USER COM

Information for users of

METTLER TOLEDO thermal analysis systems December 1997

Dear customer
Yet another successful year for
Mettler Toledo is drawing to a
close. In the field of thermal
analysis once again we succeeded
in launching many new products
in 1997.
We would like to take this oppor-
Calibration

1.1 General observations

6
TA TIP
tunity to thank you for the numer-
A calibration shows you whether your module supplies you with correct
ous recommendations which
measured values. Depending on the number of sensors in your instrument,
continue to help us optimize our
you have to perform different calibrations (heat flux, temperature, mass,
products.
force and length).
The Mettler-Toledo TA team wish
you a successful 1998.
Adjustment: Change of instrument parameters
Calibration: Determination of the deviation
Contents Reference substance: Substance with known literature values
needed for the calibration
TA TiP: Limits of permissible Permissible deviation from desired
– Calibration error: value

New in the sales program: All STARe calibration methods can be used for the calibration and the adjust-
– TMA/SDTA840 ment. The decision whether the determined deviation should be corrected or
– STARe SW V5.1 not always rests with you. If you press CANCEL in the determination of the
– Food application handbook deviation, you leave things as they are. On the other hand, with OK the old
– Pharmaceutical application adjustment data are replaced by the values you have just determined.
handbook
1.2 Prior considerations
Applications Before the first calibration, thought should be given to the following three
– Modern building materials (FTIR) points:
– Selection of MaxRes parameters 1. Limits of permissible error
– Investigation of the memory effect 2. Calibration interval
of polyethylenes 3. Possible measurement combinations (module, crucible and gas)
– Investigation of copolymers with
DSC30 1.2.1 Limits of permissible error
– Denaturation of proteins In the determination of the limits of permissible error and the calibration in-
– Thermoanalytical investigation of terval, one should abide by the principle "as accurately and as frequently as
hydrate necessary".
– Phase correction in ADSC Starting from your (validated) methods, you can define the limits of permis-
measurements in glass transition sible error appropriate to your situation. The adjustment and calibration
– ADSC during the glass transition methods available in the database of METTLER TOLEDO are based on the

USER COM December 97 1

STARe instrument specifications and combination), a set of adjustment You must adapt these methods to
thus have very narrow limits of per- data can be stored in the database. your measurement combination(s)
missible error. The correct adjustment data appro- 1. Ensure that your module can at-
priate to the experimental conditions tain the defined heating and
1.2.2 Calibration interval at hand are transferred to the module cooling rates, otherwise you
With regard to the calibration inter- in the measurement so that you must adapt the rates
val, we recommend a monthly test measure correctly even if the gas is 2. In the case of crucibles with a
based on Fig. 1: Flow chart of meas- switched from helium to oxygen. relatively large mass and/or rela-
urements. If the test results are cor- tively poor heat conduction, the
rect 2 months in succession, the cali- 1.2.4 Adapting the adjustment temperature range must be in-
bration interval can be doubled, oth- and calibration methods creased as the stabilization time
erwise it must be halved. As there are innumerable measure- is longer
If you have very exacting demands, ment combinations, adjustment and 3. The crucible type must be
you can perform each measurement calibration methods are stored in the changed if you do not measure
between two calibrations database as examples only for the with the standard crucibles
standard case (STARe module, stand- 4. The reference substances should
1.2.3 Measurement combination ard aluminum crucible 40 µl (DSC), be selected so that they lie in the
For each module, crucible and purge aluminum oxide crucible 70 µl temperature range you are inter-
gas combination (= measurement (TGA) and air). ested in (extrapolation has an ad-
verse effect on the accuracy of
the results)
Determination of the Determination of the 5. Select the correct purge gas.
limits of permissible error measurement combination(s) To achieve the greatest accuracy, all
measurement combinations used
later should be adjusted beforehand.
Determination of the Without an adjustment, the adjust-
calibration interval ment data for a nonadjusted meas-
urement combination are extrapo-
lated from the standard adjustment
data and determined factors, but the
Adapting the adjustment same high measurement accuracy
and calibration methods
can not be achieved by this means.

1.3 Adjustment procedure

In the adjustment we recommend
Adjustment the following sequence:
1. Tau lag adjustment
2. Temperature adjustment (neces-
sary only for your standard mea-
surement combination)
The furnace sensor (temperature
Calibration
adjustment) is not influenced by
the purge gas and the crucible
and need not therefore be read-
justed for every combination
3. Sensor adjustment (heat flux,
Measurements
sample temperature, force or
length)
The "total adjustment" makes all
three adjustments (tau lag, tempera-
OK ture and sensor) using a single meas-
Calibration urement thus saving you a great deal
Not OK of time.
Fig. 1: Flow chart of measuremnets

2 USER COM December 97

1.3.1 Tau lag adjustment been previously adjusted, the selec- material that generates reversible
With the tau lag adjustment the dy- tion of the heating rate is no longer length changes and is recognized
namic behavior of the measuring cell important here (the only restriction is as a reference substance.
is corrected. Two simple control that this should not be less or greater 3. For the DSC modules the heat
measurements suffice to determine than the heating rates selected for the flux measurement is performed
whether a tau lag adjustment is nec- tau lag adjustment). only on the basis of the sub-
essary. Determine the onset tempera- Again we recommend an adjustment stance with the lowest melting
ture of indium with two different with at least two substances with dif- temperature (entry of the sample
heating rates of 5 and 20 K/min. If ferent onset temperatures. mass possible only for one sub-
the onset temperatures are different, stance)
which is physically not possible, a 1.3.3 Sensor adjustment 4. You should use the total adjust-
tau lag adjustment is needed. The sensor adjustment corrects the ment only for your standard
We recommend performing this ad- signal value (DSC: heat flux, TMA: measurement combination
justment with at least two different length, SDTA: sample temperature).
substances with different onset tem- This is another case where it is ad- 1.4 Calibration
peratures which lie in the tempera- visable to perform the adjustment (dynamic case)
ture range of interest. A module with with at least two substances with dif- Select a heating rate in the region of
correct tau lag values shows no de- ferent literature values to attain a the tau lag adjustment and measure a
pendence of the temperature on the high accuracy in the temperature known substance. After the auto-
heating rate range of interest. matic or manual evaluation, you
know whether or not you meet the
1.3.2 Temperature adjustment 1.3.4 Total adjustment requirements you have defined re-
The temperature adjustment ensures With the total adjustment we offer garding temperature or signal size.
that the onset temperatures corre- you the possibility to make all ad-
1.5 Calibration
(isothermal case)
With the isothermal step method you
can determine the isothermal tem-
perature very accurately. If the iso-
thermal temperature is not correct, it
can be used for the temperature ad-
justment. Without a correct tau lag
adjustment, however, it is never pos-
sible to measure accurate tempera-
tures in either dynamic or isothermal
measurements.
Care is also required when the mod-
ule is used for both isothermal and
dynamic methods. In this case, it is
essential to make a tau lag adjust-
ment beforehand.
Selection of the step (in °C) in the
isothermal step gives the temperature
accuracy.
Example of a test at 200 °C:
Fig. 2: Shift in the onset temperature owing to wrong tau lag values
1. Isostep method for indium (with
steps of 0.1 °C)
spond exactly to the literature values. justments mentioned above with a 2. Isostep method for tin (with
Depending on the literature data, the single measurement. steps of 0.1 °C)
values vary slightly but the values in Attention must be paid to the follow- 3. Draw diagram as follows: Iso-
the database can be adjusted very ing: thermal temperature deviations
easily as long as the substance has 1. The reference substances must as a function of temperature
never been used. If this is not the not exhibit any mutual interfer-
case, the substance can be stored un- ence (local separation).
der a new name with a new value. 2. For the TMA40 there is no total
As the dynamics of the module have adjustment as we know of no

USER COM December 97 3

Fig. 3: Onset temperatures after the tau lag adjust- Fig. 4: Onset temperatures after the tau lag adjust-
ment independent of the heating rate, but still with ment, but still with wrong heat flux
wrong absolute temperature and wrong heat flux

Fig. 5: Fully adjusted DSC module Fig. 6: Isostep measurement for indium and tin for an
adjusted module

Fig. 7: Isostep measurement for indium and tin for a mod-

ule without tau lag adjustment

4 USER COM December 97

4. The temperature deviation at and subsequent, dynamic tempera- Based on the error diagram, the iso-
200 °C can now be taken from ture adjustment the isostep measure- thermal temperature can now be
the diagram; in the measured ex- ments were repeated. corrected for a desired temperature
amples (with tau lag adjustment: It is clear that large isothermal devia- for this case. A tau lag adjustment is
0.0 °C, without tau lag adjust- tions appear although the tempera- preferable to such a correction to en-
ment 1.6 °C). ture adjustment for the module was sure the module measures correctly
As an example of a module without correct. in the dynamic and in the isothermal
or with a wrong tau lag adjustment case.

Temperature

Fig. 8: Isothermal temperature deviation as a function of temperature

1.6 Reference substances

The reference substances needed for the calibration and adjustment are marketed by METTLER TOLEDO. The fol-
lowing reference substances are available and can be traced to the producer:
Indium In 156.6 °C 28.5 J/g ME 119442
Tin Sn 231.9 °C 60.1 J/g ME 51140621
Lead Pb 327.5 °C 23.0 J/g ME 650013
Zinc Zn 419.6 °C 107.5 J/g ME 119441
Aluminum Al 660.3 °C 397.0 J/g ME 51119701

The following are also available for the TMA40 and TG50 measuring cell, but are without a producer's certificate:

Aluminum AI 660.3 °C ME 29593

Silver Ag 961.8 °C ME 29594
Isatherm(1) NiMn3AI 144.5 °C ME 29800
Nickel Ni 357.0 °C ME 29799
Trafoperm(2) Fe 748.0 °C ME 29798

(1)
Isatherm minus (Ni (94 %), Mn (1-3 %), AI (1-2%), Si (1-2 %), Fe (0.3 %), Mg (0.15 %), Cu (0.1 %),
C (0.05 %))
(2)
Trafoperm C5 (Fe (95 %), Si ( 3.5-4.5 %, Mn (<0.02 %), Cu(<0.2 %), C (<0.07 %), Cr (<0.06 %),
P (0.03 %), S (0.02 %))

If you require certified reference substances which can be traced to a national or international standard, you can ob-
tain these from LGC, for example:

LGC
The Office of Reference Materials
Laboratory of the Government Chemist
Queens Road
Teddington
Middlesex, TW11 OLY, UK

Tel: +44 (0) 181 943 75 65

Fax: +44 (0) 181 943 75 54
E-mail: [email protected]

USER COM December 97 5

TMA/SDTA840
We are pleased to be able to intro-
duce you to our new TMA/SDTA840
module less than a year after the
launch of the TGA/SDTA851e. This
module replaces the TMA40 measur-
ing cell, which has been and will
continue to be used for years in hun-
dreds of labs.

SDTA signal
Analogous to the TGA/SDTA851e
module, we now measure the sample
temperature right at the sample. The
R type thermocouple is protected
against contamination by a thin
quartz glass coating. This now al-
lows an adjustment with length
change and/or with melting points of
pure metals (your own choice).
In addition, the DTA signal can be
calculated. Analogous to TGA, si-
multaneously with the length change
in the DTA signal you have another
measured quantity available which
can facilitate your interpretation.

Gas-tight measuring cell

The measuring cell is gas tight so Fig 9: The new TMA/SDTA840
that measurements can be performed
under a defined atmosphere.

Thermostating
The mechanical part of the measur-
ing cell is accommodated in a Features of the TMA/SDTA840 module at a glance
thermostated housing thus guaran-
teeing the highest accuracy in the de-
termination of the coefficients of ex- Large measurement range ± 5.0 mm
pansion. High resolution 10 nm
Long sample lengths up to 20 mm
Length measurement Large force range -0.1 ... 1 N
The entire electronics have been up- High force resolution 1.3 mN
graded to state of the art. The range Large temperature range RT ... 1100 °C (*)
switching in the length measurement High temperature accuracy ± 0.25 °C
is a thing of the past SDTA resolution 0.005 °C
Automation Automatic opening and closing of the
Automation furnace by pressing a button
The furnace can be opened and DLTMA mode < 1 Hz (user definable up to 1 Hz)
closed at the press of a button mak- Options Gas controller, MS/FTIR coupling,
ing the operation simpler and more switched line socket
dependable. Cooling Cryostat cooling
(*) Low temperature option in preparation

6 USER COM December 97

Software V5.1
The STARe SW V5.1 replaces the STARe SW V5.0. The new software version incorporates control of the new TMA/
SDTA840 module.
In addition, a few of your wishes have again been fulfilled with this software release:
• MaxRes for TMA curves (SW Option MaxRes)
• ADSC phase correction (SW Option ADSC)
• Configurable "segment separation ..." evaluation
• E module evaluation (SW Option TMA)
• X-Y signal value transferrable to diagram
• Multiplication and division with curves (SW Option Mathematics)
• Logarithmic representation
• Superimposable coordinate network
• Configurable data export (selectable number of data points)
• Selectable line type
• Several databases (one must be selected on startup)

Fig. 10: E module calculation

Minor improvements have also been implemented such as the insertion of arrows, copy/paste of texts, marker shift-
ing using the keypad and many more.

Food application handbook food industry and supplements the and Ms Schwarz from Novartis (ex
The new food application handbook collection of application handbooks Sandoz), we have produced an appli-
has been produced in cooperation from Mettler-Toledo (German cation handbook for the pharmaceu-
with Dr Behlau from the Fraunhofer 51725003, English 51725004). tical industry with over 40 examples.
Institute for Food Technology and Examples from actual practice are
Packaging in Freising. Using 20 in- Pharmaceutical application shown in which thermal analysis can
teresting examples, it shows how handbook supply valuable information (Ger-
thermal analysis can be used in the Together with Dr Pffeffer, Dr Giron man 51725005, English 51725006).

USER COM December 97 7

Modern building materials

Today's building materials such as qualitative nature of the substance approx. 100 ml/min) to a heated
tile adhesives not only comprise the involved can seldom be answered. glass cell with KBr windows in the
classical ingredients such as cement Additional information and compari- ray path of the spectrometer.
and additives - sand, lime, etc. - but son measured curves of known sys- The timing of the measurements of
also a complex mixture of polymers tems would be necessary for this. the two instruments is electrically
in the form of dispersions. These However, the nature of the gases synchronized so that time-dependent
polymer additives provide the build- evolved in the decomposition proc- functions such as chemigrams and
ing materials with the required prop- esses allows deductions regarding Gram-Schmidt curves can be com-
erties in regard to elasticity, adhesive the type of substance which has re- bined in real time with the TG
power, frost resistance, etc. leased them. This also permits quali- curves. The data of the FTIR
Such complex formulas also require tative compositions to be deter- spectrometer are stored in the
a corresponding number of quality mined. JCAMP format using its own soft-
controls during the production. In
addition, the increasing competition
in this sector necessitates pressing
ahead with further development and
comparing rival products with one's
own.
In addition to the classical mechani-
cal and chemical test methods, ther-
mal analysis including primarily
thermogravimetry has gained great
importance and significant applica-
tion possibilities. The advantage of
this method is that a type of "finger-
print" of the substance mixture under
investigation is obtained in very little
time and without the use of chemi-
cals. This is in the form of an experi-
mental curve which describes the
mass change as a function of tem-
perature. Quantitative percentages of
the individual constituents can thus
be evaluated. In the following exam-
ple, the mass decrease, e.g. between Fig. 11: TGA and FTIR curves of a tile adhesive
300 °C and 500 °C corresponds to
the decomposition of the polymer The following example shows the ware and can then be read into the
fraction and hence its content. From thermogravimetric analysis of a STARe software.
the mass loss between 550 °C and modified tile adhesive with coupled Figure 11 first shows the experimen-
750 °C, the loss of carbon dioxide infrared spectrometry of the evolved tal curve in the temperature range
from calcium carbonate, the content gases. 25 °C to 1000 °C at a heating rate of
of the latter can be calculated. The measurement module TGA/ 20 K/min. Several step-like mass
While thermogravimetry by itself SDTA851e is connected to a FTIR losses can be seen here which stem
provides quantitative content infor- spectrometer via an electrically in part from water losses from hy-
mation, this is generally group infor- heated copper transfer line with an drate salts and in part from the de-
mation; the individual polymer types inner glass coating. composition processes of the poly-
in a mixture can usually not be sepa- The sample vapors are transferred by mers and carbon dioxide loss from
rated. The question regarding the the carrier gas (here nitrogen with carbonates. The time-differentiated

8 USER COM December 97

curve (DTG curve) provides addi- 2-butenal (crotonaldehyde) was pends on the one hand on the size of
tional clarification of these proc- found. Its spectrum together with the the spectra database and on the other
esses, it is a measure of the mass measured spectrum is shown in Fig- hand on the homogeneity of the
change rate. In addition, several time ure 12. The other spectra were as- transferred gases. While accompany-
functions from the IR spectra are re- signed to the following compounds ing gases such as water vapor or CO2
corded. The Gram-Schmidt diagram or compound classes in the same among others may be removed from
shows the integral change of the manner: 42 minutes: acetic acid; 50 the spectra by software, they may
spectra over the entire wavelength minutes: acetone; 59 minutes hydro- have an adverse effect on the de-
region. As a result, the temperature carbon mixture (including methane); pendability that the most suitable
and time regions in which processes 90 minutes: carbon dioxide; 115 compounds have been traced.
with drastic changes in gas composi- minutes: sulfur dioxide . The two From the fragments found in this
tion occur can be identified. It can be last mentioned gases probably arise manner, the substances in the sample
easily seen how this curve reflects from additives containing carbonate matrix can now be reconstructed.
the mass changes (DTG curve). and sulfate. The assignments men- Their amount can then be calculated
The chemigrams provide analogous tioned can naturally be assessed only from the TG mass losses.
information, but in a greatly re- in a limited sense as the "hit rate" de-
stricted wavelength region in which,
for example, typical absorption
bands of assumed decomposition
gases appear. In this manner, the ap-
pearance of particular substances can
be shown during the measurement.
The example shows a chemigram be-
tween 2765 and 2646 cm-1 as well as
one between 1817 and 1753 cm-1.
The first represents the appearance
of a typical absorption band of an
a,b-unsaturated aldehyde, the second
the carbonyl bands of ketones or es-
ters.
The IR spectra stored during the
measurement time can be compared
with those in a database of IR spec-
tra of substances in the gas phase.
Using the example of the spectrum
after 31 minutes measurement time
(first significant mass change step), Fig. 12: FTIR spectrum after 31 minutes

USER COM December 97 9

MaxRes: Event-controlled adaption of
the heating rate
Dr Benedikt Schenker1, Dr Rudolf Riesen2
1
Technisch-Chemisches Laboratorium, ETH Zurich, CH-8092 Zurich, Switzerland, Tel: +41 (1) 632 30 59,
FAX: +41 (1) 632 12 22, E-mail: [email protected].
2
Mettler Toledo, CH-8603 Schwerzenbach.

Summary fects in close proximity, but leads to Selection of the method

Today, most thermoanalytical meas- long experiment times. In the decision regarding whether a
urements are performed with Although modern instruments with a measurement should be performed
predefined constant heating rates. high sensitivity and a quick-response with a constant or effect-dependent
Despite the great success and wide furnace have reduced the time heating rate, the following points
application of this method, it has needed for an experiment, high reso- must be considered:
been known for forty years that lution measurements always need a • Time available
concepts such as thermal effects of a great deal of time. • Simultaneous DTA measurement
sample exist which must be enlisted A dynamic switching of the heating necessary or not?
in the determination of the experi- rate as available with MaxRes allows • Is the mass change and/or the tem-
mental conditions [1 - 4], i.e. par- measurements with a clearly higher perature of a particular event of in-
ticularly how the heating rate can be resolution during the same experi- terest?
adapted during the analysis. ment time (see also example 2). • Repeat measurements necessary?
This article describes the basic dif-
ferences between these two methods
with constant or effect-dependent Table 1 shows an overview of the advantages and disadvantages of both
heating rate, their specific advan- methods.
tages and disadvantages and offers
tips on the selection of valid experi-
mental parameters using the example Constant heating rate: Effect-dependent heating rate
of the MaxRes method in (MaxRes):
thermogravimetry [5].
Adv.: Simple parameter selection Increased resolution
Introduction DTG allows step separation Time saving
In the determination of the condi- Simultaneous DTA meas. possible Quasi-equilibrium conditions
tions for a conventional thermal Suitable for curve comparisons during the effects
analysis, the user is forced to decide Evaluations with kinetic models
between two different, frequently Subtraction of baseline possible
contradictory goals (experiment time
or resolution). The selection of the Disad.: Insufficient step separation Simultaneous DTA measure-
heating rate is a determining factor: with high heating rates ment not interpretable
while a high heating rate leads to an Time consuming with low Change in heating rate can
amplification of an effect and to heating rates simulate a step
short experiment times, it can also No subtraction of baseline
result in an unsatisfactory separation
of thermal events; a low heating rate Table 1: Advantages and disadvantages of constant and effect-dependent
allows the separation of thermal ef- heating rate

10 USER COM December 97

MaxRes - algorithm Example 1 MaxRes measurement the two steps
A MaxRes experiment starts in ex- Figure 13 shows the decomposition are clearly separated and within the
actly the same manner as a conven- of calcium oxalate monohydrate same amount of time available. In
tional experiment. The furnace is (CaC2O4 * H2O). The solid lines both measurements, the total weight
heated at a constant heating rate. show the set of curves which were loss corresponds to the theoretical
However, when a signal change ap- measured with the parameters in the value for the sample weights used. In
pears and its derivative exceeds a value range of Table 2. It is clearly the MaxRes experiment, 21.032 mg
certain amount (high threshold apparent that all parameter sets used strontium carbonate and 20.136 mg
value), the heating rate is reduced. separate the various steps (decompo- barium carbonate were mixed and
As soon as the derivative drops be- sitions) very well. The different step heated from 500 to 1600 °C, result-
low a different, defined amount (low heights and the different transforma- ing in a weight loss of 10.75 mg
threshold value), the heating rate is tion temperatures can be determined CO2. The CO2 partial pressure of the
raised again. This algorithm allows a with high accuracy. incipient BaCO3 decomposition de-
high heating rate to be used in re- The curve which was measured with layed the SrCO3 decomposition
gions in which nothing changes and a high heating rate is shown as a somewhat (appreciably less in the
a low heating rate to be employed in dashed line. MaxRes measurement). As a result,
regions in which a transformation The constant heating rate was se- the measurement shows the first
takes place. lected so that this experiment lasted weight step is too small compared
An initial measurement with a large, twice as long as the fastest of the with the theoretical value (28.14 %
constant heating rate should never be MaxRes experiments shown. Despite instead of 29.8 %) and that of the se–

Recommended parameters
For MaxRes experiments the parameters listed in Table 2 are recommended, but for special analyses primarily a
change in the heating rate and secondly the threshold values should be effected.

Parameter Recommended value Minimum recommended Maximum recommend

(standard setting) value value
Min. heating rate 1 K/min 0.1 K/min 5 K/min
Max. heating rate 20 K/min 5 K/min 50 K/min
Upper threshold value 3 µg/s 1 µg/s 20 µg/s
Lower threshold value 1 µg/s 0.33 µg/s 7 µg/s
Factor 2 2 2
Time delay 0.3 min 0.1 min 0.5 min
Filter 10 s 5s 30 s

Table 2: Recommended parameters: The ratio of the upper to the lower threshold value should be at least three
to one.

omitted. This measurement allows double the experiment time, the second step correspondingly too
the selection of optimum MaxRes steps are clearly less well separated large (24.0 % instead of 22.3 %).
parameters. In addition, from the de- (poorer resolution). Parameters used : Standard settings
rivative of the signal the number of at a maximum and minimum heating
effects can be found and whether or Example 2 rate of 40 and 1.5 K/min.
not these overlap. It should be noted The thermal decomposition of car-
that the MaxRes measurements can bonates takes place over a wide Conclusions
never be corrected by the baseline. temperature range even if a rela- MaxRes allows measurements of
In the case of low steps which tively low heating rate is used. As samples with overlapping thermal
stretch over a large temperature Figure 14 shows, the weight loss effects with a higher resolution and
range, the error can already lead to steps with a mixture of strontium within a considerably shorter time.
inaccurate results owing to the den- and barium carbonates overlap ex- Thanks to better separation, the
sity change during heating of the fur- tensively even at the selected heat- evaluation and interpretation is
nace atmosphere (Archimedes). ing rate of 12 K/min. With a easier and more dependable.

USER COM December 97 11

 References
[1] L. Edrey, F. Paulik, and J.
Paulik, Hungarian Patent No.
152 197 (1962)
[2] J. Rouquerol, Bull. Soc. Chim.
Fr., (1964), pp 31-32
[3] F. Paulik, Special Trends in
Thermal Analysis, John Wiley
& Sons, Chichester (1995)
[4] H.G. Wiedemann, D. Nehring,
Zeitschrift für anorganische
und allgemeine Chemie, 304
(1960) 137
[5] USER COM 4, Information for
users of Mettler Toledo thermal
analysis systems December
1996, page 4

Fig. 13: Decomposition of CaC2O4 • H2O.

Fig. 14: TGA curves as well as the associated temperature profiles of the
decomposition of a carbonate mixture, once with event-controlled adaption
of the heating rate (MaxRes) and at constant heating rate (12 K/min) with
the same experiment time.

12 USER COM December 97

Investigation of the memory effect of
polyethylenes
L. Pheulpin, Cable Alcatel Suisse SA

Summary 70 °C are formed. These crystals range causes this effect. If the treat-
When a PE sample is exposed to produce an additional peak on the ment temperature exceeds the melt-
temperature in the melting range of DSC curve on reheating of previ- ing range, PE changes to the amor-
the crystalline fractions for a certain ously cooled sample. Only condi- phous state and its thermal prehis-
time, the crystal structure is changed. tioning within the crystal melting tory is lost.
This phenomenon is known as the
memory effect ("thermal memory ca-
pacity") and can be measured using
DSC. The memory effect is mani-
fested as a deviation in comparison
with a DSC curve of a sample with-
out a thermal prehistory.
The aim of this article is to show that
these deviations have a reproducible
magnitude which depends on the
temperature and the treatment time.
As a result, it is possible to deter-
mine how long a sample has been
subjected to a particular temperature.

Introduction
Partially crystalline PE, which is fre-
quently used as an insulation mate-
rial for cables, comprises:
• Amorphous zones, also known as
Fig. 15: PE with and without thermal prehistory
the matrix, in which polymer
chains are not arranged geometri-
cally. The structure of these zones Practical procedure
is equivalent to those of a liquid. The principle is relatively simple: The samples are conditioned at different
• Crystalline zones in which the temperatures for different lengths of time. They are then measured using
polymer chains have a geometric DSC and the deviation evaluated. Relatively small samples of approx. 3 to
arrangement (zigzag). 5 mg mass are used to avoid a smearing of the effects owing to low ther-
In the melting of these crystals in the mal conductivity of the sample.
range of approx. 50 to approx.
130 °C, DSC shows an endothermic Measurement program: 30 ... 130 °C at 10 K/min
peak. The larger the crystalline frac- Measuring cell: DSC30
tion, the larger this melting peak. Evaluation: The additional peak is integrated in comparison
A completely crystalline PE has an with the PE without thermal prehistory, which
enthalpy of fusion of 290 J/g, a com- serves as a baseline (integral over the subtracted
pletely amorphous PE one of 0 J/g. curve)
The crystalline zones are always Sample: PE low density (PE LE4244) before and after
formed when the melted sample is crosslinking
cooled. It is important to perform the measurements using the same heating rate.
The crystal formation is promoted by
conditioning, e.g. for 20 min. at Results
70 °C . Here, additional crystals with The area of the additional peak due to the memory effect increases with
a melting range somewhat above increasing conditioning time and finally reaches a limit value.

USER COM December 97 13

 Conclusions
It follows from the representation of
the heat of fusion of the conditioning
peak against conditioning time that:
• the heat of fusion increases with
increasing conditioning time
• the heat of fusion approaches a
maximum value asymptotically
(equilibrium condition)
• the thermal prehistory is more
marked with crosslinked PE (ex-
cept at 90 °C). The exception can
perhaps be explained by the fact
that after crosslinking the polymer
chains are already somewhat or-
dered and are better suited for
crystallization.
Fig. 16: Memory effect of crosslinked PE
If the function of the heat of fusion
of the conditioning peak against the
conditioning time is known, DSC al-
lows determination of how long a
PE-insulated cable has been exposed
to a particular temperature. This ena-
bles quality assurance of the thermal
aftertreatment of the insulating mate-
rial.

Fig. 17: Memory effect of uncrosslinked PE

14 USER COM December 97

Investigation of copolymers with DSC30
J.J. Suñol, J. Saurina, R. Berlanga, J. Farjas, Materials Research Group,
Universitat de Girona Av. Lluís Santaló s/n, E-17071, Girona. E-mail: [email protected].

Introduction tory destroyed with an isotherm of Fig. 18 shows DSC curves with two
This article investigates the influence 5 minutes. Finally, the samples were different maximum temperatures.
of additives as well as the oxidative cooled to room temperature at con- Kinetic investigations under isother-
decomposition on the crystallization stant cooling rates of 2.5, 5, 10, 20 mal conditions can be performed
of copolymers. Copolymers are used and 40 K/min. All experiments were with the aid of the Avrami equation.
frequently in industry as they are repeated at least 3 times. The Avrami equation describes the
favorably priced and their properties If the sample is heated to just above dependence of the degree of crystal-
can be very easily changed. the melting range, the DSC curve lization on the crystallization time.
In the shaping of thermoplastic, they shows only the endothermic melting In the case of nonisothermal crystal-
are crystallized from the melt by peak. After cooling, the sample crys- lization, a modified Avrami equation
cooling. This process induces tallizes exothermically. If heating is can be used [2, 3].
nonisothermal crystallization which appreciably higher, e.g. up to 300 °C The left side of Figure 19 shows the
is of great interest for the processing, a certain oxidative degradation takes crystallization peaks of samples A
e.g. by injection molding. place which results in the sample and B. The conversion curve (crys-
The investigated material is a PP- subsequently crystallizing less well. talline fraction) represents the basic
rich polypropylene-polyethylene In the extreme case, the material re- information for the crystallization ki-
(PP-PE) copolymer (95 % weight mains in the amorphous condition. netics. On the right side of the dia-
percent). The two samples called A The lower the maximum tempera- gram the conversion curves together
and B contain REPSOL PPR 1042 ture, the greater the enthalpy of crys- with the associated tabulated values
(melting index 66.5, melting point tallization. are represented.
temperature 162 °C, density 0.903
g/cm3). Various additives were used:
• Antioxidants (Tinuvin 327,
Tinuvin 770, Tinuvin 770-DF,
Kronos CL 220 and Irganox BZ15)
• UV stabilizers (Quimasorb 144
and Chimasorb 944)
• Dyestuffs (Iagacolor 10401, Elf
Tex 415, Cromoftal A3R,
Cromoftal DPP-BO and Cinquasia
RRT 891D)
DSC is used to measure the heats of
fusion and crystallization. The influ-
ence of additives on the kinetics of
the crystallization and on the melting
temperatures of copolymers was al-
ready investigated in earlier work
[1].

Results
All measurements were performed
with a DSC30 measuring cell under Fig.18: Cooling curves of PP copolymer at -10 K/min in dry air.
dry air. The samples were brought Top: heated to maximum 185 °C. The enthalpy of crystallization is 81.5 J/g.
from the solid to the liquid state at Bottom: heated to maximum 240 °C, where clearly oxidation takes place.
5 K/min and then the thermal prehis- This sample has has a heat of crystallization of only 58 J/g.

USER COM December 97 15

Sample B (base polymer plus nucle-
ating agent) already crystallizes at a
higher temperature than A (base
polymer) thus proving the effective-
ness of the nucleating agent.

Conclusion
DSC has been used to measure PP-
PE copolymers with various addi-
tives. Small amounts of additives
have a considerable influence on the
crystallization temperature. The
crystallization progress can easily be
measured with DSC. It is also appar-
ent that with increasing oxidative
degradation during conditioning in
air, the tendency to crystallize on
subsequent cooling decreases. Ow-
ing to the heating, the enthalpy of
crystallization is increased.
Fig. 19: Crystallization of PP copolymer that has been heated to 185 °C.
The cooling rate is -10 K/min. Sample A is the basic polymer, sample B
contains nucleating agent. Left: DSC curves, right: resulting conversion
curves with the corresponding tabulated values for the crystallized frac-
tion.

Referenzen [2] J.J. Suñol. Thesis, 1996.

[1] J.J. Suñol, J. Saurina, Universitat Autònoma de Barcelona.
D. Herreros, P. Pagès, [3] N. Clavaguera, J. Saurina,
F. Carrasco, „Análisis J. Lheritier, J. Masse, A. Chauvet,
calorimétricø de copolímeros de M.T. Clavaguera-Mora, „Eutectic
base polipropileno-polietileno“ mixtures for Pharmaceutical Ap-
Afinidad 1996, submitted for plications: A Thermodynamic and
puplication. kinetic study“ Termochimica Acta
1997, accepted.

16 USER COM December 97

Denaturation of proteins
In addition to fats and carbohydrates, eters used, their processing may in- it is of great importance for the proc-
proteins, long chain molecules com- volve denaturation. As the extent of ess control. As the following exam-
prising amino acids, are one the most this denaturation influences the sub- ple shows, the denaturation can eas-
important food components. sequent properties such as water ily be measured using DSC.
Depending on the process param- binding power, emulsifiability, etc.,

Fig. 20: DSC measurements of different proteins

Samples commercial raw materials (wheat, spelt, lupin, soya) from a health food store.

Meas. conditions Measuring cell: DSC20

Crucible: 40 µl aluminum, hermetically sealed, reference side filled with same
amount of water
Sample preparation: grind seeds, aqueous extraction at pH 4.5, centrifuge, discard
supernatant, extract residue again at pH 8.5, supernatant evaporated to
desired dry substance content under vacuum.
Sample weight: between 4 – 6 mg
Measurement program: 30 – 110 °C at 5 K/min

Atmosphere: stationary air

Interpretation usual range of 72 to 100 °C. The range 3 to 10 J/g protein. The
4 different, untreated plant proteins proteins differ in their thermal stabil- enthalpies are dependent on the cur-
were investigated. All show a char- ity and in the enthalpy of denaturation. rent phase of the proteins; with seed
acteristic, endothermic peak, that of The enthalpies of denaturation for proteins in the original state the
the protein denaturation. It lies in the grain and oil seed proteins lie in the enthalpy is less than in the dissolved

USER COM December 97 17

state in aqueous solutions. On the other hand, processed protein usually exhibits lower reaction enthalpies as possi-
bly parts of the protein are denatured during the treatment.
Spelt has temperature sensitive proteins with the highest enthalpy of denaturation Whereas wheat proteins are al-
ready extensively denatured at 86 °C, the main fraction of the soya proteins is still native. Here, denaturation does
not start until 88 °C.

Evaluation
Sample DS content Weight Reaction enthalpy Tpeak
(DS, mg) (J/gDS) (°C)
1) Soya 13.0 % 4.78 5.2 94.9
2) Lupin 23.0 % 6.80 4.2 90.9
3) Wheat 12.5 % 3.44 3.5 80.2
4) Spelt 20.0 % 5.40 17.2 80.7

DS = dry substance

Conclusion
The above measurements show that in principle each product containing protein can be investigated and character-
ized using the DSC method. The DSC curve is a type of "fingerprint" of the measured sample. It shows characteris-
tically the condition of the protein. On the other hand, identification of plant proteins alone using a single DSC
curve is difficult as the enthalpies can fluctuate as a function of the variety and growth condition. A native sample
must therefore always be measured as a reference to assess the degree of denaturation.

Thermoanalytical investigation of
hydrate
Many substances used in the pharmaceutical industry have the ability to form so-called hydrates or solvates. In
these, water is not only present on the surface as moisture, but also bound permanently in the crystal. This property
is known as pseudopolymorphism and usually leads to a really complex melting behavior being obeserved with
such hydrates. A combination of DSC and TGA can be used for a complete characterization.

Samples Glucose, monohydrate and anhydrate

Meas. conditions Measuring cells: DSC820 and TGA850

Crucible: DSC 40 µl aluminum, pierced lid
TGA 100 µl aluminum, pierced lid
Sample preparation: as delivered
Sample weight: between 5 and 15 mg
Measurement program: DSC 30 – 250 °C at 20 K/min
TGA 30 – 300 °C at 20 K/min
Atmosphere: Nitrogen, DSC 50 ml/min and TGA 80 ml/min

Interpretation clear difference between the two can be ascribed to the loss of hydrate
Glucose can occur as the monohy- samples. The anhydrate shows no water and does not fully agree with
drate or anhydrate, depending on the noticeable moisture loss, on the other the stoichiometry.
prevailing conditions. As the TGA hand with the monohydrate a step of In DSC, the anhydrate shows only its
and the DSC curves show, there is a around 7 % can be observed which melting peak at around 161 °C. In

18 USER COM December 97

the case of the monohydrate, several
effects, namely water loss, melting
and recrystallization overlap. This
results in a broad peak in the range
between 60 and 125 °C. The
anhydrate formed in the recrystalli–
zation then melts again at around
154 °C. This shift is due to the some-
what lower purity of the substance.
The evaporated amount of water can
also be roughly estimated from the Bild Gluose, Pseudopolymorismph
first DSC peak if a heat of evapora-
tion of around 2300 J/g is assumed
for water. This would give here a
value of about 0.45 g water
(around 9%), somewhat higher than
the value determnined with TGA.
However, this method should be
used only if the ongoing reaction is
known exactly. The crucible should
also be back weighed after the meas-
urement. Fig. 21: TGA and DSC curve of glucose, present as anhydrate and monohydrate.

Evaluations
DSC is used to determine the onsets and TGA the weight loss.
Sample
TGA: Step %
Monohydrate 7.09 (hydrate water loss)
Anhydrate < 0.1 (residual moisture)

DSC: Range °C Onset °C

Monohydrate 60 – 125 (water loss) 153.8 (melting anhydrate)
Anhydrate 160.9 (melting anhydrate)

Conclusion
The combination of DSC and TGA curves allows indentification of pseudopolymorphism as well as a clear distinc-
tion between anhydrate and monohydrate.

USER COM December 97 19

Phase correction in ADSC measure-
ments in glass transition
Corrie T. Imriea, Zhong Jianga and John M. Hutchinsonb
Departments of Chemistrya and Engineeringb, University of Aberdeen, Scotland, UK

In alternating differential scanning Theoretically the phase angle in the this is a phase angle due to heat
calorimetry (ADSC), the temperature glass transition region of a polymer transfer, m andCp are the mass and
is varied sinusoidally as a function of is predicted to be zero before and af- specific heat capacity of the sample,
time and is superimposed on a con- ter the transition and to deviate from respectively, K is Newton’s law con-
stant underlying heating rate. zero only during the transition [2,3]. stant and ω is the frequency of
Schawe [1] has proposed that the The experimentally measured phase modulation [5]. It is important to
data obtained using the technique angle, however, behaves in a quite note that φht does not include any
may be best interpreted in terms of a different fashion. The phase angle is contribution from relaxation proc-
complex heat capacity (Cp*) an in- not zero before the transition, devi- esses in the sample. From this equa-
phase heat capacity (Cp') and an out- ates from this value at approximately tion we can see that the phase angel
of-phase heat capacity (Cp") which the same temperature as the step φht increases linearly as the specific
are defined as: change in Cp* and then returns to a heat capacity increases. Figure 22
Cp* = AHF / Aq (1) different non-zero value. This devia- shows how the heat capacity of
In-phase heat capacity: tion from zero before and after the polycarbonate varies with tempera-
Cp' = Cp* cosφ (2) phase transition is easy to understand ture, and it increases by ca 15 % in
Out-of-phase heat capacity: and is caused by the problem of heat the glassy region. If we now look at
Cp" = Cp* sinφ (3) transfer between the instrument and the dependence of the negative phase
where AHF is the amplitude of the the sample and within the sample it- angle on temperature in the glassy
heat flux modulations, Aq is the am- self, an experimental difficulty not region φht then that too increases by
plitude of the heating rate modula- included in the current theoretical the same relative amount, as pre-
tions and φ is the phase angle. The analysis [4]. This problem of heat dicted by equation (4). Weyer et al [6]
phase angle is defined as a negative transfer will exist irrespective of the suggested that this relationship could
quantity within the Mettler-Toledo make of differential scanning calo- be used in correcting the phase angle
STARe software, which is intuitively rimeter used in the experiments. It is for heat transfer effects. Specifically,
pleasing because it indicates that the important for the user to be aware, the baseline used to correct the phase
heat flux modulations lag behind the therefore, that if the phase angle ap- angle should be a sigmoidal curve
heating rate modulations. pears to be zero before and after the which mirrors the change in Cp*
Considerable excitement surrounds transition this indicates that the raw with temperature. Thus, if we take
this technique and the reason for this data must have undergone a correc- the phase angle curve and subtract
lies to a large extent with our ability, tion procedure. from it the heat capacity curve,
for the first time, to measure these The simplest method of correcting scaled to make incremental differ-
heat capacities. It is true that their the phase angle would be to manipu- ence before and after the transition
physical significance has yet to be late the data in such a way as to arbi- equal to that seen in the phase angle,
established but here we have previ- trarily make the phase angle zero be- we obtain a phase angle which has a
ously unattainable information fore and after the transition, but such value of zero either side of the tran-
which should enhance our under- an approach is quite clearly unsatis- sition as predicted by theory. This
standing of how materials respond to factory! To develop a scientifically procedure removes the effects of
changes in temperature. Clearly the acceptable correction procedure we heat transfer and we obtain the cor-
evaluation of the in-phase and out- must consider how the phase angle rected phase angle which arises from
of-phase heat capacities relies on the depends on the experimental vari- relaxation processes within the sam-
evaluation of the phase angle and so ables. It has been shown that, provid- ple, see figure 22. Using this phase
we must understand the factors that ing the phase angle is small, which it angle the in-phase and out-of-phase
influence the measurement of φ and invariably is, then, heat capacities may now be calcu-
develop methods to correct for spuri- φht ≈ m Cp*ω/K (4) lated.
ous instrumental effects. where the subscript ht indicates that

20 USER COM December 97

 [1] J. E. K. Schawe, Thermochim.
Acta, 260 (1995) 1
[2] J. M. Hutchinson and S.
Montserrat, J. Thermal Anal,
47, 103 (1996)
[3] J. M. Hutchinson and S.
Monserrat, Thermochim. Acta,
286, 263 (1996)
[4] B. Schenker, J. Thermal Anal.,
48 (1997) 1097
[5] B. Wunderlich, Y. Jin and A.
Boller, Thermochim, Acta, 238,
277 (1994)
[6] S. Weyer, A. Hensel and C.
Schick, Thermochim, Acta, in
the press (1997)

Fig.22: Complex heat capcity of polycarbonate

USER COM December 97 21

ADSC in the glass transition region:
the appearance of ripples
John M. Hutchinsonb, Corrie T. Imriea and Zhong Jianga
Departments of Chemistrya and Engineeringb, University of Aberdeen, Scotland, UK

The application of ADSC to the glass heat flux and phase angle traces. In Figure 24, the heating rate modu-
transition is now reasonably well un- They are also visible in the heat ca- lations had a period of 60 s and an
derstood in respect of the complex pacity traces at an enlarged scale. amplitude of ± 3.1 K/min around and
specific heat capacity Cp*, its in- The origin of these ripples lies in the underlying heating rate of 0.5 K/min.
phase and out-of-phase components, Fourier transformation of the modu- The heat flux modulations, on the
Cp’ and Cp’’ respectively, and the lated heat flux signals in the ADSC other hand, are not perfectly sinusoi-
phase angle f between heating rate procedure and arises from the dal in the transition region, as a re-
and heat flux [1-3]. For example, the “windowing” procedure that is used. sult of the relaxation processes that
“step-change” in Cp* and Cp’ oc- This can be seen rather clearly in the occur there (in practice, there are
curs in a temperature range where theoretical model predictions [3] for also additional effects due to prob-
the timescale for molecular motion is the phase angle shown in Figure 24. lems of heat transfer, which are not
approximately equal to the period of Here the main effect is the departure present in this idealised theoretical
the ADSC modulations. At lower of phase angle from zero as the glass model). What happens is that, as the
temperatures, the molecular transition interval is traversed on underlying endothermic process be-
timescale is much longer than the pe- heating. Superimposed on this are gins, the heat flux begins to lag the
riod, so that the response is glassy, ripples, which appear very similar to heating rate, and as a consequence
with the value of Cp corresponding those observed in practice (e.g. Fig- the period of the heat flux modula-
to that of a glass; on the other hand, ure 23). The window used in the tions increases slightly relative to
at higher temperatures, the molecular theoretical model was a single cycle that of the imposed heating rate
timescale is much shorter than the of the heating rate, which, as the modulations. The Fourier transfor-
period, so that the response is liquid- controlled variable, was a perfect si- mation interprets this as a phase lag
like and gives a value of Cp corre- nusoidal modulation. of the first harmonic component, but
sponding to that of a liquid. Clearly,
the temperature at which this “step-
change” occurs will depend on the
chosen period of the modulations;
the shorter is the period, the higher
the temperature at which this transi-
tion occurs.
This behaviour, as well as other
common features of ADSC traces in
the glass transition region (for exam-
ple a peak in the negative phase an-
gle) can be explained by a theoretical
model [1-3] and are universally ac-
cepted as resulting from the relaxa-
tion processes. Another feature, how-
ever, that is often observed in ADSC
traces in the glass transition region
has yet to obtain such universal rec-
ognition. This is the appearance of
“ripples” superimposed on the
curves which result from the ADSC
analysis. An example is shown in
Figure 23, which was obtained for a Fig. 23: ADSC evaluation of PVAc in the glass transition from -10 to 70 °C.
sample of polyvinyl acetate, where The selected experimental parameters were: Period = 60 s, temperature am-
these ripples are easily seen in the plitude = 1 °C, mean heating rate = 1 K/min and sample mass = 12.38 mg.

22 USER COM December 97

the use of sliding window equal to
0.02
one cycle of heating rate modula-
tions, which is of a slightly different
frequency from that of the heat flux 0

modulations, results in the ripples

observed in the phase angle. -0.02
An exact consideration of the ripple
on the phase curve in Figure 24 -0.04

phase angle / rad

shows that the period of these ripples
corresponds exactly to half the im- -0.06
posed period of the heating rate.
On the mean value curve of the heat -0.08
flux signal, the period is always
equal to the period of the heating -0.10
rate and this can be explained by the
Fourier algorithm. -0.12
In conclusion, the ripples seen on the
ADSC traces of Fourier transformed
-0.14
quantities are a natural consequence -10 -8 -6 -4 -2 0 2 4 6 8 10
of the data analysis procedure temperature, T – Tr / K
adopted. Ripples will always be
present in the glass transition region, Fig. 24: Theoretical phase during the glass transition. The selected experi-
where the phase angle departs from mental parameters were: Period = 60 s, temperature amplitude = 0.3 °C,
zero, unless a data smoothing routine mean heating rate = 0.5 K/min. The temperature range was TR - 10 °C to TR
is used. They should not, however, + 10 °C, where TR is chosen at random.
be confused with noise on the signal;
on the contrary, their appearance rep- [1] J.M. Hutchinson and S. Montserrat, J. Thermal Anal, 47, 103 (1996)
resents an ability to measure phase [2] J.M. Hutchinson and S. Monserrat, Thermochim. Acta, 286, 263 (1996)
angle changes with great sensitivity. [3] J.M. Hutchinson and S. Monserrat, Thermochim. Acta, in press (1996)

Tips:
ADSC
The following points must be considered in ADSC measurements:
1. Use thin samples with a large contact area with the crucible to assure optimum heat conduction between the
crucible and the sample
2. Use small samples to minimize errors due to the thermal conductivity of the sample itself
3. With helium as the purge gas, the heat conductance to the sample can be optimized
4. Press sample to the crucible bottom with the crucible lid to ensure the contact area does not change during the
measurement
5. At least 6 periods should be measured during the effect
–> determines the maximum mean heating rate
6. The amplitude of the temperature modulation must be selected so that the maximum heating and cooling rate of
the instrument is not exceeded or dropped below
The follows holds as a rule of thumb: "1-1-1" (mean heating rate: 1 K/min, amplitude: 1 °C, period 1 min)

Storage life of tapes and DATs

According to the information from tape and DAT manufacturers, your backups can be reliably read for 10 years.
After this time, it is advisable to transfer the backup to a new tape or DAT if the data have to be available for a
longer period.
A tape or DAT should not be used for more than 100 backups.

Reproducibility
If you do not have your TA module in permanent operation and rely on the highest reproducibility of the measure-
ment (e.g. in determination of the residue or determination of the cp function), you should discard the first meas-
urement after putting the instrument back into operation.

USER COM December 97 23

Exibitions, conferences and courses
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(near Rostock)
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24 USER COM December 97