Commercial thermal analysis instrumentation

Perhaps the most important advance in commercial thermal analysis instrumentation during the past 10-12 years has been the use of microprocessors and/or dedicated microcomputers to control the operating parameters of the instrument and to process the collected experimental data. This innovation is by no means unique to thermal analysis instrumentation alone since these techniques have been applied to almost every type of analytical instrument. Unfortunately, the automation of thermal analysis has not become a commercial reality. Complete automation is defined here as automatic sample changing, control of the instrument, and data processing. Such instruments were first described by Wendlandt and co-workers in the early 1970s (See Chapters 3 and 5) although they lacked microprocessor control of the operating conditions. 

While TGA provides useful data when a mass change is involved in a reaction, we have seen that many reactions do not have a change in mass associated with them. The use of both TGA and DTA or TGA and DSC provides much more information about a sample than either technique alone provides. There are several commercial thermal analysis instrument manufacturers who offer simultaneous combination systems, often called simultaneous thermal analysis (STA) systems. Simultaneous TGA-DTA and simultaneous TGA-DSC instruments are available. Instrument combinations cover a wide temperature range and come in both analytical sample size (1-20 mg)... 

Commercial thermal analysis instrumentation is relatively new, a product of the last four decades or so. Mass production of TA instruments started in the early 1950s. From then to the 1970s, several major TA instruments were marketed, and some of them are still manufactured even today. This was the... 

A variety of techniques have been used to determine the extent of crystallinity in a polymer, including X-ray diffraction, density, IR, NMR, and heat of fusion [Sperling, 2001 Wunderlich, 1973], X-ray diffraction is the most direct method but requires the somewhat difficult separation of the crystalline and amorphous scattering envelops. The other methods are indirect methods but are easier to use since one need not be an expert in the field as with X-ray diffraction. Heat of fusion is probably the most often used method since reliable thermal analysis instruments are commercially available and easy to use [Bershtein and Egorov, 1994 Wendlandt, 1986], The difficulty in using thermal analysis (differential scanning calorimetry and differential thermal analysis) or any of the indirect methods is the uncertainty in the values of the quantity measured (e.g., the heat of fusion per gram of sample or density) for 0 and 100% crystalline samples since such samples seldom exist. The best technique is to calibrate the method with samples whose crystallinites have been determined by X-ray diffraction. 

This chapter attempts to summarize the important applications of digital, and, in certain cases, analog computers to thermal analysis instrumentation. No attempt has been made to make it comprehensive in scope, due to the voluminous literature on this subject. Instead, it is hoped that the discussion will provide a background on the general subject of computerization of TA techniques and an insight into what to expect from commercially available computer-assisted instruments. The latter subject changes at very short-time intervals due to the rapid advances in the technology of small computers. 

Due to the rapid changing technology in microcomputers and microprocessors, data and control systems have evolved rapidly a life time of 3-4 years is about the maximum for such a system. Thus, only the most current computer system will be described here for a particular type of thermal analysis system. No attempt will be made to give details on the software programs in use these can be obtained from the commercial vendor of the system, if desired. Almost all the commercially available thermal analysis instrumentation employs a microprocessor for operating system control or a microcomputer for data processing. Either a proprietary or a commercially available microcomputer is employed to process the experimental data into conventional thermal analysis plots or to perform more sophisticated kinetics or purity determination calculations. 

With Figs. 4.4 to 4.6, six different, commercial, advanced differential thermal analysis instruments are introduced. They were picked because of the change in design from instrument to instrument. This selection by no means covers all available commercial equipment. Only the most prominent types of... 

The purpose of differential thermal systems is to record the difference in the enthalpy changes that occurs between the reference and the test sample when both are heated in an identical fashion. Several publications are available concerning the theoretical aspects and applications of various thermal analysis techniques, including the DSC [71-74]. Commercial instruments are available from a number of companies including Perkin-Elmer, TA Instruments, Toledo-Mettler, SET ARAM, Seiko, and Polymer Laboratories. 

DSC and related methods (differential thermal analysis, DTA) are of great practical importance. Therefore, one finds highly sophisticated commercial instruments for a variety of applications. DTA has been combined with in-situ emf and Knudsencell measurements. The interested reader is referred to the special literature on this subject [M.E. Brown (1988)]. 

Interest in the use of calorimetry as a routine diagnostic or analysis tool has gained significant momentum only in the last 50 years. This interest has lead to the development of popular procedures such as differential thermal analysis (DTA) and differential scanning calorimetry (DSC). A wide variety of solution calorimetric techniques exist today. These techniques include thermometric titration, injection and flow emhalpimetry. The major growth of commercial instrumentation for calorimetry has occurred to address applications in routine analysis and the rapid characLerizaiion of materials. 

Dynamic testing DMTA, DMA, torsional braid analysis (Enns and Gillham, 1983) is first used as a thermal analysis method to detect the transitions, using dissipation peaks. Certain commercial DMTA instruments have a relatively low accuracy in measuring forces and/or strains. In contrast, they give relatively accurate values of the damping factor tan 5, so that dissipation spectra tan 8 = f (oo, T), are very useful analytical tools. 

Thermal analysis involves observation of the usually very delicate response of a sample to controlled heat stimuli. The elements of thermal-analysis techniques have been known since 1887 when Le Chatelier used an elementary form of differential thermal analysis to study clays (4), but wide application did not come until the introduction of convenient instrumentation by du Pont, Perkin-Elmer, Mettler and other sources in the 1960 s. Currently, instrumentation and procedures are commercially available for DTA, DSC, TGA, TMA, and a number of so-called hyphenated methods. Several methods are currently under study by ASTM committees for consideration as to their suitability for adoption as ASTM standards. 

The other common category of calorimetry is differential methods, in which the thermal behavior of the substance being measured is compared to that of a reference sample whose behavior is known. In differential scanning calorimetry (DSC), the instrument measures the difference in power needed to maintain the samples at the same temperature. In differential thermal analysis (DTA), the samples are heated in a furnace whose temperature is continuously changed (usually linearly), and the temperature difference between the sample and the reference sample as a function of time can yield thermodynamic information. DSC and DTA are most commonly used for determining the temperature of a phase transition, particularly for transitions involving solids. In addition, DSC experiments can yield values for the enthalpy of a phase transition or the heat capacity. Commercial DSC and DTA instruments are available. 

Two other important milestones in the development of the modern thermobalance occurred in 1958 and 1964. A multifunctional instrument, called the Derivatograph. was described by Paulik 35) et al. in 1958. The instrument could record not only the TG curve, but also its first derivative (DTG) and the differential thermal analysis jDTA) curve. In 1964. Weide-mann (3) described the Mettler system, which was perhaps the most sophisticated thermobalance ever commercially available. This system is described in detail by Wiedemann and Bayer (8). 

The main changes in this edition are as follows (1) Numerous new applications of thermal analysis techniques have been added to the chapters on TG, DTA, DSC, EGD/EGA, and others. (2) Other techniques, not used as often, are described in greater detail, such as EGD/EGA, TMA, DMA. thermoptometry, thermoelectrometry, thermosonimetry, and others. (3) The chapter on EGD/EGA has been rewritten, as has the chapter on miscellaneous techniques. (4) The determination of purity by DSC has been rewritten. (5) Commercially available instruments have been briefly described for each technique, including the application of microcomputers to many of these instruments. 

Ail chapiei s have been revised and updated with recent references to the literature of analytical chem-i.stry. Among the chapters that have been changed extensively are those on mass spectrometry (Chapters 11 and 20). surface characterization (Chapter 21). voitammetry (C hapter 2.s), chromatography (Chapters 26 and 27). and thermal analysis (Chapter 31). Tiiroughout the book, new and updated methods and techniques are described, and photos of specific commercial instruments have been added where appropriate. Some of these modern topics include plasma spectrometry, fiuores-cence quenching and lifetime measurements, tandem mas,s spectrometry, and biosensors. 

The aim here is simply to present an overview of the various features on offer. The range of instruments extends from differential scanning calorimeters in a suitcase for on-site use to spatially resolved micro-thermal analysis equipment for samples as minute as 2 x 2 fim. Between these rather extreme examples there is a wide choice of commercial DTA and DSC equipment which allows samples to be studied at temperatures ranging from — 150°C to about 1600°C. For higher temperature measurements (above 1600°C) the equipment becomes increasingly more specialised. The detailed specification of equipment is often difficult (sometimes impossible ) to decipher - there appears to be no common practice between manufacturers. Information can best be obtained by raising questions directly with the manufacturers. Even so, hands-on experience is to be recommended when choosing equipment. 

---