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Information for users of METTLER-TOLEDO thermal analysis systems

July 1996

Dear customer
Thank you for the interest you have shown in our customer magazine. In compliance with your wishes, we are including more application examples. Yet again, we were able to present new products at important exhibitions last spring. Even if you are on a tight budget, we can offer you an extremely attractive and powerful solution. The new STARe software and a new application collection covering the topic of thermoplasts have been available since the beginning of May 96.

Investigating unknown samples

Sample Preparation

3
TA TIP

Contents
TATiP: Investigating unknown samples NEW in the sales program: STARe software V3.10 Application collection Thermoplastics i.e.: PE, melting curve and thermal prehistory Engineering polymers Applications Elastomer analysis in the TGA850 Selection of experimental parameters for the cp determination with ADSC
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With the right sample preparation you can avoid unreasonable results. The main goals of sample preparation are: Minimum Temperature Gradients Within the Sample Pan to achieve sharp thermal effects. Sharply defined, well pronounced effects increase the precision of numeric results as well as the resolution of overlapping peaks. Small temperature gradients are achieved by a good thermal contact between sample and pan and by good thermal conductivity of the sample. In this connection, ideal sample forms are plane disks, dense powders as well as liquids. Improve the sample shape of irregular objects, e.g. plastic parts by sawing or face grinding of at least the bottom surface. Pulverize brittle objects in a mortar. Fill the powder in a pan and compress it with the teflon bar supplied. Also press down pasty samples. Care: the pan must not be deformed, place it on a flat surface (with a hole for pans with center pin). Remove the punch brow of punched samples or simply place them in the pan with the flat side down. Liquids: immerse a spatula in liquid and touch the inner surface of the pan. The suspended droplet will flow down. You may use a small syringe, but some plastic parts of the syringe could be attacked by certain organic liquids. Fibers can be difficult, too. Cut sufficiently thick fibers into short pieces that fit flat in a pan. Wrap thin fibers in the smallest piece of degreased aluminum foil possible and compress the package. Place it in the pan with the flat side down.If you expect very highly exothermic reactions or wish to facilitate the diffusion of gases you can mix a powdered or liquid sample with an inert solid diluent such as relatively coarse alumina or glass powder. Defined Atmosphere in the Area of the Sample: An open pan allows free access of the furnace atmosphere. Such a measurement takes place at the practically constant atmospheric pressure (isobar). However, there exists a danger that the measuring cell can be spoiled by material creeping or splashing out of the pan. Use a pierced lid to avoid such problems. A hindered gas exchange (self-generated atmosphere) is necessary, e.g. for determination of the boiling point (in an open pan the liquid would
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Sample preparation
good thermal contact between sample and crucible

vaporize before reaching the boiling point). For this purpose put the aluminum lid upside down on a solid support, e.g. the crucible box and pierce the lid once with a sharp pin. Check the hole diameter under the microscope or by holding against a light source. The diameter should be 20 through 50 m. Fill the sample into pan and close it with the pierced lid in the sealing press. If you seal your sample hermetically, you suppress any volume work, e.g. the vaporization endotherm. Since the sample is exposed to the increasing vapor pressure and the pressure of its decomposition products, you shift the onset of the decomposition to higher temperature. Such a measurement takes place at practically constant volume (isochor) up to the pressure strength of the crucible (Al standard pan approx. 200 kPa above ambient, gold plated steel pan approx. 15 MPa).

Selection of the sample atmosphere

open crucible, selfgenerated atmosphere or closed crucible

Experimental Conditions
Advice for first measurements:

Selection of the measurement conditions

organic substances inorganic substances

Offline Thermogravimetrie
comparison of the weight before and after measurement

Visual check
open crucible and study sample changes

Organic substances: Amount of sample 1 10 mg in Al pan with pierced lid. Temperature range: ambient 350 C, rate: 10 or 20 C/min, atmosphere: N2 (approx. 50 ml/min). With inorganic substances use 10 30 mg and a higher maximum temperature of, e.g. 600 C. In DSC compare the total pan weight before and after the measurement to detect a possible weight loss ("offline thermogravimetry"). Examine the measured sample: Does it look molten? Can you identify a fusion peak on the DSC trace? If you are interested in the crystallisation behaviour, run a new sample with a cooling segment (-10 K/min) after the fusion peak. Avoid a super cooling of 150 C! Many substances are difficult to crystallise from the melt, they form a glass on cooling. Did it become discolored? Organic compounds turn brownish when decomposing. Are there gas bubbles? Together with a weight decrease of >30 g this indicates decomposition. Has there been a reaction with the crucible material? A pan that is not inert begins to dissolve or can be destroyed completely. Try to find a really inert pan material. Sometimes chemical analyses of the investigated sample can provide important information. Very often a second run under identical conditions is helpful. Compare the curves of first and second run. To separate overlapping effects try a lower or a higher (!) heating rate or apply self- generated atmosphere. In most cases a smaller sample mass gives better separation. With organic substances: measure a new sample in air or oxygen. The exothermic oxidation reaction occurs at a heating rate of 10 C/min in the range approx. 150 to 300 C. When only small effects appear (DSC < 2 mW, TGA < 1 mg), run a blank curve under identical conditions and subtract it from the sample curve.

Possible 2nd measurement

identical or new parameter offline blank curve correction

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STARe software V3.10

With the new STARe SW (a further development of the TSW870), we are now in a position to offer a specific solution to customers in all branches. If need be, the SW can be expanded at a later date to meet the latest requirements. We are convinced that this will provide you with a tool which can be used to analyze both simple and very complex problems. If you already possess the TSW870 SW, you can update your SW at a favorable price and make use of the numerous new possibilities. If a SW option which you have already purchased has been improved, all new possibilities of this SW option can be used (e.g. if the kinetics SW option has been enhanced with an addiModule control window with Routine window tional ASTM evaluation). NEWS 1st option: Routine window With this option a numeric experiment and method editor can be started directly in the Module control window. Without the need to switch windows, you need only develop simple methods and supplement them by data specific to an experiment such as sample weight and you are ready to start the measurement. In the same window you can observe the measurement or store it for the analysis. At the same time, however, additional new methods or experiments can be developed. These are then processed in their order in the experiment buffer. Illustration "Module control window with Routine window" 2nd Option: Application database As you have continually requested more applications, we are pleased to introduce you to the first application collection dealing with thermoplastics. As all curves and evaluations in the handbook are also integrated in the database, you can call these up at any time for comparison or training purposes.
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General expansions TA basis software With the new STARe SW the data from AE, AG, AT and MT balances can be transferred directly to the computer at a keystroke. The DOS data export is now included in the basic software and contains the following data formats: - HPGL - PostScript - TIFF (PACK and LZW) - BMP (mono and color) - PCX (mono, gray and color) A new feature is support for numerous printers. The data backup possibility via the network to a different PC instead of on DAT or tape will also be found extremely valuable. To ensure greater clarity, only the menu points for which you have purchased a licence appear. The deletion of database entries has also been considerably simplified. Several objects can now be selected at the same time and deleted. In data import, complete diskettes

can be loaded simultaneously. In addition, you also have many data formats of other manufacturers available. Method window In this window together with the relative loops option you can generate sinusoidal temperature programs. You have the following parameters available: Start temperature Mean heating rate Amplitude Period (= 1/frequency)

Experiment window The possibility to screen a sample without the need to develop a method is included as standard in the Experiment window (earlier Rapid Experiment option). By popular request, you can now define the position on the sample turntable when developing the experiment.

Evaluation window The following new improvements have been implemented in the basic evaluation window: Various coordinate systems can be automatically arranged one above the other. Curve and curve name are linked with each other (if the curve is deleted, the name also disappears) Huge expansion of the Eval Macro capabilities (all points under Info can now be integrated in a macro, moreover this list has been expanded, e.g. numeric output of the temperature program). At the request of our customers, it is now possible to configure the numeric printout (what should be printed out with what title) The calibration printout can be generated directly at a keystroke in conformance with GLP. In curve searching, the search can now also be made on the basis of the order number of the experiment The temperature calibration has been expanded so that with more than 3 different substances a 2nd order correction is now made.

ADSC evaluation

evaluation for temperature-modulated signals. In contrast to the sinusoidal excitation, work is performed here with a saw-tooth temperature excitation. If the individual segments are sufficiently long, the sample changes to a quasi-stationary state. Errors due to frequency and amplitude response of the system (furnace and sample) are thus minimized. This evaluation allows a very accurate quantitative determination of the reversing (cp) signal component. Further, the non reversing signal In addition to these numerous, minor component is also calculated. improvements, existing evaluation options have been expanded: With the ADSC evaluation you have a new evaluation available which 1st SW option ADSC (formerly provides a huge wealth of informaFFT) tion. All temperature modulated TA This option has been expanded by 2 curves can be evaluated. additional evaluations and today of- In addition to the non reversing fers you 3 different evaluations for curve, the reversing signal (cp) is periodically induced (force or temcalculated and is also separated into perature) signals: the inphase and outphase compo- Fourier analysis (FFT) nents thanks to the phase informa(force or temperature excitation) tion. As an additional curve, the - Steady state ADSC phase signal is also calculated for (temperature excitation) each harmonic excitation; this signal - ADSC (temperature excitation) is very sensitive. Fourier analysis is used to split the measured signal into its harmonic 2nd SW option Kinetics nth order signal parts. Depending on the setThe ASTM E1641 TGA kinetic ting, separation into the amplitudes evaluation has been newly impleof the sine and cosine or the cosine mented. Following the calculation with phase is possible. using the new procedure, you can Steady state ADSC is a special use the applied kinetics as before.

3rd SW option DSC Purity (formerly Purity) To date, the purity has been calculated based on the simplified Vant Hoff law. Impurities up to approx. 5 mol% could be detected by this method. This evaluation is eminently suitable for unknown samples or those which already start to decompose during melting. The purity can now also be calculated using the complete Vant Hoff law. This allows the evaluation of samples with up to around 10 mol% impurities. 4th SW option Mathematics This option has been extended by a mathematical integration evaluation. The curve is simply integrated over the x axis. A new feature is the possibility to enter a mass unit in the multiplication or division. This allows, e.g. cp curves to be reconverted into heat flow curves. It goes without saying that we are interested in your future criticism, however we believe that an optimum product can be developed only through cooperation between producer and user.

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Application collection Thermoplastics

We are now in a position to introduce the collection of thermoplastic applications as the first part of a planned series of such brochure. As all evaluations in the brochures can also be integrated in the STARe SW, you have innumerable comparison curves available. If you have purchased the SW new, you can call up these applications directly with the SW option Application Database. All measurements are described using the same scheme enabling you to find your way around very quickly. Thanks to the detailed description, you will find it childs play to comprehend all steps up to and including the evaluation. PE, melting curve and thermal history Sample Measurement conditions PE-HD film Measuring cell: Crucible: DSC821e with air cooling Aluminum standard 40 l, lid hermetically sealed

Sample preparation: DSC measurement

disk of 2.33 mg punched from film Pretreatment: 60 min isothermally at 129 C and cooling to 40C at program: 5 K/min. Heating from 30 to 160 C at 5 K/min gives the measured curve Tempered at 129 C, cooling from 160 to 40 C with 5 K/min. Second heating from 30 to 160 C at 5 K/min gives the measured curve Deleted Thermal.

Atmosphere: Interpretation

Quiet air In the isothermal pretreatment crystal segregation appears: some amorphous regions can form crystallites with a melting point sufficiently high to lead to a melting gap at this temperature ("memory effect"). After complete melting, the thermal history is again cleared. No numeric evaluation is needed here. Naturally, the melting gaps can be evaluated as, e.g. onset or the melting behavior assessed with the conversion curve and table. The DSC melting curve depends on the thermal history of polyethylene. The melting gap is often used to check the conditioning temperature of e.g. PE high voltage cables. Complete melting of PE deletes the thermal history and is a prerequisit for the comparison of different PE qualities.
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Evaluation

Conclusion

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Engineering Polymers
Samples Polyetheretherketone, PEEK Victrex 450G, injection moulded, Polyethersulfone, PES Victrex 200P, injection moulded, Polytetrafluoroethylene, PTFE Film supplied in the sample set of the Arbeitsgemeinschaft Deutsche Kunststoff-Industrie Measuring cell: Pan: Sample preparation: DSC821e with air cooling Aluminum standard 40 l, lid pierced Disk cut from injection moulded parts or punched of film Heating from 30 to 400C at 20 K/min Nitrogen, 50 ml/min

Conditions

DSC measurement: Atmosphere:

Interpretation

PES is entirely amorphous and just shows the glass transition (one of the highest of all organic matter!). At room temperature PEEK and PTFE are semicrystalline. They cannot be frozen in the glassy state by quenching from melt in the sample robot (the mean cooling rate amounts to approx. 3000 K/min when the robot places the hot pan on the cold turntable). The chosen representation of the DSC curves in W/g and with automatic blank subtraction is directly proportional to the specific heat capacity of the samples. The proportionality constant is the heating rate of 0.333 K/s. Thus, the heat capacity of PTFE surprisingly amounts to approx. 0.5 J/gK at 60C whereas PES and PEEK are in the range of 1 J/gK that is typical for organic matter. The high sensitivity (low signal noise level) of the DSC821e allows problem free determination of small effects that occur especially with highly filled polymers.

Conclusion

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Elastomer analysis in the TGA850

Horst Wyden, Georg Widmann
aluminum oxide crucibles. Without a and the sample changer removes sample changer, rubber samples can the ashed sample. At the same also be placed directly on the sample time, the automatic evaluation Thermogravimetric analysis detersupport. There are two reasons for starts using the evaluation procemines the mass change of a sample the relatively low amount of sample: dures defined in the EvalMacro of subjected to a temperature program Fast reaction and hence in general the method. and a defined atmosphere. The first good separation of neighboring For quantitative TG measurements, derivative of the TG curve, called elastomer steps. a blank curve is recorded beforeDTG, is used for the interpretation of Low amount of depolymerization hand and is automatically subthe reactions of the sample. In the analysis of the main components of elastomers, the classical extraction processes and also the qualitative and quantitative analysis of the elastomer components with IR spectroscopy or gas chromatography have been virtually completely supplanted by the more elegant thermogravimetric rubber analysis. The main components usually determined are: 1. Volatile components, which are driven off between room temperature and approx. 300C. They chiefly comprise added oils and other plasticizers, as well as moisture, solvent residues, monomers and, e.g. stearic acid. Fig.1: Example of an automatically evaluated rubber analysis with 4 2. Content of elastomers, such as steps. Here, the usual representation of a TG curve in percent of the natural rubber and EPDM. Under a sample weight as a function of temperature is selected. nitrogen atmosphere and the usual heating rate of 30 K/min, pyrolysis tracted in the subsequent measureproducts. Elastomers frequently follows between 300 and 550C, dements. This compensates influproduce oily and tacky decomposipending on the chemical structure of tion products which are deposited ences such as a buoyancy change the elastomer molecule. on cool parts and necessitate cleanand flow effects. 3. Content of carbon black by burning from time to time. The automatic step analysis is so ing in air or oxygen (automatic gas After insertion of the sample in the designed that components which switching!). are sufficiently well separated measuring cell (isothermally at 4. Residue: Inorganic fillers (plus 25C), atmospheric oxygen is dis(clear DTG minimum) are autoash). Any CaCO3 loses CO2 at played by nitrogen as early as the matically recorded ("multi limits"). approx. 800C. The stoichiometric temperature equilibration phase. The usually extensively overlapCaCO3 content follows from the This is possible within a short ping volatile components are weight loss. evaluated with fixed temperature space of time as the furnace volume is very low (and as the ballimits. Measurements ance chamber is continuously The DTG peak temperatures (inAn NR/EPDM rubber and an NR/ flection point of the TG curve) purged with nitrogen). The optiSBR rubber with known composition mum heating rate is 30 K/min. characteristic for the identification (see table) were investigated. Sam Gas switching to air occurs at at 30 K/min are: ples with a mass of 4 6 mg were 600C without interruption of the cut out with a sharp knife. dynamic temperature program. At NR: 390C, BR: 445C, In work with a sample changer, they the final temperature of 800C the SBR: 460C, EPDM: 480C are placed in reusable 70 l measuring cell starts to cool down
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Introduction

Formulation

Volatiles: Stearic acid, sulfur and 3,78 accelerators Natural rubber, NR 49,66 EPDM 12,41 Styrene-butadiene Carbon black 31,06 Residue: zinc oxide 3,10

NR/EPDM-rubber, n=5 Formula M 4,42 0,21

NR/SBR-rubber, n=4 Formula M 3,96 0,15 3,56

47,55 13,49 30,81 3,52

0,43 0,12 0,02 0,23

29,22 29,22 35,07 2,92

30,74 27,0 34,88 3,29

0,21 0,22 0,08 0,13

Table, formulas and results in percent.

Fig.2: Overview of the TG and DTG curves of the investigated rubber samples. The ordinate unit is percent per degree Celsius and corresponds to the reaction rate.

n is the number of measurements, M are the mean values, the standard deviations. The first weight step up to approx. 300C corresponds to the vaporization or sublimation of volatile substances such as oil, sulfur and stearic acid, as well as readily volatile components of the elastomers. As a result, the natural rubber content found is somewhat too low. The clearly lowest standard deviation is attained with carbon black as the step in question is completely isolated from neighboring effects. The residue comprises ZnO and the sum of the ash contents of the components.

Conclusions The TGA850 assures high analytical accuracy with minimal labor and a high level of operating convenience. Thanks to the sample changer, the measurements are fully automatic. Even the evaluation of the experimental curves obtained can be performed automatically with the new STARe software. An analysis takes less than 30 minutes (increasing the start temperature to, e.g. 100C would save time).
References [1] G. Widmann und R. Riesen, Thermoanalyse, Hthig, Heidelberg [2] H. Wyden, Kunststoffe-Plastics, 5, 1982

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Selection of experimental parameters for the cp determination with ADSC

Benedikt Schenker, Technical chemistry laboratory, Swiss Federal Institute of Technology, Zurich Tel: + 41 1 / 632 30 59 Fax: + 41 1 / 632 12 22 E-mail: schenker@tech.chem.ethz.ch
Figure 1

DSC system

Introduction ADSC allows simultaneous determination of the heat capacity and thermal events in the sample. Here, a periodic signal, the so-called modulation, is superposed on the conventional, generally linear temperature program: Tp = T0 + bt + Asin(t2/p) where Tp is the program temperature, T0 the start temperature, b the heating rate, A the modulation amplitude, t the time and p the modulation period. In the evaluation, the differential heat signal is split into a cp component and a heat of reaction component (thermal event). The question now arises regarding the "correct" choice of the experimental parameters: sample size, mean heating rate, modulation amplitude and modulation period. As the period of the modulation determines the time resolution and through this together with the mean heating rate of the basic temperature program also the resolution in the temperature range, the aim is to have periods as short as possible. However, the period can not be shortened at will as both the DSC furnace and the sample have a finite thermal conductivity and hence periods which are too short are misrepresented. Figure 1 outlines the falsification, which is manifested as damping (too small an amplitude) and as a phase shift (time shift compared with the excitation signal). The limited ability of the furnace to handle short cycle times is intuitively easy to understand when
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the relatively large mass and expansion of the furnace are considered. However, it is surprising that for substances with a thermal conductivity (0.1 to 1 W/(m K)) in the range of typical polymers, the minimal time is determined by the sample and not by the DSC furnace. In a forthcoming publication [1], the autor describes the simulation of a greatly simplified DSC. In this simulation, the partial differential equation which describes the heat transport in the sample was solved by a finite element analysis. Figure 2 shows a scheme of the simulation. This work has shown that weights of typically not more than 5 mg and cycle times of 2 to 4 minutes are needed for accurate determinations of the heat capacities of polymers.
Sample Reference

thickness 0.3 mm, diameter 4.5 mm and a mass of 27.245 mg. The measurements were performed quasi-isothermally at a temperature of 75C. The ADSC evaluation of the STARe software was used for the evaluation. 4 DSC runs were performed for each frequency with the same crucibles: a no-load curve, without crucible at the sample and reference positions a blank curve with a crucible with lid on the sample side and a crucible without lid on the reference side and a measured curve for both the polystyrene and the sapphire sample in a crucible with lid and a crucible without lid on the reference side. The following heat capacities were calculated from these experimental data:

TR TS TC Heater
Figure 2

TR

TC TS Tf1 Tf2 Tf3 ...

Measurements The heat capacity of polystyrene and sapphire was measured with the ADSC method for different cycle times. The polystyrene samples were cut from a sheet. The sample cuboid had a thickness of 1.34 mm, side lengths of approx. 3 x 3.5 mm and a mass of 12.755 mg. The sapphire sample was a circular disk of

cp(corr): The no-load curve and the blank curve are used for calibration of the DSC cell and for compensation of the cell asymmetry. cp(conv): Only the cell asymmetry is compensated. Results Table 1 and Figure 3 show the results of the individual
9

modulation in the sample finally leads in the evaluation to a value of the thermal conductivity which is too cp (corr) cp error cp (corr) cp error low. Recommendations The simulations and measurements [s] [J/(gK)] [%] [J/(gK)] [%] lead to derivation of the following 20 0.75 -48.9 0.69 -20.2 30 1.00 -31.4 0.78 -10.4 recommendations for the procedure 45 1.17 -19.7 0.85 -1.6 in the determination of the experi60 1.31 -10.0 0.88 1.3 mental parameters: 90 1.37 -6.2 0.89 2.5 With an unknown sample, a 120 1.38 -5.5 0.88 1.2 traditional measurement must first be 180 1.42 -2.3 0.89 2.2 performed. This measurement shows 240 1.43 -1.6 0.86 -0.9 the extent of the effects important for the determination of the mean Table 1: Measurement results heating rate and supplies values for measurements for the different cycle conductivity. The results for sapphire c for verification of the measured p times. It can clearly be seen that the in Table 1 show that the DSC values of the ADSC method. relatively thick 1.3 mm polystyrene furnace can readily propagate the sample even with relatively long modulation down to a period of 30 Sample periods shows a cp value that is seconds. Use samples as flat as possible obviously too low. The agreement Figure 3 also clearly shows the having a large contact surface with between the simulation and the effect of the correction by the nothe crucible. measurements is satisfactory. The load and the blank curve when
Period Polystyrene, = 1.09 W /(mK) Sapphire, = 34.7 W /(mK)
1.5 1.4 1.3

* * *
x

x *

x *

Heat capacity [J/(gK)]

1.2 1.1 1 0.9 0.8 0.7 * 0.6 x 0.5

*
x

Sample weight For substances with a moderate thermal conductivity of 0.1 to 1 W/(m K) of typical polymers, even for flat samples no more than approximately 5 mg should be weighed in. Accurate weighings require an accurate (micro) balance. A weighing error of 0.1 mg means a relative error of at least 2%. Period Sufficiently long periods should be used. 60 seconds appear to be the lower limit for polymers even with favorable sample geometry and 5 mg sample weight. For good heat conducting samples, modern DSC furnaces allow markedly shorter measurement times. The measurements for sapphire show that even for cycle times of 30 seconds reasonable results can be obtained. If possible, the results should be verified by the conventional cp determination. Figure 5 shows the maximum sample thickness for different cycle times which allows the determination of cp with a relative error of 2%. The characteristic parameter which describes the
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50

100

150 200 Period time [s]

250

300

Figure 3
differences can be explained by the fact that the simulation is based on the assumption that the heat is transferred only via the base area of the sample and not by the other surfaces. As in the actual measurement the heat is also transferred by the other surfaces, however, this leads to a lower influence of the thermal
10

cp(corr) is compared with cp(conv). An additional sapphire run is not needed. Figure 4 shows the calculated temperature from the simulation for the polystyrene sample at a cycle time of 45 seconds. The inhomogeneous temperature distribution is clearly visible. The pronounced damping of the

Figure 4

The effects are thus smeared over a period. For a high resolution in the temperature range, preferably low mean heating rates should thus be selected. On the other hand, low mean heating rates lead to correspondingly long experiment times and to low heat generation rates of the thermal events in the sample. The results obtained at a particular mean heating rate should therefore be verified by measurements with other mean heating rates. The mean heating rate should be chosen so that during an event (e.g. a glass transition) around 6 cycles occur. Here, also ensure that the amplitude selected is not so large that the temperature range of the event is already totally exceeded in the initial cycles. Heating rate The selection of a suitable mean heating rate is determined by many factors. The evaluation for the cp determination always takes into account all values within a period.
2

Sample thickness [mm]

effects of heat conduction is the thermal diffusivity a=l/(rcp). a is 110-4 m2/s for aluminum, 910-6 m2/s for sapphire, 810-7 m2/s for quartz glass and 110-7 m2/s for polystyrene. The importance of flat samples and large cycle time is clearly apparent. Modulation amplitude The size of the modulation amplitude must be selected so that the periodic temperature changes do not have any great influence on the processes occurring in the sample. Amplitudes from 0.5 to 1 K have proved their worth in practice. However, it should be ensured that the maximum cooling rate of the furnace is not reached. bmin = b - A2/p >> bcooling system In the present measurements, the amplitudes for the measurements with cycle times of less the 90 seconds were so reduced that a maximum cooling rate of approx. 5 K/min was not exceeded. The maximum possible cooling rate of the DSC furnace used was approx. 15 K/min under the conditions employed.

References [1] B. Schenker, F. Stger, Influence of the Heat Conductivity on the cp Determination by Dynamic Methods, Thermochimica Acta, 1996, submitted for publication.

Period duration: 240 180 120 90 60 45 30 20

1.5

0.5

0 10-8

10-7 Thermal diffusivity [m^2/s]

10-6

Figure 5

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Exhibitions/conferences
ICTAC Het Instrument GEFTA/AFCAT/STK Ilmac 96 August 12 16, 96 October 7 10, 96 Sept. 23 26, 96 Nov. 19 22, 96 Philadelphia (USA) Utrecht (NL) Freiburg im Brsg. (D) Basle (CH)

TA customer courses and seminars (CH)

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

TA information days and training courses (USA)

Please contact your local instrument specialists or R. Truttman Phone 1 800 METTLER (63 88 537) 88 21 or fax 1 609 448 47 77 If you have any questions concerning other meetings, the products or applications, please contact your local METTLER-TOLEDO dealer. Internet: http://www.mt.com Editorial office Mettler-Toledo AG, Analytical Sonnenbergstrasse 74 CH-8603 Schwerzenbach, Switzerland Phone ++41 1 806 73 87 Fax ++41 1 806 72 60 E-mail: joerimann@ana-ta.mt.com U. Jrimann, Dr. B. Benzler, Dr. J. deBuhr, Dr. R. Riesen, G. Widmann Layout and production: Promotion & Documentation Schwerzenbach G. Unterwegner ME 51 709 584

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