25

Thermal Analysis User

Information for Users
Com

Dear Customer, Contents 1/2007

We are very pleased to receive more and more articles from you for publication in UserCom. Thanks to new
techniques and better performance, thermal analysis is being used in an ever-increasing number of scien- TA Tip
tific fields. Hyphenated techniques such as evolved gas analysis, microscopy and chemiluminescence yield - Choosing the right baseline 1
much more information about samples and very often greatly simplify the interpretation of measurement Applications
results. - Determination of the Noack
We think this issue of UserCom will once again give you ideas for applications in new and interesting areas evaporation loss of lubricants
using the multitude of techniques now available. by TGA 7
- The characterization of poly-
morphs by thermal analysis 9
- Analysis of melting processes
using TOPEM® 13

Choosing the right baseline - Characterization of delivery

systems by thermogravimetry 18
Tips and hints
Dr. Rudolf Riesen
- Detection and evaluation of
weak sample effects in DSC 21
Dates
Choosing the correct baseline is crucial for the determination of the enthalpy of a transi-
tion or a reaction. The baseline represents the DSC curve that would be measured if no - Exhibitions 23
transition or reaction occurred. The examples described in this article illustrate how to - Courses and Seminars 23
choose the right baseline for a particular evaluation.

Introduction
In thermal analysis, baselines are mostly used in connection with the integration of peaks. The peak area
is determined by integrating the area between the measurement curve and a virtual or true baseline. In
the same way, the peak temperature is defined as the point on the curve where the distance to the baseline
is greatest. Extrapolated baselines are important for the determination of glass transition temperatures
 and the onset temperatures of effects. In
the literature and in standards, the term
“baseline” is sometimes defined differ-
ently, or different terms are used for the
same thing. The terms most frequently
TA Tip
encountered have therefore been sum-
marized together with some brief com-
ments. A number of application examples
are then discussed to illustrate the rules
governing the choice of baselines and
that show which type of baseline should
be used for the optimum evaluation of a
particular DSC curve.
Terminology
The terms used in thermal analysis are
summarized and explained in various
standards.
However, since the definitions are not al-
ways the same, the terms used have been
summarized below for the discussion of
baselines that follows. Further definitions
can be found in the book by Höhne [1] as
well as in the standards mentioned (ISO
[2], DIN [3], ASTM [4, 5]). The preferred
terms are highlighted, but other terms
are also included.
Blank, blank curve, zero line [3], in-
strument baseline [2]: A thermal analysis
curve measured under the same condi-
tions as the sample but without the sam-
ple; the mass of the crucibles used must
be the same. Blank curves are essential
for specific heat capacity determinations.
Comment: In some cases, the zero line
[1] is also understood as a curve meas-
ured without the sample or crucibles.
Figure 1.
Drawing interpo-
lated DSC baselines
(the endothermic
direction is upward).
2 METTLER TOLEDO UserCom 1/2007
Sample blank: A curve that is obtained
from a “fully converted” sample. This
is usually the second heating run of the
same sample under the same conditions.
The effect measured in the first heating
run no longer appears.
Baseline (also sample baseline [2]):
Part of the curve that does not exhibit
any transitions or reactions.
This is an isothermal baseline if the
temperature is held constant. A dynamic
baseline is obtained when the tempera-
ture is changed through heating or cool-
ing.
The baseline depends on the heat capac-
ity of the sample (with an empty refer-
ence crucible) and the blank curve.
Comment: In practice, the term is also
used to mean the virtual baseline used
for integration.
Virtual baseline [2]: An imaginary
line in the region of a reaction or tran-
sition that the DSC curve would show if
no reaction or transition enthalpy were
produced.
Interpolated baseline [1]: This is a line
that joins the measured curve before and
after the peak.
Extrapolated baseline: This is a line that
extends the measured curve before or af-
ter the thermal effect.
The types of virtual baselines normally
used are explained in the applications.
True baseline: In the region of the
transition or reaction, the baseline can
be calculated according to physical data
or even measured.
Factors influencing the base-
line
The influence of measurement condi-
tions on the DSC curve and the baseline
should always be taken into account
when interpreting curves and evaluating
numerical data. Furthermore, the course
of the blank curve and its reproducibility
should be known.
Possible important parameters that can
change during a transition are [1]:
1. Mass, shape and structure of the
sample, e.g. powder or film;
2. Thermal conductivity and contact
of the sample with the bottom of the
crucible, e.g. a powder liquefies during
melting;
3. Heat transfer from the crucible to the
sensor, e.g. deformation of the cruci-
ble due to an increase in the internal
pressure or through products escaping
from the crucible;
4. Heating rate, e.g. when it changes
from dynamic to isothermal;
5. Thermal history of the sample and
measuring system.
If it is difficult to choose the baseline, it
often helps to examine the sample and
crucible after measurement with regard
to the above points.
Principles for constructing
virtual baselines
The basic principle for constructing a
virtual baseline can be summarized as
follows:
The interpolated baseline for the de-
termination of the transition enthalpy
or the reaction enthalpy leaves the DSC
curve tangentially before the thermal
effect and joins the curve again tangen-
tially after the effect.
A good example to illustrate this is the
take-off and landing of an aircraft. In
special cases there are some exceptions
to this that will be described in the ex-
amples. Figure 1 shows how these princi-
ples are applied.
a) 1 nonsensical; 2 good (Line),
b) 1 unsatisfactory (horizontal straight
line); 2 good (integral baseline, pos-
sibly Spline),
c) good (Integral tangential, or pos-
sibly Spline),
d) melting with exothermic decomposi-
tion, 1 good (straight line to the point
of intersection with the DSC curve);
2 rather arbitrary because the DSC
curve is the sum of simultaneously
occurring processes,
e) two overlapping peaks, e.g. eutectic
and melting peak of the main com-
ponent, 1 good for the total integral,
2 good for the integration of the first
peak (peak interpreted as sitting on
the main peak, Spline).
The transition line from one tangent to
another can have different shapes and be
displayed as a straight line or as a sig-
moidal curve (S-shaped function). The
type of interpolated baseline chosen de-
pends mostly on the physical conditions
or chemical changes involved, for exam-
ple:
• The specific heat capacity of the
sample, cp, hardly changes during the
transition or it changes linearly with
temperature.
• The transition is accompanied by a
significant change in the heat capacity
• The heat transfer to the sample
changes during the transition.
• The mass of the sample changes dur-
ing the transition.
The STARe software provides several dif-
ferent types of baseline to accommodate
the changes shown by the DSC curve dur-
ing a transition.
Table 1 describes the baselines and their
typical applications.
The extrapolated virtual baselines are
the tangents to the measured curve at the
evaluation limits, just as they are used
for interpolation with the baselines. Typi-

Baseline type Description
Line This is a straight line that joins two evaluation
limits on the measured curve.
Tangential left This is the extension of the tangent to the
measured curve at the left evaluation limit.
Tangential right This is the extension of the tangent to the
measured curve at the right evaluation limit.
Horizontal left This is the horizontal line through the point of
intersection of the measured curve with the left
limit.
Horizontal right This is the horizontal line through the point of
intersection of the measured curve with the
right limit.
Spline The Spline baseline is the curve obtained using
a flexible ruler to manually interpolate between
two given points (known as a Bezier curve).
It is determined as a 2nd order polynomial
through the tangents at the evaluation limits.
This bow-shaped or S-shaped baseline is
based on the tangents left and right.
Integral tangential Starting with a trial baseline, the integral base-
line is calculated using an iterative process.
The conversion calculated from the integration
between the evaluation limits on the measured
curve is normalized. Like the Spline curve, this
bow-shaped or S-shaped baseline is based on
the tangents left and right.
Integral horizontal This baseline is calculated using an iterative
process like the Integral tangential baseline.
This S-shaped baseline always begins and
ends horizontally.
Zero line This is the horizontal line that intersects the
ordinate at the zero point. It requires a blank
curve subtraction.
Polygon line The baseline can be determined through a
curved line or a straight line from individually
chosen points.
The polygon line is then first subtracted from
the measured curve and the resulting peak in-
tegrated using a straight baseline.
Table 1.
Typical DSC application
List of virtual
Reactions, without abrupt cp changes, that baseline types for
exhibit a constant cp increase or a constant cp. integration.
This baseline is the default setting.
Integration of a melting peak on a measured
curve with subsequent decomposition of a
substance.
Melting of semicrystalline plastics with signifi-
cant cp temperature function below the melting
range.
Peak integration when substances decompose.
Isothermal reactions, DSC purity determination.
With overlapping effects.
Samples with different cp temperature functions
before and after the effect. The Line baseline
would possibly cross the DSC curve and lead
to large integration errors depending on the
limits chosen.
Samples whose heat capacity changes mark-
edly, e.g. through vaporization and decompo-
sition. The Line baseline would possibly cross
the DSC curve and lead to large integration
errors depending on the limits chosen.
Determination of transition enthalpies including
sensible heat.
In special cases.

METTLER TOLEDO UserCom 1/2007 

 cal applications of extrapolated baselines
are for the determination of the:
• glass transition temperature
• extrapolated onset temperature (also
as first deviation from the measured
TA Tip
ing practical examples. Figure 2 shows
the most frequently used virtual base-
lines:
a) Spline: This is used to determine the
reaction enthalpy of a postcuring reac-
ally to the amount vaporized. At the
end of the measurement the crucible
is empty and the DSC signal is practi-
cally 0 mW.
d) Line: The DSC curve shows a glass

curve)
• step height.
In all evaluations in which extrapolated
tangents are used, one must make sure
that artifacts on the measured curve or
signal noise do not interfere with the de-
termination of the slope of the tangent.
This would result in the tangents being
in the wrong place.
Application examples
The different types of baseline presented
in Figure 1 are illustrated in the follow-
Figure 2.
Examples of fre-
quently used types
of baseline.
tion that is overlapped by the begin-
ning of decomposition.
b) Horizontal right: Isothermal cur-
ing of an epoxy resin at 140 °C. When
the reaction has finished the DSC
curve is horizontal. The baseline can
be drawn horizontally through the last
measured points.
c) Integral horizontal: The DSC curve
of 1.162 mg water, which on heating
evaporates through a 50-µm hole in
the crucible lid. The loss of mass
causes a change in the sample heat
capacity, which is reduced proportion-
transition of the amorphous part of
the polyethylene terephthalate (PET)
followed by cold crystallization and
melting of the crystallites. The straight
baseline is the virtual extension of the
DSC curve after the glass transition to
the curve after the melting and shows
the trend of the curve without crystal-
lization and melting. The integral of
the two effects yields 22.8 J/g as the
difference between the exothermic and
endothermic processes. This means
that crystallites were already present
at the beginning of the measurement.
In relation to the melting enthalpy of
100% crystalline PET, this shows that
the degree of crystallization of the
sample was initially about 16% and
was therefore not fully amorphous.

Figure 3 discusses how to draw the interpo-

lated baseline if the baselines before and
after the peak are at different levels, for
example because the specific heat capac-
ities of ice (2.1 J/gK) and water (4.2 J/gK)
are very different. The figure shows four
identical curves of the same part of
the DSC melting peak of 1.87 mg water
measured at 5 K/min (melting enthalpy
333 J/g). Each curve has a different base-
line type.
1) The Horizontal left baseline does
not take the change in heat capacity in
Figure 3. the evaluation range into account and
Example for the yields a peak area that is too large.
change of the heat 2) The Line baseline is clearly unfa-
capacity during the
transition ice/water. vorable and contradicts the basic
principles (no tangents, it crosses the
DSC curve). In reality, the change in
heat capacity is of course not linear
with temperature between the evalua-
tion limits as the dotted line wrongly
shows.
3) The Spline baseline is somewhat bet-
ter, but also crosses the DSC curve.
4) In this case, the Integral horizontal
baseline is optimal. It draws the
baseline proportional to the peak area
from the level before the peak to the
level after the peak and so takes into
account the change in heat capacity.

4 METTLER TOLEDO UserCom 1/2007

In the first three cases, the result of the Figure 4.
Example showing
integration can be improved by choos- a special baseline
ing better limits, but even so, the virtual (Polygon using just
baselines do not correspond to the physi- two points, X) to
determine the post-
cal facts. curing reaction. The
Zero line baseline
Overlapping thermal effects are usually was used to inte-
grate the peaks in
the most difficult with regard to choosing curve 4.
a realistic virtual baseline.

Figure 4 shows how a second heating run

of the reacted sample helps to locate the
exact position of the baseline. An epoxy
resin was partially cured at 100 °C for
80 min, causing the material to vitrify
[6]. The DSC curves shown in Figure 4
were then measured at 5 K/min. The
postcuring reaction begins at the glass
transition (curve 1). Curve 2 shows the
Figure 5.
DSC second measurement of the same, Curve interpretation
fully cured, sample. The straight line 3 and the choice of
(dotted) describes the course of the DSC integration limits
and baselines.
curve after complete curing above the
glass transition. It therefore represents
the baseline for the integration and
serves as a tangent for the determination
of the glass transition temperature. It
can be assumed that the behavior of the
heat capacity above the glass transition
during postcuring is about the same as
that of the fully cured sample.

The postcuring enthalpy is determined

as follows: The dotted line (curve 3) is
subtracted from curve 1 yielding curve 4.
The peak in this curve is integrated using
the Zero line baseline type within the
limits shown. Separation of the partially
overlapping peaks could also be achieved
using temperature-modulated DSC.
The purpose of the example in Figure 5
is to show how important correct inter-
pretation of the DSC curve is. The choice
of the integration limits and the baseline
type should be good enough to obtain re-
sults that provide consistent information
for further investigations.
Figure 5 shows the DSC curve of a 40%
solution of sucrose in water measured
at 5 K/min after slow cooling. The glass
transition occurs at about −45 °C and
the ice that had crystallized out melts in
the sucrose solution in the range −37 °C
to 0 °C. Integration from −29 °C (dotted
line) would assume that the specific heat
capacity decreases, which is not the case
here. The Line and Spline baselines
yield enthalpy values that are 5% too low.
Only the Integral tangential baseline
from −37 °C gives the correct value that
can be used for a consistent quantitative
evaluation.
Although one thinks mostly about inter-
polated baselines, extrapolated baselines
are in fact just as important.
This is shown in the examples in Fig-
ure 6:
a) Oxidation induction time (OIT) of a
mineral oil, measured at 180 °C at an
oxygen pressure of 3.5 MPa.
b) Melting point of benzoic acid deter-
mined as the extrapolated onset.
c) Glass transition temperature of poly-
styrene determined as the midpoint
according to how the tangents are
constructed (depends on the particu-
lar standard).
d) At the glass transition, the specific
heat capacity, cp, increases leading to
a step in the cp curve. The step height
is characteristic of the amorphous
content of the sample.
Conclusions
Whenever possible, physical changes must
be taken into account when choosing the
optimum baseline for an integration or
onset determination.
Since jumps in heat capacity rarely oc-
cur, a virtual baseline should be con-

METTLER TOLEDO UserCom 1/2007 5

TA Tip
Figure 6.
Examples of extrap-
olated baselines.
structed that is smooth and free from any
irregularities or discontinuities.
The correct choice of baseline assumes
that the curve has been properly and
consistently interpreted [7]. Furthermore,
the integration limits must be carefully
chosen depending on the information
required.
The rules and types of baseline discussed
here using DSC measurements as exam-
ples can be applied to other TA measure-
ment techniques, e.g. for the integration
of peaks from SDTA, DTG analyses and
other mathematically derived measure-
ment curves.
6 METTLER TOLEDO UserCom 1/2007
Literature
[1] G. W. H. Höhne, W. Hemminger and
H.-J. Flammersheim: Differential
Scanning Calorimetry, Springer Ver-
lag, 1996. Chapter “The DSC Curve”
[2] ISO 11357-1 (1997) Plastics – DSC.
General principles
[3] DIN 51005 Thermal analysis; Terms
[4] ASTM E473 Standard Terminology
Relating to Thermal Analysis and
Rheology
[5] ASTM E 2161 Standard Terminology
Relating to Performance Validation in
Thermal Analysis
[6] J. Schawe, METTLER TOLEDO
UserCom 14, 17
[7] METTLER TOLEDO UserCom with
articles on curve interpretation:
DSC, UserComs 11 and 12;
TGA, UserCom 13
 Determination of the Noack evaporation loss of
lubricants by TGA
Applications
Dr. Rudolf Riesen
Abstract
For quality and environmental reasons,
lubricants for engines and other applica-
tions must only exhibit a low evaporation
rate. The loss of volatile components from
an oil increases its viscosity and leads to
increased oil consumption, coking and
wear. The Noack method is a widely used
standard test method for measuring the
evaporation loss from lubricating oils.
According to the ILSAC GF-3 and API-SL
specifications the evaporation loss must
not be greater than 15%.
The ASTM standard test method D6375
for the determination of the evapora-
tion loss of lubricating oils by the Noack
method [1] uses thermogravimetric anal-
ysis, TGA. This method yields the same
results as other standard test methods
(e.g. ASTM D5800 [2], DIN 51581-1 [3],
JPI-5S-41-93 [4]).
This article describes how the Noack
evaporation loss is determined in com-
parison to a reference oil sample using
TGA.
Introduction
The increase in the usable lifetime of
lubricants coupled with faster oil circu-
lation rates, longer oil change intervals
and lower lubricant consumption means
that lubricants are subjected to greater
stress. Higher temperatures coupled with
smaller oil volumes and higher perform-
ance lead to a constant increase in the
demands placed on the performance and
quality of the lubricants. To ensure that
the lubricants are properly used, they
must be properly specified and classified.
The specifications describe the physical
properties of engine oils such as the vis-
cosity, evaporation loss and shear stabil-
ity. Performance behavior is also tested
in engine tests. This includes wear pro-
tection and cleanliness as well as the
influence on fuel consumption and the
changes in the engine oil during opera-
tion due to viscosity changes (thicken-
ing). The classification is provided by
organizations such as ILSAC, API or SAE
(see the table of acronyms).
One of the commonly used specifications
is the evaporation loss. The low molecular
mass constituents of an engine oil, which
consists of fractions of different hydro-
carbons with different chain lengths and
molecular masses, can evaporate under
increased thermal stress. This usually
leads to an increase in the viscosity of the
lubricant. At the same time, the solubil-
ity of the additives in the base oil is af-
fected.
The evaporation is important for all lubri-
cant groups (e.g. also for synthetic oils) if
they are used at higher temperatures. For
example with engine oils, evaporation
losses can occur through high tempera-
tures at the piston rings and elsewhere.
These losses lead to undesirable oil thick-
ening and increased oil consumption.
The Noack evaporation loss
test according to ASTM D6375
The Noack test to quantitatively deter-
mine the evaporation loss of oils under
standard conditions was introduced many
years ago. For example, the DIN 51581
[3] test method measures the evaporation
loss over a period of one hour at 250 °C
under vacuum (2 mbar).
The ASTM D6375 standard thermogravi-
metric test method was developed [5] to
combine the advantages of the gas chro-
matographic method [6] with the real-
istic conditions of the traditional Noack
test. The method is quicker and more
reliable than both and can be performed
with less sample material.
According to the ASTM D6375 method, a
sample is heated rapidly in a crucible to
249 °C and held isothermally for 30 min
at this temperature during which time
the TGA curve is recorded. The Noack
evaporation loss is the loss in mass up to
the Noack reference time.
This time is determined beforehand
under the same experimental condi-
tions with a Noack reference oil. In this
method, it is important that the sample
temperature quickly rises to a value be-
tween 247 and 249 °C but does not over-
shoot. To simulate the traditional Noack
method, a sample is usually heated to
220 °C at 100 K/min and then to 249 °C
at 10 K/min. The sample mass (m s) to
be used is determined from the internal
diameter of the crucible (d) using the fol-
lowing equation:
ms = 350d3
where d is in cm and ms in mg.
Performing a Noack test
The Noack evaporation test (also referred
to as Noack volatility) was performed
under the following conditions using a
METTLER TOLEDO TGA instrument:
• Crucible: 100 µL aluminum without
lid (internal diameter 0.56 cm)
• Sample mass: 61 ± 3 mg
• Purge and protective gas:
total 80 mL/min air
• Noack reference oil: W4520001 with
10.93% mass loss up to the Noack
time; supplier: Walter Herzog GmbH
• Temperature program: 50 to 220 °C
at 100 K/min, followed by heating to
249 °C at 10 K/min and isothermal
at 249 °C. To achieve the above condi-
tion, the tlag parameter for this cruci-
ble was adjusted to zero.
The sample (test oil) used was a synthetic
5W40 engine oil.
Figure 1 shows the TGA curve (black
line) of the reference oil. The Noack ref-
erence time is 17.56 min; this is the time
at which the certified loss of 10.93% is
reached (see the black arrows). The TGA
METTLER TOLEDO UserCom 1/2007 
 curve of the sample is shown as the red
curve. After 17.56 min the loss is read off
as 7.80% (see red arrows): the synthetic
5W40 engine oil thus has a Noack evapo-
ration loss of 7.8%. This is often given
Applications
uid and additives) that have been opti-
mized for the different tasks, for example
with low evaporation losses,
• save energy
• reduce service intervals
Literature
[1] ASTM D6375 Standard Test Method
for Evaporation Loss of Lubricating
Oils by Thermogravimetric Analyzer
(TGA) Noack Method.
[2] ASTM D-5800 Test Method for Evapo-

ration Loss of Lubricating Oils by the

in the oil specification simply as NOACK
7.8%.
According to ASTM D6375, the repeat-
ability with 8% loss is about 1% for two
determinations by the same laboratory,
and the reproducibility is about 1.4% for
two determinations by different labora-
tories.
According to ASTM D6375, the TGA fur-
nace must be regularly heated out. The
method recommends that this is done
after about ten determinations. The fur-
nace should be heated to 1000 °C with-
out a crucible and held isothermally at
this temperature for about 5 min. The air
gas flow is left at about 80 mL/min.
Conclusions
Over the past years, the demands placed
on lubricants in many application areas
have changed significantly. Thermal oxi-
dation stability, low tendency to evaporate
and their influence on our natural and
working environments have become very
important. The innovative development
of modern lubricants and their proper
application have far-reaching economi-
cal consequences. Lubricants (base liq-
• minimize wear
• increase engine service life
• increase oil change intervals (life-
time)
and result in considerable economi-
cal savings. The determination of the
evaporation loss by thermogravimetry
is therefore an important step in the
qualification of lubricant. The METTLER
TOLEDO TGA system with sample robot
and automated evaluation provides high
sample throughput and rapid pass/fail
assessment of the oil in question.
Acronyms
API: American Petroleum Institute
ASTM: ASTM International, originally
known as the American Society
for Testing and Materials
DIN: Deutsches Institut für Normung
(German Institute for Stand-
ardization)
ILSAC: International Lubricant Stand-
ardization and Approval
Committee
JPI: Petroleum Association of Japan
SAE: SAE International, Society of
Automotive Engineers
Noack Method.
[3] DIN 51581-1, 2003-02 Determination
of the evaporative loss of petroleum
products by the Noack method – Part
1 (original in German).
[4] JPI-5S-41-93 Determination of Evap-
oration Loss of Engine Oils (Noack
Method).
[5] E. F. de Paz, C. B. Sneyd – The Ther-
mogravimetric Noack Test: a Precise,
Safe and Fast Method for Measuring
Lubricant Volatility, Subjects in Engine
Oil Rheology and Tribology, SP1209,
International Fall Fuel and Lubricants
Meeting, San Antonio 1996, available
also as SAE Technical Papers, Docu-
ment Number: 962035.
[6] DIN 51581-2, 1997-05 Determination
of the evaporation loss of petroleum
products by gas chromatography –
Part 2 (original in German).

Figure 1.
Determination of the
evaporation loss
(Noack volatility)
from a synthetic
engine oil using
the TGA Noack test
method.
Black continuous
curve: reference
oil; red curve: syn-
thetic 5W40 engine
oil; black dashed
curve: sample tem-
perature.

8 METTLER TOLEDO UserCom 1/2007

The characterization of polymorphs by thermal
analysis
Saikat Roy, Bipul Sarma und Ashwini Nangia, School of Chemistry, University of Hyderabad, India
Dr. Matthias Wagner, Dr. Rudolf Riesen

TGA-FTIR was used to characterize Figure 2 (a).

and distinguish between different poly-
morphs. If two polymorphic forms of
a solid are present, whereby one form
melts and the other sublimes or vapor-
izes at about the same temperature, then
evolved gas analysis can be used to ob-
tain quantitative (mass loss) and quali-
tative (spectral) data to analyze such sol-
ids. The two pharmaceutically important
compounds shown in Figure 1, the active
pharmaceutical ingredient (API) venla-
faxine hydrochloride (Structure 1) and
the well-known host material 1,1-bis(4-
hydroxyphenyl)cyclohexane (Structure
2), were analyzed by DSC, TGA, hot-stage
microscopy (HSM) and TGA-FTIR to
study the phase transitions that occur on
heating.
A substance is said to exhibit polymor-
phism if it can exist in two or more
crystal lattice forms. These are called
polymorphs and have different physical
properties [1].
Figure 1.
Venlafaxine ((±)-1-[2(dimethylamino)-1-
(4-methoxyphenyl)ethyl]cyclohexanol
hydrochloride (Structure 1)) and
1,1-bis(4-hydroxyphenyl)cyclohexane
(Structure 2).
TGA (above) and
DSC (below) of
VenHCl Form 1 and
Form 2.
Note the mass loss
that accompanies
sublimation.
204 °C, phase from the melt) and Form 4 gaseous products formed in the TGA were
(219-220 °C, hydrate/alcoholate). A new passed through a heated transfer line to
amorphous, transient, glassy (semisolid) the FTIR spectrometer and FTIR spectra
phase (Form 5) was isolated by sublima- continuously recorded. The TGA-FTIR
tion under vacuum during the course of spectra of the vaporized VenHCl Forms 1
our thermal studies on this API [2]. and 2 were identical and the main peaks
matched the peaks in the solid state FTIR
TGA, TGA-FTIR and DSC measure- spectrum of VenHCl. This meant that
ments VenHCl vapor is evolved from both forms
The TGA curves of the marketed drug after the phase change between 214 and
Forms 1 and 2 showed complete loss
Figure 2 (b).
of mass between 220 and 260 °C (Fig- FTIR spectra of the
ure 2a). We interpreted the mass loss as vapor from Forms 1
(black) and 2 (red).
being due to decomposition or vaporiza-
tion of the sample after melting.

Venlafaxine hydrochloride The vaporization products were analyzed

(VenHCl) by simultaneous FTIR spectroscopy. The
VenHCl is a widely sold anti-depressant.
The hydrochloride salt of venlafaxine, Figure 2 (c and d).
FTIR spectra as a
(±)-1-[2(dimethylamino)-1-(4-meth- function of tempera-
oxy-phenyl)ethyl]cyclohexanol, exists in ture (220–260 °C)
several different polymorphic modifica- in (c) Form 1 and
(d) Form 2.
tions.
The polymorphs of VenHCl are classified Absorbance
Units
Absorbance
Units
Tempera- Tempera-
according to their main melting temper- ture °C ture °C

atures in the DSC: Form 1 (210-212 °C),

Wavenumber cm-1 Wavenumber cm-1
Form 2 (208-210 °C), Form 3 (202-

METTLER TOLEDO UserCom 1/2007 9

 216 °C, a phenomenon that accompa-
nies sublimation of the solid during the
broad endothermic effect between 220
and 260 °C.
The TGA curves show that Form 2 sub-
Applications
amorphous, semi-solid droplets formed
on the cold finger (Figure 3a). The glassy
mass was immediately transferred to a
glass plate as liquid-like droplets (Fig-
ure 3b). The DSC curve of the sublimed
broad endothermic effect between 220
and 260 °C due to sublimation/vapori-
zation (Figure 3d, left). The exothermic
effect at 100 °C is due to the solidifica-
tion of the glassy mass, the endothermic

limes more rapidly than Form 1.
When VenHCl was sublimed/vaporized
at reduced pressure (0.2 Torr, ~160 °C),
semi-solid material showed crystalliza-
tion between 95 and 100 °C (exother-
mic) followed by melting between 216
and 218 °C (endothermic), and finally a
effect between 217 and 218 °C from melt-
ing. Vapor loss occurs between 220 an
260 °C.
Figure 3d, right, shows the DSC of Ven-
HCl hydrate obtained from Form 5 after
one day exposure in open air (above) and
the hydrate Form 4 prepared by crystalli-
zation from methanol (below). The endo-
thermic effect at 80 °C is due to the loss
of solvent/water.

Figure 3 (a, b and c). DSC heating-cooling-heating

The transient semi-solid, glassy phase on the cold finger of the sublimation apparatus
experiments
(a) and droplets immediately placed on a glass plate (b). The sublimed material, Form 5,
transforms to the hydrate, Form 4, after exposure to the Hyderabad climate (25-30 °C, The presence of two endotherms between
RH 40–50%) for one day. 210 and 220 °C in the DSC curves of
Forms 1 and 2 (Figure 2 effects marked 1
Figure 3 (d). and 2) raised the following questions.
DSC curves of the
freshly formed 1) Is the first endothermic effect due to
Forms 4 and 5. a phase transition and the second due
to melting, or vice versa?
2) Is the endo-exo peak in Form 2 a
melting crystallization phenomenon?
3) Which polymorph is more stable? Do
they interconvert or transform to a
new, different phase?

To clarify this, a number of DSC heat-

ing-cooling-heating experiments were
performed.
A) Form 1 was heated at 2 K/min to
212 °C, a temperature that is just
after the larger endothermic peak
marked 1 (in Figure 2) but before the
small peak marked 2. The sample was
Figure 4 (a). then cooled to room temperature at
Heating-cooling- 5 K/min in the DSC cell (Figure 4a).
heating experiments Reheating at 2 K/min showed a broad
performed on Form 1
with different maxi- endothermic peak at 212 °C. This
mum temperatures meant that the solid is still in Form 1
resulting in the for-
and not a transformed product. The
mation of different
end products. exothermic behavior at 195 °C in the
cooling segment is due to solidifi-
cation/crystallization of the melted
Form 1. We believe that the peak
between 210 and 212 °C in Figure 4a
is due to melting and is not a phase
transition.
B) When the same procedure was re-
peated but heating was continued to
219 °C, just past the second small
peak, the DSC curve of the reheated
Form 1 is very different. There is now

10 METTLER TOLEDO UserCom 1/2007

 a broad exothermic effect at 110 °C Figure 4 (b).
Heating-cooling-
and an endothermic effect at 200 °C. heating experiments
The exothermic effect corresponds to performed on Form
the crystallization of the transformed 2 to two different
end temperatures
Form 3, which melts at 200 °C. Thus again yield different
Form 1 undergoes a phase change to results.
Form 3 on heating to 218−219 °C and
cooling.
C) In a similar procedure, Form 2 was
heated in the DSC at 2 K/min to the
endo-exo peak at 213 °C and then
cooled at 5 K/min to room tempera-
ture (Figure 4b). The cooling curve
is flat and shows no crystallization,
which means that the crystalliza-
tion of Form 2 (exothermic effect
at 213 °C) was correctly assigned.
Reheating at 2 K/min shows a sharp
endothermic peak between 218 and Figure 5 (a and b).
Form 1 Form 2
220 °C corresponding to the melting HSM of Form 1 and
of Form 5, the phase obtained by HSM of Form 2.
sublimation.
D) On heating Form 2 to beyond the se-
cond endothermic effect up to 220 °C, 30 °C 150-190 °C 30 °C 150-195 °C
cooling to room temperature and
then reheating, different peaks occur.
Now the DSC cooling curve shows
crystallization at 150 °C and endo-
thermic peaks that resemble Form 3. 209-210 °C 210-215 °C 208-209 °C 210-217 °C

The heating-cooling-heating curves

show that Forms 1 and 2 first melt and
then phase transform to different solid-
state forms (3 and 5) in the range 210 to 215-216 °C Microcrystals under 217-218 °C Microcrystals under
polarized light after polarized light after
220 °C.
cooling cooling

Hot-stage microscopy (HSM)

Morphological and phase transitions in Figure 6. BHPC
Forms 1 and 2 and the thermal events (Structure 2) p 12.
leading to sublimation of Form 5 were DSC of 2m and 2s
polymorphs. The
studied by HSM. metastable phase
2m has a lower
The photomicrographs in Figure 5 show melting temperature
and shows phase
snapshots of the transformation of both transition to the
solids to Form 5. higher melting
thermodynamically
stable Form 2s.
Whereas the extent of vaporization was
almost complete when the starting form
was Form 2, it was only partial in the
case of Form 1.

HSM measurements confirm the inter-

pretation of the DSC curves in Figure 4
and the existence of the new transient,
glassy phase Form 5.

METTLER TOLEDO UserCom 1/2007 11

 1,1-Bis(4-hydroxyphenyl)cyclo-
hexane (BHPC)
1,1-bis(4-hydroxyphenyl)cyclohexane
molecules are highly prone to forming
inclusion complexes in over 30 host-guest
Applications
(Tpeak , peak 1), while 2m shows two
sharp endothermic peaks at 183 ºC and
188 ºC (Figure 6, peaks 2 and 3). These
two peaks were assigned to the melting of
2m (peak 2), then crystallization (exo-
This was done by heating 8−12 mg of
substance at 10 K/min in a dry nitrogen
gas flow of 50 mL/min. The FTIR spectra
showed that vaporization of both forms
occurs after the phase change between

crystal structures.
We employed two solvent-free condi-
tions, melt crystallization and sublima-
tion under vacuum, to crystallize guest-
free forms. Single crystals of BHPC were
solved and refined in triclinic space
group P1 (2s, Z′ = 1, sublimation phase)
and in orthorhombic space group Pbca
(2m, Z′ = 2, phase from the melt). Z′ is
the number of symmetry-independent
molecules in the crystallographic unit
cell.
TGA, TGA-FTIR and DSC measure-
ments
Phase relationships of 2s and 2m and
possible mechanisms for their intercon-
version were studied by DSC and HSM
[3].
The DSC curve of 2s showed a single
broad endothermic peak at ~184 ºC
Figure 7 (a, b
and c).
TGA (a) and FTIR
spectra of the
evolved vapor of
polymorphs 2s (b)
and 2m (c).
The measured FTIR
peaks match with
those expected for
BHPC.
thermic, peak 4) to 2s and finally fusion
of the sublimed form (peak 3). On heat-
ing a second time in the DSC, both forms
showed a single endothermic peak (peaks
5 and 6), implying transformation to the
stable 2s polymorph. Polymorph 2m is a
metastable phase, which shows a phase
transition to the thermodynamic, sub-
limation polymorph 2s on heating to
200 °C. Under the same conditions, poly-
morph 2s does not show phase changes
except the vaporization endotherm. In
general, the endothermic peak obtained
on reheating is shifted by about 5 K to
lower temperature compared to the first
heating run due to better thermal con-
tact of the sample with the crucible after
melting.
TGA-FTIR measurements of the evolved
vapor were performed in order to con-
firm the sublimation process in BHPC.
183 and 185 ºC (Figure 7). Sublimation
below melting is two to three times more
pronounced with polymorph 2s com-
pared to the melt phase 2m, even though
only a marginal loss of mass is observed
on the TGA curve (Figure 7a).
Hot-stage microscopy (HSM)
Hot-stage microscopy shows blocks of
melt crystals beginning to melt between
178 and 182 ºC with complete melting be-
tween 183 and 185 ºC. With both forms,
cooling resulted in sublimed crystals
with fine needle morphology (Figure 8).
On the other hand, sublimed crystals 2s
did not show any apparent crystal form
change in a similar heating-cooling cy-
cle on the hot stage.
A combination of thermoanalytical meth-
ods such as TGA, DSC and HSM indicate
that 2m is the metastable polymorph and
2s the thermodynamically stable phase
(T2m = 183 ± 1 ºC; T2s = 188 ± 1 ºC).
The single endothermic peak after re-
heating is the thermodynamically stable,
Form m Form s

(a) (d)

(b) (e)

(c) (f)

Figure 8 (a to f).
Trans- Trans- HSM images.
mitance mitance
in % in % 2m: (a) at 25 ºC, (b) 181−182 ºC,
(c) after cooling to room temperature
2s: (d) at 25 ºC, (e) 183−184 ºC,
Time Time
in min
(f) after cooling to room temperature.
in min
Wavenumber cm-1 Wavenumber cm-1 Phase transition of a block crystal of 2m
to needle fibers of 2s (a−c).
(b) (c)

12 METTLER TOLEDO UserCom 1/2007

higher melting crystallized phase. TGA- Figure 9.
Phase transforma-
FTIR confirms the vaporization/subli- tions in VenHCl
mation of BHPC. polymorphs 1 to 5.

Conclusions
The phase relationships between VenHCl
polymorphs are summarized in Figure 9.
In addition to recording quantitative
and reproducible data on four previously
reported Forms 1 to 4 of VenHCl, a new
form, Form 5, was obtained by sublima-
tion. Form 5 is short-lived under inert
conditions (stable for a few hours up to
one day). It transforms to the hydrate,
Form 4, in the open air and to Form 1
under dry conditions.

TGA, DSC and hot-stage microscopy show

that the 5 K lower melting solid 2m form
of BHPC is the metastable modification
and 2s is the thermodynamically stable
phase. The single endothermic peak after
reheating both forms is ascribed to the
thermodynamically stable, higher melt-
ing phase, which can also be obtained by
vaporization/sublimation.
In addition to the above application, we
have also used TGA-FTIR to differentiate
between aniline and phenol inclusion in
a guest-selective host lattice [4].
Literature
[1] W. C. McCrone, in Physics and Chem-
istry of the Organic Solid State, Vol. 2,
D. Fox, M. M. Labes and A. Weiss-
berger (Eds.), Wiley Interscience:
New York, 1965, pp. 725–767.
[2] S. Roy, S. Aitipamula and A. Nangia,
Cryst. Growth Des. 2005, 5, 2268–
2276.
[3] B. Sarma, S. Roy, and A. Nangia,
Chem. Commun. 2006, 4918–4920.
[4] S. Aitipamula and A. Nangia, Chem.
Eur. J. 2005, 11, 6727–6742.

Analysis of melting processes using TOPEM®

Dr. Jürgen Schawe

This article discusses the conditions required for analyzing melting proc- able examples how melting behavior can
esses using TOPEM®. If these conditions are fulfilled, the reversing be investigated using TOPEM®.
heat flow measures processes that occur under equilibrium conditions
and the non-reversing heat flow processes that involve supercooling or Basic principles of temperature
superheating. This separation allows a classification of melting proc- modulated DSC
esses and the differention of crystal structures of different stability.
Measurement principles and
Introduction up to a critical analysis. Despite this, requirements
The measurement and interpretation TMDSC can provide interesting and im- In TMDSC, a conventional temperature
of melting processes using temperature portant information about melting be- program (heating or cooling at a con-
modulated DSC (TMDSC) is one of the havior that would otherwise be difficult stant rate, or isothermal conditions) is
more demanding tasks in thermal analy- to obtain. overlaid with a small temperature pertur-
sis. bation (modulation). In the evaluation
This is possibly the reason why a number Starting out from the basic principles of algorithm, it is assumed that the reaction
of ideas and proposals can be found in melting behavior discussed in reference of the sample to the conventional tem-
the scientific literature that do not stand [1], we want to show with the aid of suit- perature program and the modulation do

METTLER TOLEDO UserCom 1/2007 13

 not influence each other. The underlying
part (from the conventional temperature
program) and the part from the modula-
tion can then be separated. While just as
in conventional DSC the underlying part
Applications
of the heat flow (total heat flow) contains
the entire information, the part that is
generated by the modulation, only con-
tains information about processes that
can more or less follow the modulation.
In all modulation techniques, the meas-
urement conditions must be chosen so
that measurement and evaluation take
place under linear and almost station-
ary conditions. This means that the re-
sult is independent of the intensity (am-
plitude) of the modulation and that the
total heat flow during a relevant evalu-
ation window (period) does not change
much. The quality of the measurement
improves as the underlying heating rate
is reduced. Especially in the analysis of
melting processes, small modulations
must be used because otherwise artifacts
are measured that lead to the misinter-
pretation of results.
TOPEM® is a modern TMDSC technique
that differs from conventional TMDSC
with regard to the type of modulation
function and evaluation. In TOPEM®,
a stochastic function is used for modu-
lation. The intensity of the modula-
tion function is the height of the pulse.
The evaluation consists of a correlation
analysis of the measured heat flow and
heating rate in a selectable evaluation
window. [2, 3].
Figure 1.
Schematic diagram
of free enthalpy as a
function of tempera-
ture. Processes are
shown that occur
under local stable,
metastable and un-
stable conditions.
14 METTLER TOLEDO UserCom 1/2007
Total, reversing and non-reversing
heat flow
In all TMDSC techniques, three heat flow
components are determined from the
measured heat flow. These are the total
heat flow, Φtot, the reversing heat flow,
Φrev, and the non-reversing heat flow,
Φnon.
In conventional TMDSC, the total heat
flow is obtained from the measured
heat flow by averaging over at least one
period. The reversing heat flow is deter-
mined from the modulated component.
The non-reversing heat flow is given by
the difference:
In TOPEM® the evaluation is carried out
by means of a correlation analysis of the
heat flow and the heating rate.
This yields the component of the meas-
ured heat flow that correlates with the
heating rate and another component that
does not correlate with the heating rate.
The non-correlating component is the
non-reversing heat flow, Φnon. The re-
versing heat flow is determined from the
correlating heat flow part [3]. The total
heat flow is calculated from the sum of
the two quantities:
At first sight, this difference in ap-
proach seems relatively unimportant. In
TOPEM®, however, it allows a consist-
ency test of the measurement to be per-
formed as described below.
Sensible and latent heat flow
In principle, the heat flow consists of two
components namely the sensible heat
flow, Φs, and the latent heat flow, Φl,
[3, 4].
The latent heat flow does not explicitly
depend on the temperature but on the ki-
netics of the thermal event. An example
is the curing reaction of an adhesive. A
temperature change during the reaction
cannot cause the sample to return to its
initial state. It will only change the reac-
tion rate.
The sensible heat flow depends explicitly
on the heating rate. An example is the
heat flow into an inert sample, which is
directly proportional to the heating rate.
Here, the proportionality factor is the
heat capacity.
Basic principles
The starting point is the description of
melting and crystallization processes by
means of free enthalpy given in refer-
ence [1]. A diagram summarizing this
is shown in Figure 1. The red, black and
green curves are the free enthalpies of
the melt, the crystal and the glass. The
dashed curves represent intermediate
states. The curve with the smallest free
enthalpy characterizes the stable state.
All other states are metastable. The sys-
tem tries to achieve the stable state but
is hindered by kinetic processes (e.g. nu-
cleation).
Processes occurring in a TOPEM® meas-
urement are marked by blue ellipses or
arrows in Figure 1. These are processes
that occur under quasi-stable, metastable
and unstable conditions:
• Quasi-stable processes in (local) equi-
librium are for example the measure-
ment of heat capacity without another
thermal event occurring.
• In processes under metastable condi-
tions the system departs only slightly
from local equilibrium. Examples of
this are glass transitions or melting
and crystallization processes close to
local equilibrium conditions such as
those occurring in the melting region
of impure substances (see [1]). These
processes can be practically reversed
through a small change in tempera-
ture.
• In processes with a large change in
free enthalpy, the system starts in
metastable equilibrium and “drops
down” into the new more stable state.
The process is hardly influenced by
small temperature changes. Examples
are crystallization processes after a
sufficiently large degree of supercool-
ing or melting processes of crystals
with superheating.
Description of sensible and latent
heat flows
Let us assume that two different process-
es take place in a sample that can each
be described with an order parameter,
x. On melting, x, describes the degree of
disorder and changes from x = 0 (ideal
crystal) to x = 1 (equilibrated melt). The
process with the order parameter, x me,
takes place close to local equilibrium.
The other process begins far way from
equilibrium and has the order parameter
xi. The measured heat is given by:
where c p is the specific heat capacity,
dT/dt is the heating rate, ∆hme and ∆hi
are the specific transition enthalpies as-
signed to the corresponding processes.
Since the process (me) takes place close
to local equilibrium, x me can follow the
small temperature modulation. For this
case, we can write:
In the non-equilibrium process (i), the
order parameter does not follow the small
temperature change, ∆T, determined by
the modulation function. So that in this
case:
Substitution of eq (4) in eq (3) gives the
measured heat flow:
The first term in eq (6) is an explicit
function of the heating rate. Here it is
the sensible heat flow, which includes the
processes that take place close to equilib-
rium. The latent heat flow is described by
the last term. It includes processes that
start far way from equilibrium.
Heat flow separation by TOPEM®
The reversing and non-reversing heat
flows measured by TOPEM®can be as-
signed to the sensible and latent heat flow
if the linearity and stationarity require-
ments are adhered to within the bounds
of measurement accuracy:
Testing measurement condi-
tions
Linearity
Since the evaluation methodology in
TMDSC is based on the analysis of linear
systems, the measurement program must
be chosen so that the measured heat flow
satisfies linear conditions.
This is the case if the reversing heat
flow is independent of the intensity of
the temperature modulation (the pulse
height, i.e. the amplitude). The maxi-
mum intensity depends on the material
and the events to be investigated. With
melting, the linearity limit is usually less
than 0.1 K. Figure 2 shows an example of
a linearity test using the melting of poly-
ethylene terephthalate (PET). Two sam-
ples of similar mass were measured with
different pulse heights and an underly-
ing heating rate of 0.3 K/min. The pulse
heights were ±5 mK and ±50 mK. The
reversing heat flow curves in Figure 2
are independent of the pulse height. The
noise is however larger with the small
modulation intensity. The blue curve
is the difference between the two Φrev
curves. This material can be measured
with a pulse height of ±50 mK.
Stationarity
The total heat flow should at the most
change only slightly in an evaluation
window. This condition cannot always
be fulfilled particularly at higher heat-
ing rates during relatively rapid thermal
events.
In contrast to conventional TMDSC,
TOPEM® offers the possibility to detect
regions of curves in which an interpreta-
tion is critical. This is done by compar-
ing the measured heat flow and the total
heat flow.
Figure 3 shows these curves in the melt-
ing region of a 40:60 mass % sucrose-wa-
ter mixture. Over a wide range, the total
heat flow corresponds to the mean value
of the measured heat flow. In this range,
the curves obtained can be evaluated
both quantitatively and qualitatively. The
total heat flow is however too small in
the region of the peak maximum and the
Figure 2.
Test of the linearity
condition using PET
that had been crys-
tallized at 170 °C.
Above: measure-
ment curves.
Below: reversing
heat flow and the
difference between
the two curves
(blue).
METTLER TOLEDO UserCom 1/2007 15
 high temperature side of the peak. The
measurement curve is primarily deter-
mined by the heat transport and less by
the melting process. To obtain quantita-
tive results with TOPEM® in this region,
Applications
transport conditions. TMDSC methods
are thus unsuitable for the measurement
of sharp transitions of this type.
Reversible melting close to local
equilibrated crystals. This gives rise to
a melt with a critical concentration of
about 80 mass% sucrose. The non-revers-
ing heat flow shows the corresponding
peak. Afterward the melting process fol-

the heating rate must be reduced.
Melting processes
When TOPEM® is applied to melting
processes, several different cases have to
be considered.
Melting of pure materials
Pure materials (e.g. indium) melt at the
equilibrium melting temperature. Dur-
ing the melting process the sample tem-
perature does not change [5] and can not
therefore follow a temperature modula-
tion.
The measured TMDSC curves originate
mainly from the change in the heat
Figure 3.
TOPEM® measure-
ment in the melting
region of a sucrose-
water mixture.
equilibrium
Melting processes during which crystals
and melt exist in local equilibrium oc-
cur for example with mixtures that have
a broad melting range. Such processes
should according to eqs (8) and (9) sup-
ply a contribution to the reversing heat
flow, while the non-reversing heat flow
is small.
The diagram on the left side of Figure 4
shows the simplified phase diagram of
the sucrose-water system [10]. The path
taken on heating is marked by arrows.
The melting process begins at about
−36 °C with the melting of small non-
lows the liquidus line whereby crystals
and melt are in local equilibrium. This
part of the melting process supplies a
contribution to the reversing heat flow.
The melting processes that give rise to a
reversing heat flow are called reversible
melting and the others non-reversible
melting.
Non-equilibrium melting behavior:
superheating of polymers
With many semicrystalline polymers, rel-
atively stable crystallites superheat and
melt above their thermodynamic melting
temperature. In this situation, the melt
and crystallites are not in thermody-
namic equilibrium. The melting process
is non-reversible.
A sample of polyethylene terephthalate
(PET) was first crystallized for 10 min at
170 °C. The sample was then measured
using a pulse height of ±50 mK and an
underlying heating rate von 0.3 K/min.

The measurement curves in the region of

the main melting peak are shown in Fig-
ure 5. As expected, the peak in the Φnon
curve is significantly larger than in the
Φrev curve.

Differentiation of different stable

crystallites
PET crystallizes on cooling at 0.5 K/min
from the equilibrated melt. In the follow-
Figure 4. ing heating measurement at 0.5 K/min,
Left: Simplified the total heat flow curve exhibits a dou-
phase diagram of a
ble peak (Figure 6).
sucrose and water
mixture. The path The TOPEM® measurement shows that
taken by the meas- the reason for the double peak lies in the
urement is marked
by red arrows.
existence of crystallites of different sta-
Right: Curves bility. In the first peak, the reversing heat
obtained from a flow predominates. Smaller crystallites
TOPEM® measure-
ment.
melt reversibly close to their equilibrium
melting temperature. In the second peak,
crystallites melt with superheating. This
peak is almost entirely to be found in
the non-reversing heat flow. The melt-
ing process is fundamentally different
to that observed at a temperature about
10 K lower.

16 METTLER TOLEDO UserCom 1/2007

Conclusions Figure 5.
® Heat flow curves in
When TOPEM is used to investigate the melting region
melting processes, attention must be paid of PET that had
to the linearity of the measurement. The been crystallized for
10 min at 170 °C.
linear region is determined beforehand The underlying
in preliminary experiments. heating rate was
0.3 K/min.

The range in which TOPEM® curves are

valid can be established by comparing
the total heat flow and the mean value of
the measured heat flow.

Processes that take place under condi-

tions of local equilibrium can be de-
tected in the reversing heat flow because
they more or less follow the temperature
modulation. Processes that take place far
from equilibrium do not follow the tem-
perature modulation and thus contribute Figure 6.
to the non-reversing heat flow. The melting behav-
ior of PET that had
been previously
cooled at 0.5 K/min
Literature shows two different
[1] J. Schawe, UserCom 24, 11. melting processes.
[2] UserCom 22, 6.
[3] J. Schawe, T. Hütter, C. Heitz, I. Alig,
D. Lellinger, Thermochimica Acta 446
(2006) 147.
[4] J. Schawe, UserCom 22, 16.
[5] J. Schawe, UserCom 23, 6.
[6] J. Schawe, Thermochimica Acta 451
(2006) 115.

METTLER TOLEDO UserCom 1/2007 17

 Characterization of delivery systems by
thermogravimetry
Applications
Dr. V. Normand, K. Aeberhardt, Firmenich S.A., Geneva, Switzerland
Introduction
A “good” perfume is of course expected
to provide a pleasant and distinctive
odor. At the same time, the fragrances
should remain perceptible for as long as
possible at a constant level of intensity.
For this reason, the fragrances in per-
fumes are now being encapsulated in
so-called delivery systems. The release
of fragrances then occurs under control,
allowing the perception of the perfume
to be optimized with respect to intensity
and lasting effect.
The encapsulation of fragrances in suit-
able delivery systems is therefore a topic
of great importance for producers of per-
fumes.
To identify the most suitable delivery sys-
tem from the very large number of pos-
sible carriers available requires a rapid
analytical screening technique that can
describe the stability and release per-
formance of a fragrance from the deliv-
ery system. Thermogravimetry (TGA) is
an excellent technique for this purpose.
In this article, the release of Romascone®
from three different delivery systems has
been investigated using thermogravim-
etry. Romascone® is a fragrance that
finds application in women’s perfumes.
The delivery systems utilized three dif-
ferent types of polymeric nanoparticles
based on crosslinked vinyl acetate.
Experimental details
The investigations described here were
performed with a METTLER TOLEDO
TGA851/SDTAe equipped with the small
furnace. Samples masses of typically
8 mg (fragrance and nanoparticles to-
gether) were measured in aluminum cru-
cibles. The mass fraction of the nanopar-
ticles made up 40% of the total mass. The
purge gas was nitrogen at 20 mL/min.
The measurements were performed iso-
thermally at different temperatures.
18 METTLER TOLEDO UserCom 1/2007
Theoretical principles
Evaporation of pure liquids
If volatile compounds (such as fra-
grances) are measured in the TGA, a con-
tinual loss of mass is expected because
the furnace is open and an equilibrium
state is never reached.
This is because there is a steady trans-
fer of molecules from the liquid phase to
the gas phase. Molecules that reach the
boundary layer between the liquid and
the gas phase are swept out of the TGA
furnace by the purge gas. Under isother-
mal conditions, this results in a constant
rate of loss of mass which is determined
by the vapor pressure of the compound
and the mass transfer at the boundary
layer, i.e.
where m is the mass, k is a constant that
describes the mass transfer at the bound-
ary layer between the liquid and the gas
phase and Pvap is the vapor pressure.
Evaporation of a compound from
a binary mixture
In a mixture of two compounds, the
chemical potentials of the two com-
pounds in the mixture are reduced com-
pared to the chemical potentials of the
individual pure compounds.
In a binary mixture of two ideal non-
interacting compounds with molecules
of equal size, Raoult’s law predicts that
the partial pressure of each compound is
proportional to the mole fraction of each
species in the mixture, that is:
Here P1 and P2 are the partial pressures
of the two compounds, x1 and x2 are their
mole fractions and P10 and P20 are the
vapor pressures under normal condi-
tions. For real compounds and assuming
that only one substance is volatile, the
Flory approximation applies and the par-
tial pressure of the volatile component is
given by:
Here f1 stands for the volume fraction
of the volatile component (solvent) and
c for the so-called Flory interaction pa-
rameter.
For mixing of the two components to
occur spontaneously, the mixing en-
thalpy (expressed here by the Flory in-
teraction parameter, c) must be small.
Typically c varies between 0 (for good
solvents, athermic mixing) and 0.5 (for
bad solvents, endothermic mixing). If
the interaction parameter is greater than
0.5, demixing of the system is expected.
If the density of the two compounds in
the mixture is about the same, the vol-
ume fraction of the solvent (f1) equals its
mass fraction (w1). The rate of mass loss
is then given by the equation:
If the first derivative of the TGA signal is
plotted as a function of the mass frac-
tion of the solvent, the parameters k ·Pvap
and c can be determined from a fit of
this curve with the function according
to eq 4.
If several isothermal measurements of
the evaporation behavior are performed,
the temperature dependence of the two
parameters can be investigated. The fol-
lowing relationship is then expected for
the interaction parameter:
where W is the mixing enthalpy of the
system, k the Boltzman constant and T
the temperature.
Evaporation limited by diffusion
In eq 4 it is assumed that the evaporation
rate of the volatile component is given
solely by its vapor pressure. In a deliv-
ery system, the evaporation rate of the
volatile component can also be limited
by diffusion of the volatile molecules to
the surface of the delivery system. In this
case Fick’s law applies and we obtain:
Here D stands for the diffusion coeffi-
cient in the delivery system, which here
depends on whether the delivery system is
liquid, rubbery or glassy. A is the surface
area of exchange, dc/dr the concentra-
tion gradient within the delivery system
and a, a′ and a″ are constants that take
into account the dependence of the dif-
fusion on the volume or mass fraction
of the volatile component in the delivery
system.
If the delivery system consists of nano-
particles as in the case described here, it
can be assumed that the concentration
gradient within the particles is constant
after a short time. In this case, the rate of
mass loss is proportional to the diffusion
coefficient.
Results and discussion
In the delivery system investigated here,
Romascone® was encapsulated in na-
noparticles made of different types of
crosslinked vinyl acetate. With Samples
A and B the degree of crosslinking was
chosen so that the delivery system was in
a rubbery elastic state. With Sample C,
more heavily crosslinked nanoparticles
were used so that the delivery system was
in the glassy state.
Evaporation of pure Romascone® Figure 1.
Evaporation of pure
Figure 1 shows the isothermal TGA curves Romascone® at
of pure Romascone® measured at differ- various tempera-
ent temperatures. The curves show that tures.
although the rates of mass loss for the
various temperatures are different, they
do not change during the experiment.
Physically, this means that the rate of
evaporation is only determined by the Figure 2.
temperature-dependent vapor pressure Evaporation of
of the fragrance, which means that the Romascone® from
a delivery system in
evaporation process can be described by the rubbery-elastic
eq 1. If the slopes of the curves are plot- state at various
ted logarithmically as a function of the temperatures.
reciprocal temperature in Kelvin (red
curve), the straight line expected from
the Clausius-Clapeyron equation is ob-
tained.
Figure 3.
Evaporation of Romascone® from Rate of loss of mass
of Romascone®
a rubbery delivery system from a rubbery-elas-
In these experiments, the delivery system tic delivery system
at 40 °C. Inserted
was in a rubbery-elastic state. The results
diagram: the pa-
(see Figure 2) show that in these samples rameter k ·Pvap for
a bend appears in the TGA curve after a the delivery system
and pure Romas-
certain time (except for the measurement cone® at various
at 25 °C; in this case the measurement temperatures.
time was not sufficiently long). This bend
Figure 4.
occurs when evaporation is limited by Temperature de-
the transport processes in the polymer pendence of the
(diffusion). The slope of the TGA curves interaction param-
eter, c. The slope of
before the bend is not constant either. the curve describes
the interaction
According to eq 4, the evaporation rate energy between
Romascone® and
depends on the Romascone® fraction the nanopolymer. It
(the evaporation rate corresponds to the can be seen that the
interaction energy
slope of the TGA curve). The evaporation
between the more
rate as a function of the Romascone® lightly crosslinked
mass fraction can be calculated based on The temperature dependence of the in- nanoparticles
and Romascone®
the amount of Romascone® present after teraction parameter, c, is plotted for two (Sample B) is larger
a certain time. different rubbery delivery systems in Fig- than that between
ure 4. The two samples (Samples A and the more heavily
crosslinked delivery
The corresponding data for the measure- B) differ in the degree of crosslinking of system and
ment at 40 °C together with the “best fit” the nanoparticles used for the delivery Romascone®.
curve according to eq 4 is displayed in system (nanoparticles in Sample A are
Figure 3. more strongly crosslinked that those in
Sample B). The figure shows the expected
In the same figure, the values found with linear increase with increasing tempera-
the fit for k ·P vap for the three tempera- ture (see eq 5).
tures (25 °C, 40 °C and 70 °C) were com-
pared with the corresponding values for Evaporation of Romascone® from
pure Romascone® (calculated from the a glassy delivery system
slopes of the mass loss curves in Figure 1). In these measurements, the evaporation
It was found that the values for k ·Pvap of Romascone® from a glassy delivery
for the delivery system are systematically system (Sample C) was investigated. The
lower than those for pure Romascone®. results of the measurements at different
METTLER TOLEDO UserCom 1/2007 19
 temperatures are displayed in Figure 5.
It shows that in each case the system as-
ymptotically approaches a constant, tem-
perature-dependent composition.
This means that in this delivery system,
Applications
for this behavior is that Romascone®acts
as a plasticizer for the nanoparticles. De-
pending on the Romascone® fraction and
the temperature, the delivery system is ei-
ther in the glassy or rubbery state, which
Conclusions
The evaporation of volatile substances
from delivery systems can be investigated
by thermogravimetry.

part of the Romascone® remains in the leads to the different slopes in the figure: In the example, the evaporation of
delivery system and is not released. The the blue curves describe data for a deliv- Romascone® from nanoparticles based
equilibrium concentration is however not ery system in the rubbery elastic state, on crosslinked vinyl acetate was inves-
reached with the timescale of the experi- and the red lines for a delivery system tigated.
ment. in the glassy state. Whether the delivery If the delivery system is in the rub-
system is in the glassy or rubbery state bery-elastic state, the evaporation of
The analysis of the data according to the depends on the actual Romascone®mass Romascone® can be described by the
approach of Flory (eq 4) gives unrealis- fraction at a particular temperature. The Flory theory (evaporation is limited by
tic values for the unknown parameters point of intersection of a red and the the volatility of the volatile substance).
k ·P vap and c. In fact, in this case the corresponding blue curve therefore cor- If the delivery system is in the glassy
evaporation rate is determined by the responds to the “critical” Romascone® state, the evaporation is limited by the
diffusion of the Romascone® molecules mass fraction for the temperature: above diffusion of the volatile substance within
to the surface of the nanoparticles prac- this mass fraction the delivery system is the nanoparticles and takes correspond-
tically from the beginning, so that the rubbery elastic, and below it is glassy. ingly longer.
evaporation behavior of the fragrance is
described by eq 6. Accordingly, a linear The figure shows that at high tempera- The method described here is simple
relationship between the logarithm of the tures and high Romascone® fractions, and allows delivery systems to be quickly
evaporation rate and the volume fraction the rate of mass loss is higher. In the characterized and optimized.
of the volatile components is expected. same way, it is clear that the diffusion of
Romascone® in a glassy delivery system Literature
The results in Figure 6 show that appar- is appreciably slower than in the rub- [1] L. Ouali, G. Léon, V. Normand,
H. Johnsen, A. Dyrli, R. Schmid and
ently two curves with different slopes are bery-elastic delivery system. D. Benczédi, Mechanism of
required to describe the data. The reason Romascone® Release from Hydro-
lized Vinyl Acetate Nanoparticles,
The different slopes at the different tem-
Figure 5. Polymers for advanced Technologies,
Evaporation of peratures therefore describe the tempera- 2006 (17), 45-52.
Romascone® from ture dependence of the diffusion coef-
glassy polymeric ficient. If the logarithm of the slopes of
nanoparticles.
the curves in Figure 6 are displayed as
a function of the reciprocal tempera-
ture, the curves shown in Figure 7 are
obtained. The evaporation process can
therefore be understood as an activated
process according to the equation
Figure 6.
Evaporation of
Romascone® from
a glassy delivery
system at different Here a(T) represents the slope of the mass
temperatures. loss curve, Ea is the activation energy,
R the gas constant and T the tempera-
ture.
The blue curve describes the evaporation
from the rubbery-elastic delivery system,
and the red the evaporation from the
Figure 7. glassy delivery system. The two curves
Arrhenius diagram
for glassy (red have approximately the same slope. This
curve) and rubbery indicates that the activation energy of
elastic (blue curve) the evaporation processes is independent
delivery systems.
The activation ener- of the state of the delivery system (rub-
gy for both delivery bery-elastic or glassy), at whose surface
systems is about
the evaporation takes place. Evaluation
17.2 kJ/g.
of the data gives an activation energy of
about 17.2 kJ/g.

20 METTLER TOLEDO UserCom 1/2007

 Detection and evaluation of weak sample
effects in DSC
Tips and hints

Marco Zappa

In DSC measurements, a large sample mass is often used in order to thermal mass is equivalent to that of the
detect weak sample effects. Despite the large mass, it is often still sample.
difficult to detect and evaluate very weak effects. This has to do with The compensation of the heat capacity of
the high heat capacity of a large sample, which increases both the sig- the sample by the reference material at
nal noise and the slope of the DSC curve. The noise and slope can be a particular temperature is given by the
reduced by using a suitable reference material in the reference cruci- equation
ble. This largely ”balances out“ or compensates the effect of the heat
capacity of the sample during the measurement. The sample effects
are then much more clearly observed and evaluated due to improved The mass of the sample, mS, multiplied
signal-to-noise ratio and the much flatter DSC curve. by its specific heat capacity, cpS, should
be equal to the specific heat capacity of
Improving the signal-to-noise ferential heat flow signal outside regions the reference material, cpR, multiplied by
ratio – reducing the slope in which thermal effects of the sample its mass, mR.
The larger the difference of the heat flows occur is then zero. Noise and slope are
between the reference and sample sides thereby reduced to the level of that ob- Example:
of the detector outside regions in which tained with empty sample and reference To compensate the heat capacity of a
thermal events occur, the greater the crucibles (see Figure 1). sample of polystyrene (30.0 mg) using
noise and the steeper the slope of the DSC aluminum oxide powder as reference
curve. How to compensate the sample material on the reference side:
heat capacity
The different heat flows are a result of In general, the reference is an empty cru- Sample:
thermal asymmetry between the sample cible identical to the sample crucible. polystyrene, mS = 30 mg,
and the reference sides due to the heat The reference can however be adapted to cp = 1.17 J/g K (at room temperature)
capacity of the sample itself. This asym- the sample properties in order to achieve
metry is greater, the heavier the sample, better thermal symmetry, i.e. similar Reference material:
the larger its specific heat capacity, and heat capacities with similar temperature aluminum oxide powder, mR,
the faster the sample is heated or cooled. dependence on the sample and reference cp = 0.78 J/g K (at room temperature)
The unequal heat capacities can be com- sides.
pensated by using an appropriate refer- This is achieved by filling the reference The calculation according to eq (1) yields:
ence material. In the ideal case, the dif- crucible with a reference material whose 30.0 mg * 1.17 J/g K = mR * 0.78 J/g K

Figure 1. The required mass of the reference mate-

Despite the large rial, mR, is therefore 45.3 mg.
sample mass
(52 mg aluminum
oxide powder) and The ideal reference sample
fast heating rate An ideal reference material:
(20 K/min), the
• does not exhibit any thermal effects
noise and slope
can be reduced to or any discontinuities in specific heat
the level of that ob- capacity in the temperature range
tained with empty
sample and refer-
investigated.
ence crucibles • does not react with the crucible mate-
(rms noise < 0.5 uW, rial or with the surrounding atmos-
slope < 0.07 mW
in the temperature
phere (especially in the temperature
range shown) by range of the sample transition).
using a reference • is easy to dispense (e.g. powder or
material (aluminum
oxide powder). liquid).
• in the case of liquids, has a higher
melting and boiling point than the
sample. Here it is advisable to use her-

METTLER TOLEDO UserCom 1/2007 21

 metically sealed crucibles or to work
under pressure to prevent vaporization
of the reference material and the sam-
ple material itself.
• has a specific heat capacity whose
Tips and hints
To achieve the best accuracy, it is advis-
able to adjust the temperature and heat
flow with reference material in the sam-
ple and reference crucibles.
Evaluating weak glass transi-
tions with confidence
Composites reinforced with fibers contain
only a small amount of the matrix resin
and exhibit only a very weak glass transi-

temperature dependence is known or Detecting denaturation in tion. Often it is not possible to evaluate
is the same or similar to that of the dilute protein solutions the transition with confidence because
sample. Heat capacity compensation with a ref- of the marked slope of the DSC curve. In
erence solution improves the signal-to- this case, the slope is due to the relatively
In many cases, dry α-aluminum oxide noise ratio to such an extent that proteins large temperature dependence of the spe-
powder (cp (25 °C) = 0.78 J/g K) is a suit- can be studied in dilute solution. cific heat capacity.
able solid reference material. The determination of the glass transition
Figure 2 shows that the very weak endo- can be greatly improved if carbon fibers
For dilute aqueous solutions (e.g. sugar, thermic peak of the denaturation of lys- are used as the reference material. The
starch or protein solutions, etc.), water or ozyme in solution at a concentration of advantage compared with aluminum ox-
a suitable buffer solution (cp (25 °C) = just 0.1 mass % can easily be detected if a ide powder is that the specific heat capac-
4.18 J/g K) can be used. reference solution is used. If the 105 mg ity of the carbon fibers exhibits the same
With highly filled samples, it is best to sample mass is not compensated, the temperature dependence as a large part
use the filler itself as the reference mate- denaturation peak can no longer be de- of the sample itself. The slope is therefore
rial. tected with certainty. reduced in an ideal way and the glass
transition is clearly observed.
Figure 2.
Denaturation of
proteins: the en-
Summary
dothermic peak Heat capacity compensation using a ref-
with a peak height erence material in the reference crucible
of only 6 uW can
be measured with
is a simple and effective method to re-
confidence using a duce both the signal noise and the slope
reference solution, of the DSC curve. This is especially use-
despite the very low
protein concentra-
ful if very weak thermal effects in large
tion (0.1 weight %). samples at high heating rates have to be
In contrast, without measured, i.e. under conditions that in-
the reference solu-
tion, the presence of crease the noise and slope.
a peak is question-
able, even though Lower noise is equivalent to improved
the slope of the DSC
curve was mathe- sensor sensitivity. Together with reduced
matically corrected. slope, this allows weak effects to be de-
tected and evaluated with confidence.

The results show that denaturation in

Figure 3. very dilute protein solutions and weak
Epoxy resin/carbon glass transitions in reinforced carbon-
fiber composite fiber composite materials can only be
material. The very
weak glass transi- reliably detected and evaluated if com-
tions remain almost pensation is used.
undetected in the
non-compensated
measurements.
The unequivocal
identification of a
glass transition
would be too uncer-
tain. In contrast, in
the compensated
measurements, the
glass transitions
can be identified
and evaluated with
certainty.

22 METTLER TOLEDO UserCom 1/2007

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Editorial team

Dr. J. Schawe Dr. R. Riesen J. Widmann Dr. M. Schubnell Dr. M. Wagner Dr. D. P. May Ni Jing Marco Zappa Urs Jörimann
Physicist Chem. Engineer Chem. Engineer Physicist Chemist Chemist Chemist Material Scientist Electr. Engineer

Mettler-Toledo AG, Analytical

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