USER COM

Information for users of METTLER TOLEDO thermal analysis systems

December 1995

Dear customer
Many thanks for the confidence you have shown in us this year. It is a pleasure for us to be in regular contact with you as this continually leads to new improvements in our products. Once again, we can inform you of new products in addition to interesting application examples. May we also urge you to use User Com as a platform for the exchange of experiences with other persons interested in thermal analysis. To ensure we can give even greater consideration to your wishes, please let us know your opinion of User Com.

Selection of the heating rate

TA-TIP
With the selection of the heating rate you can facilitate or complicate the interpretation of the measurement. 1. Temperature difference between sample and temperature sensor As the temperature sensor does not measure the temperature directly in the sample, but only in the vicinity of the sample, a temperature difference between sample and temperature sensor appears with every thermal analysis measuring cell. This depends on the heating rate and the temperature. If it can not be calibrated, the temperature results must be corrected by hand when the heating rate differs from the calibration. With Mettler you can calibrate this heating rate dependence (tau lag calibration). In accord with the physics, the onset values become practically identical even with different heating rates (Fig. 1: Indium melting peaks).
Indium with different heating rates 18.12.1995 07:30:53

Contents TA-TIP: Selection of the heating rate NEW in sales program New DSC821e module New cooling option (intra cooler) Automatic crucible opening before the measurement Applications New possibilities with ADSC cp Measurement with TGA/SDTA Curing behavior of adhesives
Fig. 1: Indium melting peaks at different heating rates

METTLER TOLEDO TA 8000

USER COM December 95

You thus save yourself the manual result corrections with their associated errors. If you wish to use your module over a wide temperature range, we advise you to perform the tau lag calibration with several different substances so that the system can also take the temperature dependence of this correction function into account. In the case of chemical reactions, the onset temperature is naturally not constant at different heating rates (however, the difference between the onset temperatures would be even greater if the tau lag calibration were wrong or if it were not carried out). 2. Increase in the sensitivity with increasing heating rate As you have certainly already discovered, melting peaks, for example, become larger with increasing heating rate. You can thus amplify minor effects very simply by selecting a higher heating rate (Fig. 2: Glass transition).

3. Improvement in the resolution with decreasing heating rate For the peak separation, a low heating rate and a low signal time constant is necessary. With the ceramic sensor you have a rapidly reacting sensor available (signal time constant approx. 3 s with the standard aluminum crucible). To separate effects cleanly, the time between them should be approx. 5 time constants. The deflection drops back to 1% of the original baseline. If, for example, your effects are separated by around 5C, you can calculate the maximum heating rate at a signal time constant of 3 s as follows: 5C/5 * 3 s) * 60 s/min = 20C/min (Fig. 3: Peak separation) 4. Blank value correction The shape of the blank curve also depends on the heating rate. With the TSW870, the database automatically searches for the latest blank curve measured with an identical heating rate and performs an online correction during the measurement.

Fig. 2: Glass transition

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

Fig. 3: Peak separation of a liquid crystal

USER COM December 95

The new DSC module DSC821e

The DSC821e was introduced in January as a successor to the DSC820 module and is based on leading edge technology. The module is available in two temperature versions. The modular concept of the DSC820 has been extended further so that we can now give even better consideration to your specific wishes. Countless system combinations are possible with the old and the new options. We are convinced that we can now offer you exactly the right solution. You pay only for what you actually need. But the future is still open to you. You can expand your instrument at any time with additional options to meet your needs.

The properties of the DSC821e module at a glance: Large measurement range High resolution Wide temperature range High temperature accuracy Excellent peak separation Modular construction Automatable with sample changer Further options 350 mW at RT 0.7 W at RT -150C max. 500/700C 0.2C low signal time constant (3 s) open for the future 34 samples Automatic sample chamber opening Gas controller Control of peripherals Power output switched by software Local module operation Liquid nitrogen (-150C) Intra cooler (-65C), cryostat (-50C) and air cooling (standard)

Cooling systems

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

METTLER TOLEDO TA 8000

USER COM December 95

Automatic crucible opening before the measurement

With the DSC820/821e and the TGA850, the sample changers can now be equipped with an accessory that automatically opens the crucible shortly before the measurement. A mechanism attached to the gripper punctures the crucible on the sample turntable. During the wait time on the sample turntable, the sample thus exchanges no moisture with the surroundings. This is a great advantage especially with the readily volatile sample fractions found in the pharmaceutical, paint and food industries. At present two types of crucibles suited to this type of measurement are available: The present standard aluminum crucible 40 l (DSC) and the new aluminum 100 l crucible (DSC and TGA). The following new crucible sets are available: Standard aluminum crucible 40 l, set of 160 without lid Standard lid, set of 160 Membrane lid, set of 160 (for the automatic opening) Existing customers of a DSC820 or TGA850 module have the following upgrade possibilities: Conversion kit for the (DSC) sample changer Calibration crucible Needles (3 types) Drive shaft Crucible holding-down ring Conversion kit for the (TGA) sample changer Calibration crucible Needles (3 types) Drive shaft Crucible holding-down ring Sample turntable type 1 (7.8 mm) Gripper type 1 (7.8 mm) Crucible holder (weighing pan plus deflector)

TGA850 specific heat from the SDTA curve?

G. Widmann Several users have asked us whether at least a semiquantitative measurement of the specific heat from the SDTA signal is possible. As the temperature function of the calorimetric sensitivity is not (yet) known, only the sapphire crucible method can be used. As the cp temperature function of sapphire is known, use is made of a standardization employing a sapphire measurement corrected by the blank curve. The software used the rule of three to calculate the specific heat from the sample measurement corrected by the blank curve: cp = cpSap mSap SDTAProbe / (mProbe SDTASap) The following Figure (Fig. 5) shows how this is achieved.

Abb. 5 cp Messung mit TGA 850

In the superimposed coordinate system you can see the sapphire and the sample SDTA curves (both corrected by the blank curve). The
4

the unit Js/gK must therefore be divided by the heating rate in K/s to obtain the result in J/g (the next software version will also include integration with respect to the abscissa). The circuitous route via the cp deterEnthalpy changes As you know, enthalpy changes with mination with the sapphire method thus allows at least semiquantitative DSC curves are calculated by intecalorimetric measurements. You gration of the heat flow with time. should use the Pt crucible for such By analogy, heat effects can be determined by integration of the spe- measurements, when possible with lid. cific heat with respect to temperature. However, version 3.01 of our software always integrates with respect to time. The result obtained in sample used was a quartz with its solid-solid transition at around 570C. The calculated cp curve of quartz is shown in the large coordinate system.
USER COM December 95

Alternating differential scanning calorimetry, ADSC, opens up new possibilities

The other part is called the latent heat flow. After the stabilization time, the ADSC measurement signal of each segment is proportional to the heat capacity of the sample. The software connects the points of the measured curve at the end of each heating segment to the lower envelope curve and those at the end of the cooling segments to the upper envelope curve. Half of the difference between the two envelope curves corresponds to the sensible heat flow. Cp changes appear with the following effects: Glass transition of amorphous substances Cold crystallization Chemical reactions (the reactants do not have the same heat capacity as the products formed). The additional latent heat flow appears with heat effects in both the heating and cooling phase. The mean value of the two envelope curves thus corresponds to the latent heat flow.

Fig. 6: Section from an ADSC measurement. The top part shows the alternating temperature program. The corresponding startup deflections are shown on the associated ADSC curve. After approx. 20 min., a heat effect starts to shift both envelope curves upward.

Dr. B. Benzler, G. Widmann In DSC, the heat flow of the sample under investigation is usually measured at a constant heating or cooling rate. High heating and cooling rates 10 K/min and higher have the advantage of high measurement sensitivity (large peak), however, this is associated with low resolution relative to the temperature axis. At low rates, on the other hand, the conditions are the opposite: virtually invisibly small peaks which are often very well separated. ADSC with its periodic temperature program combines the advantages of both measurement modes: High sensitivity thanks to high instantaneous heating rate High temperature resolution thanks to low average heating rate The temperature program of ADSC comprises a periodic succession of short, linear heating and cooling phases. The heating or cooling rates lie between 2 and 5 K/min. For a heating measurement the final temperature of the cooling phase is higher that the start temperature of the
USER COM December 95

previous heating phase by a small amount thus leading to the low, average rate: The measured heat flow comprises fractions which arise from the heat capacity Cp and those due to physical transformations or chemical reactions. The Cp part is thus also called sensible heat (specific heat is synonymous with sensible heat).

Fig. 7: ADSC curve of 20.425 mg PET in the temperature range 40 to 140C. Each heating segment increases the temperature by 4C with an instantaneous rate of 3C/min. The subsequent cooling segment lowers it at the same rate by 3C. A period thus lasts 2 min. and 20 s. The mean heating rate is 1C/2.33 min = 0.43C/min. The two envelope curves needed to calculate the curves in Fig. 8 are also shown.

This allows separation of certain latent effects from cp changes: Enthalpy relaxation peak during glass transition Cold crystallisation in the heating of supercooled melts Crystallization of melts during cooling Chemical reactions Vaporization of volatile substances (drying)

Such effects are also called nonreversing. More problematic are reversible transformations such as melting and crystallization; the crystals which have just started to melt on attainment of the melting point would immediately crystallize in the following cooling segment. To prevent this, in such cases isothermal holding times are pro-

grammed instead of cooling phases. The separation of the ADSC heating curve into the sensible and latent heat flow is shown in Figure 8 using the example of polyethylene terephthalate, PET. The usual DSC heating curve would falsify the glass transition owing to the simultaneous relaxation peak. Moreover, the cp change of the cold crystallization would scarcely be visible (Fig. 9). The separated curves can be evaluated with the software in exactly the same manner as measured curves. The separation can also be achieved by the optional Fourier analysis. (In this case, the phase shift appears as a curve.)

Summary Compared with classical DSC, the ADSC measurement technique in combination with the TSW870 TA software offers the following advantages: High resolution of the processes associated with heat effects thanks to low average heating rate. The measured temperatures are near the equilibrium values. High sensitivity of the measurement signal through relative high instantaneous heating and cooling rate. Separate representation of sensible and latent heat flow. However, there are also a few disadvantages: Additional parameters in the method development widen the range of selection possibilities. Longer measurement times owing to the low average heating rate. Standard methods require constant heating rates.

Fig. 8: Two endothermic peaks (enthalpy relaxation) during the glass transition at 70C as well as the exothermic crystallisation peak at 110C appear on the curve of the latent heat (mean value of the envelope curves). The curve of the sensible heat (half the difference between the envelope curves) shows the corresponding Cp changes.

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

USER COM December 95

Model-free kinetics
Dr. J. de Buhr The launch of the new software version also saw the introduction of the model-free kinetics in the last issue of User Com. As numerous measurements have shown, in most cases these new model-free kinetics allow a considerably more accurate prediction than the traditional model concepts, even in the case of complex or multi-stage reactions. Only three or more dynamic measured curves (recorded using DSC or TGA) are needed to analyse the dynamic or isothermal behavior of a reaction. The activation energy E() is calculated as a function of the conversion . With simple reactions, this E() is comparable with the classical activation energy Ea, but its profile allows additional information on the complexity of a reaction to be gained. The curing of a 2-component resin was recorded at heating rates of 2, 5, 10 and 20 K/min (1. Dynamic curing measured). The associated activation energy E(a) is calculated automatically (3. Activation energy calculated). For comparison, the kinetic model of the nth order was used, with the following parameters resulting for a heating rate of 5 K/min: ln (ko) = 88, Ea = 267 kJ/mol and n = 1.76. These two kinetic data records were used to simulate the isothermal curing at 60C and compare it with the curve actually measured. (4. Isothermal conversion at 60C). It is clear that the model-free kinetics can describe the behavior very much better than the nth order kinetics.

Fig. 10: Curing of a 2-component resin

The DSC analysis of a special adhesive from the automobile branch shows the rapid setting-in of curing, which is manifested in a very steep reaction peak (1. DSC curves measured). The complexity of this reaction also becomes apparent in the analysis of the activation energy E(), which assumes very high values at the start of the reaction (2. Activation energy calculated). Even with this complex reaction, the model-free kinetics allow simulation of the dynamic curing at different heating rates as the comparison between the simulated and measured curves shows (3. Simulated curves). The relation between conversion, time and temperature can also be shown in tabular form and/or graphically (4. Iso-Conversion).

Fig. 11: Curing of a special adhesive

USER COM December 95

Exhibitions/conferences
Pittsburgh Conference Forum Laboratoire Analytica (hall 18/stand B14) Instrurama ICTAC Het Instrument GEFTA/AFCAT/STK Ilmac 96 March 4 7, 96 April 1 5, 96 April 23 26, 96 June 2 7, 96 August 12 16, 96 October 7 10, 96 Sept. 23 26, 96 Nov. 19 22, 96 Chicago (USA) Paris (F) Mnchen (D) Brussels (B) 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 (French) May 7 9, 96 Greifensee (CH) TA customer course (German) May 21 23, 96 Greifensee (CH) TA customer course (English) May 29 31, 96 Greifensee (CH) TA customer course (German) Nov. 12 14, 96 Greifensee (CH) TA customer course (English) Nov. 19 21, 96 Greifensee (CH)

Lab Talk advance notices 96 (CH)

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

TA information days and training courses (USA)

Please contact your local instrument specialists or R. Truttman Phone 1 800 METTLER (63 88 537) 88 21 or fax 1 609 448 47 77 If you have any questions concerning other meetings, the products or 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.mtg.mt.com U. Jrimann, Dr. B. Benzler, Dr. J. de Buhr, Dr. R. Riesen, J. Widmann Layout and production: MCG MarCom Greifensee ME 51 709 521