Contents of the Section: History of Thermal Analysis and ICTAC and CALCON Societies

Contents of the section: History of thermal analysis and ICTAC and CALCON societies

THERMAL SCIENCE AND ANALYSIS: TERMS CONNOTATION, HISTORY, DEVELOPMENT, AND THE ROLE OF PERSONALITIES Jaroslav Šesták Journal of Thermal Analysis and Calorimetry - 2013, DOI 10.1007/s10973- 012-2848-7

HISTORICAL ROOTS AND DEVELOPMENT OF THERMAL ANALYSIS AND CALORIMETRY, Jaroslav Šesták, Pavel Hubík, Jiří J Mareš Book chapter

SOME HISTORICAL ASPECTS OF THERMAL ANALYSIS: ORIGINS OF TERMANAL, CalCon AND ICTA Jaroslav Šesták TERMANAL 2005 - published in Bratislava

FROM CALORIC TO STATHMOGRAPH AND POLAROGRAPHY Jaroslav Šesták, Jiří J Mareš Journal of Thermal Analysis and Calorimetry, Vol. 88 (2007)

CZECHOSLOVAK FOOTPRINTS IN THE DEVELOPMENT OF METHODS OF THERMOMETRY, CALORIMETRY AND THERMAL ANALYSIS Pavel Holba, Jaroslav Šesták Ceramics – Silikáty (Prague) 56 (2) 159-167 (2012) J Therm Anal Calorim DOI 10.1007/s10973-012-2848-7

Thermal science and analysis Terms connotation, history, development, and the role of personalities

J. Sˇesta´k

Received: 4 September 2012 / Accepted: 26 November 2012 Ó Akade´miai Kiado´, Budapest, Hungary 2012

Abstract History of thermoscopy and thermometry is principle on which temperature measurement is based and reviewed showing the role of temperature degrees includ- evolved as a part of the development of thermal science. ing the forgotten logarithmic scale. The importance of natural laws of energy, motion, least action, and thermal efficiency is discussed. The meaning of idiomatic terms— Thermoscope, thermometer, thermometry, thermal physics, thermodynamics, thermostatics, thermot- and temperature scales ics, and thermal analysis—is specified and revealed within two parallel developed branches of thermal science. Item- The ancient Greek discerned the expansion of air by heat ized 105 references with titles. long time ago. The earliest writings concerned that the phenomena were the Works of Philo of Byzantium and Keywords Thermometry Á Thermodynamics Á Heron of Alexandria (II Century B.C.). The Greeks made Thermostatics Á Thermotics Á Thermal physics Á simple thermometers in the first century BC, but there was Natural laws Á Temperature scales Á H.Suga Á T.Ozawa no way to quantify heat with hot and cold still following the Aristotelian tradition of being treated as fundamental qualities of the universe. The ideas of Aristotle were Introduction adopted by Galen (A.D. 130–200), who was the first FOR REVIEWdescribing the heat and cold by a number about fifteen A plentiful literature about thermal science [1–5] and its hundred years ago. And, the word temperature originated precedent thermometry [6–11], as well as historic thermal from ‘‘temper,’’ after Galen determined the ‘‘complexion’’ analysis [12–21], is available through various sources easy of a person by the proportion in which four human accessible even from internet. Therefore, we do not want to ‘‘qualities’’ were tempered [6–8]. It is known that by the repeat available figures, but prefer mentioning some hidden 16th Century, knowledge of the ‘‘weatherglass’’ (the other aspects responsive to the record of accessible citations, common name for thermoscope) became widely spread while not claiming completeness. All history records reach among educated people either due to the new edition of back to the early concept of hotness [22] as the scientific Heron’s papers or upon the accessibility of excerpts of Arabian alchemistic manuscripts. One of the first modern-times considerations on active principles (heat and cold) acting on a passive matter can be Dedicated to Prof. Hiroshi Suga and Prof. Takeo Ozawa (recently Bernar- passed away), pioneers of the advanced thermal science and the found in the treatise published in 1563 by Italian honorary chairmen of the ICTAC’15 in Osaka’2012. dino Telesio (1509–1588) and perceived by Francesco Patricio (1529–1597) and Giordano Bruno (1548–1600). J. Sˇesta´k(&) The first air thermoscope appeared in 1594 through Galileo New Technologies—Research Centre of the Westbohemian Galilei (1564–1542), but the Englishman Robert Fludd Region, University of West Bohemia in Pilsen (NTC-ZCˇ U), Universitnı´ 8, 301 14 Plzenˇ, Czech Republic (1574–1651) was also regarded as one independent e-mail: [email protected] inventor around 1617. Yet, another originator was 123 J. Sˇesta´k indicated Cornelis J. Drebbel (1572–1633) who made a of the concept of temperature are familiar and thus not two-bulbed J-shaped thermometer between 1598 and 1622. herewith reiterated [18–22, 26]. In 1626, the factual word ‘‘thermometer’’ was initially used Worth of a special attention would be 1848 Thomson’s to describe thermoscope equipped with a scale marked with approach based on thermal efficiency g (originated [29, 30] eight degrees by Jean Leurechon (1591–1670) in his book by Nicolas Leonard Sadi Carnot (1796–1832)) introducing [23]. Shortly after, the world-known Czech educator Jan thus a logarithmic temperature scale, h, in the form of

Amos Comenius (1592–1670) inserted reflections on the dh & dT/T. After integration, it follows that h = const1 role of heat and cold in nature into his book work [24] and lnT ? const2, where both constants can be determined using then, in 1659, published another worth noting book [25]on the traditionally fixed points of the melting and boiling of the nature of heat and cold. In 1665, Christian Huygens water. This more natural scale, however, would dramatically (1629–1695) had a brilliant idea to use the melting and change the customary concept of thermodynamics [26, 28] boiling points of water as a standard gauge. easing the interpretation of the third law of thermodynamics The first quantitative thermal law expressing the depen- replacing the traditional zero temperature by infinity (T = dence of temperature of a cooling body (expressed in 8 -?). However, the conventional degree of freedom, degrees) on the time was published in 1701 by Isaac Newton *1/2 kT, would revolutionize to embarrassing proportion-

(1643–1727). Such a forgotten attempt to put high temper- ality, T * exp{(h-const2)/const1}, etc. On the other hand, atures on a mathematical scale described a thermometer on the simple interpretation of heat conduction and the cus- the basis of oil and calibrated it by taking ‘‘the heat of the air tomary evaluation of efficiency for steam engines necessitate in winter when water begins to freeze’’as 0 and ‘‘blood heat’’ the temperature to behave like the potential of a heated fluid as 12 on this scale water boils at 34. The melting points of and the traditional linear scale, equivalent to the contempo- alloys were determined by an extrapolation and logarithmic rary Kelvin’s international scale, manage to survive as the temperature scale that was proposed for high experimental most opportune one. There can be seen various attempts temperatures on the basis of the equation, h = 12{2(x-1)}, introducing so far inconvenient thermodynamics concepts where h was the temperature in units of the above scale and based, for example on the Carnot use of caloric [31, 32]. x represented the logarithmic temperature [26–28]. One of the earliest challenges at calibration and standardization between thermometers was attempted in 1663 by Thermal physics, thermodynamics, thermotics, the members of Royal Society in London, who agreed to use and thermal analysis one of several thermometers made by Robert Hooke (1635–1703) as the standard so that the reading of others Early attempts to create a common scientific language can could be adjusted to it. Non-Euclidean mathematician be associated with the early work by Comenius emerging Johann H. Lambert (1728–1777) revealed in his less familiar from his effort to portray heat [25]. However, equally book ‘‘Pyrometria’’ as many as nineteen temperature scales. important was his challenge to articulate his own idea of Differential air thermometer was invented, almost simulta- universal language [33] and its relation to the encyclopedic neously, by John Leslie (1766–1832) of EdinburghFOR and byREVIEWknowledge concept of the ‘‘pansophia’’ having a profound Benjamin Thompson, Count Rumford (1753–1814) and influence on the discussion on an exploitation of such a consequently James Clerk Maxwell (1831–1879) recognized universal language in England. Inquisitively it resulted to that for thermometry (to be a logically closed system) it is his invitation offered by John Winthrop (1588–1649) a necessary to add a concept of thermal equilibrium. governor of Massachusetts to become a rector of a new Daniel G. Fahrenheit (1686–1736) proposed in 1724 a US university founded by preacher John Harvard. Later, temperature scale of 100 degrees from 0 °F (at the tem- the Comenius younger follower Gottfried W. Leibnitz perature of mixture of ammonium chloride, water, and ice) (1648–1716) used his idea of ‘‘lingua catholica’’ in an and 100 °F at the human body temperature and invented attempt to formulate mathematical, scientific, and meta- the first mercury thermometer. A year later, Joseph-Nicolas physical concepts more effective. He introduced ‘‘charac- Delisle (1688–1768) introduced an exotic scale with teristica universali’’ hopeful to create a language usable 240 degrees, which was later (1738) modified and adjusted within the framework of a universal logical calculation to 150°D corresponding to the melting point of water and [34, 35] or ‘‘calculus ratiocinator’’ convincingly affected to 0°D at boiling point of water (240°D = 60 °C), and this by Rene Descartes (1596–1650) through his correspon- scale was being used in Russia for the whole hundred dence with Comenius [21]. Descartes [36] became years. The story of different scales, from Fahrenheit and responsible for the formulation of conservation law applied Celsius degrees to the now-forgotten Rankine, Rømer, to the amount of movement (momentum-mv) later cor- Desliste, Reaumur, Lime,orAmontons scales, and the rected by Leibnitz as ‘‘vis viva’’ (mv2). On the other hand, history of the gradual scientific then popular understanding it is worth mentioning that the law of conservation was 123 Development and the role of personalities foreseen by another Czech mastermind Jan Marcus Marci transfer 1822 [55] and Lars Onsager (1903–1976) [56] (1595–1667) [37]. while depicting the equations of irreversible processes (later Another significant impact to generalized understanding of rooting the field of extended thermodynamics [57, 58]). nature was brought by Pierre de Fermat (1601–1655) when So far, the enduring term of thermodynamics subsists the introducing the principle of least time [38]:‘‘theNatureactsvia energetic concepts [59–63] of temperature and heat based the easiest and the most accessible way reached within the upon the Greek word ‘‘therme’’(= heat); however, it is worth shortest time.’’ A century later it was resumed by Pierre-Louis noting that it also involves a Greek concoction for the motive M. de Maupertuis (1698–1759) who in 1744 envisaged the least power of heat, i.e., thermodynamics factually means ‘‘heat- action premise noting [39]: ‘‘when some change takes place in engine science.’’ It is concerned with heat and its relation to nature, the quantity of action necessary for the change is the other forms of energy and work defining macroscopic vari- smallest possible.’’ The quantity of action is the product ables which describe average properties of material bodies, obtained by multiplying the mass of the bodies (m) with their and explains how they are related and by which laws they velocity (v) and the distance travelled (k), which interestingly change with equilibrating [59–71]. There are many grand- correlates with the Planck constant h(= mvk). It recently became fathers such as a UK professor Edward Armand Guggenheim the basis to explain the inborn self-periodicity of many natural (1901–1970) [3, 69]. processes [40–42]. These fundamental laws of motion became Yet, more general terms ‘‘‘thermal science‘‘ or ‘‘science equally crucial as the Carnot temperature limits for the thermal of heat’’ [2] sustain for a shared study of thermodynamics, efficiency of heat engines [20, 29, 31, 32]. fluid mechanics, heat transfer, thermal investigation, The decisive experimental studies, thanks to which tem- combustion, and thermokinetics while more restricted perature became a clearly measurable physical quantity, terms ‘‘thermal physics’’ [44, 72–74] involve the combined contributed the formation of a contemporary discipline lan- study of thermodynamics, statistical mechanics, and kinetic guage. In the 1840s, a thermodynamic discourse was worked theories providing thus an umbrella subject which is typi- up by Henri Victor Regnault (1810–1878) whose attitude, cally designed to provide a general introduction to each of however, turned out long after Joseph Black (1728–1799) core heat-related subjects. [15, 17, 26, 43] distinguishing between the specific heat (heat There is yet another a more unfamiliar term ‘‘thermotics’’ capacity) and the latent heat [19, 30]. Curiously, his less (alike the term ‘‘mathematics’’) staying also behind the gen- known correspondence [21] with James Watt (1736–1819, eralized science of heat (and also based on its Greek origin), who invented steam engine in 1776) remained unmentioned. apparently used as early as in 1837 [75]. In 1967, American Consequently, Pierre Simon de Laplace (1749–1827) and physical chemist Ralph Tykodi (1925) made an attempt to Antoine Lavoisier (1743–1794) performed in 1786 their first revive thermotics [76, 77] as an idiom which, he said, should calorimetric measurements [25, 44–50]. Yet, after the detailed be equal in usage to 1946 version of ‘‘energetics’’provided by results of 1842 Regnault’s dilatometric and heat capacity the Danish physical chemist Johannes Nicolaus Brønsted measurements, and together with 1824 theorem of Carnot (1879–1947) [59, 60]. In this view, thermotics subsist a ther- [29, 32] and its 1834 interpretation by Benoit-Paule E. Cla- mal science comprised of three sub-branches: ‘‘thermo-stat- peyron (1799–1864) it provided the basis forFOR the 1848 intro- REVIEWics’’ pertaining to the ordinary classical equilibrium aspects of ducing of absolute temperature scale by William Thomson heat, ‘‘thermo-dynamics’’ relevant to those aspects for which (baron Kelvin of Larges) (1824–1907) and for the factual time variation is important, and ‘‘thermo-staedics’’ concern- inception of thermodynamic ‘‘language’’[15, 51–53] as a new ing the aspects that are temporally steady or stationary. The science, not forgetting the work of Josiah Willard Gibbs focus of latter term may be seen more suitable to envelop the (1839–1903) [15, 21, 51]. Literally, this new science would be field of ‘‘thermal analysis’’ [1, 14–21, 26, 78] the true meaning optimally associable with the term ‘‘thermostatics’’ by way of of which was never appropriately located within the spheres of thermally equilibrated states and developed through the Carnot, thermal sciences [2, 26, 30]. Clapeyron, Clausius, and/or Gibbs work as a branch of ‘‘dis- The entire term thermal analysis was coined by Gustav sipationless work’’ understanding of the science of heat [2, 26]. Heinrich J.A. Tammann, (1861–1938) [79, 80], further Complementary approach involving the concept of accredited in [12, 13] and then particularized in our previous ‘‘workless dissipation’’ comprise, however, temperature papers [2, 14, 17–19]. Seemingly the inherent thermoana- gradients (existing everywhere and in thermostatic concepts lytical theory is historically based [12, 81] on equilibrated often neglected due to necessary simplifications) which was (i.e., thermostatic) states often omitting the non-equilibrium developed in the course of studies by Newton, Fourier, (flux) character of its measurements, which seems be a most Stokes and/or Onsager framing thus the new field of ‘‘true’’ crucial source of inaccuracy in the existing theoretic evalu- thermodynamics involving irreversible processes [1–3, 54]. ation of DTA (= differential thermal analysis) [2, 13] where Most remarkable personalities became Joseph Baptiste thermal gradients are habitually not incorporated in the Fourier (1768–1830) while publishing the laws of heat evaluation (with few exceptions [82–85]). 123 J. Sˇesta´k

A tribute paid to Japanese personalities: Hiroshi Suga the honor to publish joint studies [89–91] being also the and Takeo Ozawa guarantee of the 1996 foundation of the School of Energy Science at the Kyoto University. Both of these Japanese The field of thermal analysis became a starting point for famous persons are accountable for the augmentation of expanded cooperative studies under the umbrella of the thermoanalytical societies as well as the development of International Confederation (ICTA/ICTAC) [86, 87] which the theory of processes carried out under non-isothermal benefits from its over 40 years running established under conditions. Though the work of Ozawa (e.g., [92–99]) the profitable impact of many foremost personalities [88] received a wider recognition (H-index = 81, total citation such as the distinguished celebrities of Hiroshi Suga (1930) record = 38,580 with 2,316 feedback for his best cited and Takeo Ozawa (1932–2012) with whom the author has paper) because attentive to a more fashionable subject of thermoanalytical kinetics, the work of Suga (H-index = 40, total citation record = 5,582 with 316 feedback for his best cited paper) enveloped a more fundamental subject of generalized behavior and characterization of noncrystalline solids (e.g., [91, 100–105]). Their worldwide impact has positively affected the international cooperation, which is well illustrated by the group photos (above Figs. 1 and 2). We all are very grateful for their fruitful guidance and affable dissemination of knowledge.

Acknowledgements The results were developed within the CEN- TEM project, reg. no. CZ.1.05/2.1.00/03.0088 that is co-funded from the ERDF within the OP RDI program of the Ministry of Education, Youth and Sports. The author feels also indebted to his scientific friends, coworkers, and uppermost thermodynamists Pavel Holba (Pilsen), Gyo¨rgy Liptay (Budapest), Jiri. J. Maresˇ (Prague), Jirˇ´ı Ma´lek Fig. 1 The photo from the 28th conference of the Japanese society on (Pardubice), Nobuyoshi Koga (Hiroshima), late German K. Moiseev calorimetry and thermal analysis (JSCTA) in Tokyo (Waseda Univer- (Jekateˇrinburg), Ingo Mu¨ller (Berlin), late Tooru Atake (Tokyo), late sity, 1992) shows (from left) M. Taniguchi (Japan), late C.J. Keattch Ivo Proks (Bratislava), Vladimı´rSˇatava (Prague), Peter Sˇimon (Bra- (UK), late R. Otsuka (Japan), S. St. J. Warne (Australia, former ICTA tislava), late Bernhard Wunderlich (Knoxville), Harumi Yokokawa president), H. Suga (Japan), J. Sˇesta´k (Czechoslovakia), and H. Tanaka (Tsukuba), and Shmuel Yariv (Jerusalem). The author, however, was (Japan). The regular JSCTA conferences started in Osaka 1964 under disappointed that this tribute lecture was suspended by the conference the organization of Prof. S. Seki who became the first president when the secretary (Riko Ozao) out from the Commemorate Special Session JSCTA was officially established in 1973. Since then, the JSCTA (crediting the conference honorary chairmen) to general session only. journal NETSU SOKUTEI has been published periodically and the Sino-Japanese conferences repetitively organized too FOR REVIEWReferences 1. Truesdel C. The tragicomical history of thermodynamics: 1822–1854. New York: Springer; 1980. 2. Sˇesta´k J. Science of heat and thermophysical studies: a generalized approach to thermal analysis. Amsterdam: Elsevier; 2005. 3. Mu¨ller I. A history of thermodynamics. Berlin: Springer; 2007. 4. Bensande-Vincent B, Stenger I. History of chemistry. London: Harvard Press; 1996. 5. Holton G. Thematic origins of scientific thoughts: from Kepler to Einstein. Cambridge: Harvard University; 1973. 6. Behar MF. Temperature and humidity measurement and control. New York: Instruments Publishing Company; 1932. p. 113–22. 7. Barnett MK. A brief history of thermometry. J Chem Educt. 1941;18(8):358. 8. Sherwood Taylor F. The origin of the thermometer. Ann Sci. 1947;5:129–56. Fig. 2 A rare photo of ICTAC members participating at the ICTA’9 9. Middleton WEK. History of thermometry and its use in mete- in Israel (1988) recognizing from left the late J.H. Flynn (USA), orology. Nature. 1958;182:1487–9. P.K. Gallagher (USA, past president), S. Sr. J. Warne (Australia, 10. Ring EF. The historical development of thermometry and ther- president), E. Charsley (UK), V. Balek (Czechoslovakia), T. Ozawa mal imaging in medicine. J Med Eng Technol. 2006;30:192–8. (Japan, vice-president), D. Moron (UK), J. Dunn (Australia), and late 11. McGee TD. Principles and methods of temperature measure- W. Eysel (Germany) ment. New York: Wiley; 1988. 123 Development and the role of personalities

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123 J. Sˇesta´k

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123 21 Historical roots and development of thermal analysis and calorimetry

Jaroslav Šesták1, Pavel Hubík2, Jiří J. Mareš2

1New Technology Research Centre, University of West Bohemia, Univerzitní 8, CZ-30614 Plzeň, Czech Republic 2Institute of Physics ASCR, v.v.i., Cukrovarnická 10, 162 00 Praha 6, Czech Republic e-mail: [email protected]

21.1 Historical aspects of thermal studies, origins of caloric

Apparently, the first person which used a thought experiment of continuous heating and cooling of an illustrative body was curiously the Czech thinker and Bo- hemian educator [1], latter refugee Johann Amos Comenius (Jan Amos Komenský, 1592-1670) when trying to envisage the properties of substances. In his “Physicae Synopsis”, which he finished in 1629 and published first in Leipzig in 1633, he showed the importance of hotness and coldness in all natural processes. Heat (or better fire) is considered as the cause of all motions of things. The expansion of substances and the increasing the space they occupy is caused by their dilution with heat. By the influence of cold the substance gains in density and shrinks: the condensation of vapor to liquid water is given as an example. Comenius also determined, though very inaccurately, the volume increase in the gas phase caused by the evaporation of a unit volume of liquid water. In Amsterdam in 1659 he published a focal but rather unfamiliar treatise on the principles of heat and cold [2], which was probably inspired by the works of the Italian philosopher Bernardino Tele- sius. The third chapter of this Comenius' book was devoted to the description of the influence of temperature changes on the properties of substances. The aim and principles of thermal analysis were literally given in the first paragraph of this chapter: citing the English translation [3-5]: "In order to observe clearly the effects of heat and cold, we must take a visible object and observe its changes occurring during its heating and subsequent cooling so that the effects of heat and cold become apparent to our senses." In the following 19 paragraphs of this chapter Com- enius gave a rather systematic description (and also a partially correct interpretation) of the effects of continuous heating and cooling of water and air, and also stressed the reversibility of processes such as, for example, evaporation and condensation, etc., anticipating somehow the concept of latent heat. Comenius concludes this chapter as follows: "All shows therefore that both heat and cold are a motion, which had to be proved." In the following chapter Comenius described 2 and almost correctly explained the function of a thermoscope (‘vitrum caldarium’) and introduced his own qualitative scale with three degrees of heat above and three degrees of cold below the ambient temperature launching thus a concept of “caloric”. Nonetheless, it is difficult to trace [1,3-6] and thus hard to say if it was possible (though likely) to disseminate the Comenius idea of caloric from Amsterdam (when he mostly lived and also died) to Scotland where a century later a new substance, or better a matter of fire, likewise called caloric (or caloricum), was thoroughly introduced by Joseph Black (1728-1799) [7] and his student Irvine. Un- fortunately, Black published almost nothing in his own lifetime [5,8] and his attitude was mostly reconstructed from contemporary comments and essays published after his death. Caloric [1,7,9-11] was originally seen as an imponderable element with its own properties. It was assumed, e.g., that caloric creeps between the constituent parts of a substance causing its expansion. Black also supposed that heat (caloric) was absorbed by a body during melting or vaporization, simply because at the melting or boiling points sudden changes took place in the ability of the body to accumulate heat (~1761). In this connection, he introduced the term ‘latent heat’ which meant the absorption of heat as the consequence of the change of state. Irvine ac- counted that the relative quantities of heat contained in equal weights of different substances at any given temperature (i.e., their ‘absolute heats’) were proportional to their ‘capacities’ at that temperature and it is worth noting that the term ‘capacity’ was used by both Black and later also Irvine to indicate specific heats [7,9-11]. Black’s elegant explanation of latent heat to the young James Watts (1736- 1819) became the source of the invention of the businesslike steam engine as well as the inspiration for the first research in theory related to the novel domain of thermochemistry, which searched for general laws that linked heat, with changes of state. In 1822, Jean-Baptiste Joseph Fourier (1768-1830) published an influential book on the analytical theory of heat [12], in which he developed methods for integration of partial differential equations, describing diffusion of the heat substance. Based on the yet inconsistent law of conservation of caloric, Siméon D. Poisson (1823) derived a correct and experimentally verifiable equation describing the relationship between the pressure and volume of an ideal gas undergoing adiabatic changes. Benjamin Thompson (Count Rumford, 1753-1814) presented qualitative arguments for such a fluid theory of heat with which he succeeded to evaluate the mechanical equivalent of heat [11,13]. This theory, however, was not accepted until the later approval by Julius Robert Mayer (1814-1878) and, in particular, by James Prescott Joule (1818-1889), who also applied Rumford’s theory to the transformation of electrical work. In the year 1826 Nicolas Clement (1779-1842) [11] coined the unit of heat as amount of caloric, necessary for heating 1 g of liquid water by one degree centi- grade. Though the expected temperature changes due to “thickened caloric” did not experimentally occur (cf. measurements in “Torricelli’s vacuum” over mercury by Gay-Lussac) and in spite of that Thompson (1798) showed that the heat 3 could be produced by friction ad infinitum, the caloric theory survived many de- feats and its mathematical scheme is in fact applied for the description of heat flow until today. The above customary unit was called ‘calorie’ (cal) or ‘small calorie’, whereas a ‘large calorie’ corresponded to the later ‘kilocalorie’ (kcal). The word “calorie” was more widely introduced into the vocabulary of academic physicists and chemists by Favre and Silbermann [14] in 1852. The expression of one kilocalorie as 427 kilogram-meters was given by Mayer in the year 1845. We should add that caloric differed from the foregoing concept of phlogiston because, beside else, it could be measured with an apparatus called a calorimeter, however, it is not clear who was the first using such an instrument. If we follow the studies of Brush [8], Mackenzie [15] and Thenard [16] they assigned it to Wilcke. It, however, contradicts to the opinion presented in the study by McKie and Heathcote [17] who consider it just a legend and assume that the priority of familiarity of ice calorimeter belongs to Laplace who was most likely the acknowledged inventor and first true user of this instrument (likely as early as in 1782). In fact, Lavoisier and Laplace entitled the first chapter of their famous “Mémoire sur la Chaleur” (Paris 1783) as “Presentation of a new means for measuring heat” (without referring Black because of his poor paper evidence). Report of Black’s employment of the calorimeter seems to appear firstly almost a century later in the Jamin’s Course of Physics [1].

21.2 Underlying features of thermal physics interpreted within the caloric theory

In the light of work of senior Lazare Carnot (1753-1823) on mechanical engines [11], Sadi Carnot (1796-1832) co-opted his ideas of equilibrium, infinitesimal changes and imaginatively replicated them for caloric (in the illustrative the case of water fall from a higher level to a lower one in a water mill). He was thinking about writing a book about the properties of heat engines applying caloric hypothesis generally accepted in that time within broad scientific circles [18-20]. In- stead, he wrote a slim book of mere 118 pages, published in 200 copies only, which he entitled as the “Reflections on the motive power of fire and on machines fitted to develop that power” (1824) [21], which was based on his earlier outline dealing with the derivation of an equation suitable for the calculation of motive power performed by a water steam [11]. He discussed comprehensively under what conditions it is possible to obtain useful work (“motive power”) from a heat reservoir and how it is possible to realize a reversible process accompanied with heat transfer. Sadi also explained that a reversibly working heat engine furnished with two different working agents had to have the same efficiency related to the temperature difference, only. Among other notable achievements [14,22-27] there was the determination of the difference between the specific heats of gases measured at constant pressure and volume. He found that the difference was the same 4

for all gases, anticipating thus the Mayer’s relation for ideal gas: cp – cv = R. Sadi also introduced the “Carnot’s function” the inverse of which was later (1850) identified by Rudolph Clausius (1822-1888) [28], within the classical thermodynamics, with the absolute temperature T. Finally, Sadi adjusted, on the basis of rather poor experimental data that for the production of 2.7 mechanical units of “motive power” it was necessary to destruct one caloric unit of heat, which was in a fair correspondence with the later mechanical equivalent of heat: (4.1 J/cal). It is worth noting that already when writing his book he started to doubt the validity of caloric theory [11,27] because several of experimental facts seemed to him almost inexplicable. Similarly to his father, Sadi’s work remained unnoticed by contemporary physicists and permanently unjustly criticized for his principle of the conservation of caloric, which is, however, quite correct for any cyclic reversible thermal process. Adhering to the way of Carnot’s intuitive thinking [26,27], the small amount of work done dL (motive power in Carnot’s terms) is performed by caloric ς literarly falling over an infinitesimal temperature difference dT [11,16,26], dL = ς F(T) dT. The function F(T) here is the Carnot’s function, which has to be determined experimentally, certainly, with respect to the operative definitions of quantities ς and T. Carnot assumed that caloric is not consumed (produced) by performing work but only loses (gains) its temperature (by dT). Therefore, the caloric has there an extensive character of some special substance while the intensive quantity of temperature plays the role of its (thermal) potential; the thermal energy may be thus defined as the product ς × T, in parallel with other potentials such pressure (choric potential) for volume, gravitational potential for mass and electrostatic potential for charge. Taking into account that caloric is conserved during reversible operations, the quantity ς must be independent of temperature and, consequently, Carnot’s function F(T) has to be also constant. Putting the function equal identically 1 the unit of caloric fully compatible with the SI system is defined. Such a unit (Callendar [23]), can be appropriately called “Carnot” (abbreviated as “Cn” or “Ct”). One “Ct” unit is then such a quantity of caloric, which is during a reversible process capable of producing 1 J of work per 1 K temperature fall. Simultaneously, if such a system of units is used [26,27] , the relation dL = ς dT retains. The caloric theory can be extended for irreversible processes by adding an idea of wasted (dissipated) motive power which reappears in the form of newly created caloric [26]. Analyzing Joule’s paddle-wheel experiment from view of both this extended caloric theory and classical thermodynamics, it can be shown that the relation between caloric and heat in the form dς =J dQ/ T takes place, which, at first glance, resembles the famous formula for entropy, certainly if we measure the heat in energy units. This correspondence between entropy and caloric, may serve as a very effective heuristic tool for finding the properties of caloric by exploitation the results known hitherto from classical thermodynamics. From this point of view it is clear that the caloric theory is not at any odds with experimental facts, which are only anew explained ([26]). The factor J historically determined by 5

Joule (J ~ 4.185 J/cal) should have been rather related with the establishment of a particular system of units then with a general proof of the equivalence between heat and energy. One of the central questions of the Carnot’s theory of heat engines is the evaluation of engine efficiency. The amount of caloric ς which is entering the completely reversible and continuously working heat engine at temperature T1 and leaving it at temperature T2 will produce a motive power of amount L. Carnot’s efficiency

ηC defined as a ratio L/ς is then given by a plain temperature drop ΔT = (T1−T2) (as measured in the ideal gas temperature scale). Transforming the incoming caloric into thermal energy T1ς, we obtain immediately Kelvin’s dimensionless efficiency ηK of the ideal reversible heat engine, ηK = {1−(T2/T1)}, which is well- known from textbooks of thermodynamics [3,29].

However, ηK is of little significance for the practical evaluation of the perfor- mance of real heat engines, which are optimized not with respect to their efficiency but rather with respect to their available output power. As a convenient model for such a case it may be taken an ideal heat engine impeded by a thermal resistance [26]. The effect of thermal resistance can be understood within the caloric theory in such a way that the original quantity of caloric ς , taken from the boiler kept at temperature T1, increases, by passing across a thermal resistance, to the new quantity equal to ς + Δς , entering than the ideal heat engine at temperature T

= λ(T1−T)(T−T2)/T , where for the evaluation of temperature drop across the ther- u mal resistance we can apply the Fourier law [12] ς T1 = λ (T1−T), where λ is a constant representing the inverse of thermal resistance. The condition for the op- timum of the output power with respect to temperature T then reads dLu/dT = 0, from which we obtain T = √(T1 T2) [26]. Consequently, the Carnot’s true efficiency of such a system with optimized output power is thus given by a formula, ηC = T1 {1– √(T2/T1)}. Such a root square dependence, which is the direct consequence of linearity of Fourier’s law, is also obviously repeated for the above mentioned dimensionless Kelvin’s efficiency, ηK. Because of enormous effort of engineers to optimize the real output power of concrete heat engines, the above formula describes the actual efficiencies quite well as interestingly shown for authentic in- dustrial cases by Curzon and Ahlborn [30].

21.3 Early scientific and societal parentage of thermal analysis

Standard reference books [16,19,21,29,31] are rather coy about the history of thermometry and thermal analysis being the subject of specified papers and book chapters [1,4-11,15,32-35], which goes back to historic times of Isaac Newton (1642–1727) who published his temperature scale in 1701 the significance of which lies both in its range of temperature and in its instrumentation presenting 6 also the famous Newton's Law of Cooling [36]. First cornerstone of the theory of warmth propagation was provided by J.-B. J. Fourier who initiated the investigation of Fourier series and their application to problems of heat transfer [12]. The very roots of thermal analysis appear in the 19th century where temperature became an observable and experimentally decisive quantity, which thus turned into an experimentally monitorable parameter associated with an consequent underpinning of the field of thermodynamics [29,34,35]. The first characterization of thermometric measurements is identified in Uppsala in 1829 through the earliest documented experiment which nearly meets current criteria. It was Fredrik Rudberg (1800-1839) [15,22] who recorded the inverse cooling-rate data for lead, tin, zinc and various alloys which were placed in a smaller vessel surrounded by a large double-walled iron vessel where the spaces between its two walls, as well as the top lid, were filled with snow to ensure that the inner walls were always kept at zero temperature. Once the experimental condition was set up, Rudberg noted and tabulated the times taken by the mercury in thermometer to fall through each 10 degrees interval. The longest interval then included the freezing point. One of important impacts came with the discovery of thermoelectric effect [37] by Thomas J. Seebeck (1770-1831) occurring in a circuit made from two dissimi- lar metals and the consequent development of a device called thermocouple [37,38], suitable as a more accurate temperature-measuring tool, in which gas volume or pressure changes were replaced by a change of electric voltage (Augustin G.A. Charpy (1865-1945) [39]). Henry L. Le Chatelier (1850-1936) [38] was the first who deduced that varying thermocouple output could result from contamination of one wire by diffusion from the other one or from the non-uniformity of wires themselves. The better homogeneity of platinum-rhodium alloy led him to the standard platinum – platinum/rhodium couple so that almost seventy years after the observation of thermoelectricity, its use in thermometry was finally vindicated, which rapidly got a wider use. Floris Osmond (1849-1912) [15,40] investigated the heating and cooling behavior of iron with a goal to elucidate the effects of carbon so that he factually introduced thermometric measurements to then most important field: metallurgy [40]. In 1891, Sir William C. Roberts-Austen (1843-1902) [41] was accredited to construct a device to give a continuous record of the output from thermocouple and he termed it as ‘thermoelectric pyrometer’ (see Fig. 21.1) and in 1899, Stan- field published heating curves for gold and almost stumbled upon the nowadays idea of differential thermal analysis (DTA) when maintaining the thermocouple ‘cold’ junction at a constant elevated temperature measuring thus the entire differences between two high temperatures. Such an innovative system of measuring the temperature difference between the sample and a suitable reference material placed side-by-side in the same thermal environment, in fact initiated the consequent development of DTA instruments. 7

Fig. 21.1 Upper: Thermo-Electric Pyrometer of Roberts-Austen (1881) showing the instrument (left) and its cooling arrangement (right) with particularity of the sample holder. Middle: Histor- ical photo of the early set-up of Hungarian “Derivatograph” (designed by brothers Paulik), which was one of the most frequent instruments in the former Eastern bloc. Below: photo of one time very popular and widespread instruments for high -temperature DTA produced by the Netzsch Gerätebau GmbH (Selb, Germany) from its early version (left) presented to the market on fifties up to the latest third-generation rendering new STA 449 F1 Jupiter (right). The middle type (yet based on then fashionable analogous temperature control) was particularly sold during seventies and survived in many laboratories for a long period (being gradually subjected to enduring computerization and digital data processing).

In 1909 there was elaborated another reliable procedure of preserving the high- temperature state of samples down to laboratory temperature, in-fact freezing-in the high-temperature equilibrium as a suitably ‘quenched’ state for further investigation [34]. It helped in the consistent construction of phase diagrams when used in combination with other complementary analytical procedures, such as the early structural microanalysis (introduced by Max von Laue (1879-1960) and sir Wil- liam L. Bragg (1890-1971) when they detected the X-rays diffraction on crystals) along with the traditional metallographic observations. Another important step 8 toward the modern solid state physics was induction of the notion of diffusion by Adolf E. Fick (1829-1901) and its improved understanding by Ernest Kirkendall (1914-2005) as well as the introduction of the concept of disorder by Jakob I. Frenkel (1894-1952) [45] and models of glasses by Tammann [46]. By 1908, knowledge of the heating or cooling curves, along with their rate derivatives and inverse curves were sufficient enough to warrant a first review and more detailed theoretical inspection given by George K. Burgess (1874-1932) [47]. Not less important was the development of heat sources where coal and gas were almost completely replaced by electricity as the only source of controllable heat. Already in 1895, Charpy described in detail the construction of wire-wound, electrical-resistance based, tube furnaces that virtually revolutionized heating and temperature regulation [39]. Control of heating rate had to be active to avoid possibility of irregularities; however, little attention was paid to it as long as the heat source delivered a smooth temperature-time curve. All early users mention temperature control by altering the current and many descriptions indicate that this was done by manual or clockwork based operation of a rheostat in series with the furnace winding, the system still in practical use up to late fifties. However, the first automatic control was published by Carl Friedrich in 1912, which used a resistance box with a specially shaped, clock-driven stepped cam- plate on top. As the cam rotated it displaced a pawl outwards at each step and this in turn caused the brush to move on to the next contact, thus reducing the resistance of furnace winding. Suitable choice of resistance and profiling of the cam achieved the desired heating profile. There came also the reduction of sample size from 25 g down to 2.5 g, which lowered the ambiguity in melting point determination from about >2 C down to ~0.5 C. Rates of about 20 K/min were fairly common during the early period later decreased to about quarter. Early in 1908, it was Burgess [47] who considered the significance of various experimental curves in detail concluding that the area of the inverse-rate curve is proportional to the quantity of heat generated divided by the rate of cooling. The few papers published in the period up to 1920 gave, nonetheless, little experimental details so that White [48] was first to show more theoretically the desirability of smaller samples providing a more exhaustive study of the effect of experimental variables on the shape of heating curves as well as the influence of temperature gradients and heat fluxes taking place within both the furnace and the sample. It is obvious that DTA was initially more a qualitative empirical technique, though the experimentalists were generally aware of its quantitative potentialities. The early quantitative studies were treated semiempirically and based more on instinctive reasoning. Andrews (1925) was first to use Newton’s law while Berg gave the early bases of DTA theory [49,50], which was independently simplified by Speil. In 1939 Norton published his classical paper on differential thermal techniques where he made rather excessive claims for their value both in the identification and quantitative analysis exemplifying clay mixtures [51]. Vold (1948) [52] and Smyth (1951) [53] proposed a more advanced DTA theory, but the first detailed theories and applicability fashions, free from restrictions, became 9 accessible by followers in fifties [3,50,54-58], e.g., Keer, Kulp, Evans, Blumberg, Erikson,Soule, Boersma, Borchard, Damiels, Deeg, Nagasawa, Tsuzuki, Barshad, Strum, Lukaszewski, etc. In general, the thermoanalytical methods gained theoretical description early sixties [59-61]. The resulting thermal effects, explicitly temperature disparity (ΔT), can be analyzed at four different but gradually escalating levels [3,34,62,63]: fingerprinting (identity), quality, quantity (peak areas) and kinetics (peak shape) which were extensively applied to assessments of phase diagrams, transition temperatures, and chemical reactions, as well as to the qualitative analysis of metals, oxides, salts, ceramics, glasses, minerals, soils, and foods. Because of its easy accessibility DTA was used to study behavior of the constrain states of glasses [64-68], inherent processes conventionally viewed as a diagram of temperature (T) versus enthalpy (H) [66], which derivative resembles the entire DTA curve (informative for the analysis of glassforming processes [34]) .

21.4 Theoretical basis, quantitative thermometric and calorimetric measurements

In the beginning, DTA could not be classified as a calorimetric method since no heat was measured quantitatively [59-62]. Only the temperature was determined with the precision of the thermocouple. The quantitative heat effects were traditionally measured by calorimetry. Beside the above quoted ice-calorimeter pioneered by Laplace the early instrumentation for the determination of heat capacity was based on the classical adiabatic calorimeter and designed by Walther H. Nernst (1864-1941) [69,70] for low temperature measurements [71] (in Germany 1911). Its original experimental arrangement involved the introduction of helium gas as a thermally conducting medium by which the specimen would rapidly reach the temperature required for the next measurement. Although the measurements of heat changes is common to all calorimeters, they differ in how heat exchanges are actually detected, how the temperature changes during the process of making a measurement are determined, how the changes that cause heat effects to occur are initiated, what materials of construction are used, what temperature and pressure ranges of operation are employed, and so on. If the heat, Q, is liberated in the sample, a part of this heat accumulates in the calorimetric sample-block system and causes a quantifiable increase in the temperature. The remaining heat is conducted through the surrounding jacket into the thermostat. The two parts of the thermal energy are closely related. A mathematical description is given by the basic calorimetric equation, often called the Tian equation [72]. The calorimetry classification came independently from various sources, e.g. [3,73-75]. The principal characteristics of a calorimeter are the calorimeter capacity, effective thermal conductivity, and the inherent heat flux, occurring at the in- 10 terface between the sample-block, B, and the surrounding jacket, J. The temperature difference [3] , TB – TJ , is used to classify calorimeters, i.e., diathermal (TB ≠ TJ), isodiathermal (TB – TJ) = constant and d(TB – TJ)→0, adiabatic (TB = TJ), isothermal (TB = TJ = const.) and isoberobolic (TB – TJ)→0. The most common version of the instrument is the diathermal arrangement where the thermal changes in the sample are determined from the temperature difference between the sample- block and jacket. The chief condition is, however, the precise enough determination of temperatures. With an isodiathermal calorimeter, a constant difference of the block and jacket temperatures is maintained during the measurement, thus also ensuring a constant heat loss by introducing extra heat flux to the sample from an internally attached source (often called ‘microheater’). The energy changes are then determined from the energy supplied to the source. For low values of heat, the heat loss can be decreased to minimum by a suitable instrumental set-ups and this version is called as adiathermal calorimeter. An adiabatic calorimeter sup- presses heat losses by maintaining the block and jacket temperatures at the same temperature. Adiabatic conditions are more difficult to assure at both higher temperatures and faster heat exchanges so that it is preferably employed at low temperatures. Eliminating the thermal gradients between the block and the jacket by using an electronic regulation requires, however, sophisticated circuits and more complex set-ups. For this reason, the calorimeters have become experimentally very multi- faceted instruments. With compensation “quasiadiabatic” calorimeter, the block and jacket temperatures are kept identical and constant during the measurement as the thermal changes in the sample are suitably compensated, so that the block temperature remains the same. If the heat is compensated by phase transitions in the reseivoir in which the calorimetric block is contained, the instrument are often termed transformation calorimeter. Quasi-isothermal calorimeters are, in turn, instruments with thermal compensation provided by electric microheating and heat removal is accomplished by forced flow of a fluid, or by the well-established conduction through a system of thermocouple wires or even supplemented by Peltier cooling effect. The method in which the heat is transferred through a thermocouple system is often called Tian-Calvet calorimetry. A specific group is formed by isoperibolic calorimeters, which essentially operate adiabatically with an isothermal jacket. Even in the 1950s, it was a doubtful prediction that classical DTA and adiabatic calorimetry would merge, producing a differential scanning calorimeter (DSC). The name DSC was first mentioned by O’Neil [78] for a differential calorimeter that possessed continuous power compensation (close-to-complete) between sample and reference. This development came about because the key concern of calorimetry is the reduction of, and certainly also correction for, heat losses and/or gains due to inadvertent temperature distribution in the surroundings of the calorimeter. The heat to be measured can never be perfectly insulated; even in a true adiabatic calorimeter certain heat-loss corrections have to be made and resulting adiabatic deviation must then be corrected through extensive calibration experi- 11 ments. In order to cancel the heat losses between two symmetric calorimeters were used (e.g., twin calorimetry – one cell with the sample and the other identical, but empty or filled with a reference material), however presented control problems were not easy to handle [3]. True DSC is monitoring the difference between the counterweighing heat fluxes by two extra micro-heaters respectively attached to both the sample and reference in order to keep their temperature difference minimal, while the samples are maintained in the pre-selected temperature program. This technique was originally introduced by Eyraund in fifties [84]. Such an experimental regime bears a quite different measuring principle when comparing with DTA because the temperature difference is not used for the observation itself but is exclusively employed for the regulation only. Certainly, it is the way for accomplishing the most precise measurements of heat capacity (close to adiabatic calorimetry) but technically restricted, to the temperature range up to about 700 °C, where heat radiation become decisive making consequently the regulation and particularly compensation complicated. Three major types of DSCs emerged that all are classified as scanning [79], isoperibolic twin-calorimeters. One type makes use of approximate power compensation between two separately heated calorimeters, and the other two merely rely on heat exchange of two calorimeters placed symmetrically inside a single heater, but differing in the positions of the controlling thermometers. Even the ma- jority commercial DTA instruments can be classified as a double non-stationary resembling calorimeter in which the thermal behaviors of sample are compared with a correspondingly mounted, inert reference [3]. It implies control of heat flux from surroundings and heat itself is a kind of physico-chemical reagent, which, however, could not be directly measured but calculated on the basis of the measurable temperature gradients. We should remark that heat flow is mediated by massless phonons so that the inherent flux does not exhibit inertia as is the case for the flow of electrons. The thermal inertia of apparatus (as observed in DTA experiments) is thus caused by heating a real body and is affected by the entire properties of materials, which structure the sample under study. The decisive theoretical analysis of a quantitative DTA was based on the calculation of heat flux balances introduced by Factor and Hanks [80], detailed in 1975 by Grey [81], which premises were completed in 1982 by the consistent theory made up by Holba and Šesták [3,82,83]. It was embedded within a ‘caloric-like’ framework centred on macroscopic heat flows encountered between large bodies (DTA cells, thermostats). Present DTA/DSC instruments marched to high sophistication, computerization and miniaturization, see, e.g., Fig. 21.1 All the equations derived to the description of theoretical basis of DTA/DSC methods can be summarized within the following schema [3,34], which uses a general summation of inherent terms (each being responsible for the subsequent distinct function): Enthalpy + Heating + Inertia + Transient = Measured Quanti- ty. It implies that the respective effects of enthalpy change, heating rate and heat transfer are reflected in the value of the measured quantity for all set-ups of the 12 thermal methods commonly exercised. Worth noting is the inertia term, which is a particularity for DTA (as well as for heat-flux DSC) expressing a specific correction due to the sample mass thermal inertia owing to the inherent heat capacity of real materials. It can be visualized as the sample hindrance against immediate ‘pouring’ heat into its heat capacity ‘reservoir’ and it is apparent similarity to the definite time-period necessary for filling a bottle by liquid. Keep in mind, that the consequential compensation DSC calorimetry is of a different nature because it evaluates, instead of temperature difference (ΔT ⇒ 0), compensating heat fluxes and thus the heat inertia term is absent [3,34,82]. The practice and basis of DSC has been treated numerously [85,86]. In order to meet an experimental pre-requisition of the transient term (involving the instrumental constant characteristic of a particular DTA apparatus), the routine procedure of calibration is indispensable for a quantitative use of DTA. It is commonly guaranteed by a practice of an adequate incorporation of defined amounts of enthalpy changes by means of the selected test compounds (which widespread standardization, however, failed so that no ICTAC recommendation was issued). Nevertheless, in the laboratory scale, certain compounds (and their tabulated data) can be employed, but the results are questionable due to the various levels of the tabulated data accuracy. Thus it seems be recommendable to use the sets of solid solutions because they are likely to exhibit comparable degree of uncertainty (such as Na2CO3-CaCO3 or BaCO3-SrCO3 or various sesquioxides mixtures like manga- nese spinels) [3]. However, the use of the Joule heat effect from a resistance element on passage of electric charge is a preferable method for achieving a more ‘absolute’ calorimetric calibration. It certainly requires special set-ups of the measuring head enabling the attachment of the micro-heater either on the crucible surface (similarly to DSC) and/or by direct immersing it into the mass of (often pow- dered) sample. By combination of both experimental methods (i.e., substance’s enthalpies and electric pulses) rather beneficial results [87] may be obtained, particularly, when a pre-selected amount of Joule heat is electronically adjustable (e.g., simple selection of input voltage and current pairs) [3,34]. It was only a pity that no commercial producer, neither an ICTAC committee, have ever became active in their wider application.

21.5 Modulated temperature, exploration of constrained and nano-crystalline states, perspectives

Yet another type of thermal measurement that had an early beginning, but initially did not see wide application, is the alternating current (AC) calorimetry) [79,88]. Advantage of this type of measurement lies in the application of a modulation to the sample temperature, followed by an analysis of responses. By eliminating any signal that does not correspond to the chosen operating frequency, many of the heat-loss effects can be abolished. Furthermore, it may be possible to probe rever- 13 sibility and potential frequency-dependence of changes of the studied sample. The heat capacity Cs of the sample can be determined from the ratio of the heat-flow response of the sample, represented by its amplitude AHF, to the product of the amplitude of the sinusoidal sample-temperature modulation ATt and the modulation frequency ω=2π/p (p being the period). The next advancement in calorimetry occurred in 1992 with the amalgamation of DSC and temperature modulation to the temperature-modulated DSC (TMDSC) [79,89-91]. In this quasi-isothermal operation, sample temperature TS oscillates about the underlying temperature T0 (constant/increasing) similarly as in an AC calorimeter (which bears an analogy modulus of a familiar isothermal dynamic mechanical analysis - DMA). The en- suing phase lag, ε, is taken relative to a reference oscillation, TS = T0 + ATt sin (ωt - ε), and by deconvolution of the two signals; an average signal, practically identical to the standard DSC output and a reversing signal, related to the AC calorimetry. There, however, are additional factors necessary for consideration because of the peculiarity of twin calorimeter configuration, such as there is no thermal conductance between the sample and reference calorimeters, zero temperature gradients from the temperature sensors to the sample and the reference pans, and, also, zero temperature gradients within the contents of the pans. In other words, an infinite thermal conductance between temperature sensors and the corresponding calorimeters should be assumed. In summary, three directions of calorimetry were, thus, combined in the 20th century, which dramatically changed the capabilities of thermal analysis of materials [79]: The high precision of adiabatic calorimetry, the speed of operation and small sample size of DSC, and the possibility to measure frequency dependence of thermal behavior in AC calorimetry. Another reason for both the modulation mode and the high-resolution of temperature derivatives is the fight against ‘noise’ in the heat flow signal in temperature swinging modifications. Instead of applying a standard way of eliminating such noise (and other unwanted signal fluctuations) by a more appropriate tuning of an instrument, or by intermediary measurements of the signal in a preselected distinct window, the fluctuations can be forcefully incorporated in a controlled and regulated way of oscillation. Thus the temperature oscillations (often sinusoidal) are located to superimpose over the heating curve and thus incorporated in the entire experimentation (temperature-modulated DTA/DSC) [89]. This was, in fact, preceded by the method of so-called periodic thermal analysis introduced by Proks as early as in 1969 [92], which aimed at removing the kinetic problem of ‘undercooling’ by cycling temperature. Practically the temperature was alternated over its narrow range and the sample investigated was placed directly onto a thermocouple junction) until the equilibrium temperature for the coexistence of two phases was attained. Another way of a more clear-cut investigation was introduction of microanalysis methods using very small samples and millisecond time scales [93,94]. It involved another peculiarity of truthful temperature measurements of nano-scale crystalline samples [95] in the particle micro range with radius r. The measurement becomes size affected due to increasing role of the surface energy usually 14

p described by an universal equation: Tr/T∞ ≅ (1 – C/r) where ∞ portrays standard state and C and p are empirical constants (≈ 0.15 nm < C < 0.45 nm and p = 1 or ½) [96-98]. Measurement in such extreme conditions brings extra difficulties such as measuring micro-porosity [99], quenching [94] and associated phenomena of the sample constrained states [64-68], variability of polymeric macromolecules [100,101] together with non-equilibrating side effect or competition between the properties of the sample bulk and its entire surface [97] exposed to the contact with the cell holder [34]. Increasing instrumental sophistication and sensitivity provided possibility to look at the sample micro-locally [93,101-103] giving a better chance to search more thoroughly toward the significance of baselines, which contains additional but hidden information on material structure and properties (inhomogenei- ties, local nonstoichiometry, interfaces between order-disorder zones [104]). Pop- ular computer built-in smoothing of the noised experimental traces (chiefly baselines) can, however, become counterproductive. In the future, we may expect certain refining trends possible returning to the original single-sample set-ups with recording mere heating/cooling curves. How- ever, it will happen at the level of fully computerized thermal evidence involving self-evaluation of ‘calibration’ behavior of the sample thermal inertia and its sub- traction from the entire thermal record in order to proliferate thermal effects possibly computing the DTA-like records. In addition, it may even incorporate the application of an arbitrary temperature variation enabling the use of self-heating course by simple placing the sample into the preheated thermostat and consequent computer evaluation of standardized effects or hitherto making possible to intro- duce fast temperature changes by shifting the sample within the temperature gradient of a furnace [3,34], etc.. Worth noting are special trends [105] particularly based on the modified thermophysical procedure of the rate controlled scope of thermal analysis (RCTA) [106] and/or on the diffusion structural diagnostics as a result of suitably labeled samples [107]. Upcoming prospect of thermal analysis scheme may go down to the quantum world [108] as well as may extend to the global dimension [109] touching even the remote aspects of temperature relativity [110], which, however, would become a special dimension of traditional understanding yet to come.

21.6 Some issues of socially shared activity, thermoanalytical and calorimetric journals and societies

The historical development and practical use of DTA in the middle European territory of former Czechoslovakia [33] was linked with the names Otto Kallauner (1886-1972) and Joseph Matějka (1892-1960) who introduced thermal analysis as the novel technique during the period of the so called “rational analysis” of ceramic raw materials [111] replacing the process of decomposition of clay minerals 15 by digestion with sulphuric acid, which factually played in that time the role of the contemporary X-ray diffraction. They were strongly affected by the work of H. LeChatelier [38] and their visits at the Royal Technical University of Wroclaw (K. Friedrich, B. Wohlin) where the thermal behavior of soils (bauxite) was investigated during heating and related thermal instrumentation was elaborated. Calori- metric proficiency was consequently gained from Polish Wojciech Świętosławski (1881-1968). Much credit for further development of modern thermal analysis was attributed with Rudolf Bárta (1897-1985) who stimulated thermal analysis activity at his coworkers (Vladimír Šatava, Svante Procházka or Ivo Proks) and his students (Jaroslav Šesták) at the Institute of Chemical Technology (domestic abbrev- iation VŠChT) in Prague. In this aspect a special notice should be paid to the lengthy efforts, long journey and fruitful service of International Confederation of Thermal Analysis (ICTA and Calorimetry – ICTAC, instituted later in the year 1992 and facilitated by G. Della Gatta) as an important forerunner and developer in the field of thermal analysis, cf. Fig. 22.2. It has an important preceding history [6,112,113] connected with the former Czechoslovakia and thermoanalytical meetings organized by Prof. R. Bárta just mentioning the earliest 1st Conference on DTA, (Prague 1956), the 2nd (Pra- gue 1958) and the 3rd Conference on Thermography (Prague 1961) and the 4th Conference on DTA (Bratislava 1966). Robert C. Mackenzie (1920-2000) from Scotland was an invited guest at the 1961 meeting and upon the previous communication with Russian L.G. Berg and US P.D. Garn as well as Hungarian L. Erdey an idea for the creation an international society was cultivated aiming to enable easier contacts between national sciences, particularly across the separating ‘iron curtain”, which in that time divided the East and West Europe [6]. The first international conference on thermal analysis was then held in the Northern Polytechnic in London, April 1965 and was organized by British scientists namely B.R. Cur- rell, D.A. Smith, J.P. Redfern, W. Gerrard, C.J. Keattch and D. Dollimore with a help of R.C. Mackenzie, B. Stone and US professors P.D. Garn and W.W. Wen- dlant, Canadien H.G. McAdie, French M. Harmelin, Hungarian L. Erdey, Japanese T. Sudo, Swedish G. Berggrenn and Italian G. Lombardi. Some invited speakers from the East Europe were particularly asked to come to bridge then existing tough political control on physical, freedom and civil frontiers strongly restricting the human rights of the Easterners (dominated by Soviet Union until the late 80s), such as F. Paulik (Hungary) and J. Šesták (Czechoslovakia). The consequent ICTA foundation in Aberdeen, September 1965, was thus established by these great progenitors of thermal analysis, Russian Lev G. Berg being the first ICTA presidents (with the councilors J.P. Redfern, R.C. Mackenzie, R. Bárta, S.K. Bhat- tacharrya, C. Duval, L. Erdey, T. Sudo, D.J. Swaine, C.B. Murphy, and H.G. McAdie). The progress of thermal analysis was effectively supported by the allied foundation of international journal, which editorial board was recruited from the key- speaker of both 1965 TA conferences as well as from the renowned participants at the 2nd ICTA in Worcester (USA 1968). In particular it was Journal of Thermal 16

Analysis, which was brought into being by Judit Simon (1937-, who has been serving as the editor-in-chief until today) and launched under the supervision Hunga- rian Academy of Sciences (Akadémiai Kiadó) in Budapest 1969 (L. Erdey, E. Bu- zagh, F. and J. Paulik brothers, G. Liptay, J.P. Redfern, R. Bárta, L.G. Berg, G. Lombardi, R.C. Mackenzie, C. Duval, P.D. Garn, S.K. Bhattacharyya, A.V. Niko- laev, T. Sudo, D.J. Swaine, C.B. Murphy, J.F. Johanson, etc.) to aid preferably the worthwhile East European science suffering then under the egregious political and economic conditions. Secondly it came to pass Thermochimica Acta that appeared in the year 1970 by help of Elsevier [114] and, for a long time, edited by Wesley W. Wendlandt (1920-1997) assisted by wide-ranging international board (such as B. R. Currell, T. Ozawa, L. Reich, J. Šesták, A. P. Gray, R. M. Izatt, M. Harmelin, H. G. McAdie, H. G. Wiedemann, E. M. Barrall, T. R. Ingraham, R. N. Rogers, J. Chiu, H. Dichtl, P. O. Lumme, R. C. Wilhoit, etc.). The field growth lead, naturally, to continuous series of the US Calorimetry Conferences (CalCon) [115-117], which supposedly evolved from a loosely knit group operating in the 1940s to a recent highly organized assembly working after the 1990s. Worth mentioning are Hugh M. Huffman (1899-1950) and James J. Christensen (1931-1987), whose names were recently used to shield the CalCon Awards presented annually for achievements in calorimetry. There is a number of other respectable cofounders, pointing out D.R. Stull, G. Waddington, G.S. Parks, S. Sunner, F.G. Brickwedde , E.F. Westrum, J.P. McCullough, D.W. Osborne, W.D. Good, P.A.G. O’Hare, P.R. Brown, W.N. Hubbart, R. Hultgren, R.M. Izatt, D.J. Eatough, J. Boerio-Goates, J.B. Ott). It provided a good example how the democracy-respecting society changing their chairmanships every year, which, however, did not find a place in the statutes of later formed ICTA. Consequential- ly, the Journal of Chemical Thermodynamics began publication in the year 1969 firstly edited by L.M. McGlasham, E.F. Westrum, H.A. Skinner and followed by others. More details about the history and state-of-art of thermal science and the associated field of thermal analysis were published elsewhere [3-6,32- 35,79,112,113,115-117]. A specific domain of thermal analysis worth of attention (but laying beyond this file) is the weight measurement under various thermal regimes, pioneered by Czech Stanislav Škramovský (1901-1983) who coined the term ‘statmograph’ (from Greek stathmos = weight) [1,6,35], which, however, was overcome by the generalized expression ‘thermogravimetry’ as early introduced by French Clément Duval (1902-1976) or Japanese Kotaro Honda (1870-1954) [33-35, 118-121]. Consequently, it yielded a very popular topic of simultaneous weight-to-caloric measurements under so called quasi-isothermal and quasi-isobaric conditions [35,122] making use of the apparatus ‘derivatograph’, see Fig. 21.1, originated in Hungary in late 1950’s [122], see Fig. 21.3. It apparently lunched an extended field of microbalance exploitation and their presentation in regular conferences [123]. 17

; 18

Fig. 21.2 Portraits show some influential personalities on the international scene, which are noteworthy for their contributions to the progress of the fields of thermal analysis (TA) and calorimetry including the founders of ICTA/ICTAC (around the inserted emblem), living persons limited to age above 75. Upper from left: Cornelius B. Murphy (1918-1994), USA (TA theory); Robert C. Mackenzie (1920-2000), Scotland (DTA, clay minerals, history); Sir William C.Roberts-Austen (1843-1902), England (thermoelectric pyrometer); Gustav H.J. Tammann (1861-1938), Germany (inventing the term thermal analysis) and Nikolaj S. Kurnakov (1860-1941), Russia (contriving the first usable DTA); below: Lev G. Berg (1896-1974), Russia (TA theory); Rudolf Bárta (1897-1985), Czechoslovakia (ceramics, cements); Walther H. Nernst (1864-1941), Germany (originating low-temperature calorimetry); Edouard Calvet (1895-1966), France (heat-flow cao- lrimetry) and Henry L. Le Chatelier (1850-1936), France (devising thermocouple); yet below: David J. Dollimore (1927-2000), England (later USA – theory, kinetics) ; Hugh M. Huffman (1899-1950), USA, founder of CalCon; James J. Christensen (1931-1987), USA (calorimtery); Wojciech Świętosławski (1881-1968), Poland (calorimetry); Čeněk Strouhal (1850-1922), Cze- choslovakia (thermics, Strouhal numbers); yet below: Hans-Joachim Seifert (1930-), Germany (phase diagrams); Takeo Ozawa (1932-), Japan (energetic materials, kinetics); Eugene Segal (1933-), Romania (kinetics); Hiroshi Suga (1930-), Japan (calorimetry) and Giuseppe Della Gatta (1935-), Italy (calorimetry); yet below: Wesley W. Wendlandt (1920-1997), USA (TA theory, instrumentation); Bernhard Wunderlich (1931-), USA (macromolecules, modulated TA); Paul D. Garn (1920-1999), USA (TA theory, kinetics) ; Jean-Pierre E. Grolier (1936-), France (calorimetry) and Ole Toft Sǿrensen (1933-), Denmark (CRTA, non-stoichiometry); Bottom: Cyril J. Keattch (1928-1999), England (thermogravimetry); Hans G. Wiedemann (1920-), Switzerland (TG apparatuses, instrumentation); Shmuel Yariv (1934-), Israel (earth minerals); Joseph H. Flynn (1922-), USA (DSC, kinetics) and Patrick K. Gallagher (1931-), USA (inorganic materials)

Fig. 21.3 Recognized pioneers of thermal analysis, of Hungarian origin, who were accountable for the development of instruments (popular East- European TA apparatus “derivatograph”) - Fe- renc Paulik (1922-2005), right, and for initiation of fingerprint methodology (multivolume atlas of TA curves by Akademia Kiado) - Geörge Liptay (1931-), left

Fig. 21.4 The photo from 28th conference of the Japanese Society on Calorimetry and Thermal Analysis (JSCTA) in Tokyo (Waseda University, 1992) shows (from left) M. Taniguchi (Japan), late C.J. Keattch (GB), late R. Otsuka (Japan), S. St. J. Warne (Australia, former ICTA president), H. Suga (Japan), J. Šesták (Czechoslovakia) and H. Tanaka (Japan). The regular JSCTA conferences started in Osaka 1964 under the organization of Prof. S. Seki who became the first president when the JSCTA was officially established in 1973. Since then, the JSCTA journal NETSU SOKUTEI has been published periodically. 19

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IN:

http://www.springer.com/materials/special+types/book/978-90-481- 2881-5?detailsPage=free

Glassy, Amorphous and Nano-crystalline Materials

Thermal Physics, Analysis, Structure and Properties Series: Hot Topics in Thermal Analysis and Calorimetry, Vol. 8 Šesták, Jaroslav; Mareš, Jiri J.; Hubik, Pavel (Eds.) 1st Edition., 2010, Approx. 350 p., Hardcover ISBN: 978-90-481-2881-5 Due: October 2, 2010 SOME HISTORICAL ASPECTS OF THERMAL ANALYSIS: ORIGINS OF TERMANAL AND ICTA

Jaroslav Šesták

Institute of Physics, Academy of Sciences Cukrovarnicka 10, CZ-16253 Prague 6 and Faculty of Applied Science, West Bohemian University, Universitni 8, CZ-30614, Pilsen, Czech Republic [email protected]

This brief story of the birth and early growth of the field of thermal analysis has been prepared in order to celebrate the coincidence jubilee of the 140th Anniversary of the Czech-and-Slovak Chemical Society, 50th Anniversary of Czechoslovak and Slovak thermoanalytical conferences and 40th Anniversary of the International Confederation of Thermal Analysis. It includes both the scientific and societal figures about international and national backgrounds.

There is a rather extensive literature dealing with the subject of thermal analysis including its historical aspects, which thorough survey [1–22] is not the aim of this article. Here we would like to concentrate to some objective aspects and personal experience seen and witnessed during the 40 years of the domain growth and maturing when taking into account that thermal analysis (thermometry) is the hierarchically superior as well as joining subject for later separated calorimetry and general non- isothermal studies (particularly in kinetics). The first person to use a kind of continuous heating and cooling of a sample for investigation of the properties of substances was curiously Czech thinker and Bohemian educator Jan Amos Comenius (1592–1670). In his Physicae Synopsis, which he finished in 1629 and published first in Leipzig in 1633, the importance of hot and cold in all natural processes was frequently stressed. Heat (or better fire) is considered as the cause of all motions of things. The expansion of substances and the increased space they occupy is caused by their dilution with heat. By the influence of cold the substance gains in density and shrinks. The condensation of vapor to liquid water is given as an example. Comenius also determined (although very inaccurately) the volume increase in the gas phase caused by the evaporation of a unit volume of liquid water. In Amsterdam in 1959 he published a treatise investigating the principles of heat and cold [24], which was probably inspired by the works of the Italian philosopher Bernardino Telesius. The third chapter of Comenius’ book was devoted to the description of the influence of temperature changes on the properties of substances. The aim and principles of thermal analysis were literally given in the first paragraph of this chapter: citing the English interpretation “In order to observe clearly the effects of heat and cold, we must take a visible object and observe its changes occurring during its heating and subsequent cooling so that the effects of heat and cold become apparent to our senses”. In the following 19th paragraphs of this chapter Comenius gave a

1 rather systematic description (and also a partially correct interpretation) of the effects of continuous heating and cooling of water and air, and also stresses the reversibility of processes like, for example, evaporation and condensation, etc., preceding somehow the concept of latent heat. Comenius concludes this chapter as follows: “All shows therefore that both heat and cold are a motion, which had to be proved.” In the following chapter Comenius described and almost correctly explained the function of a thermoscope (‘vitrum caldarium’) but introduced his own qualitative scale with three degrees of heat above and three degrees of cold below with the ambient temperature in the middle. The modern interpretation of heat was given by Čeněk Strouhal (1850–1922) [24] and its historical aspects were later detailed in [18, 21, 22]. Some historical features of measuring heat and temperature With little doubts, until the work of Black and Irvine in the middle of 18th Century, the notions of heat and temperature (from temper or temperament first used by Avicenna in the 11th Century) were not yet distinguished in-between. Black’s work, together with that done by Magellan, revealed the quantity that caused a change in temperature (but which was itself not temperature) providing thus the modern concepts of latent heat and heat capacity. They explained how heat is absorbed without changing temperature and what amount heat is needed to increase a body’s temperature by one unit. The key factor in his theory was the new substance of heat (or ‘matter of fire’), called caloric, which crept in among the constituent parts of a substance and gave it expansibility. Caloric differed from foregoing concept of phlogiston because it could be measured with an apparatus called a calorimeter, which was first designed by Wilcke and later used by Laplace, Lavoisier and others. Nevertheless, caloric was seen as an imponderable element with its own properties. Unfortunately, the great pioneers, Irvine and Black, published almost nothing in their own lifetimes and their attitudes were mostly reconstructed from contemporary comments and essays published after their death. Irvine supposed that heat was absorbed by a body during melting or vaporization, simply because at the melting or boiling points sudden changes took place in the ability of the body to contain heat. Irvine’s account that the relative quantities of heat contained in equal weights of different substances at any given temperature (i.e., their ‘absolute heats’) were proportional to their ‘capacities’ at that temperature and it is worth noting that the term ‘capacity’ was used by both Irvine and Black to indicate specific heats. They also introduced the term ‘latent heat’ which meant the absorption of heat as the consequence of the change of state. Black’s elegant explanation of latent heat to the young Watts became the source of the invention of the businesslike steam engine as well as the inspiration for the first research in theory related to the novel domain of thermochemistry, which searched for general laws that linked heat, with changes of state. Rumford presented qualitative arguments for such a fluid theory of heat with which he succeeded to evaluate the mechanical equivalent of heat. This theory, however, was not accepted until later approved by Mayer and, in particular, by Joule, who also applied Rumford’s theory to the transformation of electrical work. The use of customary units called ‘calories’ was introduced by Favren and Silbermann in 1853. The characterization of one kilocalorie as 427 kilogram-meters was first launched by Mayer in the year 1845. The caloric-like description of heat as a fluid has survived, nevertheless, until today being a convenient tool for easy mathematical depiction of flows. The roots of modern thermal analysis extends back to the 18th Century, again, because the temperature became better understood as an observable and experimentally decisive quantity, which thus turned into an experimentally monitorable parameter. Indeed, its development was gradual and somewhat international so that it is difficult to ascribe an exact date. First accepted definition of

2 thermal analysis permits, however, identification of the earliest documented experiment to meet current criteria. In Uppsala 1829, Rudberg [14, 21] recorded inverse cooling-rate data for lead, tin, zinc and various alloys. Although this contribution was recognized even in Russia by Menshutkin it was overlooked in the interim and it is, therefore, worthwhile to give a brief account here.

Early thermometry showing the time-honored ice calorimeter, which was first intuitively used by Black and in the year 1780 improved by Lavoisier and Laplace. The heated body is cooled down while placed in ice and the heat subtracted is proportional to the amount of melted water. In the year 1852, Bunsen proposed its more precise variant while determining volume instead of weight changes (middle). The cooling calorimeter was devised 1796 by Mayer, Dulong and Petit, but became known through the experiments by Regnault. Thermochamical measurements were furnished by Favre and Silbermann in 1852 using the idea of Bunsen ice calorimeter but replacing ice by mercury the volume measurement of which was more sensitive. Favre and Silbermann are not widely known for their early construction of a combustion calorimeter, which was adjusted for higher pressures by Berthelot (known as today’s calorimetric bomb).

The bare equipment thus used consisted of an iron crucible suspended by thin platinum wire at the center of a large double-walled iron vessel provided with a tight-fitting, dished with iron lid, through which passed a thermometer with its bulb in the sample. The inner surface of the outer container and the outer surface of the crucible were blackened to permit the maximum achievement of heat transfer. The spaces between two walls of the outer large vessel, as well as the top lid, were filled with snow to ensure that the inner walls were always kept at zero temperature. In this way a controlled temperature program was ensured once the crucible with molten metal or alloy had been positioned inside and the lid closed. Once the experiment was set up Rudberg noted and tabulated the times taken by the mercury in thermometer to fall through each 10 degrees interval. The longest interval then included the freezing point. The experimental conditions were, if anything else, superior to those used by careful experimentalist, such as Roberts-Austen some 60 years later. The next experiment that falls into the category of thermal analysis was done in 1837 by Frankeheim who described a method of determining cooling curves (temperature vs. time). This method was often called by with his name but later also associated with the so-called Hannay’s time method, when temperature is increased every time (such a plot would resemble what we now call ‘isothermal mass-change curves’). In 1883, Le Chatelier [26] adopted a somehow more fruitful approach immersing the bulb of thermometer within the sample in an oil bath, which maintained a constant temperature difference (usually 20º between the thermometer and another one placed in the bath). He plotted time temperature curve easily convertible to the sample vs. environmental temperatures, factually introducing the ‘constant-rate’ or ‘quasi-isothermal’ program. At that time, thermocouples were liable to give varying outputs so that Le Chatelier was first

3 to attribute an arrest at about red heat in the output of the platinum-iridium alloy to a possible phase transition. He deduced that thermocouple varying output could result from contamination of one wire by diffusion from the other one possibly arising also from the non-uniformity of wires themselves. The better homogeneity of platinum-rhodium alloy led him to the standard platinum – platinum/rhodium couple so that almost seventy years after the observation of thermoelectricity, its use in thermometry was finally vindicated. The development of thermocouple, as an accurate temperature measuring device, was rapidly followed by Osmond (1886) who investigated the heating and cooling behavior of iron and steel with a view to elucidating the effects of carbon so that he factually introduced thermal analysis to then most important field: metallurgy. However, in 1891, Roberts-Austen [26] was known to construct a device to give a continuous record of the output from thermocouple and he termed it as ‘Thermoelectric Pyrometer’. Though the sample holder was a design reminiscent of modern equipment, its capacity was extremely large decreasing thus the sensitivity but giving a rather good measure for reproducibility. It was quickly realized that a galvanometer was rather insensitive to pick up small thermal effects. This disadvantage was improved by coupling two galvanometers concurrently and later the reflected light beam was directed to the light-tight box together with the slit system enabling exposition of the repositioned photographic plate. Stanfield (1899) published heating curves for gold and almost stumbled upon the idea of DTA (Differential Thermal Analysis) when maintaining the ‘cold’ junction at a constant elevated temperature measuring thus the differences between two high temperatures. Roberts-Austen consequently devised the system of measuring the temperature difference between the sample and a suitable reference material placed side-by-side in the same thermal environment, thus initiating development of DTA instruments. Among other well-known inventors, Russian Kurnakov [2, 5] should be noticed as he improved registration building his pyrometer on the photographic, continuously recording drum, which, however, restricted his recording time to mere 10 min. The term thermal analysis was introduced by Tamman within the years 1903–1905 [27] who demonstrated theoretically the value of cooling curves in phase-equilibrium studies of binary systems. It was helped by this new approach that enabled the determination of composition of the matter without any mechanical separation of crystals just on basis of monitoring its thermal state by means of its cooling curves – the only method capable of the examination of hard-to-melt crystal conglomerates. It brought along a lot of misinterpretations – the legendary case of the high-alumina regions of the quartz-alumina binary system continuously investigated for almost hundred years. It, step by step, revealed that the mullite phase irregularly exhibited both the incongruent and congruent melting points in dependence to the sample course of equilibration. It showed that mere thermal analysis is not fully suitable for the study of phase equilibria, which settle too slowly. In 1909 there was elaborated another reliable procedure of preserving the high-temperature state of samples down to laboratory temperature, factually freezing-in the high-temperature equilibrium as a suitably ‘quenched’ state for further investigation. It helped in the consistent construction of phase diagrams when used in combination with other complementary analytical procedures, such as early X-ray diffraction or metallographic observations. By 1908, the heating or cooling curves, along with their rate derivatives and inverse curves, assumed enough sufficient importance to warrant a first review and more detailed theoretical inspection, Burgess [28]. Not less important was the development of heat sources where coal and gas were almost completely replaced by electricity as the only source of controllable heat. In 1895, Charpy described in detail the construction of wire-wound, electrical resistance, tube furnaces that

4 virtually revolutionized heating and temperature regulation [29]. Control of heating rate had to be active to avoid possibility of irregularities; however, little attention was paid to it as long as the heat source delivered a smooth temperature-time curve. All early users mention temperature control by altering the current and many descriptions indicate that this was done by manual or clockwork based operation of a rheostat in series with the furnace winding, the system still in practical use up to late fifties. The first automatic control was published by Friedrich in 1912, which used a resistance box with a specially shaped, clock-driven stepped cam on top. As the cam rotated it displaced a pawl outwards at each step and this in turn caused the brush to move on to the next contact, thus reducing the resistance of furnace winding. Suitable choice of resistance and profiling of the cam achieved the desired heating profile. There came also the reduction of sample size from 25 g down to 2.5 g , which reduced the uncertainty in melting point determination from about 2 °C to 0.5 °C. Rates of about 20 K/min were fairly common during the early period later decreased to about quarter. It was Burgess [28] who considered significance of various curves in detail and concluded that the area of the inverse- rate curve is proportional to the quantity of heat generated dived by the rate of cooling. The few papers published in the period up to 1920 gave little experimental details so that White was first to show theoretically in 1909 the desirability of smaller samples. He described an exhaustive study of the effect of experimental variables on the shape of heating curves as well as the influence of temperature gradients and heat fluxes taking place within both the furnace and the sample [30]. It is obvious that DTA was initially more an empirical technique, although the experimentalists were generally aware of its quantitative potentialities. The early quantitative studies were treated semiempirically and based more on instinctive reasoning and Andrews (1925) was first to use Newton’s law while Berg (1942) gave the early bases of DTA theory [5,7] (independently simplified by Speil). In 1939 Norton published his classical paper on techniques where he made rather excessive claims for its value both in the identification and quantitative analysis exemplifying clay mixtures [31]. Vold (1948) [32] and Smyth (1951) [33] proposed a more advanced DTA theory, but the first detailed theories, absent from restrictions, became accessible [4–13] by Keer, Kulp, Evans, Blumberg, Erikson, Soule, Boersma, Deeg, Nagasawa, Tsuzuki, Barshad, etc., in fifties. Most commercial DTA instruments can be classified as a double non-stationary calorimeter in which the thermal behaviors of sample are compared with a correspondingly mounted, inert reference. It implies control of heat flux from surroundings and heat itself is understood to be a kind of physical- chemical reagent, which, however, could not be directly measured but calculated on the basis of the measurable temperature gradients. We should remark that heat flow is intermediate by mass-less phonons so that the inherent flux does not exhibit inertia, as is the case for the flow of electrons. The thermal inertia of apparatus (as observed in DTA experiments) is thus caused by heating a real body and is affected by the properties of materials, which structure the sample under study. Theoretical analysis of DTA is based on the calculation of heat flux balances introduced by Factor and Hanks [34], detailed in 1974 by Grey [35], which premises were completed in 1975 by the consistent theory of Holba and Šesták [13, 36]. It was embedded within a ‘caloric-like’ framework based on macroscopic heat flows between large bodies (cells, thermostats). The need of a more quantitative calibration brought about the committed work of ICTAC and the consequently published recommendations providing a set of the suitable calibration compounds. Calorimetric ‘pure’ (i.e. heat inertia absent) became the method of DSC (Differential Scanning Calorimetry), which is monitoring the difference between the compensating heat fluxes while the samples are maintained in the pre- selected temperature program (Eyraud 1954) [37]. This is possible providing two extra micro-heaters are respectively attached to both the sample and the reference in order to maintain their temperature

5 difference as minimal as experimentally possible. Such a measuring regime is thus attained only by this alteration of experimental set up where the temperature difference is not used for the measurement itself but is exclusively employed for regulation. It became a favored way for attaining the most precise measurements of heat capacity, which is close to the condition of adiabatic calorimetry. It is technically restricted to the temperature range up to about 700 °C, where heat radiation turns decisive and makes regulation complicated. Another modification was found necessary for high-resolution temperature derivatives to match to the ‘noise’ in the heat flow signal. Instead of the standard way of eliminating such ‘noise/fluctuations’ by more appropriate tuning of an instrument, or by intermediary measurements of the signal in distinct windows, the fluctuations were incorporated in a controlled and regulated way. The temperature oscillation (often sinusoidal) were superimposed on the heating curve and thus incorporated in the entire experimentation – the method known as temperature-modulated DTA/DSC (Reading 1993 [38]). This was preceded by the method of so-called periodic thermal analysis (Proks 1969 [39]), which was aimed at removing the kinetic problem of undercooling by cycling temperature. Practically the temperature was alternated over its narrow range and the ample investigated was placed directly onto a thermocouple junction) until the equilibrium temperature for the coexistence of two phases was attained.

Upper: Thermo-Electric Pyrometer of Roberts-Austen (1881) showing the instrument (left) and its cooling arrangement (right) with particularity of the sample holder. Below: Once popular DTA instruments by Netzsch showing the gradual sophistication from a manual macro-scale in early 1950s (left), additionally self-computerized in our laboratory (1970s) to the recent automatic micro-scale DSC in 2000s (right).

6 In the sixties, various thermoananytical instruments became available on the market and since that the experienced and technically sophisticated development has matured the instruments as automatons to reach a very advanced level, which certainly includes a comprehensive computer control and data processing. Their description is the subject of numerous manufacturers’ booklets and manuals, addressers on websites, etc., so that it falls beyond the scope of these notes. Thermal analysis in the territory of Czech-Slovakia and its impact on ICTA The development of standard methods of thermal analysis in the territory of present-day Czech Republic is linked with the names of O. Kallauner (1886–1972) and J. Matějka (1892–1960) [1] who enabled that this novel technique came into a common use during the course of a period of so called “rational analysis” of ceramic raw materials replacing the process of decomposition of clay minerals by digestion with sulphuric acid which factually played in that time the role of the contemporary X-ray diffraction. They were strongly affected by the work of H. LeChatelier [25] and their visits at the Royal Technical University of Wroclaw (K. Friedrich, B. Wohlin) where the thermal behavior of soils (bauxite) was investigated during heating and related thermal instrumentation was elaborated [40]. After the World War I, Matějka performed a broad investigation of chemical transformations of kaolinite under heating (5 g in-weight, 30 °C/min, reproducible location of the thermocouple junction under reproducible sample packing) and observed as the first the water liberation in the range of

500–600 °C associated with the formation of mineral Al2O3-2SiO2 (dissolvable in acids) and its further exothermic transformation to Al8Si3O18 (~dumotierite) at 900 °C and coexistence of SiO2 with sillimanite above 1100 °C [41]. This study was later esteemed by R. C. Mackenzie [8] who pioneered modern thermal evaluation of clays. The development of thermogravimetry is connected with the name S. Škramovský (1901–1983) who investigated thermal decomposition of complex oxalates (of Sc, Pb and Bi) which led him in 1932 to his own construction of an apparatus named “stathmograph” (from Greek “stathmos” = weight) [42] under consequence of the work of Guichard. A weighted sample was placed into the drying oven on a dish suspended on a long filament passing through a hole in its upper wall (forming the balance case) to a hook on the left arm of an analytical balance. A mirror was attached to the middle of the beam reflecting the image of alight slit into a slowly rotating drum lined with photosensitive paper. The vibration was reduced by an attached glass rod immersed into paraffin oil and temperature registered automatically by means of a mercury thermometer provided by platinum contacts distributed along the whole length of capillary. He pioneered his technique for various applications (pharmacology). Much credit for the development of TA methods in the former Czechoslovakia after the World War II must be attributed to R. Bárta (1897–1985) as he stimulated his coworkers (S. Procházka, V. Šatava, M. Čáp, M. Vašíček) to construct devices for DTA and TG and the application of these measurements to phase analysis 43] (respectively published in the institutional proceedings in 1954, 1955 and 1956). It also led to the development of few samples of commercially produced TG instrument “TEGRA” [44]. Some original principles and unique techniques were developed and applied by the Czech-Slovak scientists, such as I. Proks (Periodic TA [39]), J. Brandštetr (Enthalpiometry [45]), J. Komrska (Photometric TA [46]), A. Bergstein (Dielectric TA [47]), S. Chromý (Photometric TA [48]), V. Šatava (Hydrothermal TA [49]), V. Balek (Emanation TA [50]) or M. Vaniš (Accelerated TA [51]). Worth mentioning is the introduction of multi-store (ribbed) crucible for thermogravimetry [52], invention of new method for kinetic data evaluation [53], kinetic model (fractal) equation often named after the

7 authors [53] and a first attempt to solve the kinetic problem of oscillatory reactions [54]. Other important reports tackled the classification of calorimetry [55] or the application of theoretical TA (thermodynamics) in construction of phase diagram [56]. The development of the determination of heat capacities at high- and low- temperature ranges is worth mentioning. A high-temperature calorimeter was designed by the M. Roubal [57] allowing determination of heat capacities in the range of 900–1900 K. V. Pekárek initiated the construction of a isoberobolic calorimeter for the determination of hydrogenation heats in catalytic studies and V. Tydlidát designed a calorimeter for investigating the hydration of cement pastes at increased temperatures [58]. Thermochemical analysis was successfully studied by V. Velich [59] using an isoperibolic calorimeter with an already on-lined computer. The important invention was done within the work of the Slovak Institute of Physics in Bratislava where L. Kubičár [60] designed a new twin dynamic high-temperature calorimeter for the measurements of small thermal effect and introduced the pulse method for heat diffusivity measurement. Thanks to the Bárta’s undertakings the informal discussions on thermal analysis was already held just after the World II curiously unaffected by his undermined health after his return form the Nazis concentration camp. The entire series of thermoananlytical conferences were started within the continuous Bárta’s activity at the Department of Glass and Ceramics of the Prague Institute of Chemical Technology by fifties despite very sever political situation when many of renowned scientists and professor were expelled from their jobs by the communistic totalitarianism (including Bárta). Initial, recently obsolete terminology, (thermography) was gradually replaced by the recognized terms: thermal analysis or DTA and the final adjustment was made by the Slovak thermoanalysts, who started their famous and someway outstanding project of the national (and also international) conferences, abbreviated as TERMANALs, which continue their earnest to exist until today. It was positively effected by the foundation of the Slovak Group on Thermal Analysis 1972 (M. Vaniš, O. Koráb, V. Tomková, Š. Svetík, P. Králík, late A. Sopková, S. Fajnor, E. Smrčková) and the Czech Group on Thermal Analysis 1974 (V. Balek, J. Šesták, K. Habersberger, P. Holba, late J. Rosický, J. Ederová, M. Beránek, M. Nevřina) both acting under the roof of Czech-Slovak Chemical Society.

5th Congress of Czech natural scientists and physicists, Prague 1914 (already involving some aspects of thermometric studies) 0th Discussion Meeting on Thermography, Prague 1955 1st Thermography Day, Prague 1956 2nd Conference on Thermography, Prague 1958 3rd Conference on Thermography, Prague 1961 4th Conference on DTA, Bratislava 1966 5th Conference on DTA, Smolenice 1970 6th Czechoslovak Conference on TA: TERMANAL, High Tatras 1973 7th, 8th and 9th TERMANALs, High Tatras 1976, 1979 and 1982 10th TERMANAL and 8th ICTA, Bratislava 1985

Very important discussion meetings, which effected the early construction of international cooperation, were curiously held in Prague during fifties. Though kept under surveillance of communistic secret police, Prof. P. D. Garn (1920–1999) and later, for the most part, Dr. R. C. Mackenzie (1920–2000) paid personal visits to see Prof. R. Bárta. Especially, during the 3rd Thermography Meeting in Prague, Dr. Mackenzie together with Drs Šatava, Čáp, Vašíček, Procházka (curiously including Šesták, who was then a postgraduate student) agreed on the project of an

8 international organization, which would assist an international exchange and being preliminary of a help for discriminated scientists, who started to languish inside the former (so called) ‘Eastern Block’ (meticulously separated from the other world by an “iron fence”). Thus a special notice should be paid to the lengthy efforts and services of International Confederation of Thermal Analysis (ICTA) later including Calorimetry (ICTAC) as an important forerunner of the field of thermal analysis. The first international conference on thermal analysis held in the Northern Polytechnic in London, April 1965, consisted of about 400 participants from various countries, where the choice of key lectures offered the first account of thermoanalysts notable in the field progress.

Some illustrative photos from international meetings, where we can recognize some renowned personalities, for example (clockwise from the upper left) the occasions of Termanal’73: late M. Malinovský and G. Lommbardi; Termanal‘76: V. Tomková, late V. Jesenák and V. Šatava; Budapest‘75: F. Paulik, D. Schultze and W. Hemminger; Bratislava‘85: A. Blažek, P. Gallagher, M. Hucl or H. J. Seifert; Japan‘91: late C. J. Keattch, late R. Otsuka, S. Warne, H. Suga and H. Mitsuhashi; and Zakopane‘87: H. Piekrasky, K. Wiczorek-Ciurowa, B. Pacewska and J. Pysiak.

9 The 1965 meetings paved the way to the newborn opportunity for a better international environment for thermal analysis assisted by the great pioneers such as B. R. Currell, D. A. Smith, R. C. Mackenzie, P. D. Garn, R. Bárta, M. Harmelin, W. W. Wendlant, J. P. Redfern, L. Erdey, D. Dollimore, C. B. Murphy, H. G. McAdie, L. G. Berg, M. J. Frazer, W. Gerard, G. Lombardi, F. Paulik, C. J. Keattch, G. Berggren, R. S. Forsyth, J. Šesták, M. A. Dudley, K. Heide, W. L. Charsley, R. Otsuka, T. Sudo, G. Takeya, C. Duval, M. Vaniš, P. Imriš, B. Číčel, K. Melka, J. Skalný, S. Yariv, J. J. Fripiat, S. K. Bhattacharyya, H. L. Friedman, K. Heide, V. Šatava, E. Segal, T. R. Ingraham, L. Eyrund, C. D. Doyle, T. L. Webb, W. Lodding, D. J. Swaine, A. V. Nikolayev, J. E. Kruger, H. Lehmann, M. Müller-Vonmoos, F. W. Wilburn, W. Bodenheimer, A. LaGinestra, B. Dobrovišek, D. Delič, A. Langier-Kužniarowá, J. H. Sharp, J. L. White, R. L. Stone, J. L. M Vivaldi, etc., in their effort to establish such a constructive scientific forum to be cooperative for all thermoanalysts. An international platform of thermal sciences then began in earnest when ICTA was established in Aberdeen, September 1965, which has productively kept going until now appreciative the precedents of friendly manners, scientific merit and cooperative frame of minds.

Group photography of the ICTA Council meeting in the castle Liblice near Prague, which took place at the occasion 8th ICTA Conference in Bratislava 1985 (former Czechoslovakia), celebrating the 20th anniversary of ICTA foundation. From left: Edward. L. Charsley (England), behind Michael E. Brown (South Africa), Bordas S. Alsinas (Spain), late Walter Eysel (Germany), late Vladislav B. Lazarev (Russia), late Paul D. Garn (USA), John O. Hill (Australia), John Crighton (England), Tommy Wadsen (Sweden), Joseph H. Flynn (USA), Patric K. Gallagher (USA), Hans-Joachim Seifert (Germany), Slade St. J. Warne (Australia), behind Klaus Heide (Germany), Vladimír Balek (Czechia), late Viktor Jesenák (Slovakia), Milan Hucl (Slovakia), Jaroslav Šesták (Czechia), late Jaroslav Rosický (Czechia), behind Shmuel Yariv (Izrael), right Erwin Marti (Switzerland) and Giuseppe Della Gatta (Italy). Bottom are exampled the early front pages of below mentioned journals and the emblem of ICTAC.

However, the original intention of ITCA as to enhance and fully open an international cooperation was somehow elapsed and from the first incorporation of the Eastern scientists among the ICTA officers at the turn of sixties (Berg, Bárta, Erdey) no one from the East was further elected into the ICTA Executive, which was partly due to the anxiety for possible vexatiousness imposed by the

10 Eastern governments and partly due to the executive’s feeling of an unchanged comfort to stay at the office as long as possible. Unfortunately, it later created unspoken feeling of certain ‘lobbyism’ as, explicitly, there was recently elected from the North American region the forth candidate for the ICTA president leaving thus the Easterners to keep waiting in line for more than 30 years. As a very personal note, I am sorry to disclose some unfriendly attitude towards the Eastern community, which appeared even in such an unusual manner today as the early data on ICTA formation were refused to make available to the author when he was writing this article. One of the topmost achievements of the Czech-Slovak thermoanalysts was the organization of the 8th ICTA in Bratislava, August 19–23, 1985. Factually, it was a brave attempt to prepare and carry out an open international conference in communistic Czechoslovakia where a democratic presentation was yet sanctioned and where a “socialistic preferences” were enforced. In spite the political pressure and under the close watch of secret police the invited plenary lectures were equally aimed also at the Western scientists (R. C. Mackenzie, Scotland and I. Proks, Slovakia; T. Ozawa, Japan; G. Lombardi, Italy Z. G. Szabo, Hungary, E. Gmelin, Germany; V. Jesenak, Slovakia; V. V. Boldyrev, USSR; B. Wunderlich, USA and H. G. Wiedemann, Switzerland – the latter two were the first immigrant scientist from the past East Germany to be invited as honorary guests). It was also for the first time that the scientist from so called ‘hostile capitalistic countries’ were allowed to visit Czechoslovakia (such as S. Yariv from Israel or M. E. Brown from South Africa). Thus it is worth to remember and yet esteem the credibility of the ICTA’8 organizing committee that was bravely acting as follows

M. Hucl, Slovak Technical University, Bratislava, Chairman V. Balek, Nuclear Research Institute, Řež, Vice-chairman O. Koráb, Slovak Technical University, Bratislava, Secretary J. Šesták, Academy of Sciences, Prague, Scientific Program M. Vaniš, Slovak Technical University, Bratislava, Exhibition A. Blažek, Institute of Chemical Technology, Prague, Proceedings V. Tomková, Slovak Technical University, Bratislava, Executive Secretary K. Habersberger, Academy of Sciences, Prague, Conference Affairs Š. Svetík, Slovak Technical University, Bratislava, Conference Affairs P. Králík, Technical University, Košice, Conference Affairs

The progres of thermal analysis was effectively supported by the allied foundation of international journal, which editorial board was recruited from the key-speaker of both 1965 conferences. In particular it was Thermochimica Acta that appeared in the year 1970 by help of Elsevier and, for a long time, edited by Wesley W. Wendlandt assisted by wide-ranging international board (such as B. R. Currell, T. Ozawa, L. Reich, J. Šesták, A. P. Gray, R. M. Izatt, M. Harmelin, H. G. McAdie, H. G. Wiedemann, E. M. Barrall, T. R. Ingraham, R. N. Rogers, J. Chiu, H. Dichtl, P. O. Lumme, R. C. Wilhoit, etc.) see enclosed copy of its front-page on the next page. It was just one year ahead of the foundation of another specialized Journal of Thermal Analysis, which was brought into being by Judit Simon (who has been serving as the editor-in-chief even today) and launched under the supervision Hungarian Academy of Sciences (Académia Kiadó) in Budapest 1969 (L. Erdey, E. Buzagh, F. and J. Paulik brothers, G. Liptay, J. P. Redfern, R. Bárta, L. G. Berg, G. Lombardi, R. C. Mackenzie, C. Duval, P. D. Garn, S. K. Bhattacharyya, A. V. Nikolaev, T. Sudo, D. J. Swaine, C. B. Murphy, J. F. Johanson, etc.) to aid preferably the worthwhile East European science suffering then under the egregious political and economic conditions.

11 Attentive support of the West Bohemian University (MSMT 4977751303) and Grant Agency of Czech Republic (522/04/0384) is highly appreciated.

References 1. J. Matějka “Material Testing in Ceramics” Průmyslové nakl., Praha 1952 (in Czech).

12 2. M. M. Popov “Thermometry and Calorimetry” University Press, Moscow 1956 (in Russian). 3. M. Eliášek, M. Šťovík, L. Zahradník, “Differential Thermal Analysis” in the series “Chemical analysis of raw materials”, Academia, Praha 1957 (in Czech). 4. W. W. Wendlandt “Thermal Methods of Analysis” Wiley, New York 1962. 5. L. G. Berg “Introduction to Thermography” Nauka, Moscow 1964 (in Russian). 6. J. Krempaský “Measurements of Thermophysical Properties” Publ. House VSAV, Bratislava 1969 (in Slovak). 7. G. O. Piloyan “Introduction to the Theory of Thermal Analysis”, Nauka, Moscow 1969 (in Russian). 8. R. C. Mackenzie (ed.) “Differential Thermal Analysis” Academic, London 1970 and 1972. 9. A. Blažek, “Thermal Analysis” Publ. House SNTL, Praha 1972 (in Czech). 10. T. Damiels “Thermal Analysis” Kogan, London 1973. 11. J. Šesták, V. Šatava, W.W.Wendladt “The Study of Heterogeneous Processes by Thermal Analysis”, special issue of Thermochim. Acta, Vol. 13, Elsevier, Amsterdam 1973. 12. F. Sabadvary, E. Buzagh-Gére, J.Thermal Anal. 15, 1979, 389. 13. J. Šesták “Measurements of Thermophysical Properties of Solids”, Academia, Praha 1982 (in Czech). 14. R. C. Mackenzie “History of Thermal Analysis”, special issue of Thermochim. Acta, Vol. 73, Elsevier, Amsterdam 1984. 15. J. Šesták “Thermophysical Properties of Solids: their measurements and theoretical thermal analysis”, Elsevier, Amsterdam 1984. 16. J. Šesták (ed.), Thermochim. Acta 100, 1986, 255. 17. M. Nevřiva, J. Rosický, I. Proks, Thermochim. Acta 110, 1987, 553. 18. I. Proks “Evaluation of the Knowledge of Phase Equilibria” first chapter in the book “Kinetic Phase Diagrams” (Z. Chvoj, J. Šesták, A. Tříska, edts.), Elsevier, Amsterdam 1991. 19. J. Šesták, R. C. Mackenzie, “Heat/fire concept and its journey from prehistoric time into the third millennium” key lecture at the 12th ICTAC (Copenhagen) in J. Thermal Anal. Calor. 64, 2001, 129. 20. P. Cardillo “A history of thermochemistry through the tribulations of its development” key lecture at the 8th ESTAC (Barcelona ) in J. Thermal Anal. Calor. 72, 2002, 7. 21. J. Šesták “Heat, Thermal Analysis and Society”, Nucleus, Hradec Králové 2004. 22. J. Šesták “Generalized Approach to Thermal Analysis: science of heat and thermophysical study”, Elsevier, Amsterdam 2005. 23. J. A. Comenius: “Disquisitiones de Caloris et Frigoris Natura”, Amsterdam 1659. 24. Č. Strouhal “Thermics”, (Thermal science), JČMF, Praha 1908 (in Czech). 25. H. LeChateliere, Comptes Rendus 104, 1887, 14436. 26. W. C. Robert Austen, Proc. Inst. Mech. Eng. 1899, 35. 27. G. Tammann, Z. Anorg. Chem. 43, 1905, 303. 28. G. K. Burgess, Bull. Bur. Stand. Washington 4, 1908, 199. 29. R. C. Mackenzie, Platinum Met. Rev. 26, 1982, 175. 30. W. P. White, Am. J. Sci. 28, 1909, 453. 31. F. H. Norton, J. Amer. Cer. Soc. 22, 1939, 54. 32. M. J. Vold, Anal. Chem. 21, 1949, 683. 33. H. T. Smyth, J. Amer. Cer. Soc. 43, 1951, 221. 34. M. M. Factor, R. Hanks, Trans. Farad. Soc. 63, 1959, 1129.

13 35. A. P. Grey in proc. 4th ICTA, “Thermal Analysis”, Akademia Kiado, Budapest 1974. 36. P. Holba, J. Šesták, Silikáty 29, 1976, 83 (in Czech). 37. L. Eyrund, C. R. Acad. Sci., 238, 1954, 1411. 38. M. Reading, Trends Polym. Sci., 1993, 248. 39. I. Proks, J. Zlatkovský, Chem. Zvesti 23, 1969, 620 (in Slovak). 40. C. Kallauner, J. Matějka, Sprechsaal 47, 1914, 423. 41. J. Matějka, Chemicke listy 13, 1919, 164 and 182 (in Czech). 42. S. Škramovský, Chemické listy 26, 1932, 521 (in Czech). 43. R. Bárta, Silikáty (Prague) 5, 1962, 125 (in Czech). 44. A. Blažek, Silikáty 1, 1957, 177 (in Czech). 45. J. Brandštetr, Z. Anal. Chem. 254, 1972, 34. 46. J. Komrska, Silikáty (Prague) 11, 1967, 51 (in Czech). 47. A. Bergstein, Collect. Czech. Chem. Commun. 20, 1955, 1058. 48. J. Chromý, Amer. Mineral. 54, 1969, 549. 49. V. Šatava, O. Vepřek, Silikáty (Prague) 15, 197), 1 (in Czech), J. Amer. Cer. Soc. 58, 1975, 357. 50. V. Balek, Silikáty (Prague) 13, 1969, 39 (in Czech), J. Mater. Sci. 4, 1969, 919, Anal. Chem. 42, 1970, 167. 51. M. Vaniš, O. Koráb, Silikáty (Prague) 4, 1960, 266 (in Slovak). 52. J. Šesták, Silikáty (Prague) 7, 1963 (in Czech), Talanta 13, 1966, 567. 53. V. Šatava, Thermochim. Acta 2, 1971, 423. 54. J. Šesták, G. Berggren, Thermochim. Acta 3, 1971, 1. 55. V. Jesenak, Proc. TERMANAL ’82, Publ. House SVŠT, Bratislava 1982, 13. 56. J. Velíšek, Chem. Listy (Prague) 72, 1978, 51 (in Czech) 57. M. Malinovský, Chem. zvesti (Bratislava) 28, 1974, 489 (in Slovak). 58. M. Roubal, V. Landa, Strojírenství (Prague) 25, 1975, 559 (in Czech). 59. V. Tydlidát, Czech. J. Phys. B 21, 1971, 817. 60. J. Velich, Chem. Listy (Prague) 79, 1985, 661 (in Czech). 61. L. Kubičár, Czech. J. Phys. A 34, 1984, 153.

14 ICTAC 1965–68 1968–71 1971–74 1974–77 President L. G. Berg (USSR) C. B. Murphy H. R. Oswald H. Kambe (USA) (Switzerland) (Japan) Vice-President — R. Bárta H. Kambe H.G. McAdie (Czechoslovakia) (Japan) (Canada) Secretary J. P. Redfern J. A. Hill G. Lombardi G. Lombardi (England) (USA) (Italy) (Italy) Treasurer R. C. Mackenzie R. C. Mackenzie R. C. Mackenzie R. C. Mackenzie (Scotland) (Scotland) (Scotland) (Scotland) Past-President — L. G. Berg C. B. Murphy H. R. Oswald (USSR) (USA) (Switzerland) Ordinary R. Bárta S. K. Bhattacharrya P. K. Gallagher P. K. Gallagher members (Czechoslovakia) (India) (USA) (USA) S. K. Bhattacharrya C. Duval M. Harmelin M. Harmelin (India) (France) (France) (France) C. Duval H. Kambe M. D. Karkhanavala M. D. Karkhanavala (France) (Japan) (India) (India) L. Erdey G. Krien G. Krien V. B. Lazarev (Hungary) (BRD) (BRD) (USSR) T. Sudo G. Lombardi O. T. Sörensen H. Lehmann (BRD) (Japan) (Italy) (Denmark) F. Paulik (Hungary) D. J. Swaine D. J. Swaine S. St. J. Warne O. T. Sörensen (Australia) (Australia) (Australia) (Denmark) T. L. Webb T. L. Webb S. St. J. Warne (South Africa) (South Africa) (Australia) E. I. Yarembash (USSR) Chairmen of R. Bárta, Honorary Committees president (Czechoslovakia) Standardisation H. G. McAdie H. G. McAdie H. G. McAdie P. D. Garn (Canada) (Canada) (Canada) (USA) Nomenclature R. C. Mackenzie R. C. Mackenzie R. C. Mackenzie R. C. Mackenzie (Scotland) (Scotland) (Scotland) (Scotland) Publications J. P. Redfern J. P. Redfern J. P. Redfern J. P. Redfern (England) (England) (England) (England) Organising for C. B. Murphy M. Müller Von F. Paulik S. Seki next Conference (USA) Moos (Switzerland) (Hungary) (Japan)

15 Journal of Thermal Analysis and Calorimetry, Vol. 88 (2007) 3, x–x

FROM CALORIC TO STATHMOGRAPH AND POLAROGRAPHY

J. esták1,2* and J. J. Mareë1 1Institute of Physics, Academy of Sciences, Cukrovarnická 10, 16253 Praha 6, Czech Republic 2Faculty of Applied Sciences, University of West Bohemia, Universitni 8, 30614 Pilzen, Czech Republic

Present contribution briefly describes some historical features, which are focused back to the history of the Middle European learning as promoted by the foundation of the Charles University in Prague 1348. Physics and its neighboring areas are mentioned dis- cussing some crucial scientific contributions and stressing out some prominent scholars, such as Tycho de Brahe, Johannes Kepler, Tadeáë Hájek, Marcus Marci, Jan A. Commenius (caloric), Prokop Divië, Bernard Bolzano, Christian Doppler, Ernst Mach, Albert Einstein, Václav imerka, Frantiëek Záviëka, enÆk Strouhal, Reinhold Fürst or Stanislav kramovskú (statmograph) and Jaroslav Heyrovskú (polarography), the latter being already the representative of modern age.

Keywords: ???

Historical Prague and its famous Charles indel had also a share in designing the advanced as- University trolabe in the famous Prague’s astronomical clock. Little renown is Ioannes Marcus Marci (Jan One of the most important moments in the history of Marek Markö 1595–1667) who probably helped to re- old Bohemia was the foundation of Charles Univer- veal the fundamental properties of the spectral colors sity in Prague, as the first European university north that emerge when light passes through glass prism, of the Alps, by Emperor Charles the IV. One of its was already aware of their monochromatic properties, first achievements was the introduction of medieval i.e., any succeeding refraction or reflection did not kinematics, which was brought to Prague by Johannes change colors. He also studied the color change in de Holandria, an Oxfordian from Merton College, rays when spectral colors are mixed and in the field of who in the year 1368 provided the so-called Merton’ spectral dispersion of light he was actually a prede- theorem of uniform acceleration to public and de- cessor of Isac Newton. He wrote for that time very ad- tailed this approach during his stay in Prague. Later vanced books. e.g. [1], which possibly foreshadowed Czech astronomer Jan indel (1375–1456) was study- some laws. Besides the refraction of light he con- ing the planetary motion and his astronomical tables ducted the first-ever systematic study of the impact of were greatly appreciated by Tycho de Brahe while bodies, he discovered the difference between elastic staying in Prague at the end of the 16th century. and inelastic impacts intuitively moving his thoughts within the reach of the conservation laws. Marci,

Fig. 1 From left: Charles University in Prague (founded by Emperor Charles IV. 1348 and some of their exceptional members and associates, astronomer Kepler Johannes (1571–1630), rector and mathematician Marcus Marci Ioannes (from Kronland, 1595–1667) and famous professor of mathematics and practical geometry Doppler Christian (1803–1853) * Author for correspondence: [email protected]

1388–6150/$20.00 Akadémiai Kiadó, Budapest, Hungary © 2007 Akadémiai Kiadó, Budapest Springer, Dordrecht, The Netherlands ESTÁK, MARE however, was strongly convinced that white light was Foremost Czech physician and astronomer, Chef the simplest element (‘quinta essentia’), which, inter- Medical Supervisor of the Kingdom of Bohemia at estingly, was close to the subsequent concept of ‘ele- the court of Rudolph the II, was Thaddaeus Hagecius mentary waves’ propounded about fifty years later by ab Hagek (Tadeáë Hájek z Hájkö, 1525–1600) known Huyghens in the wave theory of light. There, how- as an author of several astronomical tractates and ever, is incomplete information concerning Marci`s books on geodesy, botanics and medicine particularly educational activities. He was the rector of the famous acknowledged for the first concise book on the Charles University and, perhaps, introduced a word beer-making, ‘De cerevisia’ (1585). He essentially first specialization called ‘chimiatrie’, which was helped the flourishing period of alchemy and played a conceivably taught as an unusual subject with regards significant role in persuading Rudolph the II to invite the traditional university disciplines: major ‘artes Tycho de Brahe to come to Prague. liberales’ and minor ‘artes mechanicae’ (i.e., learning Special attention should be paid to the Czech common crafts such as warfare, navigation, business, thinker and Bohemian educator, latter refugee Jan agriculture, hunting, medicine or veterinary) but not Amos Comenius (Komenskú 1592–1670). In his in ‘artes incertae’ (that was a part of the habitually re- Physicae Synopsis, which he finished in 1629 (pub- jected ‘equivocal arts’ associated with occultism, lished first in Leipzig in 1633), he showed the impor- which traditionally involved alchemy). tance of hotness and coldness in all natural processes. Heat (or better fire) is considered as the cause of all motions of things. The expansion of substances and the in- Some medivial alchemists and the creasing the space they occupy is caused by their dilu- introduction of caloric tion with heat. By the influence of cold the substance gains in density and shrinks: the condensation of vapor When Rudolph the II (1552–1612) became the Em- to liquid water is given as an example. Comenius also peror of the Holy Roman Empire and the King of Bo- determined, though very inaccurately, the volume in- hemia, he provided in Prague court a vital support to crease in the gas phase caused by the evaporation of a alchemists, astronomers and physicists. Among the unit volume of liquid water. In Amsterdam in 1659 he most outstanding scientists were Tycho de Brahe published a treatise on the principles of heat and (1546–1601) and Johannes Kepler (1571–1630) cold [2], which was probably inspired by the works of whose astronomical observations and calculations the Italian philosopher Bernardino Telesius. The third were published in the well-known Rudolphine tables. chapter of Comenius’ book was devoted to the descrip- After the death of Tycho de Brahe, Johannes Kepler tion of the influence of temperature changes on the replaced his position of a royal mathematician in properties of substances. The aim and principles of ther- Prague in the year 1601. Using Tycho de Brahe’s mal analysis were literally given in the first paragraph of data, Kepler determined elliptic orbit of Venus. In his this chapter: citing the English translation [3] ‘In order 1609 treatise ‘Astronomia Nova’ Kepler published to observe clearly the effects of heat and cold, we must his two first laws, controlling the motion of planets take a visible object and observe its changes occurring and according to which the orbit of a planet/comet during its heating and subsequent cooling so that the ef- about the Sun is an ellipse with the Sun’s center of fects of heat and cold become apparent to our senses.’ In mass at one focus. the following 19 paragraphs of this chapter Comenius gave a rather systematic description (and also a partially

Fig. 2 From left: Hájek Tadeáë (from Hájkö, 1526–1600), Komenskú Jan Amos (Comenius, 1592–1670), Prokop Divië (1696–1765) and Bolzano Bernard (1781–1848)

2 J. Therm. Anal. Cal., 88, 2007 HISTORICAL SURVEY correct interpretation) of the effects of continuous heat- term ‘latent heat’ which meant the absorption of heat ing and cooling of water and air, and also stressed the as the consequence of the change of state. reversibility of processes such as, for example, evapora- Black’s elegant explanation of latent heat to the tion and condensation, etc., anticipating somehow the young Watts became the source of the invention of concept of latent heat. Comenius concludes this chapter the businesslike steam engine as well as the inspira- as follows: ‘All shows therefore that both heat and cold tion for the first research in theory related to the novel are a motion, which had to be proved.’ In the following domain of thermochemistry, which searched for gen- chapter Comenius described and almost correctly ex- eral laws that linked heat, with changes of state. plained the function of a thermoscope (‘vitrum Rumford presented qualitative arguments for such a caldarium’) and introduced his own qualitative scale fluid theory of heat with which he succeeded to evalu- with three degrees of heat above and three degrees of ate the mechanical equivalent of heat. This theory, cold below the ambient temperature. however, was not accepted until the later approval by It is difficult to trace and thus hard to say if it was Mayer and, in particular, by Joule, who also applied possible (though likely) to disseminate the idea of calo- Rumford’s theory to the transformation of electrical ric from Amsterdam (when Comenius mostly lived and work. The use of customary units called ‘calories’ also died) to Scotland where a century later a new sub- was coined by Clément, who was giving in 1824 the stance, or better a matter of fire, likewise called caloric following definitions: a ‘small calorie’ allowed to in- (caloricum), was thoroughly introduced. It was as- crease by one degree the temperature of 1 g of water, sumed, e.g., that caloric creeps between the constituent whereas a ‘large calorie’ allowed to melt 1 g of ice. parts of a substance causing its expansion. Although The word ‘calorie’ was then introduced into the vo- caloric differed from foregoing concept of phlogiston cabulary of academic physicists and chemists (Favre (because it could be later measured with an apparatus and Silbermann [9]) in 1845. The characterization of called a calorimeter) it is not clear who was the first us- one kilocalorie as 427 kilogram-meters was launched ing such an instrument. If we follow the studies of by Mayer in the year 1845. The caloric-like descrip- Mackenzie and Brush [4, 5] and Thenard [6] they as- tion of heat as a fluid has survived, nevertheless, until signed it to Wilcke. It, however, contradicts to the today being a convenient tool for easy mathematical opinion presented in the study by McKie and description of heat flows [3, 10–14]. Recently we Heathcode [7] who consider it just a legend and as- tried to refresh the concept of caloric in the view of sume that the priority of familiarity of ice calorimeter entropy and its connection to information [15]. belongs to Laplace who was most likely the acknowl- Worth noting is the theory of Prokop Divië edged inventor and first true user of this instrument (Divisch 1696–1765), which belongs to early pioneer- (likely as early as in 1782). In fact, Lavoisier and ing times. Accordingly, ‘Light of the First Day of Cre- Laplace entitled the first chapter of their famous ation’ is regarded to be identical with electricity, which ‘Mémoire sur la Chaleur’ (Paris 1783) as ‘Presentation is an inherent quality of all things, permeating the of a new means for measuring heat’ whereas the report whole Universe and manifesting itself by electric and of calorimetric employment by Black seemed to first thermal phenomena [16]. Such an idea is, surprisingly, appear almost a century later in the Jamin’s Course of in an apparent agreement with the modern idea of elec- Physics (Mallet–Bachelier, Paris 1868). tromagnetic zero-point background radiation [17]. Caloric was seen as an imponderable element Important role played the Prague Jesuit College with its own properties. Unfortunately, the great prop- of Clementinum and its famous library and observa- agator, Joseph Black (and his student Irvine), pub- tory (opened in the 1720s) where about 1780 Antonin lished almost nothing in their own lifetimes [8] and Strnad (1747–1799) laid the foundation to the oldest their attitudes were mostly reconstructed from con- known series of systematic metrological observa- temporary comments and essays published after their tions. Worth noting are physicists and mathemati- deaths. Black supposed that heat was absorbed by a cians Josef Stepling (1716–1778) and Jan Tesánek body during melting or vaporization, simply because (1728–1788) who published many original studies at the melting- or boiling- points sudden changes took and initiated publishing of Prague edition of New- place in the ability of the body to accumulate heat ton’s ‘Principia’ supplemented with his own com- (~1761). Irvine’s account that the relative quantities mentaries, in that time best edition reasoned with of heat contained in equal weights of different sub- better mathematical background. stances at any given temperature (i.e., their ‘absolute heats’) were proportional to their ‘capacities’ at that temperature and it is worth noting that the term ‘ca- Renaissance of Prague physics pacity’ was used by both Black and later also Irvine to indicate specific heats [8]. Black also introduced the The first half of the 19th Century mathematical and physical studies in Prague became again on a par with

J. Therm. Anal. Cal., 88, 2007 3 ESTÁK, MARE

Fig. 3 From left: Václav imerka (1819–1887), Friedrich Reinitzer (1857–1927), Ernest Mach (1838–1916), Albert Einstein (1879–1955)

Fig. 4 From left: enÆk Strouhal (1850–1922), Frantiëek Záviëka (1879–1945), Jaroslav Heyrovskú (1890–1967), Stanislav kramovskú (1901–1983) the world science. Important role paid some scientists correctly describes the dispersion of light, dichroism such as Frantiëek J. Gestner (1756–1832) who is also and circular birefringence. The Mach successor at known as a pioneer of the railway transport in Europe. Prague German University was Ernst Lecher Excellent achievements are duly associated with the (1856–1926) who is well known for his research on name of Bernard Bolzano (1781–1848) particularly in electromagnetic waves (i.e. Lecher wires). Mach also mathematical logic and analysis and with his friend analyzed conceptual basis of calorimetry from more Christian Doppler (1803–1853) who came to Prague general, almost philosophical, point of views [18]. from Vienna in 1829. His famous paper was inspired His influence on the further development of physics by astronomical phenomenon: the components of was tremendous and he established a mathematically many binary stars differ from each other in color. specialized school – a great deal of his attention de- Though, according to present knowledge, the ob- voted to optics and acoustics. One of his personal sci- served color difference is due to the difference of sur- entific contacts was Czech famous Jan E. PurkynÆ face temperatures and not to the difference in radial (1787–1869) internationally known for discoveries in velocities, the principle itself is correct, being veri- physiology. Another young assistant of Mach was fied, e.g., in acoustics and optics. In 1867 arrived to enÆk Strouhal (1850–1922), later first Czech profes- Prague Ernest Mach (1838–1916) and spent there sor appointed for experimental physics. His studies in nearly 30 years. He is known for his discussion of acoustic are well known and the Strouhal’s number Newton’s Principia and critique of conceptual mon- concerning friction tones (oscillation) is named after strosity of absolute space in his book ‘The Science of him. He wrote and exceptional book on heat called Mechanics’ (1883). Mach encouraged and inspired ‘Thermics’ [19]. one of his students (later professor of theoretical Czech priest (and, unfortunately, rather un- physics) Jan Kolá¹ek (1851–1913) to study some of known mathematician) Václav imerka (1819–1887) his hypothesis later approving that the Mach’s theory introduced quantitative evaluation in psychology

4 J. Therm. Anal. Cal., 88, 2007 HISTORICAL SURVEY

(logarithmic connotation of feelings) providing early tion with matter and effort to construct a relativistic basis for the theory of information [20]. Czech-born theory of gravitation [25]. Friedrich Reinitzer (1857–1927) is famous as the dis- Worth noting is the so-called Planck-Einstein coverer of cholesterol (including its metamorphosis transformation formula for temperature which reads 2 and stoichiometry formulae C27H46O) and is also T=T0 [(/)]1- vc [25] and is possibly related to the known for his pioneering work in the field of liquid previous dissertation work by K. von Mosengeil, post- crystals (latter widespread by O. Lehmann). Bohumil humously published in Ann. Physik 22 (1907) 867. It Ku¹era (1874–1921) examined effect of electrical po- means that the temperature of a body observed from larization on surface tension in the interface of two the system moving with a relative velocity, v, is lower liquids prompting the idea of a new technique latter than the temperature in rest system. Basing on this idea known as the drop-weight method, which provided in the article published in Ann. Physik 26 (1908) 1, physical basis for a new, today widely utilized, ana- Planck assumed that the First and Second Law of ther- lytical method called polarography [21] as introduced modynamics keep their form in all inertial frames. In by Jaroslav Heyrovskú (1890–1967), which was the year 1953, however, Einstein wrote a letter to M. awarded by Nobel price in 1959 [22]. von Laue in which he doubts the correctness of this An original development of weight measurements formula and rather speculated about a formula used in- is connected with the name Stanislav kramovskú verse (temperature as observed in moving system is (1901–1983), who, at the Charles University, investi- higher). This statement, which was later proved by H. 2 gated thermal decomposition of complex oxalates Ott [26], thus reads as T=T0 [(/)]1- vc . In both these which led him in 1932 to his own construction of an cases information about the temperature is regarded to apparatus named ‘stathmograph’ (from Greek be mediated by the coherent electromagnetic radiation. ‘stathmos’=mass, weight) [23] that made it possible to Interestingly, in the case, where temperature is consid- measure mass changes. Independently, in the same ered to be essentially local property and the thermome- time Duval used for his way of weight measurements ter reading is transferred to moving system, e.g., by the Latin-based term ‘thermogravimetry’ that later be- means of digital coding, the temperature, in the con- came generally accepted in thermal analysis. As the trast to both above formulae, must be considered as principle scheme of the stathmograph instrument is not ralativistically invariant. generally known, it is perhaps worth mentioning to de- Another distinguished, but unjustly not very ap- scribe the arrangement. kramovskú placed a weighted preciated, savant born in Prague was Reinhold Fürth sample into the drying oven on a dish suspended on a (1893–1979) who devoted his scientific life to the re- long filament passing through a hole in its upper wall search into the fundamentals of statistical phys- (forming the balance case) and hooked to the left arm ics [27]. Besides an extensive work concerning of an analytical balance. A mirror attached to the beam Brownian motion and noise phenomena he is also au- was reflecting the image of a light slit into a slowly ro- thor of stochastic interpretation of quantum mechan- tating drum lined with photosensitive paper. The un- ics [28]. Accordingly to this theory, the Schrödinger wanted vibration was reduced by an attached glass rod equation is nothing but the classical diffusion equa- immersed into paraffin oil and temperature was regis- tion with complex diffusion constant ~jÉ/2m.This tered automatically by means of a mercury thermome- statement became later a corner–stone of so-called ter provided by platinum contacts distributed along the stochastic electrodynamics, which provides an alter- whole length of capillary. native to quantum mechanics [29]. A most prominent personality, which spent fruit- One of the outstanding teachers, who earned ful time in Prague was Albert Einstein (1879–1955) great merit for introducing modern theoretical physics [24], a German physicist, originator of theories of rel- and thermodynamics to the curriculum of Charles ativity, laws of motion and rest, simultaneity and in- University, was Frantisek Záviëka (1879–1945). One terrelation of mass and energy, quantum theory of of his textbooks was the first monograph on relativity photoelectric effect, theory of specific heats, published in Czech and he is an author of excellent Brownian motion, etc. (see the book ’Builders of the books on thermodynamics [30]. He also concerned Universe’ 1932). In 1911 he obtained his first profes- waveguides and independently deduced relevant the- sorship at theoretical physics at the German Univer- ory early before the microwave technique became im- sity of Prague where he closely cooperated with his portant. Other notable physicist was Augustin ¦á¹ek friend professor of mathematics, Georg Pick (1886–1961) who studied damped electromagnetic (1859–1942). While in Prague he published 11 pa- oscillations in vacuum electronic systems. His ex- pers, most extensive being the survey of the theory of tended studies culminated at 1924 in the discovery of specific heats and very important were studies related the principle of magnetron, later becoming the basis with his favorite problem – the interaction of radia- of radar systems.

J. Therm. Anal. Cal., 88, 2007 5 ESTÁK, MARE

The historical development and use of the meth- 13 R. B. Lindsay, ‘Energy: historical development of the ods of thermal analysis in the territory of former concept’, Dowden, Stroudburg 1975. Czechoslovakia is linked with the names Otto 14 J. J. Mareë, J. Therm. Anal. Cal., 60 (2000) 1081. ë Kallauner (1886–1972) and Jospeh MatÆjka 15 J. J. Mare and J. esták, J. Therm. Anal. Cal., 82 (2005) 681. (1892–1960) who introduced thermal analysis as the 16 P. Divisch, ‘Längst verlangte Theorie von der novel technique during the period of the socalled ‘ra- meteorologischen Electricite, Magiam Naturalem tional analysis’ of ceramic raw materials [31]. Much benahmet’, J. H. P. Schramm, Tübingen 1765. credit for further development of modern thermal 17 M. Sparnaay, ‘Historical Background of the Casimir analysis is attributed with Rudolph Barta Effect’ in ‘Physics in the Making’ (A. Sarlemijn, (1897–1985) who stimulated his coworkers (Vladimír M. Sparnaay, Eds), Elsevier, Amsterdam 1989. atava) and his students (Jaroslav esták) at the Insti- 18 E. Mach, ‘Die Principien der Wärmelehre’, Leipzig 1896. tute of Chemical Technology in Prague (the latter 19 . Strouhal, ‘Thermika’ (Thermics), JMF, Praha 1908 mentioned names became also initiators of the foun- (in Czech). 20 P. V. imerka, ‘Síla péesvÆd¹ení: pokus v duchovní dation of the International Confederation for Thermal mechanice’ (Strength of conviction, an attempt to mental Analysis in the year 1965 [32]). mechanics), asopis pro pÆstování matemat. fyziky, Some other details were published elsewhere 11 (1882) 75 (in Czech); A. Pánek, ‘¦ivot a pösobení [31–34]. imerky’ (imerka’s life and actuation), asopis pro pÆstování matemat. fyziky, 17 (1888) 253 as well as J. Fiala in ‘Jubilejni Almanach JCSNF’, Praha 1987, p. 97. Acknowledgements 21 J. Heyrovsky, ‘Poralographie’, Springer, Vienna 1941. 22 J. Janta and J. Niederle (Eds), ‘Physics and Prague’, This study was supported by the grant No. A100100639 of the Academie, Prague 2005. ú Grant Agency of the Academy of Sciences of Czech Republic 23 S. kramovsk , Chemické Listy, 26 (1932) 521 (in and the Institutional FZU research plan No. AVOZ10100521 Czech). and the UWB project MSMT No. 4977751303. 24 J. Bi¹ák, es.as. Fyz., A29 (1979) 222 (in Czech). 25 A. Einstein, Jhb. Radioact. Electron, 4 (1907) 411. 26 H. Ott, Z. Phys., 175 (1963) 70. ë ¹ ë References 27 J. J. Mare ,J. esták, J. Stávek, H. ev íková, J. Kri tofik and P. Hubík, Physica, E29 (2005) 145. 28 R. Fürth, Z. Phys., 81 (1933) 143. 1 M. Marci, ‘De proportione motu’, Prague 1639. 29 J. J. Mareë, J. Stávek and J. esták, J. Chem. Phys., 2 J. A. Comenius, ‘Disquisitiones de Caloris et Frigoris 121 (2004) 1499. Natura’, Amsterdam 1659. 30 F. Záviëka, ‘Termodynamika’ (Thermodynamics), JMF, 3J. esták, ‘Heat, Thermal Analysis and Society’, Nucleus, Praha 1943 (in Czech). Hradec Králové 2004. 31 I. Proks, ‘Evaluation of the Knowledge of Phase 4 R. C. Mackenzie, ‘History of Thermal Analysis’, special Equilibria’ first chapter in the book ‘Kinetic Phase issue of Thermochim. Acta, 73 (1984). Diagrams’ (Z. Chvoj, J. esták, A. Téíska, Eds), Elsevier, 5 S. G. Brush, ‘The Kind of Motion we call Heat’. Amsterdam 1991. Vol.I&II,North Holand, Amsterdam 1976. th 32 J. esták, ‘Some historical aspects of thermal analysis: 6 L.Thenard, ‘Treatise of Chemistry’ 6 edition, Crochard, origin of Termanal and ICTA’ in the proceedings of Paris 1836. Termanal 2005, p. 3 (Eds E. Klein, E. Smr¹ková, 7 D. McKie and N. H. V. Heathcote, ‘The Discovery of P. imon). Specific and Latent Heats’, Arnold, London 1935. 33 P. Cardillo, J. Therm. Anal. Cal., 72 (2002) 7. 8 R. Fox, ‘The Caloric Theory of Gases: from Lavoisier to 34 J. esták, ‘Science of heat and Thermophysical Studies: a Regnault’, Claredon Press, Oxford 1971. generalized approach to thermal analysis’, Elsevier, 9 P. Favre and J. Silbermann, C. R. Acad. Sci., 20 (1845) 1567. Amsterdam 2005. 10 R. Clausius, ‘Mechanische Wärmetheorie’, Vieweg u. Sohn, Braunschweig 1876. 11 J. M. Socquet, ‘Essai sur le calorique’, Paris 1801. DOI: 10.1007/s10973-006-8210-1 12 P. Kelland, ‘Theory of Heat’, Cambridge 1837.

6 J. Therm. Anal. Cal., 88, 2007 Review papers

Czechoslovak footprints in the development of methods of thermometry, calorimetry and thermal analysis

A tribute to professor Vladimír Šatava, DrSc, a mastermind of theoretical basis of thermal analysis, who celebrates his 90th birthday dedicating also the 55th anniversary since he becomes the Editor of the journal Ceramics-Silikáty

#Pavel Holba, Jaroslav Šesták

New Technologies - Research Centre of the Westbohemian region, University of West Bohemia in Pilsen, Universitní 8, 301 14 Plzeň, Czech Republic

#E-mail: [email protected]

Submitted March 15, 2012; accepted May 16, 2012

Keywords: History, Thermal analysis, Calorimetry, Kinetics, DTA

A short history on the development of thermometric methods are reviewed accentuating the role of Rudolf Bárta in underpinning special thermoanalytical conferences and new journal Silikáty in fifties as well as Vladimir Šatava mentioning his duty in the creation of the Czech school on thermoanalytical kinetics. This review surveys the innovative papers dealing with thermal analysis and the related fields (e.g. calorimetry, kinetics) which have been published by noteworthy postwar Czechoslovak scholars and scientists and by their disciples in 1950-1980. Itemized 227 references with titles show rich scientific productivity revealing that many of them were ahead of time even at international connotation.

Historical roots of thermal sciences 100°F at the human body temperature. Reaumur (1731) - from thermoscopy to thermal analysis introduced the temperature scale with 80 degrees between 0°Re at water melting point and 80°Re at boiling point one of the first modern-times considerations of of water. A year later Delisle introduced an exotic scale heat and cold can be found in the treatise published in with 240 degrees, which was later (1738) modified and 1563 by B. Telesio. At the end of the 16th century the adjusted to 150°D corresponding to the melting point of first air thermoscope appeared (G. Galileo about 1597) water and to 0°D at boiling point of water (240°D = - and in 1626 the word „thermometer“ was for the first 60°C), and this scale was being used in Russia for the time used to describe thermoscope equipped with scale whole hundred years. Only then Celsius (1742) came with eight degrees (Leurechon in book “La Recreation with its 100-degree scale (between the melting 100 and Mathematique”). Shortly after, the world-known Czech boiling 0 points of water, later switched to nowadays educator J. A. Comenius inserted reflections on the 0-100 by Linné). role of heat and cold in nature into his work „Physicae the crucial experimental studies, thanks to which Synopsis“ (1633) and then, in 1659, published another temperature became a clearly measurable physical worth noting book „Disquisitiones de Caloris Frigoris et quantity, was executed by Regnault in the 1840th, that Natura.“ The first quantitative thermal law expressing the is long after the Black (1761) distinguished between dependence of temperature of a cooling body (expressed the specific heat (heat capacity) and the latent heat, in the scale of 8 degrees) on the time was published by I. Laplace and Lavoisier (1786) performed their first Newton in 1701. calorimetric measurements. In 1822 Fourier published meanwhile, other scientists had invented various his laws of heat transfer. Yet after detailed results of types of the dilatation thermometers and had proposed Regnault´s dilatometric and heat capacity measurements various temperature scales. Rømer (1701) had filled (1842), together with Carnot´s theorem (1824) and its glass tube of thermometer with red wine and proposed consequent interpretation by Clapeyron (1834) - the basis a 60-degree scale. Fahrenheit (1724) proposed a tem- was formed for the introducing of absolute temperature perature scale of 100 degrees from 0°F (at the temperature scale by W. Thomson (Kelvin 1848) and for the inception of mixture of ammonium chloride, water and ice) and of thermodynamics as a new science.

Ceramics – Silikáty 56 (2) 159-167 (2012) 159 Holba P., Šesták J.

the first noted use of thermometry as a method of A mirror attached to the beam was reflecting the image thermal analysis took place in Uppsala in 1829 where of alight slit into a slowly rotating drum lined with F. Rudberg (1800-1839) recorded inverse cooling-rate photosensitive paper. The unwanted vibration was data for various alloys. [1,2]. In 1883, H. L. Le Chatelier reduced by an attached glass rod immersed into paraffin (1850-1936) adopted a somehow more fruitful approach oil and temperature was registered automatically by plotting the time vs. temperature curves easily convertible means of a mercury thermometer provided by platinum to the relation of sample temperature vs. environmental contacts distributed along the whole length of capillary. temperature. in the first years after World War II the other Several years later Le Chatelier (1887) had used monographs appeared in the world literature (besides that Pt/PtRh thermocouple and the new era of thermometry by Duval [13]), which were devoted to microcalorimetry as well as of calorimetry has arrived. In 1891, W. [14] and thermal analysis [15, 16] and an initial paper C. Roberts-Austen (1843-1902) [3] became known dealing with theory of DTA [17] was also published. to construct a device to give a continuous record of At the end of 1950th a commercial device combining the output from thermocouple and he termed it as DTA and TG appeared under the name “Derivatograph” “thermoelectric pyrometer”. Later with his assistant [18] for long providing a useful service to the Eastern A. Stanfield published in 1899 heating curves for scientists. gold, which almost stumbled upon the idea of DTA much credit for the further development of modern (“Differential Thermal Analysis”). They improved thermal analysis was attributed with Rudolf Bárta the sensitivity by maintaining the thermocouple ‘cold’ (1897-1985) who stimulated thermal analysis activity at junction at a constant temperature and by measuring the his fellow workers (V. Šatava, S. Procházka, J. Vašíček, M. differences between two high temperatures [4]. Among Čáp or I. Proks) at the Institute of Chemical Technology other well-known inventors was Russian N. S. Kurnakov Prague (abbreviated as VŠChT) [19, 20, 21, 22]. Bárta (1860-1941) improving registration of his pyrometer by organized premature thermoanalytical meetings, the the photographic continuously recording drum [5]. The earliest was ”the 1st Conference on DTA” (Prague term “thermal analysis” was coined by G. H. J. Tammann 1956), the 2nd (Prague 1958) and the 3rd Conference (1861-1938) [6] around the year 1904 demonstrating on Thermography (Prague 1961) followed by the 4th the significance of cooling curves in phase-equilibrium Conference on DTA (Bratislava 1966). His friend R. C. studies of binary systems. Mackenzie (1920-2000) [23, 24] from Scotland was an the first Czech university textbook on the physics invited guest at the 1961 meeting who was also one of of heat was “Thermika” by Č. Strouhal (1850-1922) the pioneers of applied DTA [23, 24]. Upon the previous published in 1908 [7] maintaining its informative value communication with Russian L.G. Berg, Americans P. D. until today’s. The historical development and practical Garn and C. B. Murphy as well as Hungarian L. Erdey use of DTA in the territory of former Czechoslovakia [1, an idea for the creation an international society ICTA 2, 8] was linked with the names J. Burian (1873-1942), was cultivated and realized during the first international O. Kallauner (1886-1972) and J. Matějka (1892-1960) thermoanalytical conference in London 1965 [24] who introduced thermal analysis as the novel technique (where one of the authors also participated as invited during the period of the so called “rational analysis” of speaker). It aimed to enabling easier contacts between ceramic raw materials [9] in order to investigate behavior national sciences, particularly across the separating ‘iron of kaolinite [10, 11] at heating. curtain”, which in that intricate time politically divided Worth a special attention is an original development the East and West Europe. of weight measurements that is connected with the besides significance of the early Czech-written books name S. Škramovský (1901-1983), who, at the Charles on thermal science [7, 26], which appeared before and/or University, investigated thermal decomposition of simultaneously with the credited international literature complex oxalates which led him in 1932 to his own [8, 22] the indispensable figure in the Czechoslovak construction of an apparatus named “stathmograph” development of thermal analysis was undoubtedly (from Greek “stathmos” = mass, weight) [12] that made Vladimír Šatava (*1922) [27-31]. He brought to the it possible to measure mass changes. Independently Czech scientific circles necessary theoretical basis on (twenty years later), C. Duval used for his way of weight solid-state chemistry and physics [29, 30], pioneered measurements the Latin-based term “thermogravimetry” methods of thermal analysis [18, 19, 27, 26], educating that later became generally accepted in thermal analysis his students who thus followed his professional guidance [13]. As the principle scheme of the stathmograph and published esteemed books [27-33] completing thus instrument is not generally known, it is perhaps the rich spectrum of Czech thermoanalytical literature worth mentioning to describe this early arrangement. [31-38], cf. Fig. 1. The individual contributions and Škramovský placed a weighted sample into the drying innovative approaches have been affluent and focal which oven on a dish suspended on a long filament passing is worth of a more detailed portrayal, as exposed in the through a hole in its upper wall (forming the balance next paragraph, especially accentuating Czechoslovak case) and hooked to an arm of an analytical balance. source journals. Unfortunately, most of these rather cru-

160 Ceramics – Silikáty 56 (2) 159-167 (2012) Czechoslovak footprints in the development of methods of thermometry, calorimetry and thermal analysis cial papers disappeared in the shadows of time due to journal Chemické Zvesti. the Czech written texts. Only consequently a supply the second category “Special methods of TA” is role started playing the novel thermoanalytical journals, devoted to original principles and unique techniques Thermochimica Acta, which was cofounded by one of developed and put into operation by Czechoslovak the authors back in the year 1970 as well as Journal of scientists. The articles described e.g. dielectric TA [58], Thermal Analysis instigated by R. Bárta in 1969. thermogravimetry [59, 60, 63], accelerated TA [62], less known book by J. A. Komenský “Investigation permeability TA [65], photometric TA [66], perio- of the nature of heat and cold.” (Amsterodam 1659) in dic TA [68] (becoming a forerunner of today’s tem- which the predicament of heat and cold is well discussed; perature modulated methods of TA), differential hydro- “Thermics” by Č. Strouhal (1908) was an unique book thermal analysis [70] and [71, 74], quick TA [78], describing the early but elementary treaties on heat, the thermoelectrometry [79, 80], decrepitating TA [82] and almost unknown book on DTA (1957) was published thermomagnetometry [83]. A distinctive consideration ahead of time, basic book of solid-state chemistry and should be allocated to the characterization of radioactive material thermal behavior was also published (1965) measurement called emanation thermal analysis (ETA) beforehand of international literature (unfortunately which is connected mainly with authors V. Jesenák [64], never translated). Far right is the Russian translation V. Balek [67, 75, 76] and J. Tölgyessy [81]. of Czech original book on theoretical basis of thermal an explicit part of the papers was devoted to the analysis (1988), which became curiously a scientific description of own constructions of apparatuses for TA bestseller as whole 2000 issues were sold in the former measurement as a consequence of at that time existing USSR within one week. inaccessibility of commercial TA instruments. This type of articles is included into category Apparatuses of TA [84-101]. Early instruments as were opportunely Methodical footpath identifiable produced by laboratory groundwork, such as DTA be- on the territory of former Czechoslovakia long into this category. The production way of latterly produced TG apparatuses was paved by the development the greatest promotion of thermoanalytical methods of a Czech thermogravimetric instrument named came after fifties when the methodical bases were formed “TEGRA” and constructed by A. Blažek [37, 87]. Early [39] and new techniques specified.I n this period various instruments were opportunely produced by laboratory Czechoslovak scientists played an important role as it is groundwork, such as DTA [84, 86, 91, 97]. documented in the achievement book [40] and citation a rich sphere of Czechoslovak research was records [41]. Below listed papers relating the field ofTA also formed by calorimetric contributions [103-127] promoted in the former Czechoslovakia are assorted into registered in category Calorimetry. Worth accentuating several (but not very strict) categories. The referenced is an initial classification of calorimeters according to the papers are supplied by original titles (given in English) temperature difference between the sample-block TB and and they are chronologically ordered within individual surrounding jacket TJ as early suggested by J. Velíšek categories. All references were checked and corrected [117]. according to database WOS (Web of Science). Consequent category Theory of DTA/DCS is asso- the first category „TA generally” consists of artic- ciated with a gradual development of theoretical basis les [42-57] deals mostly with thermal analysis in a ge- of thermal measurements mostly focused on the DTA neral way including papers published mainly in Czech [128-140] curiously noting early the associated effect journals Silikáty and Chemické listy, and in Slovak of gradients [129, 130]. It involved problems of

Figure 1. Some favored book related to the topic of thermal science

Ceramics – Silikáty 56 (2) 159-167 (2012) 161 Holba P., Šesták J. calibration and standardization of temperature and heat last category of Czechoslovak papers dealing with TA measurements by employing solid solution [135, 140], is labeled as History and nomenclature. It contains application of heat pulses [134], conductivity issues reviews of historical aspects of thermometry and [138] as well as a detailed analysis of the complex thermodynamics [221-227] and associated nomenclature composition of a DTA peak including the effect of heat issues [219, 220]. inertia [135, 137]. One of the frequently cited and widely applied treaties was the Hrubý glassforming coefficient [133] based on the DTA determination of characteristic Conclusions temperatures during glass crystallization (inquisitively becoming the best cited paper in the history of Journal the Czech researches have richly contributed Czechoslovak Physicists with 372 citations). Such to thermal science and it would be a misfortune to achievements were only possible by the impact of allow their input to slip into oblivion. Clearly, one of prosperous Czechoslovak school on thermodynamics the most important moments in the development of [27-34]. The other corresponding papers [141-162] are modern thermal analysis was the establishment of the included into category Thermodynamics and phase journal Ceramics-Silikáty, launching 1956 by Rudolf equilibria Bárta. Vladimír Šatava was its chief editor within another special attention is paid to the studies the years 1957-1967. This period was also credited on reaction dynamics which topic is included into the with creating the foundations of thermal analysis and category Kinetics [163-199]. Early kinetic studies were physical chemistry in general [29-31]. Šatava inspired explicitly offered by studies of V. Šatava whose kinetic his students and coworkers, cf. photo, by continuously evaluation method [175] have been broadly exploited broaden his own scientific interest in elucidating solid- and quoted by international resources (several hundreds state reactions which subsequently flourished into of citations) and frequently named as the “Šatava kinetic publication of various thermoanalytical books [34-39]. method” [31, 34, 35, 174, 183]. Such a popularity of Equally important was the introduction of various novel theoretical works aimed to elucidate predicaments thermoanalytical methods [58-83] which preceded the of reaction kinetics [34, 35, 183] became the heart of international know how, e.g. the emanation thermal the so-called Czech school of nonisothermal kinetics analysis [50, 64, 67, 75, 76, 99] that has become the recently continued both in Czech [195-198] and Slovak source of a commercially produced instrument. Specially republic [190, 191, 199]. Worth noting is the first ever the Czech contribution to the DTA technique [62, 71, published algorithm for the computer calculation of 84-86, 91, 96, 97, 128, 131, 133, 136, 137] deserves a kinetic data [171] and the review paper [170] which distinctive attention, the Czech written book published despite the Czech language became the best cited article in 1957 [26] preceded international publications and in the journal history. In feedback stance the papers was later followed by well cited Czechoslovak books [177, 179] undertook abundant citation responses [31-38]. Solid grounds of DTA were accomplished in becoming thus the best cited papers in relevant journals 1976 by the consistent theory made up by Holba and (562 and 132 respectively) and bringing into literature Šesták and published in Ceramics-Silikáty [135, 136]. the notations named in the international literature after Fundamental contributions already appeared in the first the authors (i.e., the Šesták-Berggren [178] as well as issues of the journal Silikáty, Unfortunately, they did the Holba-Šesták [180] kinetic equations). Not less not get into a wider attention of international public due important have been the contributions by recently to the Czech language,. Nevertheless the Czech journal deceased Ivo Proks (1926-2011), who factually paved the way to the development of methods using the modulated temperature modes [68], early accounting on temperature gradients and measurement accuracy [129, 132], improved solution calorimetry [104, 113, 118] thus significantly contributing the elementary attributes of thermochemistry and thermodynamics. Worth mentioning are also his imperative studies on historical root of thermodynamics [8, 220, 222, 224, 225] as well as the work by J. Brandštetr [93, 100, 108, 115, 120, 125] in the field of titrimetry. not less important were also the related articles about mechanic properties (which was one of favored of the Šatava’s research topics [208, 217]), diffusion studies [203-212] and early measurements of electrical and Figure 2. Vladimir Šatava between his former students (gra- heat conductivity [202, 214-217] inserted into category duating VŠChT in 1962 under his supervision) Jaroslav Šesták Mechanical and transport properties [200-216]. The (left) and Pavel Holba (right) when celebrating his 89th birthday.

162 Ceramics – Silikáty 56 (2) 159-167 (2012) Czechoslovak footprints in the development of methods of thermometry, calorimetry and thermal analysis Ceramics-Silikáty as well as its sister’s Chemické Listy Stavivo 31, 15 (1953). and Czechoslovak Journal of Physics has remained 21. bárta R.: International directions for thermal analysis; important domestic as well as international sources Chem. Listy 62, 454 (1968). and platform of many original ideas and we should be 22. Šatava V.: Rudolf Bárta-Obituari; Silikáty 29, 289 (1985). thankful to the effort of their originators as well as their 23. mackenzie R. C. (ed.): The differential thermal current editors. investigation of clays; Mineral. Society, London 1957. 24. lombardi G., Šesták J.: Ten years since Robert C. Mackenzie’s death: a tribute to the ICTA founder; J. References Thermal Anal. Calor. 105, 783 (2011). 25. Currell B. R.: Thermal Analysis; Science 13, 765 (1965). 1. Šesták J., Mareš J. J.: From caloric to statmograph and 26. eliáš M., Šťovík M., Zahradník L.: Diferenční termická polarography; J. Thermal Anal. Calor. 88, 763 (2007). analýza; (Differential Thermal Analysis), AVČR, Praha 2. Šesták J., Mareš J. J., Hubík P.: Historical roots and 1957. development of thermal analysis and calorimetry; chapter 27. Šatava V.: Documentation on thermal analysis; Silikáty 1, 21 in the book Glassy, amorphous and nano-crystalline 240 (1957). materials, Šesták J., Mareš J. J., Hubík P. (edts), Springer, 28. Šatava V.: Utilization of thermographic methods for Berlin 2011, pp. 347-370 (ISBN 978-90-481-2881-5). studying reaction kinetics; Silikáty 5, 68 (1961). 3. Roberts-Austen W. C.: Fifth report to the alloys research; 29. Šatava V.: Úvod do fyzikální chemie silikátů; (Introduction Nature 59, 566-567 (1899); and Proc. Inst. Mech. Eng. 35 to Physical Chemistry of Silicates), SNTL, Praha 1965. (1899). 30. Šatava V.: Fyzikální chemie heterogenních soustav - 4. Stanfield A.: On some improvements in the Roberts- základy klasické a statistické termodynamiky; (Physical Austen recording pyrometer, with notes on thermo-electric chemistry of heterogeneous systems – foundation pyrometry; Phil. Mag. 46, 59 (1898). of classical and statistical thermodynamics), SNTL, 5. kurnakov N. S.: Eine neue Form des Registrierpyrometers; Praha 1977 and: Fyzika pevných látek; (Solid state Z. anorg. Chemie 42, 184 (1904). physics), SNTL 1979 and: Fyzikální chemie silikátů na 6. tammann G.: Über die Anwendung der Thermische bázi racionální termodynamiky; (Physical chemistry Analysen in abnormen Fällen; Z. anorg. Chem. 45, of silicates based on rational thermodynamics), SNTL 24 (1905) and: Über die Anwendung der Thermische 1981 and: Fyzikální chemie silikátů – kinetika; (Physical Analysen III;. Z. anorg. Chem. 45, 289 (1905). chemistry of silicates – kinetics), SNTL 1982. 7. Strouhal Č.: Thermika; JČMF, Praha 1908. 31. Šesták J., Šatava V., Wendlandt W. W.: The Study 8. Šesták J., Proks I., Šatava V., Habersberger K., Brandštetr of Heterogeneous Processes by Thermal Analysis; J., Koráb O., Pekárek V., Rosický J., Vaniš M., Velíšek Monography as a special issue of Thermochimica Acta 7, J.: History of thermal analysis on the territory of former 333 (1973). Czechoslovakia; Thermochim. Acta 100, 255 (1986). 32. Šesták J.: Měření termofyzikálních vlastností pevných 9. kallauner O., Matějka J.: Beitrag zu der rationellen látek: teoretická termická analýza; Akademia, Praha 1982 Analyse; Sprechsaal 47, 423 (1914). and English translation: Thermophysical Properties of 10. matějka J.: Chemical changes of kaolinite on firing; Solid: theoretical thermal analysis; Elsevier Amsterdam Chemické listy 13, 164 (1919); and 182 (1919) 1984 and: Russian translation Mir, Moscow 1988. 11. matějka J.: Thermal analysis as a tool for determination 33. holba P.: Thermodynamics and ceramic systems; chapter of kaolinite in soils; Chem. Listy 16, 8 (1922). 1 in book Structure and Properties of Ceramic Materials; 12. Škramovský S.: Apparatus for automatic registration of (A. Koller, ed.). Elsevier, Amsterdam 1994, pp. 17-113. dehydration at rising temperature; Chemické listy 26, 34. Šesták J.: Science of Heat and Thermophysical Studies: 521 (1932). a Generalized Approach to Thermal Analysis; Elsevier, 13. duval C.: Inorganic Thermogravimetric Aanalysis; Else- Amsterdam 2005. vier, Amsterdam 1953. 35. Šesták J., Šimon P. eds.: Thermal Analysis of Micro- 14. Swietoslawski W.: Microcalorimetry, Reinhold, New nano- and non-crystalline Materials: transformation, York 1946. crystallization, kinetics and thermodynamics; Springer, 15. Vold M. J.: Differential thermal analysis, Anal. Chem. 21, Berlin 2012 (ISBN 978-90-481-3149-5). 683 (1949). 36. balek V., Tölgyessy T.: Emanation Thermal Analysis 16. Berg L. G.: Скоростной количественный фазовый and other Radiometric Emanation Methods; Elsevier, анализ; (Rapid Quantitative Phase Analysis), Akad. Amsterdam 1984 and: Russian translation Mir, Moscow Nauk, Moscow 1952. 1987. 17. Boersma S. L.: A theory of DTA and new methods of 37. blažek A.: Termická analýza; SNTL, Praha 1972 and: measurement and interpretation; J. Amer. Cer. Soc. 38, English translation: Thermal Analysis; Van Nostrand- 281 (1955). Reinhold, London, 1973. 18. paulik F., Paulik J., Erdey, L.: Der Derivatograph; Z. 38. kubičár L.: Pulse Methods of Measuring Basic Thermo- anal. Chem. 160, 241 (1958); and: Derivatographie; physical Parameters; Elsevier, Amsterdam 1990. Bergakademie 12, 413 (1960). 39. liptay G., (ed). Atlas of Thermoanalytical Curves: (TG, 19. bárta R., Šatava V.: DTA as a quick control and DTG, DTA curves measured simultaneously); London, investigative method in chemical industry; Chem. prům. New York: Heyden and Son 1971. 3,113 (1953). 40. liptay G., Simon J. (eds): Who is who in thermal analysis 20. Šatava V.: Significance of DTA in the industry of cements; and calorimetry; Akademiai Kiado, Budapest 2004.

Ceramics – Silikáty 56 (2) 159-167 (2012) 163 Holba P., Šesták J.

41. Šesták J.: Citation records and some forgotten 66. Chromý S.: Photoelectric apparatus for refractive index anniversaries in thermal analysis; J. Thermal Anal. Calor. determination by the immersion method; Amer. Mineral. in print 2012 (DOI:10.1007/s10973-011-1625-3). 54, 549 (1969). 67. balek V.: Use of methods of emanation thermal analysis in TA generally the study of solid-state processes; Silikáty 13, 39 (1969). 42. Šatava V.: Temperature regulators for thermography; 68. proks I., Zlatkovský J.: Laboratory Techniques and Silikáty 1, 204 (1957). Methods. Periodic Thermal Analysis; Chem. Zvesti 23, 43. Šatava V.: Thermische Zersetzung von Ammoniummeta- 620 (1969). vanadat; Coll. Czech. Chem. Comm. 24, 2171 (1959). 69. kolomazník K., Zapletal J., Soukup J.: Application of 44. blažek A.: Beitrag zur experimentellen Methodik der electronic microbalance for gravimetric thermal analysis; thermische Analyse; Bergakademie 12, 191 (1960). Chemické listy 11, 1203 (1971). 45. Číčel B.: Thermal methods of analysis; Chem. Zvesti 20, 70. vepřek O., Rykl D., Šatava V.: The study of hydrothermal 154 (1966). processes by the DTA method; Thermochim Acta 12, 7 46. biroš J.: Techniques and methods of polymer evaluation (1974). by TA; Chem. Listy 61, 1243 (1967). 71. Šatava V.: New method of differential hydrothermal 47. habersberger K.: Application of TA to investigation of analysis – DHTA; J. Amer. Cer. Soc. 58, 357 (1975). catalysts; J. Thermal Anal. 12, 55 (1977). 72. Šatava V., Vepřek O.: Effect of the sample thermal 48. pospíšil Z.: Complex thermal analysis and its utilization conductivity on the calibration constant in DTA; in the field of ceramics; Silikáty 25, 263 (1981). Thermochim Acta 17, 252 (1976). 49. fellner P., Votava I.: Numerical treatment of cooling/ 73. blažek A, Ederová J, Endrýs J.: Thermal conductivity of heating curves at thermal analysis; Chem. Zvesti 35, 31 glass and the methods of its measurements; Silikáty 25, (1981). 359 (1981). 50. balek V, Beckmann I.: Use of labeled atoms in thermal 74. Šatava V., Vepřek O.: Differential hydrothermal analysis; analysis; Chem. Listy 79, 19 (1985). Stavivo 12, 68 (1981). 51. mentlík V.: New application of DTA in heavy-current 75. balek V.: Use of emanation TA in the evaluation of electrotechnology; Thermochim Acta 93, 353 (1985). sinterability; Silikáty 27, 257 (1983). 52. holba P.: Processing of TA curves and the exact use of 76. balek V.: Emanation TA and its application; Silikáty 28, thermal analysis. Thermochim Acta 110, 81 (1987). 147 (1984). 53. habersberger K., Balek V.: Present state of commercially 77. hrabě Z., Svetík S.: The application of heat flow sensor available thermoanalytical equipment; Thermochim Acta to study the hydration of inorganic binders; Thermochim. 110, 47 (1987). Acta 93, 299 (1985). 54. kubičár L.: Trends in the methods of measurement of 78. Chromý S., Hložek M.: Method of quick thermal analysis; thermophysical properties in the solid state; Thermochim Thermochim. Acta 92, 433 (1985). Acta 110, 209 (1987). 79. Šolc Z., Trojan M.: Application possibilities for thermo- 55. Šatava V., Lach V.: Thermal analysis and chemistry of electrometry; Silikáty 29, 351 (1985). inorganic binders; Thermochimica Acta 110, 467 (1987). 80. Šolc Z., Trojan M., Kuchler M.: Thermoelectrometry 56. Šesták J.: Non-traditional and traditional methods of as a method for reactivity estimation of solid powdery thermal analysis in solid-state chemistry and physics; materials; Thermochim. Acta 92, 425 (1985). Thermochim Acta 148, 79 (1989). 81. lukáč, P., Tölgyessy, J., Vaniš, M., Lapc̆ ík: Thermal de- 57. balek V., Karabascheva N. A., Györyová K.: Literature kryptonation characterization of some solid materials; survey on thermal analysis reference materials; J. Thermochim. Acta 92, 429 (1985). Thermal Anal. 40, 1459 (1993). 82. lach, V.: Some applications of the decrepitating technique and thermosonimetry in research of materials. Special methods of TA Thermochim. Acta 110, 265 (1987). 58. bergstein A.: Changes during ignition of equimolecular 83. Illeková E., Ambrovič P., Czomorová K.: Investigation mixtures of barium carbonate and titanium dioxide, of structural relaxation of amorphous metallic alloy by followed by measurement of dielectric properties; Collect. thermomagnetometry. J. Thermal Anal. 32, 9 (1987). Czech. Chem. Com. 20, 1041 (1955). 59. Šatava V.: Simple registration thermobalance; Silikáty 1, Apparatuses of TA 188 (1957). 84. Sokol L.: Automatic apparatus for DTA; Silikáty 1, 177 60. blažek A.: Electronic thermobalance with simultaneous (1957). recording of DTA curves and decomposition product gas 85. Šatava V., Trousil Z.: Simple construction of apparatuses analysis; Hutnické listy 12, 1096 (1957). for automatic DTA; Silikáty 4, 272 (1960). 61. Šatava V., Stránský K.: Gradient furnace with defined 86. proks I., Šiške V.: Low temperature DTA apparatus; atmospheres; Silikáty 3, 343 (1959). Chem Zvesti 15, 309 (1961). 62. vaniš M., Koráb O.: Simple apparatus for quick DTA; 87. blažek A., Halousek J.: Instrumentation for thermo- Silikáty 4, 266 1960). gravimetry in vacuum; Silikáty 6, 100 (1962). 63. blažek A., Halousek J.: A registering thermobalance; 88. hrubý A., Beránková J.: Apparatus with a large tempe- Silikáty 6, 100 (1962). rature gradient for preparation of single crystals; Czech. 64. Jesenák V., Tölgyessy J.: Radioactive kryptonates; Chem. J. Phys. A15, 740 (1965). Listy 60, 577 (1966). 89. němec L.: A device for measurement of electrode impe- 65. komrska J.: Permeability thermal analysis; Silikáty 11, dance; J. Electroanal. Chem 18, 467 (1968). 51 (1967). 90. malinger M., Brandštetr J.: Use of Czechoslovak ther-

164 Ceramics – Silikáty 56 (2) 159-167 (2012) Czechoslovak footprints in the development of methods of thermometry, calorimetry and thermal analysis

mistors in thermometric analysis; Chem. Listy 63, 931 on basis of thermal losses; Silikáty 21, 71 (1977). (1969). 115. Brandštetr J.: Precision of proposed double injection 91. Šesták J, Burda E, Holba P, Bergstein A.: An apparatus methods for direct enthalpiometric analysis; Coll. Czech. for DTA in vacuum and regulated atmospheres; Chem. Chem. Comm. 42, 56 (1977). Listy 63, 785 (1969). 116. Brandštetr J.: New instruments and methods for enthal- 92. mráček J.: Utilization of DTA principle for primary piometric analysis and calibration; J. Thermal Anal. 14, calibration of thermocouples; Silikáty 15, 381 (1971). 157 (1978). 93. brandštetr J., Malinger M.: Device for differential 117. Velíšek J.: Calorimetric methods; Chemické listy 72, 801 thermometric measurements at constant temperature; (1978). Chem. Listy 66, 88 (1972). 118. Proks I., Kosa I.: Evaluation of the use of dissolution 94. brown A, Šesták J, Kronberg A.: Vertical tungsten furnace calorimetry in phase analysis; Silikáty 24, 271 (1980). for thermal studies up to 2700 oC; Czech J Phys. B23, 612 119. Velíšek J.: High-temperature twin calorimeter for the (1973). measurement of mixing heats of alloys in solid state; 95. nývlt J., Crha J., Sura J.: A laboratory programmed Chem. Listy 75, 201 (1981). thermoregulator; Chem. Listy 68, 164 (1974). 120. Brandštetr J.: Present state and future development of 96. velišek J.: Apparatus for quantitative thermal analysis; instruments for thermometric analysis; J. Thermal Anal. Chem. Listy 68, 1185 (1974). 21, 357 (1981). 97. Rosický J., Kmoničková S.: Apparatus for quantitative 121. Hakl J.: Over-adiabatic calorimetry (OAC); Thermochim. DTA; Silikáty 20, 373 (1976). Acta 81, 319 (1984). 98. procházka S., Sura J., Nývlt J.: Programmed temperature 122. Velich V., Dittrich F., Timar J.: Isoperibolic calorimeter controller used in investigation of crystallization; Chem. with an online computer; Chem. Listy 79, 661 (1985). Listy 71, 1086 (1977). 123. Kubičár L., Illeková E.: Use of pulse method for study 99. Jesenák V., Tomková V.: Apparatus for thermal of structural changes of materials; Thermochim. Acta 92, dekryptonation thermal analysis; Radiochem. and Anal. 441 (1985). Let. 30, 89 (1977). 124. Kubičár L.: Trends in methods of measurements of 100. Brandštetr J.: New instrument and method for thermophysical properties of solids; Thermochim. Acta enthalpiometric analysis and calibration; J. Thermal 110, 205 (1987) Anal. 14, 157 (1978). 125. Brandštetr J.: Outline of some new calorimetric techniques 101. Nerad I., Proks I., Zlatkovský I.: Apparatus for determining and instrumentation; Thermochim. Acta 110, 165, (1987). the time of passage of a solid particle through a steady 126. Nerad I., Proks I.: Determination of equilibrium quantities temperature fields; Silikáty 28, 261 (1984). of the system formed by thermal decomposition: 102. Šolc Z., Trojan M.: Simple program control furnace; Experimental equipment; Chem. Zvesti 41, 3 (1987). Silikáty 31, 365 (1987). 127. Nerad I., Vítková S., Proks I.: New method for determination of the equilibrium state in the system involving Calorimetry binary reactions; J. Thermal Anal. 33, 291 (1988). 103. Krupka F., Horák Z.: The determination of the specific heat of a liquid in an electric calorimeter; Czech. J. Phys. Theory of DTA/DCS A6, 619 (1956). 128. Šatava V.: Differential thermal analysis; Silikáty 1, 207 104. Proks I., Eliášová M., Pach L.: Calorimeter for measure- (1957). ments of heats of solution; Chem. Zvesti 21, 908 (1967). 129. Proks I.: Influence of rate of temperature increase on the 105. Abbrent M., Sojka B., Pekárek V.: Isothermal differential quantities important for the evaluation of DTA curves; calorimeter. Chem. Listy 63, 1042 (1969). Silikáty 5, 114 (1961). 106. Velíšek J.: High-temperature calorimetry; Čs. čas. fyz. 130. Šesták J.: Temperature effects influencing kinetic data A20, 513 (1970). accuracy obtained by thermographic measurements 107. Tydlitát V., Blažek A., Halousek J.: A copper drop-calori- under constant heating; Silikáty 7, 125 (1963). meter with adiabatic shield for enthalpy measurement up 131. Šesták J., Berggren G.: DTA: Use for enthalpic and kinetic to 1700 K; Czech. J. Phys. A 21, 817 (1971). measurements; Chem. listy 64, 695 (1970). 108. Brandštetr J., Malinger M., Kupec J.: Devise for differential 132. Proks I.: Effect of quantities controlling DTA on the diffe- thermometric (enhalpiometric) measurements; Chem. rence between measured and theoretical temperatures; Listy 66, 88 (1972). Silikáty 14, 287 (1970). 109. Smíšek M., Rameš J., Křesťanová V.: Calorimeter for 133. Hrubý A.: Evaluation of glass forming tendency by means measurement of heats of evaporation on a microscale; of DTA; Czech J. Phys. B22, 1187 (1972) and B23, 1623 Chem. Listy 68, 738 (1974). (1973). 110. Smíšek M., Křesťanová V.: Reaction calorimeter; Chem. 134. Svoboda H., Šesták J.: A new approach of DTA calibration Listy 68, 738 (1974). by predetermined amount of Joule heat; In “Thermal 111. pekárek V.: Possibilities and present state of calorimetric Analysis” (proceedings of 4th ICTA,, E. Buzagh, Ed.) experiments; Chem. Listy 69, 785 (1975). Akademia Kiado, Budapest 1974, pp.726. 112. Blaho D., Abbrehnt M., Pekárek V.: Differential quasi- 135. Nevřiva M., Holba P., Šesták J.: Application of DTA in isothermal calorimeter with digital output; Chem. Zvesti determination of transformation heats; Silikáty 20, 33 30, 621 (1976). (1976). 113. Proks I., Eliášová M., Zlatkovský I.: High-temperature 136. Šesták J., Holba P., Bárta R.: Theory and practice of TA drop calorimetry in phase analysis; Silikáty 21, 253 (1977). methods based on the indication of enthalpy changes; 114. Zlatkovský I.: Evaluation of calorimetric measurements Silikáty 20, 83 (1976).

Ceramics – Silikáty 56 (2) 159-167 (2012) 165 Holba P., Šesták J.

137. Šesták J., Holba P., Lombardi G.: Quantitative evaluation Thermochim. Acta 132, 285 (1988). of thermal effects: theory and practice; Annali di Chimica 162. Liška M., Daněk V.: Computer calculation of the phase Roma 67, 73 (1977). diagrams of silicate systems. Ceramics-Silikaty 34, 215 138. Šatava V, Vepřek O.: Effect of sample thermal conductivity (1990). on the calibration constant in DTA; Thermochim. Acta 17, 252 (1977). Kinetics 139. Hrubý A.: Study of glass formation applicability and 163. Šatava V., Körbel J.: Kinetics of thermal decomposition phase diagram; J. Non-cryst. Solids 28, 139 (1978). of silver permanganate; Collect. Czech. Chem. Com. 22, 140. Nevřiva M.: Mn-Cr-O solid solutions as materials for 1380 (1957). thermoanalytical calibration; Thermochim. Acta 22, 187 164. Šatava V.: Reactions of solids; Silikáty 4, 67 (1960). (1978). 165. Šatava V.: Reaction of solids with liquids; Silikáty 5, 171 (1961). Thermodynamics and phase equilibria 166. Šatava V., Marek J., Matoušek J.: Dehydration kinetics 141. Šatava V.: Contemporary foresight on the structure of of α- a β- calcium sulphate hemihydrates in suspension; glasses; Sklář a keramik 13, 6 (1956). Silikáty 5, 309 (1961). 142. Holba P., Pollert E., Kitzinger E.: Experimental 167. Šatava V., Šesták J.: Kinetic analysis of thermogravimetric arrangement for investigation of solid-gas equilibria; data; Silikáty 8, 134 (1964). Silikáty 13, 271 (1969). 168. Šesták J.: Errors of kinetic data obtained from TG curves 143. Holba, P.: On calculations of activities of chemical at increasing temperature; Talanta 13, 567 (1966). individuals from disorder models; Thermochim Acta 3, 169. Hulínský V., Šatava V.: Gypsum solubility within 475 (1972). temperatures 100-140 °C; Silikáty 11, 47 (1967). 144. Šatava V.: Nature of vitreous state and conditions of 170. Šesták J.: Review of kinetic data evaluation from glass-formation; Czech J Phys A23, 565 (1973). nonisothermal and isothermal TG data; Silikáty 11, 153 145. Kratochvíl J.: Rational thermodynamics; Czech J Phys (1967). A23, 1 (1973). 171. Šesták J., Šatava V., Řihák V.: Algorithm for kinetic data 146. Malinovský M.: Concentration vectors in phase diagrams; computation from thermogravimetric data obtained at Chem. Zvesti 28, 463 (1974). increasing temperature; Silikáty 11, 153 (1967). 147. Malinovský M.: Criteria of thermodynamic consistency; 172. Procházka S.: Surface area changes during sintering; Chem. Zvesti 28, 489 (1974). Amer. Cer. Soc. Bull. 47, 753 (1968). 148. Malinovský M.: Equation of liquidus curve in eutectic 173. Vašková L, Hlaváč J. Crystallization of quartz glass; systems; Chem. Zvesti 30, 721 (1976). Silikáty 13, 211 (1969). 149. Hrma P.: Modern Approach to Classical Thermodynamics; 174. Šatava V., Škvára F.: Mechanism and kinetics of solid- Chem. listy 69, 1229 (1975). state reactions; J. Am. Ceram. Soc. 52, 591 (1969). 150. Holba P.: Determination of binary phase diagram curve 175. Šatava V.: Mechanism and kinetics of crystallization from using invariant point data; Silikáty 20, 193 (1976). nonisothermal measurements; Thermochim. Acta 2, 423 151. Holba P.: Thermodynamic aspects of thermal analysis; (1971) Silikáty 20, 45 (1976). 176. Vachuška J., Vobořil M.: Kinetic data computation from 152. Šesták J.: Thermodynamic basis for the theoretical non-isothermal thermogravimetric curves of non-uniform description and correct interpretation of thermoanalytical heating rate; Thermochim. Acta 2, 379 (1971). experiments; Thermochim. Acta 28, 197 (1979). 177. Šesták J., Berggren G.: Study of the kinetics of the mecha- 153. Holba P.: Enthalpy and phase relations at melting in nism of solid-state reactions at increasing temperatures; heterogeneous systems; Silikáty 23, 289 (1979). Thermochim. Acta 3, 1 (1971). 154. Hrma P.: Thermodynamics of batch melting; Glastech. 178. Šimon P.: Fourty years of the Sestak-Berggren equation; Ber. 55, 138 (1982). Thermochim. Acta 520, 156 (2011). 155. Šesták J.: Thermodynamic aspects of glassy state; Ther- 179. Holba P., Šesták J.: Kinetics with regard to the equilibrium mochim Acta 95, 459 (1985). of processes studied by non-isothermal techniques; Zeit. 156. Nevřiva M., Šesták J.: On the study of solid-liquid stable- physik. Chem. N.F. 80, 1 (1972). metastable phase equilibria; Thermochim. Acta 92, 623 180. Mianowski A.: Consenquences of Holba-Sestak equation; (1985). J. Thermal Anal. Calor. 96, 507 (2009). 157. Šatava V.: Determination of standard enthalpies, Gibbs 181. Šesták J., Kratochvil J.: The role of state constitutive energies and entropies of formation of hydrated calcium equations in chemical kinetics; Thermochim. Acta 7, 330 sulphoaluminates; Silikáty 30, 319 (1986). (1973). 158. Majling J., Jesenák V.: Algorithmizing the calculation of 182. Šatava V., Šesták J.: Kinetics and mechanism of thermal equilibria phase composition of multicomponent systems; decomposition at iso- and non-iso- thermogravimetry; Silikáty 30, 319 (1986) Anal. Chem. 45, 153 (1973). 159. Sopková A.: Inorganic complexes; Thermochim. Acta 183. Šatava V.: Fundamental principles of kinetic data eva- 110, 389 (1987). luation from TA curves; J. Thermal Anal. 5, 217 (1973). 160. Šesták J., Chvoj Z.: Thermodynamics and thermochemistry 184. Kratochvíl J., Šesták J.: Rational approach to thermo- of kinetic (real) phase diagrams involving solids; J. dynamic processes and constitutive equations in iso- and Thermal Anal. 32, 1645 (1987). non-isothermal kinetics; J. Thermal Anal. 5, 193 (1973). 161. Šatava, V.: Direct determination of standard enthalpies 185. Šesták J.: Applicability of DTA to the study of crystallization and Gibbs energies of formation and absolute entropies of kinetics; Phys. Chem. Glasses 15, 137 (1974). hydrated calcium sulphoaluminates and carboaluminates; 186. Matuchová M., Nývlt J.: Theory of crystallization rate;

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Chem. Listy 69, 1 (1975). 209. Hrma P.: Diffusion theory of ceramic body growth; 187. Holba P., Nevřiva M., Šesták J.: Analysis of DTA curve Silikáty 22, 357 (1978). and related calculation of kinetic data using computer 210. Kubíček P., Wozniaková B., Leško J.: Determination of technique; Thermochim. Acta 23, 223 (1978). diffusion coefficients with a general temperature program 188. Kubíček P., Leško J.: Determination of the kinetic para- using DTA; Thermochim. Acta 64, 229 (1983). meters from non-isothermal measurements with a general temperature program; Thermochim. Acta 31, 21 (1979). 211. Illeková E.: Model of mass transport in amorphous 189. Šesták J.: Philosophy of nonisothermal kinetics; J. Ther- metallic materials; Acta Phys. Slov. 34, 255 (1984). mal Anal. 16, 503 (1979). 212. Šajgalík P, Haviár M, Pánek Z, Contribution to the 190. Šimon P., Valko L.: Autocatalytic effect of hydrogen sintering diagrams; Zeits. Metall. 77, 193 (1986). chloride on the thermal dehydrochlorination of polyvinyl 213. Liška M., Hamlík L., Kanclíř E.: Enamel viscosity depen- chloride; Chemické Zvesti 37, 581 (1983). dence on modeling compositional and thermal relations; 191. Illeková E.: On the Various Activation Energies at Silikáty 31, 43 (1987). Crystallization of Amorphous Metallic Materials; J. Non- Cryst. Solids 68, 153 (1984). 214. Málek J., Klikorka J., Tichý L.: Conductivity measurements 192. Nývlt J.: Crystal growth measurements; Cryst. Res. Tech. during crystallization of glasses; Mater. Sci. Let. 5, 183 18, 1461 (1983). (1986). 193. Jesenák V.: Philosophy of the mechanism of diffusion 215. Mareš J., Krištofík J., Šmíd V.: On the conductivity in controlled processes; Thermochim. Acta 92, 39 (1985). semiinsulating semiconductors; Sol. State Com. 60, 275 194. Jesenák V.: Thermal effects of oscillating solid-state (1986). reactions; Thermochim. Acta 85, 91 (1985). 216. Málek J., Klikorka J., Šesták J., Tříska A.: Thermoelectrical 195. Kemény T., Šesták J.: Comparison of crystallization conductivity as a complementary method to DTA; kinetics determined by isothermal and non-isothermal methods; Thermochim. Acta 110, 113 (1987). Thermochim. Acta 110, 281 (1987).

196. Málek J.: The crystallization of Ge40S60 glass. Thermochim. 217. Helebrant A., Matoušek J.: Mathematical models of Acta 129, 293 (1988). the interaction of glass with water and with aqueous 197. Militký J., Málek J., Šesták J.: Parameter distortion by solutions; Silikáty 32, 173 (1986). unappropriate nonisothermal treatment; J. Thermal Anal. 218. Šatava V.: Strength and microstructure of cast gypsum; 35, 1837 (1989). Ceramics-Silikáty 40, 72 (1996). 198. Chvoj Z., Kožíšek Z., Šesták J.: Nonequilibrium processes of melt solidification during programmed temperature History and nomenclature changes and the metastable phases formation; Thermochim. Acta 153, 349 (1989). 219. Holba, P., Šesták J.: On the nomenclature of thermo- 199. Šimon P.: Kinetics of polymer degradation involving the analytical methods associated with energy changes; splitting-off of small molecules; Polym. Degrad. Sta. 29, Thermochim. Acta 13, 471 (1975). 155 (1990). 220. Šesták J., Holba P., Fajnor V.: System of Czech and Slovak Mechanical and transport properties terms used in thermal analysis; Chem. Listy 77, 1292 (1983). 200. Bárta R., Šatava V, Procházka S, Hlaváč J: Základní výzkum silikátů; (Basic Research of Silicates), SNTL 221. Hlaváč J.: The present state and perspective view of the Praha 1957. material research; Silikáty 29, 169 (1985). 201. Šatava V., Šesták J.: Influence of setting temperature on 222. Mackenzie R., Proks I.: Comenius and Black as proge- the structure and strength of the plaster of Paris; Silikáty nitors of thermal analysis; Thermochim. Acta 92, 3 6, 178 (1962). (1985). 202. Hrubý A., Kubelík I.: Electrical conductivity and thermo- 223. Šesták J., Mackenzie R.C.: Bárta Rudolf (1897-1985); J. electric power in semiconductors; Czech. J. Phys. B 15, Thermal Anal. 31, 3 (1986). 740 (1965). 224. Nevřiva M , Rosický J, Proks I, Kanclíř E.: Pioneers of 203. Hrma P.: Corrosion of refractory materials by molten glass; Silikáty 13, 165 (1969). thermal analysis in Czechoslovakia; Thermochim. Acta 204. Hlaváč J., Matoušek J.: Diffusion in molten oxide silica 110, 553 (1987). glasses; Silikáty 15, 333 (1971). 225. Bartuška M., Götz J.: The Silikáty periodical in future; 205. Matoušek J., Hlaváč J.: Study of volatilization of lead Silikáty 33, 289 (1989). glasses; Glass Technol. 12, 103 (1971). 226. Proks I.: Evaluation of the Knowledge of Phase Equilibria; 206. Kaščejev I., Matěj J., Bartuška M.: Corrosion of mullite In book “Kinetic Phase Diagrams: nonequilibrium phase ceramics by binary glass under free convection; Silikáty transitions” (Z. Chvoj, J. Šesták, A. Tříska, eds.), p.1-49, 16, 25 (1972). 207. Němec L.: Dissolution and diffusion of technologically Elsevier, Amsterdam 1991. significant gases in glass; Silikáty 16, 347 (1972). 227. Proks I. Celok je jednoduchší ako jeho časti; (Whole is 208. Hrma P., Šatava V.: Model for strength of brittle porous simpler than its parts), Publ. House of Slovak Academy materials; J. Am. Ceram. Soc. 57, 71 (1974). of Sciences, Bratislava 2012.

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