actually measured is
solid-solid transition of the anhydrous CaSO4 formed. The evaluation limit for the calculation of regarded as good.
the kinetics was therefore set before this peak. On the right an enlarged portion of the calculated
conversion curves is shown. It is clear that the curve for 2 K/min (dashed line) does not corre-
spond to the others. This is due to the use of an incorrect evaluation limit (see arrow).

Fig. 2. Below left are the DSC curves and below

right the resulting conversion curves; above
right are the activation energy curve and the
corresponding table obtained using model free
kinetics. Finally, above left, the conversion plots
with the conversions and temperatures
predicted by the program are displayed.

Fig. 3. This shows the optimized presentation of

the isothermal reaction conversion at 120 °C,
140 °C and 160 °C as a function of the reaction
time (here max. 120 min). The reaction time
in minutes is printed in the table for multiples
of 10% conversion. The activation energy is
shown below on the right.

USER COM 2/98 3

STARe SW V6.0
With this version we change over from a
UNIX operating system (Solaris and Inter-
active) to WindowsNT, which is widely used
today.
It is important for users to know that our
STARe applications software V6.0 is identi-
cal to Solaris version V5.12. The data are
fully compatible so that a backup from
V5.12 can be read by V6.0.
The WindowsNT operating system offers
additional advantages:
• easier data transfer with Windows appli-
cations (Copy and Paste)
• the STARe software can be used simulta-
neously with the latest Windows applica-
tions
• the system is easier to maintain thanks to
its wide use
• a larger number of printers can be used
• the operating instructions have been inte-
grated into the on-line help. This in-
cludes both a global help (keywords and
subjects) as well as a context-orientated
help (menu based).
Crucible lid
with a 50 µm
hole
These crucible lids with a standard hole
diameter of 50 µm allow approximate
equilibrium conditions to be produced (de-
fined atmosphere at practically constant
pressure). The so-called self-generated at-
mosphere has the following advantages:
• better separation of the elimination of
water of crystallization in several steps
(e.g. CaSO4 · 2H2O/CaSO4 · 0.5H20)
• exact determination of boiling points,
since evaporation is suppressed prior to
boiling.
A set 400 crucible lids suitable for 40 µl,
100 µl and 160 µl aluminum crucibles is
now available under order the number
ME 51140832.

New reference substances

We have now introduced 2 new reference ladium sample can then also be repeatedly cp determination. It has been shown that
substances for the calibration and adjust- used. better results can be achieved with a sap-
ment of the TGA and TMA modules. Gold Sapphire is often used as a reference for the phire disk than with alumina powder.
is an ideal reference substance because it
is not oxidized even by oxygen and can be Melting point Heat of fusion ME number
used repeatedly. However, gold can make a
Gold 1064.2 °C 63.7 J/g 51140816
hole in a platinum crucible. To prevent
this, you can put approx. 10 mg of pow- Palladium 1554.0 °C 162 J/g 51140817
dered alumina in the crucible and place
the gold sample carefully on top. Number of disks Weight of disk ME number
At temperatures above 1100 °C we recom-
Sapphire 5 approx. 20 mg 51140818
mend the use of argon as purge gas. A pal-

4 USER COM 2/98

Polymorphism using DSC
Introduction
A substance is said to be polymorphic if it
can exist in different crystalline forms,
i.e. if the same chemical compound occurs
in various modifications with different
physical properties. The importance of
polymorphism lies in the fact that the
physical properties (melting point, color,
solubility, refractive index, hardness, con-
ductivity, etc) of a given compound vary
from one polymorphic form to the other.
The crystalline modifications, however,
melt to the same liquid phase.
Polymorphism (in the case of elements
also known as allotropy) is exhibited by
elements such as sulfur, carbon (graphite,
diamond), phosphorus as well as by nu-
merous minerals and organic substances.
Plastics can also exist in polymorphic
forms, e.g. isotactic polypropylene.
The polymorphic forms of pharmaceuti-
cally active substances are of great practi-
cal importance [1]. Since the solubilities
and dissolution rates of individual poly-
morphic forms are very different, resorp-
tion and bioavailability in the body also
differ [2]. The therapeutic efficiency there-
fore depends on the modification in ques-
tion; a metastable form for example can be
twice as active as the stable form. Polymor-
phism is not only important for pharmaco-
logical efficiency; it also plays an impor-
tant role in production, processing and for-
mulation.
The individual crystal modifications that
are stable in particular temperature ranges
are symbolized by Greek letters (α, β) or
Roman numerals (I, II, III). In addition,
metastable states (symbolized for example
by β’) can also exist whose gradual trans-
formation into stable states may take
hours or even years.
In accordance with Ostwald’s rule, the less
stable modifications are often formed first
on crystallizing from the melt. These then
rearrange stepwise to the stable forms.
Quite often, it is easier to obtain meta-
stable forms by slowly heating amorphous
material (obtained by shock-cooling from
USER COM 2/98
the melt) above the glass transition tem-
perature [3]. The tendency to build crystals
above the glass transition temperature is
also called “devitrification”.
Metastable forms also crystallize from solu-
tions of the substance in certain solvents.
One distinguishes between two types of
polymorphism: the enantiotropic and the
monotropic polymorphism. The exothermic
(with loss of heat) solid-solid transition
from a metastable form into a stable form
is called monotropic (Fig.1), since this can
only occur in this direction and the reverse
transition b’ Æ b is not possible.
The heat of fusion of the lower melting β’
modification is usually smaller than that of
the more stable higher melting form β1).
Vapor
pressure
liquid
state
solid
solid
state II
state I
Temperature
Ttrs Tfus
Fig. 1. Enantiotropic (left) and monotropic (right) phase diagrams showing the relationship
between vapor pressure and temperature of the the phases.
The difference between the heats of fusion
corresponds to the heat of monotropic
solid-solid transition.
Reversible solid-solid transitions are called
enantiotropic (Fig.1). The transition
α ↔ β from the low temperature α form
to the high temperature β form is endo-
thermic. Therefore, in this case, the heat of
fusion of the α form is greater than that of
the form β1).
1) This rule is true only for relatively
small differences of the melting points
up to approx. 20 °C. If the differences
are larger, the cp temperature func-
tions must be taken into account.
Many substances, on crystallizing out from
solution, form compounds (solvates) with
different physical properties. If the solvent
is water, these compounds are known as hy-
drates. If such solvates are heated in a
gastight and pressure resistant container,
they melt at considerably lower tempera-
tures than the solvent free compound. The
solvent is trapped in the crystals of the sol-
vate and is often not liberated until the
melting process begins. The different melt-
ing temperatures are reminiscent of the be-
havior of polymorphic compounds, hence
the name “pseudo-polymorphism” [2].
Some organic compounds with long
stretched-out molecules with dipole proper-
ties are not transformed into the isotropic
(completely free) liquid state in one transi-
Vapor
pressure
liquid
state
metastable
solid state II
stable solid
state I Temperature
Tfus II Tfus I
tion. Above the apparent observed melting
point, a special liquid phase, called
mesophase appears, which corresponds to a
liquid crystalline state.
On further heating, the isotropic liquid is
formed. Finally, roundish shaped molecules
are produced, which on heating first form a
plastic-crystalline state. The isotropic melt
is then formed from this on further heat-
ing.
The relationship between the actual state of
aggregation and the thermodynamic pa-
rameters temperature, pressure and con-
centration is described by so-called phase
diagrams. These show the region of stabil-
ity of all the phases that can occur.
5
Detection of polymorphism
The different physical properties of the in-
dividual polymorphic forms of a compound
allow the actual form to be identified. The
methods most frequently used to study
polymorphism are:
• DSC (differential scanning calorimetry).
Monotropic solid-solid transistion
of sulfapyridine
The sample is premelted (dashed curve in
Fig. 2) and then shock-cooled in the
sample changer by placing the hot crucible
containing the molten sample on the turn-
table at 25 °C. An amorphous solid is ob-
lattice grows on crystal nuclei that prefer-
entially develop on defects of the original
crystal lattice. Because of the different de-
fect probability, a sample formed from
many single crystals shows just as many
individual reverse transitions. This is dem-
onstrated in the isothermal reverse transi-
tion shown in Figure 3: almost every crystal
grain shows its own exothermic transition
peak. Finely ground crystal powder would,
however, yield a broad bell-shaped transi-
tion peak on account of statistical prob-
ability.

Allotropy of sulfur
Sulfur is an example of allotropy that is
well known but at the same time difficult to
understand.
The stable form at room temperature is
rhombic α-sulfur, which consists of S8
molecules. At 95.6 °C, this changes into
monoclinic β-sulfur, which melts at
119 °C (“ideal melting point”). At the
same time, some S4 and S6 molecules are
formed, which cause a depression of the
“ideal melting point” to the “natural melt-
ing point”. This is given as 110 °C for α-
Fig. 2. First DSC heating run of sulfapyridine at 5 K/min (dashed line). The melting point of the sulfur and 114.5 °C for β-sulfur.
stable modification is 190 °C. The second heating run is shown above in full, and below with
ordinate scale expansion. The monotropic solid-solid transition occurs at about 125 °C. Transition of the metastable
modification of phenylbutazone to
the stable form via the liquid phase
DSC measures the heat absorbed or liber- tained. In the heating run recorded after- When phenylbutazone is heated for the first
ated when a sample is subjected to a wards (lower curve in Fig. 2), a glass tran- time, it melts at 105 °C, the melting point
temperature program, e.g. a linear heat- sition can be observed followed by the exo- of the stable modification. If the melt is
ing program. thermic “cold crystallization”. On further cooled, quite often a glass is formed but no
heating, this metastable form undergoes crystals. On heating again at 5 K/min, a
• TOA (thermo-optical analysis): the an exothermic monotropic solid-solid metastable form with a lower melting point
sample is observed between crossed polar- transition to yield a more stable modifica- crystallizes out. From the melt of the meta-
izing filters. If, at the same time, a tem- tion that melts at 179 °C. The stable form stable modification, crystals of more stable
perature program similar to that in the crystallizes from the melt and finally melts forms grow with melting points of 102 °C
DSC method is applied, the individual at 190 °C. and 105 °C. The measuring cell was purged
phase changes can be instantly observed with helium in order to achieve the best
as changes of double refraction. Enantiotropic solid-solid transition possible separation of the very close melt-
• solubility investigations of potassium perchlorate ing peaks.
• X-ray powder diffraction methods, e.g. Potassium perchlorate shows an
Debeye-Scherrer powder refractometry enantiotropic solid-solid transition at
• infrared spectrometry 300 °C corresponding to the phase transi-
tion from orthorhombic to cubic. On cool-
In the following pages we will describe the ing, the reverse transition occurs at a tem-
behavior of some typical polymorphic perature that is appreciably lower than the
substances. The curves were measured equilibrium temperature. This marked su-
with the METTLER TOLEDO STARe Sys- percooling occurs because the formation of
tem and the DSC821e measuring module. crystal nuclei takes time. The new crystal

6 USER COM 2/98

Pseudo-polymorphic transition of
glucose monohydrate
In a hermetically sealed crucible, the
monohydrate melts in its water of crystalli-
zation in the range 80 °C to 120 °C. The
first peak at 83 °C looks like a eutectikum
of glucose and water. The excess glucose
melts at about 120 °C.
The sample behaves quite differently in an
open crucible: the water of crystallization is
liberated without any change in the form of
the crystals occurring. Water evaporates up
to about 130 °C (strongly endothermic) and
the anhydrous crystal modification is formed
(exothermic). Finally, the anhydrous form
melts just below 160 °C. The shape of the
curve is very dependent on the diameter of the
hole in the crucible lid: a diameter of
0.05 mm results in a very pronounced “self-
generated” atmosphere (high partial pressure
of water vapor), whereas a diameter of 2 mm
is practically the same as using an open
crucible (the water vapor is immediately
removed by the purge gas).
The difference between the endothermic
total heat flow of the hermetically sealed
crucible (176 J/g) and that of the crucible
with pierced lid (400 J/g) is the heat of va-
porization of water: 1 g of sample liberates
99 mg of water. If this is multiplied by the
value for the heat of vaporization of water
( 2300 J/g), one obtains 228 J. The addi-
tion of 176 and 228 gives 404, which is
very good agreement.

Fig. 3. Solid-solid transition of KClO4 (13.8 mg KClO4 in a

pierced aluminum crucible). The α → β transition on
heating at 10 K/min is shown on the left. The reverse
transition was measured isothermally approx. 8 °C below
the equilibrium temperature in order to demonstrate the
effect of nucleation. Almost all of the 15 or so crystal
grains showed a different transition behavior.

Fig. 4. DSC curves of a sample of 10.56 mg of sulfur in a

hermetically sealed aluminum crucible at 5 K/min. The
solid-solid transition of 12 J/g is only completely
measured in the first heating run. The melting peak
then occurs at the ideal melting point of 119 °C . If the
sample is cooled at 5 K/min and immediately measured
again, then the melting region is noticeably depressed
due to the formation of S4 and S6 molecules. The
sample “recovered“ partially during three days storage
at room temperature: the solid-solid transition can
again be observed and the melting peak has increased to
115 °C.

Fig. 5. DSC curves of phenylbutazone in a helium

atmosphere. First heating run: the form I melts at 105 °C
(dashed line). Second heating run: a metastable modifica-
tion crystallizes at 40 °C (mainly II) and melts at 95 °C.
During the melting, more stable modifications are formed
that melt at 102 °C (III) and at 105 °C (I). A heating rate
of 5 K/min is too fast for the complete formation of the
stable modification.

USER COM 2/98 7

 Mesophase transitions of a liquid
crystal
The DSC curve shows the temperature
range in which mesophases occur. In the
case of cholesteryl myristate, we are dealing
with the smectic and the cholesteric
mesophases. The very low mesophase tran-
sition energies of 1.8 and 1.4 J/g compared
to the heat of fusion of 55 J/g are typical.

Conclusion
Fig. 6. The upper curve shows the melting behavior of 4.64 mg glucose monohydrate in a All polymorphic transitions involve a
hermetically sealed crucible at 10 K/min. The integral of the sharp eutectic peak is printed on the change in enthalpy. This is the reason why
left, and the total heat of fusion of 176 J/g on the right. In the open crucible (0.4 mm diameter DSC is an excellent technique for the in-
hole in the lid), the water of crystallization evaporates without the formation of a liquid phase vestigation of these types of transitions. In
(heating rate: 10 K/min). Finally, the anhydrous compound melts at 155 °C. The weight loss after the course of a series of such measure-
the measurement was 9.9%, The value expected stoichiometrically is 9.1%. The difference can be ments, however, one’s belief in well-defined
explained by a slight caramelization of the glucose. “melting points” is seriously shaken.
A basic knowledge of the different types of
polymorphism is necessary in order to in-
terpret the DSC curves properly. The vari-
ous examples described in this article
should help the newcomer and serve as an
introduction to this field.

References
[1] J. L. Ford and P. Timmins, Pharma-
ceutical Thermal Analysis, Ellis
Horwood, 1989
[2] D. Giron, J. Pharmaceutical & Bio-
medical Analysis, Vol. 4, n6,
755-770, 1986
[3] G. Widmann, Thermochimica Acta,
Fig. 7. The DSC curves of 12.48 mg cholesteryl myristate at 5 K/min. The melting peak (transition 112 (1987), 137-140
from the solid to the liquid crystalline state) is followed by two mesophase transitions. The melt is [4] A. Burger, Acta Pharmaceutica
isotropic above 86 °C. Technologica 28 (1) 1982

8 USER COM 2/98

Swelling measurements of thin poly-
mer films with TMA
K. Knop and K. Matthée
Institute for Pharmaceutical Technology, Heinrich-Heine-Universität Düsseldorf Universitätsstr. 1, D-40225 Düsseldorf, Germany

Introduction Film preparation sion containing 30% of a copolymer of

Pellets and tablets are often coated with
aqueous dispersions of insoluble polymers
such as polymethacrylates to provide a
means for the controlled release of active
ingredients. The mechanism of drug re-
lease can be described as diffusion of the
drug through the swollen membrane or
through the water filled pores [1].
The swelling behavior can be characterized
by the determination of the increasing wa-
ter content of the polymer films or by vi-
sual observation of the swelling process. In
both cases, relative thick films are neces-
sary in order to obtain measurable
changes. In this study, a method using
TMA (thermomechanical analysis) has
been developed that enables the swelling
behavior of thin polymer films to be mea-
sured directly. TMA allows the determina-
tion of extremely small changes in length
of samples subjected to exactly defined
forces and temperatures. In the past, TMA
methods have been described for the swell-
ing behavior of papyrus in water [2] and
for elastomers in organic solvents [3].
5 µl samples of polymer dispersion
(Eudragit RL30D) with different amounts
of plasticizer (triacetin) were spread out on
an Inconel disk (10 mm diameter, 300 µm
thick) and dried at 70 °C for 2 hours. The
resulting film thickness was measured and
found to be 55 ±10 µm.
Materials
Eudragit® RL30D RL30D, (Röhm,
Darmstadt, Germany) is an aqueous disper- Results and discussion
Fig. 1. TMA sample arrangement for the
measurement of swelling
ethylacrylate, methylmethacrylate and
trimethylammoniumethylmethacrylate
chloride in the ratio of 1 : 2 : 0.2. Triacetin
was obtained from Riedel-de Haen, Seelze,
Germany. All other materials used for the
preparation of buffer solutions as well as
the sodium chloride for the adjustment of
the ionic strength were of analytical grade
purity.
Influence of different loads
The influence of load on swelling behavior
was investigated in the range from 0.01 N
to 0.1 N with films of Eudragit RL contain-
ing 10% plasticizer (triacetin) using a
phosphate buffer at pH 6.8 as the swelling
medium. As expected, the expansion dur-
ing swelling decreased with increasing
load. For this reason the load was set to a
value of 0.02 N for all further experiments.

Experimental methods
TMA measurements
The measuring unit (Fig. 1) consists of a
glass crucible (internal diameter 10.5
mm) that rests on the sample support. An
Inconel disk with the polymer film
mounted on the upper side is placed in this
crucible and the probe (diameter 3 mm)
placed on top with a load of 0.02 N. The
TMA furnace maintains the temperature
constant at 37 °C. As soon as the sample
temperature is in equilibrium with the fur-
nace, the swelling medium (0.25 ml water
or buffer solution at 37°C) is injected into
the crucible with a syringe and the expan-
sion of the film recorded for the following
60 minutes. Most measurements were per-
formed with the Mettler TMA40 measuring
cell. Typical swelling curves are shown in Fig. 2. Typical swelling curves, measured with the TMA/SDTA840 (R. Riesen, Mettler Toledo). See
Figure 2. also Fig. 4.

USER COM 2/98 9

 Influence of film thickness Conclusions
A range of films (40 µm to 100 µm thick) 40
lonic strength 0.0 Using the TMA method described, it is pos-
was prepared from Eudragit RL containing sible to measure and characterize the swell-
30

10% triacetin by applying different
amounts of the polymer dispersion. The
swelling behavior in phosphate buffer at pH
6.8 showed a linear relationship between
the thickness of the film and the expansion
caused by swelling.
Influence of the plasticizer concentration
Eudragit RL films were prepared with tri-
acetin concentrations ranging from 0% to
20%. The swelling of the films increased
with plasticizer concentrations between 0%
and 10% (Fig. 3). The polymer film with
20% triacetin was sticky and showed almost
linear expansion during the time interval
of the measurements.
10%
60 triacetin conc.
20%
50
expansion [ µm]
expansion [ mm]
ing behavior of polymer films of various
0.05 compositions in different solutions. The
20
I-0,5 preparation of film samples of different
0.1
10
0.5 composition is easy and requires only a
1.5 small amount of polymer dispersion or so-
0
0 10 20 30 40 50 60 lution. The main advantage of the TMA
time [min] method in comparison with other methods
is that very thin films can be measured, i.e.
Fig. 4. Swelling of Eudragit RL films without
films similar in thickness to those used for
triacetin in NaCl solutions of different ionic
coating pellets and film tablets in con-
strength. The continuous curves show the mean
trolled release preparations.
values of three measurements and the vertical
lines the range of values.
Swelling in different buffer solutions
Fig. 5 shows the swelling of Eudragit RL
films with 10% triacetin in different buffer
solutions of ionic strength 0.1 mol/l. The
swelling in formate buffer was much more
pronounced than in phosphate buffer.
These differences in swelling behavior in

40
5% various buffer solutions have already been
30 reported for thicker Eudragit RS films us-
20 0% ing a method based on the determination
10 of the absorbed water [1].
0
0 10 20 30 40 50 60
time [min] 100
buffer pH 6.8 formate
80
Fig. 3. Swelling of Eudragit RL films with
expansion [ µm]

60 phosph
different concentrations of tracetin and
40
phosphate buffer at pH 6.8. The continuous
20
curves show the mean values of three measure- citrate
10
ments and the vertical lines the range of values.
0

0 10 20 30 40 50 60
Swelling in solutions of different ionic time [min]
Literature
strength Fig. 5. Swelling of Eudragit RL films with 10% [1] Knop K. - Influence of buffer
The swelling behavior of Eudragit RL films triacetin, different buffer solutions of pH 6.8 solution composition on drug
without plasticizer depends on the ionic and ionic strength 0.1 mol/l. The continuous release from pellets coated with
strength of the sodium chloride solution curves show the mean values of three measure- neutral and quaternary acrylic
(Fig. 4). The expansion in pure water was ments and the vertical lines the range of values. polymers and on swelling of free
the most marked and had still not finished polymer films. Eur. J. Pharm. Sci. 4,
even after 60 minutes. The extent of swell- 293-300 (1996)
ing decreased with increasing ionic [2] Wiedemann H.G. and Bayer G. -
strength. With solutions of ionic strength of Papyrus, the paper of ancient Egypt
1.0 mol/l , the swelling process was com- Anal. Chem. 55, 1220A-1230A (1983)
plete after 10 minutes. The rate of swelling [3] Staub F. and Riesen R. - Quellungs
was highest during the first few minutes messungen an Elastomeren. Mettler
and then decreased rapidly to a lower level. Applikation Nr. 3110

10 USER COM 2/98

Vitrification in the isothermal curing of
epoxy resins by ADSC
S.Montserrat. Department of machines and thermal motors
Universitat Politècnica de Catalunya, Carrer de Colom 11, E-08222-Terrassa, SPAIN

Introduction Experimental riod of one minute and an amplitude of

During the isothermal cure of an epoxy An epoxy resin system based on Bisphenol A 0.5 °C, whereby the average temperature
resin the system changes from a viscous Diglycidyl ether (Araldit F from CIBA SC) was kept constant (psuedo-isothermal
liquid to a highly crosslinked network. The and polyoxypropylenetriamine (Jeffamine measurement). Average curing tempera-
rate of cure of the reaction in the liquid T-430 from HAUSTMAN Co) was examined. tures (Tc) of 50 °C, 60 °C, 70 °C, 80 °C
state is controlled by chemical kinetics. The ADSC measurements were performed and 85 °C were used. A blank curve, a cali-
With increasing crosslinking, the glass with a METTLER TOLEDO DSC821e with an bration curve and a sample curve were
transition temperature (Tg) of the system IntraCooler. The DSC module was cali- measured in order to eliminate any effects
increases. When Tg equals the curing tem- brated beforehand with indium and zinc of cell asymmetry and to adjust the heat
perature Tc, the system changes to a glassy standards. An amplitude of 0.5 K and a pe- flow. For each measurement, about 10 mg
state and vitrifies. The mobility of the reac- riod of 1 minute were used for temperature of a freshly mixed sample were weighed
tive centers becomes increasingly restricted modulation. The glass transition of the into a standard aluminum crucible (40 µl)
and the reaction is controlled by diffusion. fully cured epoxy resin was determined
This results in the conversion remaining with conventional DSC (heating rate Results
practically constant [1]. 10 K/min) and found to be 85.8 ±0.7 ºC The pseudo-isothermal curing with ADSC
In the past, the curing time to vitrification (midpoint) and with ADSC (at 1 K/min) yields a total heat flow curve (average value
(the so-called “vitifrication time”) has 85.8 ±0.5 ºC (midpoint of the complex of the modulated heat flow) which shows the
been determined by conventional DSC in a heat capacity curve). heat of reaction. It could be used to per-
rather time-consuming manner. To do this, The temperature was modulated with a pe- form a kinetic analysis of the reaction.
a number of samples are cured separately
for different periods of time. The curing
temperature must, of course, lie below the
maximum attainable glass transition tem-
perature of the formulation concerned
(typically 10 ºC to 50 ºC degrees below).
Afterwards, the glass transition tempera-
tures of the partially cured samples are
measured with DSC. At the same time it is
possible to determine the degree of cure by
measuring the post-curing peak. A plot is
made of the glass transition temperatures
against the corresponding curing time. The
vitrification time is determined as the point
of intersection of the best-fit curve of these
data points with the curing temperature
used.
The purpose of this article is to show that
the vitrification time can be determined di-
rectly with the ADSC technique. The advan-
tage of ADSC is that it is more accurate and Fig. 1. ADSC curves (total heat flow and component of the complex heat flow) of the isothermal
faster than the conventional method de- curing of the epoxy-triamin system, measured with a period of 1 min and a temperature amplitude
scribed above. von 0.5 °C. The |Cp*| curve shows the onset and the endset of the vitrification and the vitrification
time as the midpoint of the large Cp change. The degree of curing is plotted below.

USER COM 2/98 11

In addition to the total heat flow, the ADSC
evaluation, as was shown in a previous
UserCom [2], yields three Cp curves:
1. Contribution of the complex heat capacity:
Cp*= AHF / Aβ
2. real component: Cp’ = Cp*cos ϕ
3. imaginary component: Cp” = Cp*sin ϕ
Fig. 2. The curing temperature-curing time diagram shows the vitrification line (—), obtained
from the midpoint of the variation of the |Cp*| curve using ADSC (•). The values obtained by
conventional DSC (▲) are also shown. The dashed lines show the vitrification range from the
onset and endset values.
Fig. 3. Phase angle shift ϕ in radians, and the imaginary component of the heat capacity cp“
during the isothermal curing of the epoxy resin at 80 °C. The broad peaks in both curves are a
result of the vitrification process.
where AHF is the amplitude of the modu-
lated heat flow, Aβ is the amplitude of the
modulated heating rate and ϕ is the phase
angle between the heating rate and the
heat flow.
12
Figure 1 shows the total heat flow and the
Cp* curve for Tc= 80 ºC. Because Tc is
lower than the maximum glass transition
temperature of the epoxy, vitrification oc-
curs.
Cp shows an initial increase but then de-
creases after about 30 minutes. After about
200 minutes of curing time, Cp decreases
dramatically. As Johari and coworkers [3]
have shown, this decrease is a consequence
of the Cp change at vitrification. As Fig. 1
shows, the rate of curing on vitrification
becomes very small and Cp remains practi-
cally constant (diffusion controlled). The
vitrification time tv is read off at the mid-
point of the Cp*  change. The tv values
obtained from the measurements at differ-
ent temperatures are now entered in the
curing temperature-curing time diagram
(Fig. 2). In addition one obtains the vitrifi-
cation range from the onset and the endset
values.
This method allows the determination of tv
with errors of about 2% to 3%, whereas with
the classical method, errors of up to 20%
must be expected. Fig. 2 shows that the val-
ues determined by ADSC agree well with
those obtained from conventional DSC.
The curve shape of the real component Cp’
is practically the same as the shape of the
Cp* curve, since the phase shift is very
small (cos ϕ ≈ 1 for small ϕ) [4]. The
curve of the imaginary part (Cp”) and the
phase angle show a broad peak in the vitri-
fication range. According to Fig. 3, the tv
read off from the peak is slightly less than
that of the average of the Cp* change.
ADSC curves for Tc > Tg show no rapid de-
crease of the Cp* because no further vit-
rification occurs and the reaction is kineti-
cally controlled.
Conclusions
The measurement of the isothermal cure of
an epoxy-triamine system with ADSC yields
two important pieces of information:
• heat of reaction
• vitrification time and vitrification range
The decrease of Cp* and the distinct
peak on the phase curve allow the vitrifi-
cation to be easily detected. From this in-
formation, the vitrification time and the
vitrification region can be determined.
References
[1] S. Montserrat, J. Appl. Polym. Sci., 44
(1992) 545-554
[2] C. T. Imrie, Z. Jiang, J, M, Hutchinson,
Phase correction in ADSC measure-
ments in glass transition, USER COM
No.6, December 97, p.20-21
[3] M. Cassettari, G. Salvetti, E. Tombari,
S. Veronesi, G. P. Johari, J. Polym. Sci.,
Polym. Phys.,
31 (1993) 199-205
[4] J. M. Hutchinson, S. Montserrat,
Thermochim. Acta 304-305 (1997)
257-265
USER COM 2/98
TGA measurements at reduced
pressure
TGA measurements are normally per- vaporization of the plasticizer and the de- • vacuum should be applied carefully.
formed at atmospheric pressure. It can of composition of the polymer. A clear separa- Otherwise there could be turbulence in
course happen that a step in a TGA curve is tion, and hence an exact determination of the furnace and it is possible that the
the result of two overlapping processes. For the plasticizer content, is difficult. One can sample, especially if in powder form,
instance, solvent or plasticizers can evapo- of course use the DTG curve to set the could be sucked out of the crucible. The
rate at the same time as the polymer has evaluation limit as the minimum between same is true for ventilation after the
already begun to decompose. In some cases the peaks. This does not, however, guaran- measurement.
the overlapping processes can be separated tee that the effects are properly separated. • for quantitative measurements, correc-
by changing the heating rate, either In comparison, the curve measured at a tion with a blank curve is essential.
manually or automatically (MaxRes). If pressure of 15 mbar shows a clear step • the sample must be weighed at atmo-
this is not possible, there is another possi- separation. The location of the polymer de- spheric pressure.
bility that will be described in more detail composition step remains unchanged but • for the total rubber analysis a measure-
below: measurements at reduced pressure. the plasticizer now vaporizes at lower tem- ment must also be made at atmospheric
While the atmospheric pressure generally peratures. pressure.
has little or no efffect on the course of a It is important to know the actual pressure The method described here is a way of
decomposition reaction, this is quite differ- during the measurement and to keep it separating two overlapping effects. As de-
ent for processes involving evaporation. In constant. Otherwise it is difficult to com- scribed in the above example, it is possible
such cases, a reduction of pressure shifts pare measurements made at different pres- to separate the vaporization of a plasticizer
the vaporization process to lower tempera- sures. No special temperature adjustment from the decomposition of a polymer. Fur-
tures. The separation of the two overlap- is necessary at a pressure of at least 10 mbar. ther applications of this technique are the
ping effects (one of which is a vaporization
process and the other a decomposition re-
action) should therefore be possible by
working at reduced pressure with the
thermobalance. But how can we reduce the
pressure in a thermobalance and yet still
measure properly?
The TGA850 and the TGA/SDTA851e are de-
signed for these types of application. A
vacuum pump (Balzers DUO 004B) was
connected to the gas outlet valve of the
TGA via a three-way valve. Adjustment of
the gas outlet valve allows the desired
vacuum to be set (measured with a Balzers
TPG 035 pressure meter). The balance was
purged with argon at 20 ml/min, mea-
sured at atmospheric pressure. At the end
of the measurement, the measuring cell
was filled with argon via the three-way
valve. Fig. 1. TGA and DTG curves of a rubber sample, measured at a heating rate of 10 K/min and
A cold trap in the system is also often nec- different pressures. The local maximum of the first derivative curve (arrow) was used to set the
essary to protect the pump, depending on right hand evaluation limit.
the volatility and quantity of substances
vaporized. Limitations: investigation of adsorption and desorption
The sample investigated was rubber that • at very low pressures, volatile substances behavior and the measurement of gas evo-
contained a mineral oil as plasticizer. The already start to evaporate at room tem- lution from samples.
TG curve measured at atmospheric pres- perature. A preliminary experiment to
sure indicated an overlap of two effects, the check this is recommended.

USER COM 2/98 13

Application of DSC to the investigation of
damaged plastic materials
Extract from a lecture given at the LabTalk -Seminar 1997 in Wetzlar, Germany
Dr. R. Düren, Plastics Control Laboratory, Marktheidenfeld, Germany

Differential scanning calorimetry (DSC) is good contact with the bottom of the cru- high PE content. Although a low content
together with thermogravimetry (TG) the cible [1]. The curves measured during this of PE improves the impact characteristics
most important thermoanalytical method work were imported into a PC with STARe of PP, polypropylene and polyethylene are
for the analysis of damage to plastic com- software. generally incompatible with each other
ponents or for the investigation of manu- [2], and the failure of the parts is clearly
facturing problems. With the aid of this Damage to high-impact due to the high PE content.
technique, possible causes of damage can polypropylene parts
be identified or eliminated. It helps the in- Problem: Consequences
terpretation of results from other methods Serious deformations and partial destruc- DSC was integrated in the goods-in control,
such as infrared spectrometry, viscosity de- tion of part of a high-impact polypropylene the manufacturer was informed and no fur-
terminations and mechanical testing. In support for a dust filter occurred in use. ther bad deliveries were received.
many cases damage could have been Tensile testing of samples taken from intact
avoided if DSC measurements had been regions of the support showed an apprecia- PE tube of inadequate rigidity
routinely performed as part of the quality bly lower tensile stress in comparison with Problem:
assurance of incoming goods. In some reference samples. Problems arose in the manufacture of PE
cases the results of DSC measurements have corrugated tubing on account of inad-
led to the integration of DSC in the goods- Results of the DSC measurements: equate rigidity of the material. Young’s
in control. In damage analysis, DSC is used The small PE peak at 115 °C (Fig. 1) modulus measurements on standard refer-
primarily to investigate the following prob- shows that the prescribed material (high- ence samples prepared from the pellets
lems: impact polypropylene) was used for the showed that the value for the Young’s
• is the plastic part made of the prescribed
polymer?
• has the type of pellet been delivered that
was ordered?
• is the material contaminated with an-
other type of plastic?
• are any internal stresses “frozen” in the
parts?
• has the plastic been thermally damaged
during processing in use?
• is the material sufficiently stabilized?
• has the material been completely cured?
A number of relevant examples will now be
discussed in order to illustrate the impor-
tant role that DSC plays in this type of
work. The DSC20 measuring cell with stan-
dard sensor and TC10A controller were used
for all measurements. Standard aluminum
crucibles with pierced lids and nitrogen or
Fig. 1. DSC melting curves of PP with different PE contents.
air purging were used for sampling. The
heating rate was normally 10 K/min. The
sample weight ranged from 5 mg to 25 mg manufacture of the undamaged support. modulus of the material was not
according to the problem concerned, The damaged support was, however, clearly 800 N/mm2 as given by the manufacturer,
whereby particular attention was paid to manufactured from a PE-PP mixture of but only 260 N/mm2.

14 USER COM 2/98

 Results of the DSC measurements:
The materials concerned were a mixture of
PE-LD with a melting peak at 110 °C, and
a PE-MD (or PE-LLD) with a melting peak
at 124 °C (Fig. 2). For additional quantifi-
cation purposes, mixtures were prepared
from 2 other types of PE with similar melt-
ing points that were available in the labo-
ratory. First of all, extrusion strands were
prepared with a MFI test apparatus at
190 °C. The strands were then cut up finely,
mixed thoroughly and used again to pre-
pare new extrusion strands under the same
conditions. Samples were taken from these
at three different points and DSC measure-
ments performed after they had first been
heated to 185 °C. After allowing the
samples to cool “naturally” in the measur-
Fig. 2. DSC melting curves of PE with different LD (or LLD) and MD content ing cell, a second measurement was made,
this time up to 250 °C. Only the second
measurements were used for the quantita-
tive evaluation. The calculation of the total
integral and the partial integral of the
higher melting components were used for
correlation purposes. The correlation is lin-
ear in the region 0% to 80% PE-MD. This
correlation gives a PE-MD content of
52.5 ±2.3% for the PE lot that is too soft.
Unfortunately, as is so often the case, no
reference samples of the “good” lot were
available.

Investigation of a PP type
Problem:
The identification symbol on a piece of
broken polypropylene tube could no longer
be recognized. Since the manufacturer pro-
Fig. 3. DSC curves of various types of PP (second heating runs). cesses 3 types of PP, the task was to deter-
mine the type of PP used.

Results of the DSC measurements:

A comparison of the melting curve of the
tube sample (Fig. 3) with the curves re-
corded from pellets of the 3 different types
of PP, allowed the PP to be identified as PP
of type 1. In these measurements, it was
very important to use the second heating
curve because the peak intensities, in par-
ticular of type 1, depend on the cooling
rate. This is noticeable in the comparison
of the curves of samples taken from the
outside of the tube (cooled rapidly) and
from the inside (cooled slowly) (Fig. 4).
Infrared spectra showed no differences be-
tween the 3 PP types.

Fig. 4. The first DSC melting curves show quite clearly the thermal history of the material.

USER COM 2/98 15

Differentiation of POM types
Problem:
It was unclear whether a molded part was
made of a homopolymer or a copolymer of
POM. Since both possible types of POM were
available, it was possible to make a
thermoanalytical comparison of the sample
Results of the DSC measurements and comparison of material properties
Property
DSC melting peak [°C]
MVI 190/2.16 [ml/10 min]*
Young's modulus [MPa]*
wide variety of different prblems with rela- Literature
tively little effort. In this work, it was pos- [1] J. Vogel „DDK - Einführung in die
sible to solve the following problems: Messtechnik, Fehlervermeidung“,
• differentiation of PA 6 and PA 66 Thermische Analyse an Kunststoffen -
• detection of impurities (PE in PP) Methoden und Anwendungen,
• identification and quantification of PE LabTalk-Seminar der Fa. Mettler-To-
blends ledo 25.11.97
[2] St. Rau „Polymerblends - Stand der
Technik zu Kombinationen aus
ausgewählten Thermoplasten und
Molded part Homopolymer Copolymer Elastomeren“, unveröffent lichte
Studienarbeit am IKV, Aachen 1991
176.8 179.4 166.0
[3] Thermische Analyse an Kunststoffen -
11 11 Methoden und Anwendungen, ME 99
458 023, Ecomed Verlagsgesellschaft
2500 2900

Yield stress [MPa]* 58 65

Ultimate elongation [%]* 30 25

Charpy test impact value [kj/m2]* 15 6

Note: *Material properties according to Campus 4.0

with the two possible types of POM. The DSC • differentiation of types of PP (types 1, 2
results showed that the molded part was and 3)
made of the homopolymer. • differentiation of types of POM (ho-
In this case, however, it was also possible to mopolymers and copolymers)
identify the sample with IR spectrometry. • detection of internal stress and brittleness
of styrene polymers
Conclusions • investigation of oxidative stability
Differential scanning calorimetry (DSC) is • investigation of the crosslinking of
a method that can be used to help solve a duroplasts

16 USER COM 2/98

 Dynamic segment
Tips D -100...+700/10 Air/50
x12345678901234567890

Position Meaning Explanations

Meaningful file names
It is advantageous to set up certain guide- x sign + or -
lines for file names at an early stage. This x+1 ... x+3 start temperature 3 numbers (°C)
facilitates a search later on. If the file
name already includes information, you x+4 ...X+6 separator ...
can avoid opening the wrong file. x+7 sign + or -
Here are some possible guidelines using a
method as an example: x+8 ...x+10 end temperature 3 numbers (°C)

x+11 separator /
x+12 ...
heating rate 2 numbers (K/min)
Method type x+13
x+14 empty
Position Meaning Explanations
x+15 ... 3 letters
D: dynamic purge gas
x+17
1 ... 2 I: isothermal
A: alternating x+18 separator /

3 empty empty x+19 ...x+20 purge gas flow rate 2 numbers (ml/min)

Isothermal segment Alternating

I +150/100 N2 /20 A -100...+300/ 2 He /20 A1.0 P120
x12345678901234 x123456789012345678901234567890

Position Meaning Explanations Position Meaning Explanations

x sign + or - analog dynamic

x+20
segment
x+1 ... x+3 temperature 3 numbers (°C)
x+21 empty
x+4 separator /
x+22 A amplitude
x+5 ... x+7 time of segment 3 numbers (min)
x+23 ... x+25 amplitude 3 numbers (°C)
x+8 empty
x+26 empty
x+9 ... x+11 purge gas 3 letters
x+27 P period
x+12 separator /
x+28 ...x+30 period 3 numbers (s)
x+13 ... x+14 purge gas flow rate 2 numbers (ml/min)

A database selection could then appear as follows: If such a code or something similar could
be agreed on, then it would be easier for
D -100...+700/10 Air/50 different people to use methods. Without
DI + 25...+200/20 N2 /50 +200/ 5 N2 /50 opening the file, you immediately see from
I +150/100 N2 /20 the name, whether the method satisfies
1234567890123456789012345678901234567890 your own requirements or not.

USER COM 2/98 17

Determination of the temperature
sensitivity (slope S) of the DSC
sensor
The default value of S for the FRS5 sensor
is 35 000 dig/K, which corresponds to about
270 µV/K. The slope normally observed
should be smaller, so that the calculated
peak temperature can never be lower than
the onset temperature.
If you wish to measure S, you can use the
well-known equation: E = Rth ·S. From this
you obtain S = E / Rth. Rth corresponds to
the reciprocal slope of the melting curve of
a pure substance. In other words, S is the
equal to the absolute value of the slope
multiplied by the calorimetric sensitivity at
the temperature in question. The slope can
be calculated with the onset evaluation (in
this example 19.82 mW/°C). The calori-
metric sensitivity can be calculated using
the Erel and dErel parameters.
Notice about the FTIR Atlas of
W.K. Schönherr
TG-FTIR Atlas of Elastomers
This 125-page atlas describes the TG-FTIR
combination and its application to the
analysis of elastomers.
Basic questions about the TG-FTIR combi-
nation as well as about the properties of the
most important types of rubber are dis-
cussed. Information such as TG curves and
IR spectra of the decomposition products
are given.
The FTIR atlas is therefore an important
source of information for anyone working
with elastomers or who use18s this combi-
nation technique.
The atlas can be ordered from Mr. W.K.
Schönherr, Nordring 1, D 34246 Vellmar,
Germany.

It is at present only available in German.

An English version should be ready by the
end of 98/beginning of 99.

Crucibles for high temperature TGA

For the high temperature region (1600 °C)
that the TGA/SDTA851e now covers, only
platinum and alumina crucibles are avail-
able. These can, however, react with the
sample under certain conditions. This can
even lead to the sample or its decomposi-
tion products fusing with and making a
The equation is: E(T) = Eindium ·(Erel (T) + dErel (T))
hole in the crucible, which would then de-
The parameters of Erel (T) can be found under “Install/Sensor” → FRS5.
stroy the crucible support. For safety, we
In the temperature region above 60 °C the following equation is valid:
recommend that you place a sapphire disk
Erel (T≥ 60 °C) = 0.457 + 0.003918· T - 0.00000303 ·T2
(not quartz!) under the crucible. The sap-
phire disks of 7 mm diameter and the ME
For this example then: Erel (156.6 °C) = 0.9963
number 00017759 are suitable. The SDTA
Eindium and dErel (T) can be taken from the adjustment parameters. dErel (T) is also a
signal is only slightly affected.
function of temperature. In this example (see plot above)
dErel (T)= 0.02285 Eindium = 1551 mW-1

From this it follows: E (156.6 °C) = 1551 · (0.9963 + 0.02285) mW-1 = 1581 mW-1
For the thermoelement sensitivity S one obtains
S = E/Rth = I slope I · E = 19.82 · 1581 K-1 = 31335 K-1

18 USER COM 2/98

Exhibitions, Conferences and Seminars - Veranstaltungen, Konferenzen und Seminare
Pittcon March 7-12, 1999 Orlando, Florida (USA)
Eurostar PhandTA 4 24.-26. März 1999 Karlsruhe (Deutschland)
13. Ulm-Freiberger Kalorimetrietage 17.-19. März 1999 Freiberg (Deutschland)
International Summer School on
Advanced Techniques in Thermal Analysis May 26-28, 1999 Copenhagen (Denmark)
15th European Conference on
Thermophysical Properties September 5-9, 1999 Würzburg (Germany)
NATAS September 20-22, 1999 Savannah, Georgia (USA)
ICTAC 2000 August 14-18, 2000 Copenhagen (Denmark)

TA Customer Courses and Seminars in Switzerland-Information and Course Registration:

TA-Kundenkurse und Seminare in der Schweiz-Auskunft und Anmeldung bei:
Helga Judex, Mettler-Toledo GmbH, Schwerzenbach,
Tel.: ++41-1 806 72 65, Fax: ++41-1 806 72 40, e-mail: helga.judex@mt.com
TMA (Deutsch) 23. März 1999 Greifensee TMA (Deutsch) 21. September 1999 Greifensee
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Cours et séminaires d’Analyse Thermique en France et en Belgique

France: Renseignements et inscriptions par Christine Fauvarque, Mettler-Toledo S.A., Viroflay,
Tél.: ++33-1 30 97 16 89, Fax: ++33-1 30 97 16 60.
Belgique: Renseignements et inscriptions par Pat Hoogeras, N.V. Mettler-Toledo S.A., Lot,
Tél.: ++32-2 334 02 09, Fax: ++32 2 334 02 10.
TMA (français) 19 Avril 1999 Viroflay (France) Jour d’information 23 Avril 1999 Viroflay (France)
TGA (français) 20 Avril 1999 Viroflay (France) Jour d’information 22 Octobre 1999 Viroflay (France)
DSC Basic (français) 21 Avril 1999 Viroflay (France) Séminaire de Validation 9 Juin 1999 Lot (Belgique)
DSC Advanced (français) 22 Avril 1999 Viroflay (France) Séminaire de Validation 11 Juin 1999 Viroflay (France)
TMA (français) 18 Octobre 1999 Viroflay (France) Road Shows (un jour) en semaine 5/1999 Lyon et Marseille
TGA (français) 19 Octobre 1999 Viroflay (France) en semaine 10/1999 Bordeaux et Toulouse
DSC Basic (français) 20 Octobre 1999 Viroflay (France) en semaine 11/1999 Lille et Strasbourg
DSC Advanced (français) 21 Octobre 1999 Viroflay (France) en semaine 12/1999 Nantes et Rennes

TA-Kundenkurse und Seminare (Region Central)

Für nähere Informationen wenden Sie sich bitte an Mettler-Toledo GmbH, Giessen:
Frau Bianca Bochem, Tel.: ++49-641 507 431 oder Frau Ina Wolf, Tel.: ++49-641 507 404.
Info-Seminar TA: 19.04.1999 Hannover/D 29.04.1999 Linz/A
20.04.1999 Berlin/D 04.05.1999 Stuttgart/D
21.04.1999 Münster/D 06.05.1999 München/D
22.04.1999 Leipzig/D
23.04.1999 Düsseldorf/D DDK-Workshop 23./24.02.1999 Giessen/D
27.04.1999 Frankfurt/D TG-Workshop 25./26.02.1999 Giessen/D
20.04.1999 Greifensee/CH STARe-Software-Workshop 23.09.1999 Giessen/D
27.04.1999 Wien/A STARe-Software-Workshop 23.09.1999 Giessen/D
28.04.1999 Graz/A STARe-Software-Workshop 24.09.1999 Giessen/D
29.04.1999 Freiburg/D TG-Workshop 28./29.09.1999 Giessen/D
22.04.1999 Lausanne/CH DDK-Workshop 30.09./01.10.1999 Giessen/D
Thermische Analyse in der Pharmazeutik - Methoden und Anwendungen: 08.06.1999 Wetzlar/D
10.06.1999 Greifensee/CH

USER COM 2/98 19

TA-Customer Courses and Seminars in the Netherlands
For further information please contact: Hay Berden at Mettler-Toledo B.V., Tiel, Tel.: ++31 344 63 83 63.
Seminar Validation June 7, 1999 Tiel

TA-Customer Courses and Seminars in Italy

For further information please contact:
Mettler-Toledo S.p.A., Novate Milanese, Tel.: ++39-2 333 321, Fax: ++39-2 356 2973.
TA Users seminars: March 9-10, 1999 Novate Milanese
June 8-9, 1999 Novate Milanese
September 21-22, 1999 Novate Milanese
InfoDays TA: March 23, 1999 Milan
April 13, 1999 Neaples
April 14, 1999 Rome
April 15, 1999 Firenze
April 27, 1999 Torino
May 12, 1999 Bologna
May 13, 1999 Venezia

TA-Customer Courses and Seminars for Sweden and Nordic countries

Please contact the product manager Fredrik Einarsson at Mettler-Toledo AB, Stockholm,
Tel.: ++0046-8 702 5024, Fax: ++46-8 642 4562, e-mail: fredrik.einarsson@mt.com
For people working in the
Polymer and Pharmaceutical field March 18-19, 1999 Stockholm

TA-Customer Courses and Seminars in USA and Canada

Please contact your local instrument specialist or Jon Foreman at Mettler-Toledo Inc.,
Tel.: 1 800 METTLER (638-8537) extension 4687 or Fax: 1 614 438-4958.

TA-Customer Courses and Seminars in UK

For details of training courses and seminars please contact:
Rod Bottom at Mettler-Toledo Ltd., Leicester, Tel.: ++44-116 234 50 25, Fax: ++44-116 234 50 25.

For further information regarding meetings, products or applications please contact your local METTLER TOLEDO agency.
Bei Fragen zu weiteren Tagungen, den Produkten oder Applikationen wenden Sie sich bitte an Ihre lokale METTLER TOLEDO Vertretung.
Internet: http:/www.mt.com

Redaktion
Mettler-Toledo GmbH, Analytical
Sonnenbergstrasse 74
CH-8603 Schwerzenbach, Schweiz

Dr. J. de Buhr, Dr. R. Riesen, J. Widmann, Dr. M. Schubnell, U. Jörimann

e-mail: urs.joerimann@mt.com
Tel.: ++41 1 806 73 87, Fax: ++41 1 806 72 60

Layout und Produktion: Promotion & Dokumentation Schwerzenbach G. Unterwegner

ME-51709909