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Chapter 1

Introduction to Recent Advances, Techniques and Applications of Thermal Analysis and Calorimetry

Michael E. Browna and Patrick K. Gallagherb,     aChemistry Department, Rhodes University, Grahamstown, 6140 South Africa; b409 South Way Court, Salem, SC 29676, U.S.A.

1 The Handbook of Thermal Analysis and Calorimetry

Details of this well-established series are given at the following website: http://www.elsevier.com/wps/find/bookseriesdescription.cws_home/BS_HATAC/description

The Series Editor is Emeritus Professor Patrick Gallagher.

VOLUME 1 - PRINCIPLES AND PRACTICE (Edited by Michael Brown) was published in 1998;

VOLUME 2 - APPLICATIONS TO INORGANIC AND MISCELLANEOUS MATERIALS (Edited by Patrick Gallagher and Michael Brown) was published in 2003;

VOLUME 3 - APPLICATIONS TO POLYMERS AND PLASTICS (Edited by Stephen Cheng) was published in 2002;

VOLUME 4 - FROM MACROMOLECULES TO MAN (Edited by Richard Kemp) was published in 1999.

Detailed Contents of these four volumes are given in the preliminary pages of this volume.

In the nine years since the appearance of Volume 1 in 1998, the techniques of thermal analysis and calorimetry have naturally advanced and the applications have broadened even further. Excellent surveys of these developments are the bi-annual reviews in the journal Analytical Chemistry, originally compiled by the late Connie Murphy and extended by the late David Dollimore and colleagues [D. Dollimore and S. Lerdkanchanaporn, Anal. Chem., 70 (12) (1998)27-36; D. Dollimore and P. Phang, Anal. Chem., 72 (12) (2000) 27-36.] and now compiled by Sergey Vyazovkin [S. Vyazovkin, Anal. Chem., 74 (2002) 2749-2762; 76 (2004) 3299-3312; 78 (2006) 3875-3886.].

2 The Literature of Thermal Analysis and Calorimetry

In Volume 1 [p 49-72] of this series, Hemminger and Sarge surveyed the literature available at that time. Since 1998 the major additions to the literature include the following.

2.1 Books

E.A. Turi (Ed.), Thermal Characteristics of Polymeric Materials, 2nd Edn, Academic, San Diego, 1997, Vols. 1 and 2.

T. Hatakeyama and F.X. Quinn, Thermal Analysis: Fundamentals and Applications to Polymer Science, 2nd Edn, John Wiley & Sons, Chichester, 1999.

A.K. Galwey and M.E. Brown, Thermal Decomposition of Ionic Solids, Elsevier, Amsterdam, 1999.

P. Haines (Ed.), Principles of Thermal Analysis and Calorimetry, Royal Society of Chemistry: London, 2002.

O.T. Sorensen and J. Rouquerol (Eds), Sample Controlled Thermal Analysis: Origin, Goals, Multiple Forms, Applications and Future, Kluwer, Dordrecht, 2003.

M.E. Brown, Introduction to Thermal Analysis, 2nd Edn, Kluwer, Dordrecht, 2001.

B. Wunderlich, Thermal Analysis of Polymeric Materials, Springer, Berlin, 2005.

G.W. Ehrenstein, G. Riedel and P. Trawiel, Thermal Analysis of Plastics: Theory and Practice, Hanser Gardner, Cincinnatti, 2004.

T. Hatakeyama and H. Hatakeyama, Thermal Properties of Green Polymers and Biocomposites, Kluwer, Dordrecht, 2004.

D. Lörinczy (Ed.), The Nature of Biological Systems as Revealed by Thermal Methods, Kluwer, Dordrecht, 2004.

M. Sorai (Ed.), Comprehensive Handbook of Calorimetry and Thermal Analysis, John Wiley, Hoboken, NJ, 2004.

B.V. L’vov, Thermal Decomposition of Solid and Liquid Substances, St. Petersburg Polytechnic University, Publisher, 2006, in Russian. English edition in preparation to be published by Springer.

2.2 Major conferences and their proceedings

2.2.1 International

1998 7th European Symposium on Thermal Analysis and Calorimetry (ESTAC), Balaton-Füred, Hungary. [J. Kristóf and C. Novák (Eds), J. Therm. Anal. Cal., 56 (1999) 1-1479.]

2000 12th International Congress on Thermal Analysis and Calorimetry (ICTAC), Copenhagen, Denmark. [O. Toft Sørensen and P. Juul Møller (Eds), J. Therm. Anal. Cal., 64 (2001) 1-1339.]

2000 2nd International Symposium on Calorimetry and Thermal Effects in Catalysis, Lyon, France [Thermochim. Acta, 379 (2001) 1-278].

2002 8th European Symposium on Thermal Analysis and Calorimetry (ESTAC), Barcelona, Spain [R. Nomen and J. Sempere (Eds), J. Thermal Anal., 72 (2003) 1-1181].

2004 13th ICTAC, Sardinia.

[A. Schiraldi and B. Marongiu, (Eds), J. Therm. Anal. Cal., 80 (2005) 1-801.]

2004 13th Conference of the International Society for Biological Calorimetry, Würzburg-Veitshöchheim, Germany [Thermochim. Acta, 422(2004) 1-130.]

2004 3rd International Symposium on Calorimetry and Thermal Effects in Catalysis, Lyon, France [Thermochim. Acta, 434 (2001) 1-182].

2006 9th ESTAC in Krakow, Poland.

Forthcoming conferences in this series are: 2008 14th ICTAC in Brazil.

2.2.2 The annual conferences of the North American Thermal Analysis Society (NATAS)

1998 26th NATAS conference, Cleveland, Ohio [Thermochim. Acta, 357/358(2000) 1-334.]

1999 27th NATAS conference, Savannah, Georgia (This conference was cancelled due to a hurricane, but the proceedings, dedicated to David Dollimore, were published in Thermochim. Acta, 367 (2001) 1-455.)

2000 28th NATAS conference, Orlando, Florida

2001 29th NATAS conference, St. Louis, Missouri

[Thermochim. Acta, 396 (2003) 1-234].

2002 30th NATAS conference, Pittsburgh, Pennsylvania

2003 31st NATAS conference, Albuquerque, New Mexico

2004 32nd NATAS conference, Williamsburg, Virginia

2005 33rd NATAS conference, Universal City, California

2006 34th NATAS conference, Bowling Green, Kentucky

Other regional and specialist group conferences have also been held. Medicta 2003, Porto, Portugal [Thermochim. Acta, 420 (2004) 1-180].

2.3 Websites

The offical website of the International Confederation for Thermal Analysis and Calorimetry (ICTAC) is: www.ictac.org

The 40th Anniversary Issue (1965-2005) of ICTAC News contains a wealth of information on the history of ICTAC and its Affiliated Societies.

The THERMAL list-server:

http://www.egr.msu.edu/mailman/listinfo/thermal initiated by Michael Rich at Michigan State University, provides a forum of experts willing to advise on thermoanalytical problems.

3 Nomenclature

The nomenclature of thermal analysis continues to be a controversial and incompletely resolved topic. The system proposed by the ICTAC Nomenclature Committee chaired by W. Hemminger and described in detail by Hemminger and Sarge in Volume 1 [Vol 1, p 1-31] has since been reconsidered by a further Committee and the latest recommendations, which have been approved by the Council of ICTAC and by ASTM, are presented by Rouquerol et al. in Chapter 2 of this Volume. The current Committee has followed the advice of the late Robert Mackenzie in that:

– terminology should be simple;

– abbreviations kept to a minimum;

– names based on particular instruments should be discouraged.

Definition of the field of Thermal Analysis (TA)

Thermal Analysis (TA) is the study of the relationship between a sample property and its temperature as the sample is heated or cooled in a controlled manner.

The nomenclature of Calorimetry is also dealt with in Chapter 2. The basic criterion that the authors use to distinguish different types of calorimeters is on the basis of the heat exchanges between the system and the thermostat. Two broad families result, namely:

Adiabatic calorimeters, where the aim is to avoid any exchange of heat between the system S and the surrounding thermostat T

Diathermal calorimeters, where the aim is, on the contrary, to favour the above heat exchange

4 Recent Advances in Techniques

Amongst the important advances in thermal analysis and calorimetric techniques have been the following.

4.1 Micro-Thermal Analysis

The introduction and development of Micro-Thermal Analysis are described and discussed by Duncan Price in Chapter 3. The atomic force microscope (AFM) forms the basis of both scanning thermal microscopy (SThM) and instruments for performing localised thermal analysis. The principles and operation of these techniques, which exploit the abilities of a thermal probe to act both as a very small heater and as a thermometer, in the surface characterisation of materials are described in detail. The coupling of thermal probes with methods of localised evolved gas analysis by pyrolysis and/or near-field photothermal infrared microscopy is also described.

4.2 Pulsed thermal analysis

The technique, named rather ambiguously as pulsed thermal analysis, is described by Maciejewski and Baiker in Chapter 4. Pulse thermal analysis (PulseTA®) is based on the injection of specific amounts of gases or liquids into the inert carrier gas stream of a thermobalance or differential scanning calorimeter and subsequent monitoring of the changes in the mass and/or enthalpy of the sample and composition of the evolved gases resulting from the incremental amount of reaction between the sample and the injected gas. The method is also particularly suitable, using a gas which does not react with the sample, for quantification of evolved gas analysis by mass spectrometry (MS) or Fourier transform infrared spectroscopy (FTIR). All types of gas-solid interactions can be studied by injecting gases that adsorb on, or react with, the sample. PulseTA® applications are illustrated using examples from various fields such as catalysis and materials science.

4.3 Fast scanning calorimetry

Most calorimeters have problems in achieving high controlled, constant rates on heating and, even more so, during cooling. In Chapter 8. Mathot, Vanden Poel and Pijpers describe and discuss means for producing controlled, fast cooling and heating by way of high-speed calorimetry. The use of a commercially available version of high-speed calorimetry: High Performance DSC (HPer DSC) is described to provide insight into the commonly occurring metastable states of substances, such as polymers and pharmaceuticals, which result from their thermal treatment and which can drastically change their end properties. Phenomena related to metastability include supercooling, amorphization, ‘hot’ crystallization (from the melt), cold crystallization (from the glass state), recrystallization (after melting), annealing, etc., are discussed with examples and the many advantages of HPer DSC are described.

5 Advances in Applications

5.1 Quartz-crystal microbalances

Although quartz-crystal microbalances are not a new invention, they have not been used extensively in thermoanalytical investigations. In Chapter 5, Alan Smith provides a historical background to quartz-crystal microbalances and describes the principles of their operation, before surveying their chemical and biological applications in thermal analysis and calorimetry.

He then discusses quartz crystal microbalance/heat conduction calorimetry, (QCM/HCC), which is a new measurement technology that permits high-sensitivity measurements, in real- time, of the mass changes, the heat generated and the change in loss compliance of nanoscale coatings or films undergoing chemical reaction. The high sensitivities enable the energetics of the formation of a self-assembled monolayer, as well as the thermodynamics of the chemical processes in nanoscale polymer coatings, to be studied.

5.2 Electrical techniques

In Chapter 7, Mano and Dionísio describe how electrical methods, and particularly dielectric relaxation spectroscopy (DRS) and thermally stimulated depolarisation current (TSDS) techniques, play a major role as tools for exploring molecular mobility. DRS enables molecular relaxational processes (both slow and fast) to be studied. For example, the localized motions of glass formers in the glassy state give rise to local fluctuations of the dipole vector that are the origin of the secondary relaxation processes detected by dielectric relaxation spectroscopy, while above, but near, the glass transition, cooperative motions result in a distinguishably different relaxation process (the α-relaxation).

DRS is also valuable for studying the translational motion of charge carriers. These effects are important in inhomogeneous materials such as biological systems, emulsions and colloids, porous media, composite polymers, blends, crystalline and liquid crystalline polymers and electrets. The results of DRS may be complemented by TSDC studies, which provide a way of probing the mobility of dipoles and electric charges over a wide temperature range.

5.3 Heating-stage spectroscopy

In Chapter 6, Frost and Kloprogge, describe the use of various heating-stages coupled with infrared, Raman, energy dispersive X-ray, or X-ray photon spectroscopy. Such techniques strongly complement the results obtained from traditional thermoanalytical techniques and enable the changes in the composition and molecular structure of minerals and materials to be obtained in situ at elevated temperatures.

5.4 Rheology

In Chapter 15, Kok describes how thermal analysis techniques can play a key role in examining the rheological behaviour of crude oils. For crude oil samples with different contents of wax, differential scanning calorimetry, thermomicroscopy and rheometry provide excellent methods of measuring the wax appearance temperatures. These techniques, together with viscometry, can be used to study the flow properties of crude oils below the wax appearance temperature and the effects of the addition of flow improvers.

5.5 Catalysis

Techniques such as TG, DTA or DSC enable the thermal behaviour of a catalyst to be examined as it undergoes heating at a constant rate (or by steps of temperature) and are particularly adapted for studying the decomposition of catalyst precursors or for desorption studies involving poisoned catalysts.

Damjanovic and Auroux in Chapter 11 describe how, by the use of adsorption microcalorimetry, where the sample is kept at a constant temperature while a probe molecule adsorbs onto its surface, values of the enthalpy of adsorption can be determined and valuable insights into the mechanism of adsorption can be obtained.

Very sensitive flow microcalorimeters provide a means of measuring the energy of adsorption as a function of coverage, thus revealing details of the surface heterogeneity and information on the strength and distribution of the different sites on the surface of a catalyst. The chapter gives some illustrations of applications in different fields of catalysis, focusing mainly on redox and acid-base catalysis.

5.6 Nanoparticles

Nanotechnology covers the search for and synthesis of new materials of advanced technology which possess the sizes of nanometres; the determination of their characteristics, and their practical application. This broad and fast-developing topic is tackled by Staszczuk in Chapter 10. Typical nanomaterials include soil mineral components, adsorbents, silica gels, latexes, synthetic zeolites modified by ions, molecular sieves, fullerenes, carbon nanotubes, active carbons, semiconductors, high-temperature superconductors, modified zeolites and adsorbents with deposited proteins, etc. Studies of the surface properties of some of these materials, including determination of their fractal dimensions, using mainly quasi-isothermal (Q-TG) thermogravimetry, are described.

6 Kinetics

The techniques of thermal analysis stimulated an interest in the estimation of reaction kinetic parameters from programmed temperature experiments. Some of this background was covered by Brown and Galwey in Chapter 3 of Volume 1 [Vol.1, Ch.3]. A major advance was the ICTAC Kinetics Project, reported on in Thermochimica Acta [TCA ref]. Participants in the project were supplied with sets of numerical data on which to test their favourite methods of kinetic analysis.

In Chapter 13 of this Volume, Sergey Vyazovkin focuses on the development and application of isoconversional methods of kinetic analysis. This approach has made a major impact on the field of kinetics and allows the kinetic model (or conversion function) to be temporarily eliminated from the analysis of sets of data obtained at different heating rates and hence provides apparent values of the activation energy and the pre-exponential factor. The way in which the activation energy appears to vary with extent of reaction is then a good guide to the complexity of the reaction model. This sort of approach has been adopted by several major manufacturers of thermal equipment. These isoconversional methods (often unwisely referred to as model-free) have been applied with great success to a wide variety of processes including polymerization, copolymerization (curing), crystallization, and relaxation.

7 Additional Topics

A preliminary survey of the Contents of Volumes 1 to 4 (see the Elsevier website) revealed that some topics had, perhaps, not received the attention which they deserved. In an attempt to rectify this, the following contributions have been provided.

7.1 Thermochemistry

In Chapter 14, Roux and Temprado have provided a detailed survey of the many facets of thermochemistry, including the history of the subject, methods of measurement of thermodynamic quantities, calibration of instruments, estimation of accuracy and the application of correction factors. Reference materials are discussed and data bases of thermodynamic properties are described, including an introduction to computational thermochemistry. The chapter concludes with some examples of the solving of thermochemical problems.

7.2 Coordination compounds and inorganics

Chapter 12 by Materazzi is a survey of the thermal analysis literature on coordination compounds and inorganics published in the years 2000-2006 and is limited to the most recent representative publications. Coordination compounds and inorganics are extensively studied for a variety of reasons, including their use as simplified models for understanding the behaviour of the more complex molecules that are involved in biological reactions or that are of biomedical interest.

The conventional thermoanalytical techniques (thermogravimetry TG, differential scanning calorimetry DSC, differential thermal analysis DTA, etc.) can provide fundamental data concerning the thermal behaviour of these substances, but the addition of mass spectrometry (TG-MS) or Fourier transform infrared spectroscopy (TG-FTIR) has permitted the identification of gaseous species evolved during thermal processes.

7.3 Thermophysical properties

"Thermophysical properties’ are defined, in Chapter 9 by Cagran and Pottlacher, as a selection of mechanical, electrical, optical, and thermal material properties of metals and alloys (and their temperature dependencies) that are relevant to industrial, scientific, and metallurgical applications, and this covers a wide range of different material properties obtained by numerous different measurement techniques. The focus in Chapter 9 is, however, on thermophysical properties that are accessible through dynamic pulse calorimetry Other non-calorimetric techniques have been developed but, with the exception of levitation (needed to measure technologically important properties like viscosity and surface tension) have been excluded from consideration.

Three Chapters complement the outstanding review of the thermal analysis and calorimetry of pharmaceuticals by Ford and Willson in Chapter 17 of Volume 4.

7.4 Polymorphism

The identification, structural and thermal characterization of new polymorphs is an important topic in solid-state chemistry and requires a battery of techniques that includes X-ray diffraction and spectroscopic methods, in addition to thermal analysis methods and dissolution techniques to determine solubility trends. Such studies are described by Caira in Chapter 16, as well as more recent theoretical techniques aimed at the prediction of the crystal structures of new polymorphs. Crystal polymorphism is particularly important in pharmaceutical products, so there is an emphasis on this area. Systems displaying solvatomorphism (the ability of a substance to exist in two or more crystalline phases arising from differences in their solvation states) molecular inclusion and isostructurality (the inverse of polymorphism) are also given due attention in this chapter.

7.5 Medical applications

In Chapter 18, Glass attributes the recent increased use of thermal methods in tackling medical problems to the improved sensitivity and usability of the instrumentation, especially differential scanning calorimetry (DSC). Investigations of the thermal properties of human and animal skin have aided understanding of drug penetration of the skin and methods of drug delivery. Isothermal titration calorimetry (ITC) has proved useful in the evaluation of thermal stability and to measure the heat generated in physical and chemical reactions. Knowledge of the effects of alteration of biological systems is not only important in medical research but also in advanced patient-care. The applications of thermoanalytical techniques to determining the thermal behaviour of prosthetics and implants are also discussed.

7.6 Dental materials

Thermal analysis techniques have had only limited use in the study of the various dental materials used for restorative, prosthetic and implant applications. The innovative research by Brantley’s group, using conventional and temperature-modulated DSC (TMDSC) to examine the thermal behaviour of several metallic and polymeric dental materials, is described in Chapter 17 and numerous matters requiring additional research are identified.

8 Quality Control

A very important contribution to the Volume, of interest to all practitioners, is the review, by Burlett in Chapter 19, of the uses of thermal analysis and calorimetry in quality control.

During the production of materials for use by consumers, the nature of the starting materials and their responses to processing and storage conditions must be fully understood. The products must then meet certain criteria to satisfy the user. Quality control (QC), or quality assurance (QA), is the name of the operation conducted to assure that the nature of a material is within certain specifications that are critical for subsequent processing or use. Legal and financial considerations are an important part of the quality control operation. Accreditation systems provide standards of operation covering the quality that must be considered. All these aspects are discussed fully, with examples, and this chapter thus forms a very fitting conclusion to the Volume.

Chapter 2

Developments in Nomenclature

Jean Rouquerol¹, I. Wadsö², T.J. Lever³ and P.J. Haines⁴,     ¹Madirel, Université de Provence-CNRS, Centre de St Jérôme 13397 Marseille Cedex 20, France; ²Chemical Center, Physical Chemistry 1, Lund University, Sweden; ³Trevor Lever Consulting, 1 Hope Close, Wells, Somerset, BA5 2FH, UK; ⁴38 Oakland Avenue, Farnham, GU9 9DX, UK

1 Introduction

The development of a clear, extensive and well-accepted nomenclature can be considered as a sign of good health for any field of science. Scientists need to understand each other precisely and to draw the best from the available literature. Unfortunately, nomenclature can also be considered as a final product which only becomes fully available when the science is mature and when the scientists, after a long period of discussion, finally agree. This is what has happened with calorimetry, in spite of its early start at the end of the 18th century (when Lavoisier coined the term calorimeter [1]). For this reason, it is not possible to provide a single system of nomenclature for calorimetry. In this chapter, after a general introduction to the field of calorimetry, a relatively simple and pedagogical system of nomenclature is provided, and is followed by descriptions of a number of other nomenclature systems used for calorimeters during the past decades. The interest and objective of each nomenclature system is stressed, so as to favour its use in the most suitable context.

By contrast, thermal analysis, which started to be recognized only one century later, developed a broadly accepted system of nomenclature more quickly. This was the result of collective work, conducted in the scope of the International Confederation of Thermal Analysis (ICTA), under the guidance of Robert Mackenzie from 1968 onwards. Once adopted by the Council of ICTA, this nomenclature was published in various papers [2–8] and also in booklets edited by ICTA [2–8]. Most importantly, it was endorsed by IUPAC [2–8] and, also, used as a reference by ASTM.

This thermal analysis nomenclature, which was progressively built up from the existing techniques, has needed to be updated to include more recent techniques and to offer a more definitive and broader frame, able to embrace techniques which still do not exist to-day. This work, which started 15 years ago in the scope of ICTAC (with the second C indicating that it then included calorimetry in its fields of interest), took more time than expected. This was due to the need to introduce changes, to adjust them at an acceptable level for the scientific community and to leave time for a broad, international, exchange of views, including scientists from non English-speaking countries. Such a duration is not abnormal and, in some respect, is even desirable: the role of an international nomenclature committee is to represent, or at least to attentively examine and take into account, if possible, the many viewpoints of scientists. Time spent on collecting these viewpoints, in evaluating them, and in building a consistent ensemble is, in reality, time saved at the end of the process, because this will make the acceptance by the scientific community easier and broader. Under these conditions, the proposed nomenclature becomes a tool really useful for a majority of people, which is the real objective of such an endeavour.

Such an updated system of nomenclature for thermal analysis was finally adopted by the ICTAC Council in August 2006. The corresponding document was prepared in its final form by Trevor Lever and Peter Haines (the Chairman and Secretary, respectively, of the ICTAC Nomenclature Committee). Those who were in charge of the Committee during the years during which the maturation and adaptation of the project took place, include the former Chairman, Wolfgang Hemminger, and the former Secretaries Fred Wilburn, Stefan Sarge and Duncan Price. The full list of members of the Committee for the period 1992-2006 can be found at the end of Section 2.

The present official nomenclature for Thermal Analysis is thus contained in the Report of the ICTAC Nomenclature Committee, which is reproduced (with the permission of ICTAC) in Section 2. In Section 3 a number of extra comments are provided in order to justify, explain or complement the material in Section 2.

After that, the nomenclature in Calorimetry is examined and a detailed nomenclature system, devised for pedagogical purposes, is presented in Section 4, which serves as an introduction to other systems described in Section 5.

Section 6 concludes the chapter with a few general comments about these two systems of nomenclature.

2 2006 ICTAC Nomenclature of Thermal Analysis

2.1 Scope

The scope of this document is to provide scientists working in the field of thermal analysis with a consistent definitions of terms that are commonly used within the field to allow precise communication and understanding. Since the scope of ICTAC also covers calorimetry, a further document dealing with this latter part of nomenclature is planned, once a satisfactory international consensus is reached on this matter.

In considering all the matters of nomenclature, the current Committee has followed the advice of the late Robert Mackenzie in that:

– terminology should be simple;

– abbreviations kept to a minimum;

– names based on particular instruments should be discouraged.

2.2 Intent

This document acknowledges that nomenclature develops – without regulated definition – as the field of thermal analysis develops. Some terms used by authors and scientists rapidly become accepted by the scientific community, even if the term is not consistent with past definitions, science or grammatically correct. However, if such a term is widely used and understood, it is reported here.

2.3 Definition of the field of Thermal Analysis (TA)

Thermal Analysis (TA) is the study of the relationship between a sample property and its temperature as the sample is heated or cooled in a controlled manner.

2.4 Techniques

A technique exists for each property or physical quantity that is measured versus temperature – a summary of some of these are presented below.

2.5 Terminology and Glossary

NOTE: For all the techniques listed here, the terminology defines the property that is measured, and each definition may be completed by adding … as a function of temperature. For example: dynamic mechanical analysis (DMA), n- a technique where moduli are determined as a function of temperature.

adiabatic, adj- indicating that the experiment is carried out so that no heat enters or leaves the system.

atmosphere, n, - the gaseous environment of the sample, which may be controlled by the instrumentation or generated by the sample.

calorimetry, n- techniques where heat is measured as a function of temperature.

combined, adj – the application of two or more techniques to different samples at the same time. This can include thermal and non-thermal analytical techniques.

controlled-rate thermal analysis (CRTA), n- a sample-controlled method where the heating is exclusively controlled by the rate of transformation

controlled temperature program, n – the temperature history imposed on the sample during the course of the thermal analysis experiment.

cooling curve, n - the experimental result of measuring the temperature of the sample as a function of time during cooling. The technique is thermometry, and heating curves are obtained for temperature-time experiments during heating.

derivative, adj – pertaining to the 1st derivative (mathematical) of any curve with respect to temperature or time.

dielectric thermal analysis (DEA), n- a technique where dielectric properties are measured.

differential, adj – pertaining to a difference in measured or measurable quantities usually between a sample and a reference or standard material.

differential scanning calorimetery (heat-flow DSC), n – technique where the heat flow rate difference into a sample and a reference material is measured.

differential scanning calorimetery (power compensation DSC), n – technique where the electrical power difference into a sample and a reference material is measured.

differential thermal analysis (DTA), n – a technique where the temperature difference between a sample and a reference material is measured.

dynamic, adj- a prefix indicating that a parameter changes continuously during the experiment. The opposite of static.

dynamic mechanical analysis (DMA), n- a technique where moduli are determined.

emanation thermal analysis (ETA), n- a special type of EGA where the emanation of previously trapped radioactive gas is measured.

evolved gas analysis (EGA), n- a family of techniques where the nature and/or amount of gas or vapour evolved is determined. The term evolved gas detection (EGD) has also been used where the nature of gas is not determined.

gas flow, n - the passage of gas from one part of the system to another, either by sorption by the sample, evolution from it, or chemical reaction.

high pressure, (HP …), adj – a prefix applied to the technique name to indicate that the pressure of the experiment is above ambient.

Note: As an example a TGA experiment carried out under elevated pressures would be High Pressure Thermogravimetric Analysis (HP-TGA)

isobaric, adj- a prefix indicating the experiment is carried out at constant pressure.

isothermal, adj, - a prefix applied to a technique to indicated that the temperature is maintained constant throughout the experiment

material, n-, the substance which is studied and from which the sample is taken.

micro-, adj,- a prefix used to denote that the technique measures small quantities, either with respect to the amount of sample studied, or with respect to the change in the properties measured.

Note: This prefix has been applied to many thermal methods, and the equipment associated with them, for example micro-balance, micro-reactor, micro-calorimeter and also to the technique itself : micro-thermal, microscopic and the property studied: micro-structural.

Note: The opposite prefix, macro- is also occasionally used.

modulated, adj- a prefix indicating that a parameter changes in a periodic manner during the experiment.

modulated temperature, (MT …), adj, - a prefix applied to the technique name to indicate that a temperature modulation has been applied to the temperature program.

Note 1: As an example a DSC experiment carried out with a modulated temperature program would be Modulated Temperature Differential Scanning Calorimetry (MT-DSC)

Note 2: Other modulated techniques are possible, such as modulated force TMA, modulated rate SCTA etc.

Note 3: The use of the prefix MT is preferred to TM.

photo-, adj, - prefix to indicate that the experiment involves the illumination of the sample or measures the amount of light emitted from a sample. Where possible the wavelength range of the light should be specified.

sample, n- the material under study during the entire experiment (starting material, intermediates and final products) and its close atmosphere. This is equivalent to the thermodynamic system.

sample-controlled, adj – prefix applied to the technique to indicate that a property of the sample is used either continuously or discontinuously to control the sample heating. With no prefix, it is assumed that the experiment is following a controlled-temperature program.

Note: the generic term for all TA techniques making use of such a feedback is Sample-Controlled TA (SCTA), whereas specific names will be of the form Sample-Controlled TGA (SC-TGA) etc.

scan, n- a term used to describe the data produced from a thermal analysis experiment. More correct usage is a thermal analysis curve, or, for a specific technique thermogravimetric curve, etc.

scanning, adj, – a prefix indicating a specified experimental parameter, usually temperature, is changed in a controlled manner.

simultaneous, adj – the measurement of two or more properties of a single sample at the same time.

Note: A hyphen is used to separate the abbreviations of the techniques; for example, simultaneous measurement of mass and heat flow rate (thermogravimetric analysis and differential scanning calorimetry) would be TGA-DSC.

static, adj- indicating a constant parameter during the experiment. The opposite of dynamic

stepwise, adj – prefix indicating discrete, discontinuous changes in an experimental parameter, e.g. force, temperature etc.

tan δ, n – is the dimensionless ratio of energy lost to energy returned during one cycle of a periodic process. For example tan δ = E" / E’, in DMA.

temperature-programmed desorption (TPD), n - EGA using an inert atmosphere or vacuum, in the absence of sample decomposition.

temperature-programmed oxidation (TPO), n - Experiment using an oxidising atmosphere, usually oxygen. Oxidation is monitored by any appropriate technique (EGA, TGA, gas sorption, etc.).

temperature-programmed reduction (TPR), n- Experiment using a reducing atmosphere, usually hydrogen. Reduction is monitored by any appropriate technique (EGA, TGA, gas sorption, etc.).

thermal curve, n – any graph of any combination of property, time, temperature derived from a thermal analysis technique.

Note: thermal curve is a loose abbreviation of the more correct term thermoanalytical curve

thermally stimulated current (TSC), n- a technique where the current from the relaxation of sample polarisation is measured.

thermo-, adj- a prefix indicating the use of changing temperature during the experiment.

thermoacoustimetry, n- a technique where the characteristics of sound waves passing through the sample are measured.

thermoanalytical, adj – of, or pertaining to, thermal analysis.

thermodiffractometry, n- a technique where the X-ray diffraction of the sample is measured.

thermodilatometry, (TD), n- a technique where one or more dimensions of the sample is measured under negligible load

thermogravimetric analysis, (TGA), n- a technique where the mass of the sample is measured.

thermogravimetry, (TG), n- see thermogravimetric analysis, which is to be preferred

thermoluminescence, n- a technique where light emission from the sample is measured.

thermomagnetometry, n- a technique where a magnetic property of the sample is measured.

thermomanometry, n- a technique where the pressure is measured.

thermomechanical analysis, (TMA), n- a technique where the deformation of the sample is measured under constant load.

thermometry, n- a technique where the temperature of the sample is measured.

thermomicroscopy, n- a technique where the optical properties of the sample are observed and measured through a microscope.

thermoptometry, n- a technique where the optical properties of a sample are measured.

thermosonimetry, n- a technique where the sound emitted by the sample is measured.

thermospectrometry, n- a group of techniques where a spectrum of the sample is measured.

torsional braid analysis (TBA), n- a dynamic mechanical analysis technique where the sample is supported on a braid.

2.6 Experimental conditions

The specifics of how the technique is used, additional experimental parameters and constraints should, of course, be reported alongside the data in all published work. It is important to separate the technique (instrumentation) from the way in which it is used (experiment). The make and model number should be included in all reports, papers and studies as well as an experimental section that describes in full all experimental parameters.

Note: For example in a Thermomechanical Analysis (TMA) experiment the sample may be subjected to no force, a constant force, an increasing force or a modulated force – or any combination of the above – during a single experiment. The technique (TMA) has not changed, only the experimental variables for that technique.

The reader is referred to the ICTA publication [9] specific guidelines.

It must also be stressed that it should be normal practice to use the standard IUPAC quantities, units and symbols when reporting any work in thermal analysis. These are listed, more especially, in the IUPAC Green Book [13].

2.7 Symbols used specifically in Thermal Analysis

2.7.1 Symbols for quantities and units

2.7.2 Symbols describing specific events or materials

• In general, symbols for physical quantities should be in italic type, or, if vectors, in bold italic type.

• The symbols for units do not take plural.

• Subscripts should generally be restricted to single letters.

• If the subscript relates to an object or property, it should be a CAPITAL letter:

• If the subscript refers to a phenomenon, it should be lower case:

• If the subscript refers to a specific event, time or point, it should be lower case or figures:

• Changes in extensive thermodynamic quantities X due to an event y should be represented by ΔyX:

• Symbols for the physical state of the material should be put in brackets after the formula symbol:

2.8 Overview and historical matters

This document is concerned with providing definitions of common terms that are used by thermal analysts to report, present and explain their work.

The ICTAC Nomenclature Committee was initiated in 1965 under the guidance of Robert Mackenzie and with the secretarial expertise of Cyril Keattch. This document acknowledges the debt to previous members of the Committee under their succeeding Chairmen, including John Sharp (1984-8), Ed Gimzewski (1988-1992) and Wolfgang Hemminger (1992-2001) who continued the discussions and published their findings as listed in the references.

The task of the current committee has been to rationalise the work of all proceeding committees and to deliver a document that covers current practice in thermal analysis that can be accepted internationally.

Thanks are due to recent members of the Nomenclature Committee listed below for their contributions to the deliberations and to others for the advice received:

2.9 Recent Members of the ICTAC Nomenclature Committee

Roger Blaine (2001-6)

Edward Charsley (2001-6)

P.C. Gravelle (1992-2001)

Peter Haines (1997-2006, Secretary 2003-6)

Wolfgang Hemminger(Chairman, 1992-2001)

Trevor Lever (Chairman, 2001-6)

Marianne Odlyha (1991-2001)

Duncan Price (2001-6, Secretary, 2001-3)

Stefan Sarge (1992-2001, Secretary, 2000-1)

Fred Wilburn (1992-2006, Secretary, 1991-2000)

Don Burlett (2001-6)

Valter Fernandez (2001-6)

B.O. Haglund (1992-2001)

Gerrit Hakvoort (1992-2001)

Takeo Osawa (2001-6)

Michael Reading (1991-7)

Judit Simon (1992-2001)

3 Comments on the 2006 ICTAC Nomenclature of Thermal Analysis

Our comments will be focussed on the general definition of thermal analysis, which has had to be modified over the last 40 years and which has attracted much interest, discussion and even controversy. The following definitions of Thermal Analysis have been successively proposed:

In 1969 [2] the official ICTA definition, later endorsed by IUPAC [11], was:

Thermal Analysis. A term covering a group of techniques in which a physical property of a substance and/or its reaction product(s) is measured as a function of temperature whilst the substance is subjected to a controlled temperature programme

This definition covered what is called to-day temperature-controlled thermal analysis [14] and whose principle is represented in Figure 1(left). Here, the heating control loop uses the sample (or furnace) temperature Tto impose a controlled temperature programme, whereas the physical property X of the substance and/or its reaction product(s) is simply measured as a function of temperature.

Figure 1 Principles of temperature-Controlled (or conventional) thermal analysis (left) and of sample-controlled thermal analysis (right), from [ 14].

The above definition did not embrace sample-controlled thermal analysis (SCTA), which was still in its infancy and on which very few papers had been published at that time. What makes sample-controlled thermal analysis special is that the physical property X (related to the behaviour of the sample) is directly involved in the heating control loop, as represented in Figure 1 (right). The heating-control algorithm can also make use of the sample (or furnace) temperature T, but this is not compulsory, hence the dotted control loop on the right hand of the figure. In such an experiment, there is no pre-determined temperature programme, because the temperature-time profile will depend directly on the – a-priori unknown – behaviour of the sample.

The definition proposed in 1991 in the ICTAC booklet For Better Thermal Analysis and Calorimetry [10] was as follows:

"Thermal Analysis. A group of techniques in which a property of the sample is monitored against time or temperature while the temperature of the sample, in a specified atmosphere, is programmed. The programme may involve heating or cooling at a fixed rate of temperature change, or holding the temperature constant, or any sequence of these.

This definition is more complicated than the first one and, in reality, although proposed to the ICTAC membership, was never officially endorsed by the ICTAC Council. It still does not embrace the case of sample-controlled thermal analysis, although SCTA is referred to in that 1991 booklet, in the form of controlled rate thermal analysis (CRTA).

The above proposal also mixes the role of a definition and that of a recommendation, by stating in a specified atmosphere. It is certainly desirable that the experimenter reports the type of atmosphere surrounding the sample during the experiment, but the absence of such an information does not, of course, put the experiment outside of the scope of thermal analysis. The definition also describes the most common temperature programmes, which involve heating or cooling at a fixed rate of temperature change, or holding the temperature constant, or any sequence of these. This sentence is not really needed in a definition. Its intended purpose was probably to provide examples of common ways to operate, but it unnecessarily restricted the scope of thermal analysis to experiments carried out with certain types of heating.

Then came the definition endorsed in 2006 by the ICTAC Council:

Thermal Analysis (TA) is the study of the relationship between a sample property and its temperature as the sample is heated or cooled in a controlled manner

This definition is shorter than the two previous ones and it corresponds to the general representation of thermal analysis given in Figure 2. The above definition and representation leave the choice of the heating control for the thermal analysis experiment totally open. Such a definition therefore embraces any type of control, present or future, and includes both temperature-controlled and sample-controlled thermal analysis. A major interest of the full official definition given above is that it was built up and accepted by a broad, international, community of scientists who had to make compromises, because at least ten other, slightly different, versions of the definition were sound enough to be accepted. It should be stressed that this definition of thermal analysis clearly excludes from the scope of thermal analysis any totally isothermal experiment. This makes sense, because, otherwise, thermal analysis would embrace any isothermal recording of any physical property of the sample as a function of time, i.e. most experiments in physics and biology! Along these lines, one should restrict the term thermogravimetry to the recording of mass vs temperature. For instance, studying the gaseous corrosion of a metal at 400 °C by following its mass uptake, even if carried out with a thermobalance, is not, according to the definition, a thermal analysis experiment. Therefore, itshould not be referred to as thermogravimetry but, more simply, as gravimetry or, to be more precise, as isothermal gravimetry. Also, one should restrict the term differential scanning calorimetry (DSC) to an experiment where there is effectively a temperature scan (to which the term scanning explicitely refers). For instance, using a standard DSC instrument to study the isothermal behaviour of a living material, or an adsorption or desorption process, should not be considered as carrying out a DSC or thermal analysis experiment. The correct name of this isothermal technique would simply be Differential Calorimetry or Isothermal Differential Calorimetry.

Figure 2 Principle of Thermal Analysis in general, from [ 14]: recording of physical property X as a function of temperature T, whatever the type of heating control.

4 A Convenient Nomenclature for Calorimeters

The classification of calorimeters presented hereafter aims at being simple and clear enough to be relatively easy to teach, learn and remember. This classification was arrived at after a time of maturation of about 35 years. There were several reasons for such a slow maturation. One was the great variety of calorimetric devices developed over the last two centuries, probably due to the labile or evanescent character of heat, so difficult to store, which excited the imagination of many scientists. More than 100 different types of calorimeters can easily be listed. This made it difficult to establish any comprehensive and ordered presentation of the calorimeters, so that the famous Polish thermochemist Swietoslavski could write, in 1933, in his handbook on thermochemistry: There is such a variety of different forms of calorimeters that we must renounce to list them, even hastily [15]. This great variety of calorimeters led to a large number of possible classifications (a number of them are described in section 5), depending on the criteria chosen.

4.1 Basic representation, criteria and categories

A calorimetric device in a simplified form is presented in Figure 3.

Figure 3 Schematic representation of a calorimeter

Here, the system S includes the sample and its container, with which it is in good thermal contact (both of them being at temperature TS). The system S is thermally connected to the surrounding thermostat T (at temperature TT) through the thermal resistance R. Let us point out that the word thermostatdesignates here a surrounding system at reasonably uniform temperature, which is an experimental prerequisite for any measurement of heat; that temperature is neither necessarily constant (like in DSC experiments) nor even controlled (like in the Thomsen or Berthelot calorimeters, cf Section 4.2 hereafter), though at least monitored.

The basic criterion we shall use to distinguish different types of calorimeters will be that of the heat exchanges between system S and thermostat T. This immediately divides the calorimeters into two broad families, namely:

1. Adiabatic calorimeters, where the aim is to avoid any exchange of heat between the system S and the surrounding thermostat T.

2. Diathermal calorimeters, where the aim is, on the contrary, to favour the above heat exchange.

The word adiabatic comes from the greek adiabatos, meaning which cannot be crossed. The word diathermal comes from the greek dia and thermos, meaning through and hot, respectively.

In adiabatic calorimeters, one thus tries to store the heat in the system S, so as to measure it in situ from the temperature change of the system. This temperature change is therefore imposed by the heat produced or absorbed in the system S and is not known a priori.

In diathermal calorimeters, where one tries to exchange most of the heat with the surroundings, the surroundings determine the temperature which can therefore be controlled by the experimenter.

The above adiabatic or diathermal functioning of a calorimeter can be achieved (irrespective of the final efficiency) either by simple design and construction (by means of appropriate thermal conductors or resistors R) or (see below) with the help of electronic control. Hence each of the two families above, can be further divided into two groups, which can be named passive and active, respectively. We therefore end up with four groups of calorimeters:

Adiabatic, passive

Adiabatic, active

Diathermal, passive

Diathermal, active

The above classification is now applied to the real world of calorimeters.

4.2 Passive adiabatic calorimeters

Heat exchange between the system S and the surrounding thermostat T (cf Figure 3) can be lowered at will by using two routes, i.e. either by increasing the thermal resistance R or by decreasing the temperature difference TS - TT. Passive adiabatic calorimeters make use of only the first route, by means of an appropriate thermal insulation. Because an infinite thermal resistance does not exist, there will always be a residual heat leak which will have to be taken into account, usually as a correction term. These calorimeters can therefore also be called, quite appropriately, quasi-adiabatic or semi-adiabatic. During half a century they were often referred to as isoperibol, after the term coined by Kubachevski and Hultgren [16] to stress that, although the system temperature TS varies (due to the thermal phenomenon under study), the surrounding thermostat usually remains at a constant temperature (as suggested from the greek iso and peribolos, meaning equal and surrounding space). Now, this condition of constant surrounding temperature, although frequent, makes the term isoperibol of less general application than the term quasi-adiabatic. Furthermore, the term quasi-adiabatic is more easily understood and self-explanatory, so that it is preferred.

The largest part of this group is made up by calorimeters, which were also called water calorimeters because the sample is in good thermal contact with an amount of water which efficiently collects any heat evolved and limits the resulting temperature change of the system S to a small, but measurable value,. These calorimeters are known under various names, such as the Thomsen reaction calorimeter or the Berthelot calorimeter (Figure 4), or, still, the Ordinary calorimeter (after Swietoslavski) or the Dewar calorimeter (which makes use of the good thermal insulation of a Dewar vessel, like Eucken and Nernst’s calorimeter shown in Figure 5, left).

Figure 4 Two historical calorimeters of the passive adiabatic group: the Thomsen (left) and Berthelot (right) calorimeters

Figure 5 Dewar vessel calorimeter from Eucken, 1909 [ 20] (left) and ultra-fast calorimeter from Adamowsky and Schick, 2004 [ 19] (right).

This category embraces simultaneously very simple and even crude calorimeters, as well as the most accurate tools of thermochemistry, like the Argonne rotating bomb calorimeter, whose inaccuracy can be as low as a few ten-thousandths of the total heat measured, or modern reaction calorimeters whose roots can be found in the one devised by Sunner et al. [17]. It also embraces the ultra-fast calorimeters from Rodriguez-Viejo et al. [18] and from Adamowsky and Schick [19] (Figure 5, right). In the latter, the thermopile is used to assess the instantaneous temperature of the micro-sample, rather than to measure the heat-flow (because the latter quantity is determined with a time-lag inconsistent with the objective of rapidity of the experiment). The heating rate can be as high as 10⁴ K min−1.

4.3 Active adiabatic calorimeters

The specific feature of these calorimeters is that they make use of the second route to lower the heat exchanges, which is to decrease the temperature difference TS - TT. This is achieved by servo-controlling the thermostat temperature TT to follow that of the sample TS. Because it is more feasible to cancel a temperature difference than to build an infinite thermal resistance, these calorimeters, especially because they usually also make use of good thermal insulation, are able to provide excellent adiabatic conditions. For instance, they enable heat to be stored, and hence phenomena to be followed, over periods of weeks. They can therefore be named « true » adiabatic calorimeters.

The first historical calorimeters of this type were manually-operated (see Figure 6). Person, in 1849 decided to cancel the temperature difference TS - TT which he could measure by means of a double-bulb differential thermometer. For this purpose, he made use of a second, external, water bath, at a higher or lower temperature, in which he could partly immerse the water thermostat surrounding the system. He adjusted the depth of immersion by means of the crank visible in the drawing. He called his set-up a cancelled heat-loss calorimeter [21]. This is the first known active adiabatic calorimeter.

Figure 6 The first active adiabatic calorimeters: Person’s, 1849 (left, figure from [ 21]) and Richards’, 1905 (right, figure from [ 22]).

In 1905 Richards proposed a chemical way to achieve the desired temperature increase of the thermostat jacket. The latter was filled with a soda solution into which sulphuric acid was dropped from burettes at the desired rate [22].

Appropriate mixing of warm and cold water was used by Swietoslawski to let the water jacket follow the sample temperature [15] but, later, an automatic cancellation of TS - TT by electrical control and heating was progressively preferred. This is used in modern calorimeters such as the low-temperature calorimeters used to determine heat capacities, like those shown in Figure 7 (calorimeters designed by Westrum [23], Suga and Seki [24], Stølen et al. [25], Gmelin and Rödhammer [26]) or the Accelerating Rate Calorimeters (ARC) used to study spontaneous self-heating and explosion during the storage or processing of new chemicals [27].

Figure 7 Active adiabatic calorimeters now in use: multi-shielded low-temperature calorimeter (left, after [ 31]) and ARC calorimeter (right, after [ 27]).

A few calorimeters have a double active control: in addition to the automatic cancellation of TS - TT by control of the thermostat temperature TT, there is also an automatic cancellation of the temperature difference between the sample and a reference (which also forms part of the system S) by supply of heat to the cooler side. The first control is to provide the adiabatic conditions, whereas the second control is to provide a heat compensation of the phenomenon studied. The measurement of heat is not derived from a temperature increase of the system but from the electrical energy provided for the compensation. This principle was followed by Clarebrough [28], Bonjour [29] and Privalov [30].

4.4 Passive diathermal calorimeters

Passive diathermal calorimeters are those in which good heat-exchange between the system S and the surrounding thermostat T is achieved by good thermal conduction. The sample temperature passively follows, here, the thermostat temperature and, except in transient situations, there is no heat stored in the system S. These calorimeters can also be called, quite correctly, thermal conduction calorimeters.

The most common way, to-day, of measuring the heat exchanged in a passive diathermal calorimeter is to make use of a heat flowmeter (Tian-Calvet, [2–8], Wadsö, [34], Du Pont heat-flux DSC, cf Figure 8).

Figure 8 Three heat-flowmeter calorimeters: Tian-Calvet, 1950, left, after [ 33] Wadsö, middle, after [ 34]and Du Pont DSC, right, after [ 35].

A heat-flowmeter is used in the combination of a diathermal, passive, microcalorimeter with a quartz crystal microbalance, proposed by Smith and Shirazi [36], to study the adsorptive behaviour of samples weighing a fraction of a milligram.

Another way to measure the heat exchanged in a passive diathermal calorimeter is to make use of a phase transformation taking place in the surrounding thermostat. This is the principle of the ice calorimeter devised and used by Lavoisier and Laplace (1783) [37] and of its modification by Bunsen (1870) [38], where the amount of molten ice is no longer determined from the mass of water produced, but from the constriction of the system, followed by the displacement of a mercury index in a glass capillary. Other phase changes proposed for operation at other temperatures are melting of di-phenyl ether to operate around room temperature, and vaporization of liquid air or liquid nitrogen.

Figure 9 Two ice calorimeters: Lavoisier and Laplace, 1783, left, after [ 37] and Bunsen, 1870, right, after [ 38].

A third way of measuring the heat exchanged in a passive diathermal calorimeter is to make use, in the surrounding thermostat, of a peripheral liquid flow (usually water) whose temperature change is determined. This is the principle followed by Junkers’ flame calorimeter [39], the Picker liquid mixing calorimeter [40], and modern reaction calorimeters developed for safety studies of chemical reactions.

4.5 Active diathermal calorimeters

These are still diathermal calorimeters, where everything happens as if there was excellent heat exchange between the system S and the surrounding thermostat T. This means that the system temperature TS closely follows that of the thermostat, TT. The good heat exchange is, in reality, « simulated ». For that purpose, the thermal transfer between sample and thermostat is complemented or replaced by a physical phenomenon taking place in close contact with the sample and able to generate or remove heat in situ.

This « power compensation » is carried out so as to servo-control the sample temperature to follow the thermostat temperature. This is, therefore, exactly the opposite situation to the « active » adiabatic calorimeter, where it is the thermostat temperature which is servo-controlled to follow that of the sample. Here, one measures the heat provided to (or removed from) system S (sample + container) by the power compensation device.

Heat compensation can be achieved by the Joule effect, if the studied phenomenon is endothermic and by the Peltier effect if it is exothermic. This was used by Tian, in 1924, to compensate the major part of the heat (by means of a constant power, which is easy to measure), whereas the remainder was measured with a heat-flowmeter [41].

A simpler and more elegant way to compensate either exothermic or endothermic effects was used by Dzhigit et al. in 1962 [42]. A Joule effect is produced in the system and this is controlled to ensure a constant temperature difference (say, 5 K) between the system S and the thermostat T and, hence, a constant heat-flow. If the phenomenon studied is endothermic, the Joule effect is automatically increased to ensure the constant heat flow required. If it is exothermic, the Joule effect is simply decreased. These changes in the Joule effect are recorded and provide a direct measurement of the heat involved in the phenomenon studied. This was also used by Hansen et al. in 1982 in their high temperature battery calorimeter [43].

An original route is that proposed by Ter-Minassian and Milliou in 1983 [44] with their pneumatic compensation calorimeter, represented in Fig 10. The tubular sample cell 4 is in good thermal contact with four metallic bulbs. Two of them operate like bulb 1 in the figure, i.e. as pneumatic thermal detectors. They are filled with gas, say around 1 bar, and their pressure is compared, by means of a differential manometer, with the constant pressure of a reference reservoir 3 immersed in the surrounding thermostat block 5. Therefore, they detect any temperature change of the sample. The two other bulbs operate like bulb 2, i.e. as pneumatic energy-compensating devices. They are also filled with gas, say around 1 bar, but they are connected to the piston-cylinder 7 which enables the heat of compression (or decompression) necessary to cancel the temperature difference between the sample and thermostat (as detected with the first set of bulbs) to be produced in the bulb. More recently, Zimmermann and Keller built a comparable pneumatic compensation calorimeter whose calorimetric performances were carefully examined