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)
Transcript
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)
FOR REVIE
W
Thermal science and analysis
Terms connotation, history, development, and the role of personalities
J. Sestak
Received: 4 September 2012 / Accepted: 26 November 2012
� Akademiai Kiado, Budapest, Hungary 2012
Abstract History of thermoscopy and thermometry is
reviewed showing the role of temperature degrees includ-
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—
105. Suga H. Frozen disorder in condensed phases. Russ J Phys
Chem. 2003;77:S7.
J. Sestak
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
21.1 Historical aspects of thermal studies, origins of caloric
Apparently, the first person which used a thought experiment of continuous heat-ing 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 con-densation of vapor to liquid water is given as an example. Comenius also deter-mined, 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 be-come apparent to our senses." In the following 19 paragraphs of this chapter Com-enius gave a rather systematic description (and also a partially correct interpreta-tion) 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 con-densation, etc., anticipating somehow the concept of latent heat. Comenius con-cludes 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
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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 “calor-ic”.
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 sub-stance, or better a matter of fire, likewise called caloric (or caloricum), was tho-roughly 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 atti-tude 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 accumu-late 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 ‘capaci-ty’ 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 influen-tial book on the analytical theory of heat [12], in which he developed methods for integration of partial differential equations, describing diffusion of the heat sub-stance. Based on the yet inconsistent law of conservation of caloric, Siméon D. Poisson (1823) derived a correct and experimentally verifiable equation describ-ing 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 par-ticular, 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 mer-cury by Gay-Lussac) and in spite of that Thompson (1798) showed that the heat
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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 ac-knowledged 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 mea-suring 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 hypo-thesis 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 meas-ured at constant pressure and volume. He found that the difference was the same
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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 thermody-namics, 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 contem-porary physicists and permanently unjustly criticized for his principle of the con-servation 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 po-tential for charge.
Taking into account that caloric is conserved during reversible operations, the quantity ς must be independent of temperature and, consequently, Carnot’s func-tion 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 exploita-tion 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
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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 evalu-ation of engine efficiency. The amount of caloric ς which is entering the complete-ly 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 ca-loric into thermal energy T1ς, we obtain immediately Kelvin’s dimensionless effi-ciency 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 efficien-cy 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 resis-tance [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<T1, and leaving it temperature T2. If we relate the quantities L and ς to an arbi-trary time unit (we conveniently use for this purpose a superscript u), it follows Lu
= λ(T1−T)(T−T2)/T , where for the evaluation of temperature drop across the ther-mal resistance we can apply the Fourier law [12] ςu 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 efficien-cy 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 de-scribes 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
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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 investiga-tion 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 be-came an observable and experimentally decisive quantity, which thus turned into an experimentally monitorable parameter associated with an consequent underpin-ning of the field of thermodynamics [29,34,35]. The first characterization of ther-mometric measurements is identified in Uppsala in 1829 through the earliest do-cumented 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 vo-lume 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 contamina-tion 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 af-ter the observation of thermoelectricity, its use in thermometry was finally vindi-cated, which rapidly got a wider use. Floris Osmond (1849-1912) [15,40] investi-gated 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 differ-ences 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 conse-quent development of DTA instruments.
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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 investi-gation [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
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 com-puterization and digital data processing).
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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 de-rivatives 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 pos-sibility 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 tem-perature 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 resis-tance 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 determina-tion from about >2 C down to ~0.5 C. Rates of about 20 K/min were fairly com-mon 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 ex-perimental details so that White [48] was first to show more theoretically the desi-rability of smaller samples providing a more exhaustive study of the effect of ex-perimental 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 tech-nique, though the experimentalists were generally aware of its quantitative poten-tialities. 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
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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 anal-ysis 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 temper-ature (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 tradi-tionally measured by calorimetry. Beside the above quoted ice-calorimeter pio-neered 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 construc-tion 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 mathe-matical 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 capaci-ty, effective thermal conductivity, and the inherent heat flux, occurring at the in-
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terface between the sample-block, B, and the surrounding jacket, J. The tempera-ture 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), iso-thermal (TB = TJ = const.) and isoberobolic (TB – TJ)→0. The most common ver-sion 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 determina-tion 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 tem-peratures and faster heat exchanges so that it is preferably employed at low tem-peratures.
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, in-struments with thermal compensation provided by electric microheating and heat removal is accomplished by forced flow of a fluid, or by the well-established con-duction through a system of thermocouple wires or even supplemented by Peltier cooling effect. The method in which the heat is transferred through a thermo-couple system is often called Tian-Calvet calorimetry. A specific group is formed by isoperibolic calorimeters, which essentially operate adiabatically with an iso-thermal 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 sam-ple and reference. This development came about because the key concern of calo-rimetry is the reduction of, and certainly also correction for, heat losses and/or gains due to inadvertent temperature distribution in the surroundings of the calo-rimeter. 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-
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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 flux-es by two extra micro-heaters respectively attached to both the sample and refer-ence 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 mea-surements of heat capacity (close to adiabatic calorimetry) but technically re-stricted, to the temperature range up to about 700 °C, where heat radiation become decisive making consequently the regulation and particularly compensation com-plicated.
Three major types of DSCs emerged that all are classified as scanning [79], isoperibolic twin-calorimeters. One type makes use of approximate power com-pensation 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 mea-surable 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 calcu-lation 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 sophis-tication, 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
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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 correc-tion 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 com-monly 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 ele-ment on passage of electric charge is a preferable method for achieving a more ‘absolute’ calorimetric calibration. It certainly requires special set-ups of the mea-suring head enabling the attachment of the micro-heater either on the crucible sur-face (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, par-ticularly, 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-
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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 modula-tion 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 iden-tical to the standard DSC output and a reversing signal, related to the AC calori-metry. 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 tem-perature derivatives is the fight against ‘noise’ in the heat flow signal in tempera-ture 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 en-tire 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 ther-mocouple junction) until the equilibrium temperature for the coexistence of two phases was attained.
Another way of a more clear-cut investigation was introduction of micro-analysis 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 measure-ment becomes size affected due to increasing role of the surface energy usually
14
described by an universal equation: Tr/T∞ ≅ (1 – C/r)p 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 mea-suring micro-porosity [99], quenching [94] and associated phenomena of the sam-ple 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 possi-bility 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 addi-tional 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 base-lines) 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 pos-sibly 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 gra-dient 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 ce-ramic raw materials [111] replacing the process of decomposition of clay minerals
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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 investi-gated 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 stu-dents (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 commu-nication 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 inter-national 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 foun-dation 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
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Analysis, which was brought into being by Judit Simon (1937-, who has been serv-ing 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 note-worthy for their contributions to the progress of the fields of thermal analysis (TA) and calorime-try including the founders of ICTA/ICTAC (around the inserted emblem), living persons limitedto 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 (calori-metry) 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 analy-sis, 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 confe-rences started in Osaka 1964 under the organiza-tion of Prof. S. Seki who became the first presi-dent when the JSCTA was officially established in 1973. Since then, the JSCTA journal NETSU SOKUTEI has been published periodically.
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78 Watson, E.S., O’Neill, M.J., Justin, J., Brenner, N.: A Differential Scanning Calorimeter for Quantitative Differential Thermal Analysis. Anal. Chem. 36, (1964) 1233-1238; and O’Neill, M.J.: The Analysis of a Temperature-Controlled Scanning Calorimeter. Anal. Chem. 36, 1238-1245 (1964)
79 Wunderlich, B.: Temperature-modulated calorimetry in the 21st century. Thermochim. Acta 355, 43-57 (2000)
80 Faktor, M.M., Hanks, R.: Quantitative application of dynamic differential calorimetry“. Part 1.-Theoretical and experimental evaluation. Trans. Faraday Soc. 63, 1122-1129; and: Part 2.-Heats of formation of the group 3A arsenides. Trans. Faraday Soc. 63, 1130 – 1135 (1967)
81 Grey, A.P.: Simple Generalized Theory for Analysis of Dynamic Thermal Measurements. In: Porter R.S., Johnson J.F. (editors) Analytical Calorimetry, Vol. 1, p. 209. Plenum Press, New York (1968). and: In: Proc. 4th ICTA, “Thermal Analysis”, Akademiai Kiado, Budapest 1974
82 Holba, P., Šesták, J., Bárta, R.: Teorie a praxe DTA/DSC. (Theory and practice of DTA/DSC). Silikáty (Prague) 20, 83-95 (1976); and Šesták, J., Holba, P., Lombardi, G.: Quantitative evaluation of thermal effects: theory and practice. Annali di Chimica (Roma) 67, 73-87 (1977)
83 Boerio-Goates, J., Callen, J.E.: Differential Thermal Methods. In: Rossiter, B.W., Beatzold, R.C. (eds.) Determination of Thermodynamic Properties, pp. 621-718. Wiley, New York (1992)
85 Flynn, J.H.: Theory of DSC. In: Porter, R.S., Johnson, J.F. (eds.) Analytical Calorimetry, p. 3 and 17. Plenum Press, New York (1974); and Thermodynamic properties from differential scanning calorimetry by calorimetric methods. Thermochim. Acta 8, 69-81 (1974)
86 Heines, P.J., Reading, M., Wilburn, F.W.: Differential Thermal Analysis and Differential Scanning Calorimetry. In: Brown M.E. (ed.) Handbook of Thermal Analysis and Calorime-try, Vol. 1, pp. 279-361. Elsevier, Amsterdam (1998)
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89 Reading, M.: Modulated differential scanning calorimetry: a new way forward in materials characterization. Trends Polym. Sci. 1, 248-253 (1993)
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96 Zhang, Z., Li, J.C., Jiang, Q.: Modelling for size-dependent and dimension-dependent melt-ing of nanocrystals. J. Phys. D: Appl. Phys. 33, 2653–2656 (2000)
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thermal analysis of polymers: current capabilities and future prospects. Macromolecular Symposia 167, 45-55 (2001)
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105 Paulik, F.: Special Trends in Thermal Analysis. Wiley, Chichester (1995); and Balek, V., Brown, M.E.: Less Common Techniques of Thermal Analysis. In: Brown M.E. (ed.) Hand-book of Thermal Analysis and Calorimetry, Vol. 1, pp. 445-471. Elsevier, Amsterdam (1998)
106 Sørensen, O.T.: Rate Controlled Thermal Analysis Used to Study solid-state Reactins. J. Thermal Anal. Calor. 56, 17-22 (1999); and Sørensen, O.T., Rouquerol, J.: Sample con-trolled thermal analysis. Kluwer, Dordrecht (2003)
107 Balek, V.: Emanation thermal analysis. Thermochim. Acta, 22, 1-156 (1978); and Balek, V., Tölgyessy: Emanation thermal analysis and other radiometric emanation methods. Elsevier, Amsterdam (1984)
108 Mareš, J.J., Šesták, J.: An attempt at quantum thermal physics. J. Thermal Anal. Calor. 82, 681-686 (2005)
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110 Mareš, J.J., Hubík, P., Šesták, J., Špička, V., Krištofik, J., Stávek, J.: Relativistic transforma-tion of temperature and Mosengeil-Ott’s antinomy. Physica E 42, 484-487 (2010)
111 Kallauner, O., Matějka, J.: Beitrag zu der rationellen Analyse, Sprechsaal 47, 423 (1914); and Matějka, J.: Chemické proměny kaolinitu v žáru“ (Chemical changes of kaolinite on fir-ing) Chemické listy 13, 164-166 and 182-185 (1919)
112 Gallagher, P., McAdie, H. (eds.) ICTAC celebrates its 40th anniversary. Special issue of ICTAC News – ISSN 1022-2510 (2006)
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116Sipowska, J.T., Izatt, R.M., Ott, J.B.: The history of the calorimetry conference. Netsu Soku-tei (Japanese Journal of TA) 37, 17 (2001)
117 Stull, D.R.: Twenty-Five Years of Calorimetry Conferences. Bull.Thermodyn. Thermochem. 14, 431–441 (1971)
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national conferences on this subject J. Thermal. Anal. Calor. 71, 7-11 (2003)
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
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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
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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
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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
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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 semi-empirically 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
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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).
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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
8
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
9
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.
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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
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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.
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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).
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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.
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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.
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ICTAC 1965–68 1968–71 1971–74 1974–77 President L. G. Berg (USSR) C. B. Murphy
(USA) H. R. Oswald (Switzerland)
H. Kambe (Japan)
Vice-President — R. Bárta (Czechoslovakia)
H. Kambe (Japan)
H.G. McAdie (Canada)
Secretary J. P. Redfern (England)
J. A. Hill (USA)
G. Lombardi (Italy)
G. Lombardi (Italy)
Treasurer R. C. Mackenzie (Scotland)
R. C. Mackenzie (Scotland)
R. C. Mackenzie (Scotland)
R. C. Mackenzie (Scotland)
Past-President — L. G. Berg (USSR)
C. B. Murphy (USA)
H. R. Oswald (Switzerland)
Ordinary members
R. Bárta (Czechoslovakia)
S. K. Bhattacharrya (India)
C. Duval (France) L. Erdey
(Hungary) T. Sudo (Japan)
D. J. Swaine (Australia)
S. K. Bhattacharrya (India)
C. Duval (France)
H. Kambe (Japan)
G. Krien (BRD)
G. Lombardi (Italy)
D. J. Swaine (Australia) T. L. Webb
(South Africa) E. I. Yarembash
(USSR)
P. K. Gallagher (USA)
M. Harmelin (France)
M. D. Karkhanavala (India)
G. Krien (BRD)
O. T. Sörensen (Denmark)
S. St. J. Warne (Australia) T. L. Webb
(South Africa)
P. K. Gallagher (USA)
M. Harmelin (France)
M. D. Karkhanavala (India)
V. B. Lazarev (USSR)
H. Lehmann (BRD) F. Paulik (Hungary)
O. T. Sörensen (Denmark)
S. St. J. Warne (Australia)
Chairmen of Committees
R. Bárta, Honorary president
(Czechoslovakia)
Standardisation H. G. McAdie (Canada)
H. G. McAdie (Canada)
H. G. McAdie (Canada)
P. D. Garn (USA)
Nomenclature R. C. Mackenzie (Scotland)
R. C. Mackenzie (Scotland)
R. C. Mackenzie (Scotland)
R. C. Mackenzie (Scotland)
Publications J. P. Redfern (England)
J. P. Redfern (England)
J. P. Redfern (England)
J. P. Redfern (England)
Organising for next Conference
C. B. Murphy (USA)
M. Müller Von Moos (Switzerland)
F. Paulik (Hungary)
S. Seki (Japan)
Historical Prague and its famous CharlesUniversity
One of the most important moments in the history ofold Bohemia was the foundation of Charles Univer-sity in Prague, as the first European university northof the Alps, by Emperor Charles the IV. One of itsfirst achievements was the introduction of medievalkinematics, which was brought to Prague by Johannesde Holandria, an Oxfordian from Merton College,who in the year 1368 provided the so-called Merton’theorem of uniform acceleration to public and de-tailed this approach during his stay in Prague. LaterCzech astronomer Jan �indel (1375–1456) was study-ing the planetary motion and his astronomical tableswere greatly appreciated by Tycho de Brahe whilestaying in Prague at the end of the 16th century.
�indel had also a share in designing the advanced as-trolabe in the famous Prague’s astronomical clock.
Little renown is Ioannes Marcus Marci (JanMarek Mark� 1595–1667) who probably helped to re-veal the fundamental properties of the spectral colorsthat emerge when light passes through glass prism,was already aware of their monochromatic properties,i.e., any succeeding refraction or reflection did notchange colors. He also studied the color change inrays when spectral colors are mixed and in the field ofspectral dispersion of light he was actually a prede-cessor of Isac Newton. He wrote for that time very ad-vanced books. e.g. [1], which possibly foreshadowedsome laws. Besides the refraction of light he con-ducted the first-ever systematic study of the impact ofbodies, he discovered the difference between elasticand inelastic impacts intuitively moving his thoughtswithin the reach of the conservation laws. Marci,
1388–6150/$20.00 Akadémiai Kiadó, Budapest, Hungary
Journal of Thermal Analysis and Calorimetry, Vol. 88 (2007) 3, x–x
FROM CALORIC TO STATHMOGRAPH AND POLAROGRAPHY
J. �esták1,2* and J. J. Mare�1
1Institute of Physics, Academy of Sciences, Cukrovarnická 10, 16253 Praha 6, Czech Republic2Faculty 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 learn-ing 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,Tadeá� Hájek, Marcus Marci, Jan A. Commenius (caloric), Prokop Divi�, Bernard Bolzano, Christian Doppler, Ernst Mach, AlbertEinstein, Václav �imerka, Franti�ek Závi�ka, �en�k Strouhal, Reinhold Fürst or Stanislav �kramovsk� (statmograph) and JaroslavHeyrovsk� (polarography), the latter being already the representative of modern age.
Keywords: ???
Fig. 1 From left: Charles University in Prague (founded by Emperor Charles IV. 1348 and some of their exceptional membersand associates, astronomer Kepler Johannes (1571–1630), rector and mathematician Marcus Marci Ioannes (fromKronland, 1595–1667) and famous professor of mathematics and practical geometry Doppler Christian (1803–1853)
however, was strongly convinced that white light wasthe simplest element (‘quinta essentia’), which, inter-estingly, was close to the subsequent concept of ‘ele-mentary waves’ propounded about fifty years later byHuyghens in the wave theory of light. There, how-ever, is incomplete information concerning Marci`seducational activities. He was the rector of the famousCharles University and, perhaps, introduced a wordfirst specialization called ‘chimiatrie’, which wasconceivably taught as an unusual subject with regardsthe traditional university disciplines: major ‘artesliberales’ and minor ‘artes mechanicae’ (i.e., learningcommon crafts such as warfare, navigation, business,agriculture, hunting, medicine or veterinary) but notin ‘artes incertae’ (that was a part of the habitually re-jected ‘equivocal arts’ associated with occultism,which traditionally involved alchemy).
Some medivial alchemists and theintroduction of caloric
When Rudolph the II (1552–1612) became the Em-peror of the Holy Roman Empire and the King of Bo-hemia, he provided in Prague court a vital support toalchemists, astronomers and physicists. Among themost outstanding scientists were Tycho de Brahe(1546–1601) and Johannes Kepler (1571–1630)whose astronomical observations and calculationswere published in the well-known Rudolphine tables.After the death of Tycho de Brahe, Johannes Keplerreplaced his position of a royal mathematician inPrague in the year 1601. Using Tycho de Brahe’sdata, Kepler determined elliptic orbit of Venus. In his1609 treatise ‘Astronomia Nova’ Kepler publishedhis two first laws, controlling the motion of planetsand according to which the orbit of a planet/cometabout the Sun is an ellipse with the Sun’s center ofmass at one focus.
Foremost Czech physician and astronomer, ChefMedical Supervisor of the Kingdom of Bohemia atthe court of Rudolph the II, was Thaddaeus Hageciusab Hagek (Tadeá� Hájek z Hájk�, 1525–1600) knownas an author of several astronomical tractates andbooks on geodesy, botanics and medicine particularlyacknowledged for the first concise book on thebeer-making, ‘De cerevisia’ (1585). He essentiallyhelped the flourishing period of alchemy and played asignificant role in persuading Rudolph the II to inviteTycho de Brahe to come to Prague.
Special attention should be paid to the Czechthinker and Bohemian educator, latter refugee JanAmos Comenius (Komensk� 1592–1670). In hisPhysicae Synopsis, which he finished in 1629 (pub-lished first in Leipzig in 1633), he showed the impor-tance of hotness and coldness in all natural processes.Heat (or better fire) is considered as the cause of all mo-tions of things. The expansion of substances and the in-creasing the space they occupy is caused by their dilu-tion with heat. By the influence of cold the substancegains in density and shrinks: the condensation of vaporto liquid water is given as an example. Comenius alsodetermined, though very inaccurately, the volume in-crease in the gas phase caused by the evaporation of aunit volume of liquid water. In Amsterdam in 1659 hepublished a treatise on the principles of heat andcold [2], which was probably inspired by the works ofthe Italian philosopher Bernardino Telesius. The thirdchapter of Comenius’ book was devoted to the descrip-tion of the influence of temperature changes on theproperties of substances. The aim and principles of ther-mal analysis were literally given in the first paragraph ofthis chapter: citing the English translation [3] ‘In orderto observe clearly the effects of heat and cold, we musttake a visible object and observe its changes occurringduring its heating and subsequent cooling so that the ef-fects of heat and cold become apparent to our senses.’ Inthe following 19 paragraphs of this chapter Comeniusgave a rather systematic description (and also a partially
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Fig. 2 From left: Hájek Tadeá� (from Hájk�, 1526–1600), Komensk� Jan Amos (Comenius, 1592–1670), Prokop Divi�(1696–1765) and Bolzano Bernard (1781–1848)
correct interpretation) of the effects of continuous heat-ing and cooling of water and air, and also stressed thereversibility of processes such as, for example, evapora-tion and condensation, etc., anticipating somehow theconcept of latent heat. Comenius concludes this chapteras follows: ‘All shows therefore that both heat and coldare a motion, which had to be proved.’ In the followingchapter Comenius described and almost correctly ex-plained the function of a thermoscope (‘vitrumcaldarium’) and introduced his own qualitative scalewith three degrees of heat above and three degrees ofcold below the ambient temperature.
It is difficult to trace and thus hard to say if it waspossible (though likely) to disseminate the idea of calo-ric from Amsterdam (when Comenius mostly lived andalso died) to Scotland where a century later a new sub-stance, or better a matter of fire, likewise called caloric(caloricum), was thoroughly introduced. It was as-sumed, e.g., that caloric creeps between the constituentparts of a substance causing its expansion. Althoughcaloric differed from foregoing concept of phlogiston(because it could be later measured with an apparatuscalled a calorimeter) it is not clear who was the first us-ing such an instrument. If we follow the studies ofMackenzie and Brush [4, 5] and Thenard [6] they as-signed it to Wilcke. It, however, contradicts to theopinion presented in the study by McKie andHeathcode [7] who consider it just a legend and as-sume that the priority of familiarity of ice calorimeterbelongs to Laplace who was most likely the acknowl-edged inventor and first true user of this instrument(likely as early as in 1782). In fact, Lavoisier andLaplace entitled the first chapter of their famous‘Mémoire sur la Chaleur’ (Paris 1783) as ‘Presentationof a new means for measuring heat’ whereas the reportof calorimetric employment by Black seemed to firstappear almost a century later in the Jamin’s Course ofPhysics (Mallet–Bachelier, Paris 1868).
Caloric was seen as an imponderable elementwith its own properties. Unfortunately, the great prop-agator, Joseph Black (and his student Irvine), pub-lished almost nothing in their own lifetimes [8] andtheir attitudes were mostly reconstructed from con-temporary comments and essays published after theirdeaths. Black supposed that heat was absorbed by abody during melting or vaporization, simply becauseat the melting- or boiling- points sudden changes tookplace in the ability of the body to accumulate heat(~1761). Irvine’s account that the relative quantitiesof heat contained in equal weights of different sub-stances at any given temperature (i.e., their ‘absoluteheats’) were proportional to their ‘capacities’ at thattemperature and it is worth noting that the term ‘ca-pacity’ was used by both Black and later also Irvine toindicate specific heats [8]. Black also introduced the
term ‘latent heat’ which meant the absorption of heatas the consequence of the change of state.
Black’s elegant explanation of latent heat to theyoung Watts became the source of the invention ofthe businesslike steam engine as well as the inspira-tion for the first research in theory related to the noveldomain of thermochemistry, which searched for gen-eral laws that linked heat, with changes of state.Rumford presented qualitative arguments for such afluid theory of heat with which he succeeded to evalu-ate the mechanical equivalent of heat. This theory,however, was not accepted until the later approval byMayer and, in particular, by Joule, who also appliedRumford’s theory to the transformation of electricalwork. The use of customary units called ‘calories’was coined by Clément, who was giving in 1824 thefollowing definitions: a ‘small calorie’ allowed to in-crease by one degree the temperature of 1 g of water,whereas a ‘large calorie’ allowed to melt 1 g of ice.The word ‘calorie’ was then introduced into the vo-cabulary of academic physicists and chemists (Favreand Silbermann [9]) in 1845. The characterization ofone kilocalorie as 427 kilogram-meters was launchedby Mayer in the year 1845. The caloric-like descrip-tion of heat as a fluid has survived, nevertheless, untiltoday being a convenient tool for easy mathematicaldescription of heat flows [3, 10–14]. Recently wetried to refresh the concept of caloric in the view ofentropy and its connection to information [15].
Worth noting is the theory of Prokop Divi�(Divisch 1696–1765), which belongs to early pioneer-ing times. Accordingly, ‘Light of the First Day of Cre-ation’ is regarded to be identical with electricity, whichis an inherent quality of all things, permeating thewhole Universe and manifesting itself by electric andthermal phenomena [16]. Such an idea is, surprisingly,in an apparent agreement with the modern idea of elec-tromagnetic zero-point background radiation [17].
Important role played the Prague Jesuit Collegeof Clementinum and its famous library and observa-tory (opened in the 1720s) where about 1780 AntoninStrnad (1747–1799) laid the foundation to the oldestknown series of systematic metrological observa-tions. Worth noting are physicists and mathemati-cians Josef Stepling (1716–1778) and Jan Tesánek(1728–1788) who published many original studiesand initiated publishing of Prague edition of New-ton’s ‘Principia’ supplemented with his own com-mentaries, in that time best edition reasoned withbetter mathematical background.
Renaissance of Prague physics
The first half of the 19th Century mathematical andphysical studies in Prague became again on a par with
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the world science. Important role paid some scientistssuch as Franti�ek J. Gestner (1756–1832) who is alsoknown as a pioneer of the railway transport in Europe.Excellent achievements are duly associated with thename of Bernard Bolzano (1781–1848) particularly inmathematical logic and analysis and with his friendChristian Doppler (1803–1853) who came to Praguefrom Vienna in 1829. His famous paper was inspiredby astronomical phenomenon: the components ofmany binary stars differ from each other in color.Though, according to present knowledge, the ob-served color difference is due to the difference of sur-face temperatures and not to the difference in radialvelocities, the principle itself is correct, being veri-fied, e.g., in acoustics and optics. In 1867 arrived toPrague Ernest Mach (1838–1916) and spent therenearly 30 years. He is known for his discussion ofNewton’s Principia and critique of conceptual mon-strosity of absolute space in his book ‘The Science ofMechanics’ (1883). Mach encouraged and inspiredone of his students (later professor of theoreticalphysics) Jan Kolá�ek (1851–1913) to study some ofhis hypothesis later approving that the Mach’s theory
correctly describes the dispersion of light, dichroismand circular birefringence. The Mach successor atPrague German University was Ernst Lecher(1856–1926) who is well known for his research onelectromagnetic waves (i.e. Lecher wires). Mach alsoanalyzed conceptual basis of calorimetry from moregeneral, almost philosophical, point of views [18].His influence on the further development of physicswas tremendous and he established a mathematicallyspecialized school – a great deal of his attention de-voted to optics and acoustics. One of his personal sci-entific contacts was Czech famous Jan E. Purkyn�(1787–1869) internationally known for discoveries inphysiology. Another young assistant of Mach was�en�k Strouhal (1850–1922), later first Czech profes-sor appointed for experimental physics. His studies inacoustic are well known and the Strouhal’s numberconcerning friction tones (oscillation) is named afterhim. He wrote and exceptional book on heat called‘Thermics’ [19].
Czech priest (and, unfortunately, rather un-known mathematician) Václav �imerka (1819–1887)introduced quantitative evaluation in psychology
4 J. Therm. Anal. Cal., 88, 2007
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Fig. 3 From left: Václav �imerka (1819–1887), Friedrich Reinitzer (1857–1927), Ernest Mach (1838–1916), Albert Einstein(1879–1955)
Fig. 4 From left: �en�k Strouhal (1850–1922), Franti�ek Závi�ka (1879–1945), Jaroslav Heyrovsk� (1890–1967), Stanislav�kramovsk� (1901–1983)
(logarithmic connotation of feelings) providing earlybasis for the theory of information [20]. Czech-bornFriedrich Reinitzer (1857–1927) is famous as the dis-coverer of cholesterol (including its metamorphosisand stoichiometry formulae C27H46O) and is alsoknown for his pioneering work in the field of liquidcrystals (latter widespread by O. Lehmann). BohumilKu�era (1874–1921) examined effect of electrical po-larization on surface tension in the interface of twoliquids prompting the idea of a new technique latterknown as the drop-weight method, which providedphysical basis for a new, today widely utilized, ana-lytical method called polarography [21] as introducedby Jaroslav Heyrovsk� (1890–1967), which wasawarded by Nobel price in 1959 [22].
An original development of weight measurementsis connected with the name Stanislav �kramovsk�(1901–1983), who, at the Charles University, investi-gated thermal decomposition of complex oxalateswhich led him in 1932 to his own construction of anapparatus named ‘stathmograph’ (from Greek‘stathmos’=mass, weight) [23] that made it possible tomeasure mass changes. Independently, in the sametime Duval used for his way of weight measurementsthe Latin-based term ‘thermogravimetry’ that later be-came generally accepted in thermal analysis. As theprinciple scheme of the stathmograph instrument is notgenerally known, it is perhaps worth mentioning to de-scribe the arrangement. �kramovsk� placed a weightedsample into the drying oven on a dish suspended on along filament passing through a hole in its upper wall(forming the balance case) and hooked to the left armof an analytical balance. A mirror attached to the beamwas reflecting the image of a light slit into a slowly ro-tating drum lined with photosensitive paper. The un-wanted vibration was reduced by an attached glass rodimmersed into paraffin oil and temperature was regis-tered automatically by means of a mercury thermome-ter provided by platinum contacts distributed along thewhole length of capillary.
A most prominent personality, which spent fruit-ful time in Prague was Albert Einstein (1879–1955)[24], a German physicist, originator of theories of rel-ativity, laws of motion and rest, simultaneity and in-terrelation of mass and energy, quantum theory ofphotoelectric effect, theory of specific heats,Brownian motion, etc. (see the book ’Builders of theUniverse’ 1932). In 1911 he obtained his first profes-sorship at theoretical physics at the German Univer-sity of Prague where he closely cooperated with hisfriend professor of mathematics, Georg Pick(1859–1942). While in Prague he published 11 pa-pers, most extensive being the survey of the theory ofspecific heats and very important were studies relatedwith his favorite problem – the interaction of radia-
tion with matter and effort to construct a relativistictheory of gravitation [25].
Worth noting is the so-called Planck-Einsteintransformation formula for temperature which readsT=T0 [ ( / ) ]1 2
� v c [25] and is possibly related to theprevious dissertation work by K. von Mosengeil, post-humously published in Ann. Physik 22 (1907) 867. Itmeans that the temperature of a body observed fromthe system moving with a relative velocity, v, is lowerthan the temperature in rest system. Basing on this ideain the article published in Ann. Physik 26 (1908) 1,Planck assumed that the First and Second Law of ther-modynamics keep their form in all inertial frames. Inthe year 1953, however, Einstein wrote a letter to M.von Laue in which he doubts the correctness of thisformula and rather speculated about a formula used in-verse (temperature as observed in moving system ishigher). This statement, which was later proved by H.Ott [26], thus reads as T=T0 [ ( / ) ]1 2
� v c . In both thesecases information about the temperature is regarded tobe mediated by the coherent electromagnetic radiation.Interestingly, in the case, where temperature is consid-ered to be essentially local property and the thermome-ter reading is transferred to moving system, e.g., bymeans of digital coding, the temperature, in the con-trast to both above formulae, must be considered asralativistically invariant.
Another distinguished, but unjustly not very ap-preciated, savant born in Prague was Reinhold Fürth(1893–1979) who devoted his scientific life to the re-search into the fundamentals of statistical phys-ics [27]. Besides an extensive work concerningBrownian motion and noise phenomena he is also au-thor of stochastic interpretation of quantum mechan-ics [28]. Accordingly to this theory, the Schrödingerequation is nothing but the classical diffusion equa-tion with complex diffusion constant ~j�/2m. Thisstatement became later a corner–stone of so-calledstochastic electrodynamics, which provides an alter-native to quantum mechanics [29].
One of the outstanding teachers, who earnedgreat merit for introducing modern theoretical physicsand thermodynamics to the curriculum of CharlesUniversity, was Frantisek Závi�ka (1879–1945). Oneof his textbooks was the first monograph on relativitypublished in Czech and he is an author of excellentbooks on thermodynamics [30]. He also concernedwaveguides and independently deduced relevant the-ory early before the microwave technique became im-portant. Other notable physicist was Augustin á�ek(1886–1961) who studied damped electromagneticoscillations in vacuum electronic systems. His ex-tended studies culminated at 1924 in the discovery ofthe principle of magnetron, later becoming the basisof radar systems.
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The historical development and use of the meth-ods of thermal analysis in the territory of formerCzechoslovakia is linked with the names OttoKallauner (1886–1972) and Jospeh Mat�jka(1892–1960) who introduced thermal analysis as thenovel technique during the period of the socalled ‘ra-tional analysis’ of ceramic raw materials [31]. Muchcredit for further development of modern thermalanalysis is attributed with Rudolph Barta(1897–1985) who stimulated his coworkers (Vladimír�atava) and his students (Jaroslav �esták) at the Insti-tute of Chemical Technology in Prague (the lattermentioned names became also initiators of the foun-dation of the International Confederation for ThermalAnalysis in the year 1965 [32]).
Some other details were published elsewhere[31–34].
Acknowledgements
This study was supported by the grant No. A100100639 of theGrant Agency of the Academy of Sciences of Czech Republicand the Institutional FZU research plan No. AVOZ10100521and the UWB project MSMT No. 4977751303.
References
1 M. Marci, ‘De proportione motu’, Prague 1639.2 J. A. Comenius, ‘Disquisitiones de Caloris et Frigoris
Natura’, Amsterdam 1659.3 J. �esták, ‘Heat, Thermal Analysis and Society’, Nucleus,
Hradec Králové 2004.4 R. C. Mackenzie, ‘History of Thermal Analysis’, special
issue of Thermochim. Acta, 73 (1984).5 S. G. Brush, ‘The Kind of Motion we call Heat’.
Vol. I & II , North Holand, Amsterdam 1976.6 L.Thenard, ‘Treatise of Chemistry’ 6th edition, Crochard,
Paris 1836.7 D. McKie and N. H. V. Heathcote, ‘The Discovery of
Specific and Latent Heats’, Arnold, London 1935.8 R. Fox, ‘The Caloric Theory of Gases: from Lavoisier to
Regnault’, Claredon Press, Oxford 1971.9 P. Favre and J. Silbermann, C. R. Acad. Sci., 20 (1845) 1567.
10 R. Clausius, ‘Mechanische Wärmetheorie’, Vieweg u.Sohn, Braunschweig 1876.
11 J. M. Socquet, ‘Essai sur le calorique’, Paris 1801.12 P. Kelland, ‘Theory of Heat’, Cambridge 1837.
13 R. B. Lindsay, ‘Energy: historical development of theconcept’, Dowden, Stroudburg 1975.
14 J. J. Mare�, J. Therm. Anal. Cal., 60 (2000) 1081.15 J. J. Mare� and J. �esták, J. Therm. Anal. Cal.,
82 (2005) 681.16 P. Divisch, ‘Längst verlangte Theorie von der
meteorologischen Electricite, Magiam Naturalembenahmet’, J. H. P. Schramm, Tübingen 1765.
17 M. Sparnaay, ‘Historical Background of the CasimirEffect’ in ‘Physics in the Making’ (A. Sarlemijn,M. Sparnaay, Eds), Elsevier, Amsterdam 1989.
18 E. Mach, ‘Die Principien der Wärmelehre’, Leipzig 1896.19 �. Strouhal, ‘Thermika’ (Thermics), J�MF, Praha 1908
(in Czech).20 P. V. �imerka, ‘Síla pesv�d�ení: pokus v duchovní
mechanice’ (Strength of conviction, an attempt to mentalmechanics), �asopis pro p�stování matemat. fyziky,11 (1882) 75 (in Czech); A. Pánek, ‘ivot a p�sobení�imerky’ (�imerka’s life and actuation), �asopis prop�stování matemat. fyziky, 17 (1888) 253 as well asJ. Fiala in ‘Jubilejni Almanach JCSNF’, Praha 1987, p. 97.
21 J. Heyrovsky, ‘Poralographie’, Springer, Vienna 1941.22 J. Janta and J. Niederle (Eds), ‘Physics and Prague’,
Academie, Prague 2005.23 S. �kramovsk�, Chemické Listy, 26 (1932) 521 (in
Czech).24 J. Bi�ák, �es.�as. Fyz., A29 (1979) 222 (in Czech).25 A. Einstein, Jhb. Radioact. Electron, 4 (1907) 411.26 H. Ott, Z. Phys., 175 (1963) 70.27 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) 143.29 J. J. Mare�, J. Stávek and J. �esták, J. Chem. Phys.,
121 (2004) 1499.30 F. Závi�ka, ‘Termodynamika’ (Thermodynamics), J�MF,
Praha 1943 (in Czech).31 I. Proks, ‘Evaluation of the Knowledge of Phase
Equilibria’ first chapter in the book ‘Kinetic PhaseDiagrams’ (Z. Chvoj, J. �esták, A. Tíska, Eds), Elsevier,Amsterdam 1991.
32 J. �esták, ‘Some historical aspects of thermal analysis:origin of Termanal and ICTA’ in the proceedings ofTermanal 2005, p. 3 (Eds E. Klein, E. Smr�ková,P. �imon).
33 P. Cardillo, J. Therm. Anal. Cal., 72 (2002) 7.34 J. �esták, ‘Science of heat and Thermophysical Studies: a
generalized approach to thermal analysis’, Elsevier,Amsterdam 2005.
DOI: 10.1007/s10973-006-8210-1
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Review papers
Ceramics – Silikáty 56 (2) 159-167 (2012) 159
CzeChoSlovak footpRintS in the developmentof methodS of theRmometRy, CaloRimetRy
and theRmal analySiSa 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
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 - from thermoscopy to thermal analysis
one of the first modern-times considerations of heat and cold can be found in the treatise published in 1563 by B. Telesio. at the end of the 16th century the first air thermoscope appeared (G. Galileo about 1597) and in 1626 the word „thermometer“ was for the first time used to describe thermoscope equipped with scale with eight degrees (Leurechon in book “la Recreation mathematique”). Shortly after, the world-known Czech educator J. A. Comenius inserted reflections on the role of heat and cold in nature into his work „physicae Synopsis“ (1633) and then, in 1659, published another worth noting book „disquisitiones de Caloris frigoris et natura.“ the first quantitative thermal law expressing the dependence of temperature of a cooling body (expressed in the scale of 8 degrees) on the time was published by I. Newton in 1701. meanwhile, other scientists had invented various types of the dilatation thermometers and had proposed various temperature scales. Rømer (1701) had filled glass tube of thermometer with red wine and proposed a 60-degree scale. Fahrenheit (1724) proposed a tem-perature scale of 100 degrees from 0°f (at the temperature of mixture of ammonium chloride, water and ice) and
100°f at the human body temperature. Reaumur (1731) introduced the temperature scale with 80 degrees between 0°Re at water melting point and 80°Re at boiling point of water. a year later Delisle introduced an exotic scale with 240 degrees, which was later (1738) modified and adjusted to 150°d corresponding to the melting point of water and to 0°d at boiling point of water (240°d = - 60°C), and this scale was being used in Russia for the whole hundred years. only then Celsius (1742) came with its 100-degree scale (between the melting 100 and boiling 0 points of water, later switched to nowadays 0-100 by Linné). the crucial experimental studies, thanks to which temperature became a clearly measurable physical quantity, was executed by Regnault in the 1840th, that is long after the Black (1761) distinguished between the specific heat (heat capacity) and the latent heat, Laplace and Lavoisier (1786) performed their first calorimetric measurements. in 1822 Fourier published his laws of heat transfer. yet after detailed results of Regnault´s dilatometric and heat capacity measurements (1842), together with Carnot´s theorem (1824) and its consequent interpretation by Clapeyron (1834) - the basis was formed for the introducing of absolute temperature scale by W. Thomson (Kelvin 1848) and for the inception of thermodynamics as a new science.
Holba P., Šesták J.
160 Ceramics – Silikáty 56 (2) 159-167 (2012)
the first noted use of thermometry as a method of thermal analysis took place in Uppsala in 1829 where F. Rudberg (1800-1839) recorded inverse cooling-rate data for various alloys. [1,2]. in 1883, H. L. Le Chatelier (1850-1936) adopted a somehow more fruitful approach plotting the time vs. temperature curves easily convertible to the relation of sample temperature vs. environmental temperature. Several years later le Chatelier (1887) had used pt/ptRh thermocouple and the new era of thermometry as well as of calorimetry has arrived. in 1891, W. C. Roberts-Austen (1843-1902) [3] became known to construct a device to give a continuous record of the output from thermocouple and he termed it as “thermoelectric pyrometer”. later with his assistant A. Stanfield published in 1899 heating curves for gold, which almost stumbled upon the idea of dta (“differential thermal analysis”). they improved the sensitivity by maintaining the thermocouple ‘cold’ junction at a constant temperature and by measuring the differences between two high temperatures [4]. among other well-known inventors was Russian N. S. Kurnakov (1860-1941) improving registration of his pyrometer by the photographic continuously recording drum [5]. the term “thermal analysis” was coined by G. H. J. Tammann (1861-1938) [6] around the year 1904 demonstrating the significance of cooling curves in phase-equilibrium studies of binary systems. the first Czech university textbook on the physics of heat was “thermika” by Č. Strouhal (1850-1922) published in 1908 [7] maintaining its informative value until today’s. the historical development and practical use of dta in the territory of former Czechoslovakia [1, 2, 8] was linked with the names J. Burian (1873-1942), O. Kallauner (1886-1972) and J. Matějka (1892-1960) who introduced thermal analysis as the novel technique during the period of the so called “rational analysis” of ceramic raw materials [9] in order to investigate behavior of kaolinite [10, 11] at heating. Worth a special attention is an original development of weight measurements that is connected with the name S. Škramovský (1901-1983), who, at the Charles University, investigated thermal decomposition of complex oxalates which led him in 1932 to his own construction of an apparatus named “stathmograph” (from Greek “stathmos” = mass, weight) [12] that made it possible to measure mass changes. independently (twenty years later), C. Duval used for his way of weight measurements the latin-based term “thermogravimetry” that later became generally accepted in thermal analysis [13]. as the principle scheme of the stathmograph instrument is not generally known, it is perhaps worth mentioning to describe this early arrangement. Škramovský placed a weighted sample into the drying oven on a dish suspended on a long filament passing through a hole in its upper wall (forming the balance case) and hooked to an arm of an analytical balance.
a mirror attached to the beam was reflecting the image of alight slit into a slowly rotating drum lined with photosensitive paper. the unwanted vibration was reduced by an attached glass rod immersed into paraffin oil and temperature was registered automatically by means of a mercury thermometer provided by platinum contacts distributed along the whole length of capillary. in the first years after World War ii the other monographs appeared in the world literature (besides that by duval [13]), which were devoted to microcalorimetry [14] and thermal analysis [15, 16] and an initial paper dealing with theory of dta [17] was also published. at the end of 1950th a commercial device combining dta and tG appeared under the name “derivatograph” [18] for long providing a useful service to the eastern scientists. much credit for the further development of modern thermal analysis was attributed with Rudolf Bárta(1897-1985) who stimulated thermal analysis activity at his fellow workers (V. Šatava, S. Procházka, J. Vašíček, M. Čáp or I. Proks) at the institute of Chemical technology prague (abbreviated as vŠCht) [19, 20, 21, 22]. bárta organized premature thermoanalytical meetings, the earliest was ”the 1st Conference on dta” (prague 1956), the 2nd (prague 1958) and the 3rd Conference on thermography (prague 1961) followed by the 4th Conference on dta (bratislava 1966). his friend R. C. Mackenzie (1920-2000) [23, 24] from Scotland was an invited guest at the 1961 meeting who was also one of the pioneers of applied dta [23, 24]. Upon the previous communication with Russian L.G. Berg, americans P. D. Garn and C. B. Murphy as well as hungarian L. Erdey an idea for the creation an international society iCta was cultivated and realized during the first international thermoanalytical conference in london 1965 [24] (where one of the authors also participated as invited speaker). it aimed to enabling easier contacts between national sciences, particularly across the separating ‘iron curtain”, which in that intricate time politically divided the east and West europe. besides significance of the early Czech-written books on thermal science [7, 26], which appeared before and/or simultaneously with the credited international literature [8, 22] the indispensable figure in the Czechoslovak development of thermal analysis was undoubtedly Vladimír Šatava (*1922) [27-31]. he brought to the Czech scientific circles necessary theoretical basis on solid-state chemistry and physics [29, 30], pioneered methods of thermal analysis [18, 19, 27, 26], educating his students who thus followed his professional guidance and published esteemed books [27-33] completing thus the rich spectrum of Czech thermoanalytical literature [31-38], cf. fig. 1. the individual contributions and innovative approaches have been affluent and focal which is worth of a more detailed portrayal, as exposed in the next paragraph, especially accentuating Czechoslovak source journals. Unfortunately, most of these rather cru-
Czechoslovak footprints in the development of methods of thermometry, calorimetry and thermal analysis
Ceramics – Silikáty 56 (2) 159-167 (2012) 161
cial papers disappeared in the shadows of time due to the Czech written texts. only consequently a supply role started playing the novel thermoanalytical journals, thermochimica acta, which was cofounded by one of the authors back in the year 1970 as well as Journal of thermal analysis instigated by R. bárta in 1969. less known book by J. a. komenský “Investigation of the nature of heat and cold.” (amsterodam 1659) in which the predicament of heat and cold is well discussed; “Thermics” by Č. Strouhal (1908) was an unique book describing the early but elementary treaties on heat, the almost unknown book on dta (1957) was published ahead of time, basic book of solid-state chemistry and material thermal behavior was also published (1965) beforehand of international literature (unfortunately never translated). far right is the Russian translation of Czech original book on theoretical basis of thermal analysis (1988), which became curiously a scientific bestseller as whole 2000 issues were sold in the former USSR within one week.
methodical footpath identifiableon the territory of former Czechoslovakia
the greatest promotion of thermoanalytical methods came after fifties when the methodical bases were formed [39] and new techniques specified. in this period various Czechoslovak scientists played an important role as it is documented in the achievement book [40] and citation records [41]. below listed papers relating the field of ta promoted in the former Czechoslovakia are assorted into several (but not very strict) categories. the referenced papers are supplied by original titles (given in english) and they are chronologically ordered within individual categories. all references were checked and corrected according to database WoS (Web of Science). the first category „TA generally” consists of artic-les [42-57] deals mostly with thermal analysis in a ge-neral way including papers published mainly in Czech journals Silikáty and Chemické listy, and in Slovak
journal Chemické zvesti. the second category “Special methods of TA” is devoted to original principles and unique techniques developed and put into operation by Czechoslovak scientists. the articles described e.g. dielectric ta [58], thermogravimetry [59, 60, 63], accelerated ta [62], permeability ta [65], photometric ta [66], perio-dic ta [68] (becoming a forerunner of today’s tem-perature modulated methods of ta), differential hydro-thermal analysis [70] and [71, 74], quick ta [78], thermoelectrometry [79, 80], decrepitating ta [82] and thermomagnetometry [83]. a distinctive consideration should be allocated to the characterization of radioactive measurement called emanation thermal analysis (eta) which is connected mainly with authors V. Jesenák [64], V. Balek [67, 75, 76] and J. Tölgyessy [81]. an explicit part of the papers was devoted to the description of own constructions of apparatuses for ta measurement as a consequence of at that time existing inaccessibility of commercial ta instruments. this type of articles is included into category Apparatuses of TA [84-101]. early instruments as were opportunely produced by laboratory groundwork, such as dta be-long into this category. the production way of latterly produced tG apparatuses was paved by the development of a Czech thermogravimetric instrument named “teGRa” and constructed by A. Blažek [37, 87]. early instruments were opportunely produced by laboratory groundwork, such as dta [84, 86, 91, 97]. a rich sphere of Czechoslovak research was also formed by calorimetric contributions [103-127] registered in category Calorimetry. Worth accentuating is an initial classification of calorimeters according to the temperature difference between the sample-block TB and surrounding jacket TJ as early suggested by J. Velíšek [117]. Consequent category Theory of DTA/DCS is asso-ciated with a gradual development of theoretical basis of thermal measurements mostly focused on the dta [128-140] curiously noting early the associated effect of gradients [129, 130]. it involved problems of
figure 1. Some favored book related to the topic of thermal science
Holba P., Šesták J.
162 Ceramics – Silikáty 56 (2) 159-167 (2012)
calibration and standardization of temperature and heat measurements by employing solid solution [135, 140], application of heat pulses [134], conductivity issues [138] as well as a detailed analysis of the complex composition of a dta peak including the effect of heat 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 temperatures during glass crystallization (inquisitively becoming the best cited paper in the history of Journal Czechoslovak physicists with 372 citations). Such achievements were only possible by the impact of prosperous Czechoslovak school on thermodynamics [27-34]. the other corresponding papers [141-162] are included into category Thermodynamics and phase equilibria another special attention is paid to the studies on reaction dynamics which topic is included into the category Kinetics [163-199]. early kinetic studies were explicitly offered by studies of v. Šatava whose kinetic evaluation method [175] have been broadly exploited and quoted by international resources (several hundreds of citations) and frequently named as the “Šatava kinetic method” [31, 34, 35, 174, 183]. Such a popularity of theoretical works aimed to elucidate predicaments of reaction kinetics [34, 35, 183] became the heart of the so-called Czech school of nonisothermal kinetics recently continued both in Czech [195-198] and Slovak republic [190, 191, 199]. Worth noting is the first ever published algorithm for the computer calculation of kinetic data [171] and the review paper [170] which despite the Czech language became the best cited article in the journal history. in feedback stance the papers [177, 179] undertook abundant citation responses becoming thus the best cited papers in relevant journals (562 and 132 respectively) and bringing into literature the notations named in the international literature after the authors (i.e., the Šesták-berggren [178] as well as the holba-Šesták [180] kinetic equations). not less important have been the contributions by recently 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 heat conductivity [202, 214-217] inserted into category Mechanical and transport properties [200-216]. the
last category of Czechoslovak papers dealing with ta is labeled as History and nomenclature. it contains reviews of historical aspects of thermometry and thermodynamics [221-227] and associated nomenclature issues [219, 220].
ConClUSionS
the Czech researches have richly contributed to thermal science and it would be a misfortune to allow their input to slip into oblivion. Clearly, one of the most important moments in the development of modern thermal analysis was the establishment of the journal Ceramics-Silikáty, launching 1956 by Rudolf bárta. vladimír Šatava was its chief editor within the years 1957-1967. this period was also credited with creating the foundations of thermal analysis and physical chemistry in general [29-31]. Šatava inspired his students and coworkers, cf. photo, by continuously broaden his own scientific interest in elucidating solid-state reactions which subsequently flourished into publication of various thermoanalytical books [34-39]. equally important was the introduction of various novel thermoanalytical methods [58-83] which preceded the international know how, e.g. the emanation thermal analysis [50, 64, 67, 75, 76, 99] that has become the source of a commercially produced instrument. Specially the Czech contribution to the dta technique [62, 71, 84-86, 91, 96, 97, 128, 131, 133, 136, 137] deserves a distinctive attention, the Czech written book published in 1957 [26] preceded international publications and was later followed by well cited Czechoslovak books [31-38]. Solid grounds of dta were accomplished in 1976 by the consistent theory made up by holba and Šesták and published in Ceramics-Silikáty [135, 136]. fundamental contributions already appeared in the first issues of the journal Silikáty, Unfortunately, they did not get into a wider attention of international public due to the Czech language,. nevertheless the Czech journal
figure 2. vladimir Šatava between his former students (gra-duating vŠCht in 1962 under his supervision) Jaroslav Šesták (left) and pavel holba (right) when celebrating his 89th birthday.
Czechoslovak footprints in the development of methods of thermometry, calorimetry and thermal analysis
Ceramics – Silikáty 56 (2) 159-167 (2012) 163
Ceramics-Silikáty as well as its sister’s Chemické listy and Czechoslovak Journal of physics has remained important domestic as well as international sources and platform of many original ideas and we should be thankful to the effort of their originators as well as their current editors.
References
1. Šesták J., mareš J. J.: From caloric to statmograph and polarography; J. thermal anal. Calor. 88, 763 (2007).
2. Šesták J., mareš J. J., hubík p.: Historical roots and development of thermal analysis and calorimetry; chapter 21 in the book Glassy, amorphous and nano-crystalline materials, Šesták J., mareš J. J., hubík p. (edts), Springer, berlin 2011, pp. 347-370 (iSbn 978-90-481-2881-5).
3. Roberts-austen W. C.: Fifth report to the alloys research; nature 59, 566-567 (1899); and proc. inst. mech. eng. 35 (1899).
4. Stanfield a.: On some improvements in the Roberts-Austen recording pyrometer, with notes on thermo-electric pyrometry; phil. mag. 46, 59 (1898).
5. kurnakov n. S.: Eine neue Form des Registrierpyrometers; z. anorg. Chemie 42, 184 (1904).
6. tammann G.: Über die Anwendung der Thermische Analysen in abnormen Fällen; z. anorg. Chem. 45, 24 (1905) and: Über die Anwendung der Thermische Analysen III;. z. anorg. Chem. 45, 289 (1905).
7. Strouhal Č.: Thermika; JČmf, praha 1908.8. Šesták J., proks i., Šatava v., habersberger k., brandštetr
J., koráb o., pekárek v., Rosický J., vaniš m., velíšek J.: History of thermal analysis on the territory of former Czechoslovakia; thermochim. acta 100, 255 (1986).
9. kallauner o., matějka J.: Beitrag zu der rationellen Analyse; Sprechsaal 47, 423 (1914).
10. matějka J.: Chemical changes of kaolinite on firing; Chemické listy 13, 164 (1919); and 182 (1919)
11. matějka J.: Thermal analysis as a tool for determination of kaolinite in soils; Chem. listy 16, 8 (1922).
12. Škramovský S.: Apparatus for automatic registration of dehydration at rising temperature; Chemické listy 26, 521 (1932).
28. Šatava v.: Utilization of thermographic methods for studying reaction kinetics; Silikáty 5, 68 (1961).
29. Šatava v.: Úvod do fyzikální chemie silikátů; (introduction to physical Chemistry of Silicates), Sntl, praha 1965.
30. Šatava v.: Fyzikální chemie heterogenních soustav - základy klasické a statistické termodynamiky; (physical chemistry of heterogeneous systems – foundation of classical and statistical thermodynamics), Sntl, praha 1977 and: Fyzika pevných látek; (Solid state physics), Sntl 1979 and: Fyzikální chemie silikátů na bázi racionální termodynamiky; (physical chemistry of silicates based on rational thermodynamics), Sntl 1981 and: Fyzikální chemie silikátů – kinetika; (physical chemistry of silicates – kinetics), Sntl 1982.
31. Šesták J., Šatava v., Wendlandt W. W.: The Study of Heterogeneous Processes by Thermal Analysis; monography as a special issue of thermochimica acta 7, 333 (1973).
32. Šesták J.: Měření termofyzikálních vlastností pevných látek: teoretická termická analýza; akademia, praha 1982 and english translation: Thermophysical Properties of Solid: theoretical thermal analysis; elsevier amsterdam 1984 and: Russian translation mir, moscow 1988.
33. holba p.: Thermodynamics and ceramic systems; chapter 1 in book Structure and Properties of Ceramic Materials; (a. koller, ed.). elsevier, amsterdam 1994, pp. 17-113.
34. Šesták J.: Science of Heat and Thermophysical Studies: a Generalized Approach to Thermal Analysis; elsevier, amsterdam 2005.
35. Šesták J., Šimon p. eds.: Thermal Analysis of Micro- nano- and non-crystalline Materials: transformation, crystallization, kinetics and thermodynamics; Springer, berlin 2012 (iSbn 978-90-481-3149-5).
36. balek v., tölgyessy t.: Emanation Thermal Analysis and other Radiometric Emanation Methods; elsevier, amsterdam 1984 and: Russian translation mir, moscow 1987.
37. blažek a.: Termická analýza; Sntl, praha 1972 and: english translation: Thermal Analysis; van nostrand-Reinhold, london, 1973.
39. liptay G., (ed). Atlas of Thermoanalytical Curves: (TG, DTG, DTA curves measured simultaneously); london, new york: heyden and Son 1971.
40. liptay G., Simon J. (eds): Who is who in thermal analysis and calorimetry; akademiai kiado, budapest 2004.
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164 Ceramics – Silikáty 56 (2) 159-167 (2012)
41. Šesták J.: Citation records and some forgotten anniversaries in thermal analysis; J. thermal anal. Calor. in print 2012 (doi:10.1007/s10973-011-1625-3).
TA generally
42. Šatava v.: Temperature regulators for thermography; Silikáty 1, 204 (1957).
46. biroš J.: Techniques and methods of polymer evaluation by TA; Chem. listy 61, 1243 (1967).
47. habersberger k.: Application of TA to investigation of catalysts; J. thermal anal. 12, 55 (1977).
48. pospíšil z.: Complex thermal analysis and its utilization in the field of ceramics; Silikáty 25, 263 (1981).
49. fellner p., votava i.: Numerical treatment of cooling/heating curves at thermal analysis; Chem. zvesti 35, 31 (1981).
50. balek v, beckmann i.: Use of labeled atoms in thermal analysis; Chem. listy 79, 19 (1985).
51. mentlík v.: New application of DTA in heavy-current electrotechnology; Thermochim Acta 93, 353 (1985).
52. holba p.: Processing of TA curves and the exact use of thermal analysis. thermochim acta 110, 81 (1987).
53. habersberger k., balek v.: Present state of commercially available thermoanalytical equipment; thermochim acta 110, 47 (1987).
54. kubičár l.: Trends in the methods of measurement of thermophysical properties in the solid state; thermochim acta 110, 209 (1987).
55. Šatava v., lach v.: Thermal analysis and chemistry of inorganic binders; thermochimica acta 110, 467 (1987).
56. Šesták J.: Non-traditional and traditional methods of thermal analysis in solid-state chemistry and physics; thermochim acta 148, 79 (1989).
57. balek v., karabascheva n. a., Györyová k.: Literature survey on thermal analysis reference materials; J. thermal anal. 40, 1459 (1993).
Special methods of TA
58. bergstein a.: Changes during ignition of equimolecular mixtures of barium carbonate and titanium dioxide, followed by measurement of dielectric properties; Collect. Czech. Chem. Com. 20, 1041 (1955).
60. blažek a.: Electronic thermobalance with simultaneous recording of DTA curves and decomposition product gas analysis; hutnické listy 12, 1096 (1957).
61. Šatava v., Stránský k.: Gradient furnace with defined atmospheres; Silikáty 3, 343 (1959).
62. vaniš m., koráb o.: Simple apparatus for quick DTA; Silikáty 4, 266 1960).
63. blažek a., halousek J.: A registering thermobalance; Silikáty 6, 100 (1962).
80. Šolc z., trojan m., kuchler m.: Thermoelectrometry as a method for reactivity estimation of solid powdery materials; thermochim. acta 92, 425 (1985).
81. lukáč, p., tölgyessy, J., vaniš, m., lapcík: Thermal de-kryptonation characterization of some solid materials; thermochim. acta 92, 429 (1985).
82. lach, v.: Some applications of the decrepitating tech-nique and thermosonimetry in research of materials. thermochim. acta 110, 265 (1987).
83. illeková e., ambrovič p., Czomorová k.: Investigation of structural relaxation of amorphous metallic alloy by thermomagnetometry. J. thermal anal. 32, 9 (1987).
98. procházka S., Sura J., nývlt J.: Programmed temperature controller used in investigation of crystallization; Chem. listy 71, 1086 (1977).
99. Jesenák v., tomková v.: Apparatus for thermal dekryptonation thermal analysis; Radiochem. and anal. let. 30, 89 (1977).
100. brandštetr J.: new instrument and method for enthalpiometric analysis and calibration; J. thermal anal. 14, 157 (1978).
101. nerad i., proks i., zlatkovský i.: Apparatus for determining the time of passage of a solid particle through a steady temperature fields; Silikáty 28, 261 (1984).
102. Šolc z., trojan m.: Simple program control furnace; Silikáty 31, 365 (1987).
Calorimetry
103. krupka f., horák z.: The determination of the specific heat of a liquid in an electric calorimeter; Czech. J. phys. A6, 619 (1956).
104. proks i., eliášová m., pach l.: Calorimeter for measure-ments of heats of solution; Chem. zvesti 21, 908 (1967).
105. abbrent m., Sojka b., pekárek v.: Isothermal differential calorimeter. Chem. listy 63, 1042 (1969).
107. tydlitát v., blažek a., halousek J.: A copper drop-calori-meter with adiabatic shield for enthalpy measurement up to 1700 K; Czech. J. phys. A 21, 817 (1971).
108. brandštetr J., malinger m., kupec J.: Devise for differential thermometric (enhalpiometric) measurements; Chem. listy 66, 88 (1972).
109. Smíšek m., Rameš J., křesťanová v.: Calorimeter for measurement of heats of evaporation on a microscale; Chem. listy 68, 738 (1974).
110. Smíšek m., křesťanová v.: Reaction calorimeter; Chem. listy 68, 738 (1974).
111. pekárek v.: Possibilities and present state of calorimetric experiments; Chem. listy 69, 785 (1975).
112. blaho d., abbrehnt m., pekárek v.: Differential quasi-isothermal calorimeter with digital output; Chem. zvesti 30, 621 (1976).
113. proks i., eliášová m., zlatkovský i.: High-temperature drop calorimetry in phase analysis; Silikáty 21, 253 (1977).
114. zlatkovský i.: Evaluation of calorimetric measurements
on basis of thermal losses; Silikáty 21, 71 (1977).115. brandštetr J.: Precision of proposed double injection
methods for direct enthalpiometric analysis; Coll. Czech. Chem. Comm. 42, 56 (1977).
116. brandštetr J.: New instruments and methods for enthal-piometric analysis and calibration; J. thermal anal. 14, 157 (1978).
117. velíšek J.: Calorimetric methods; Chemické listy 72, 801 (1978).
118. proks i., kosa i.: Evaluation of the use of dissolution calorimetry in phase analysis; Silikáty 24, 271 (1980).
119. velíšek J.: High-temperature twin calorimeter for the measurement of mixing heats of alloys in solid state; Chem. listy 75, 201 (1981).
120. brandštetr J.: Present state and future development of instruments for thermometric analysis; J. thermal anal. 21, 357 (1981).
122. velich v., dittrich f., timar J.: Isoperibolic calorimeter with an online computer; Chem. listy 79, 661 (1985).
123. kubičár l., illeková e.: Use of pulse method for study of structural changes of materials; thermochim. acta 92, 441 (1985).
124. kubičár l.: Trends in methods of measurements of thermophysical properties of solids; thermochim. acta 110, 205 (1987)
125. brandštetr J.: Outline of some new calorimetric techniques and instrumentation; thermochim. acta 110, 165, (1987).
126. nerad i., proks i.: Determination of equilibrium quantities of the system formed by thermal decomposition: Experimental equipment; Chem. zvesti 41, 3 (1987).
127. nerad i., vítková S., proks i.: New method for deter-mination of the equilibrium state in the system involving binary reactions; J. thermal anal. 33, 291 (1988).
129. proks i.: Influence of rate of temperature increase on the quantities important for the evaluation of DTA curves; Silikáty 5, 114 (1961).
130. Šesták J.: Temperature effects influencing kinetic data accuracy obtained by thermographic measurements under constant heating; Silikáty 7, 125 (1963).
131. Šesták J., berggren G.: DTA: Use for enthalpic and kinetic measurements; Chem. listy 64, 695 (1970).
132. proks i.: Effect of quantities controlling DTA on the diffe-rence between measured and theoretical temperatures; Silikáty 14, 287 (1970).
133. hrubý a.: Evaluation of glass forming tendency by means of DTA; Czech J. phys. B22, 1187 (1972) and B23, 1623 (1973).
134. Svoboda h., Šesták J.: A new approach of DTA calibration by predetermined amount of Joule heat; in “thermal analysis” (proceedings of 4th iCta,, e. buzagh, ed.) akademia kiado, budapest 1974, pp.726.
135. nevřiva m., holba p., Šesták J.: Application of DTA in determination of transformation heats; Silikáty 20, 33 (1976).
136. Šesták J., holba p., bárta R.: Theory and practice of TA methods based on the indication of enthalpy changes; Silikáty 20, 83 (1976).
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166 Ceramics – Silikáty 56 (2) 159-167 (2012)
137. Šesták J., holba p., lombardi G.: Quantitative evaluation of thermal effects: theory and practice; annali di Chimica Roma 67, 73 (1977).
138. Šatava v, vepřek o.: Effect of sample thermal conductivity on the calibration constant in DTA; thermochim. acta 17, 252 (1977).
139. hrubý a.: Study of glass formation applicability and phase diagram; J. non-cryst. Solids 28, 139 (1978).
140. nevřiva m.: Mn-Cr-O solid solutions as materials for thermoanalytical calibration; thermochim. acta 22, 187 (1978).
Thermodynamics and phase equilibria
141. Šatava v.: Contemporary foresight on the structure of glasses; Sklář a keramik 13, 6 (1956).
142. holba p., pollert e., kitzinger e.: Experimental arrangement for investigation of solid-gas equilibria; Silikáty 13, 271 (1969).
143. holba, p.: On calculations of activities of chemical individuals from disorder models; thermochim acta 3, 475 (1972).
144. Šatava v.: Nature of vitreous state and conditions of glass-formation; Czech J phys A23, 565 (1973).
152. Šesták J.: Thermodynamic basis for the theoretical description and correct interpretation of thermoanalytical experiments; thermochim. acta 28, 197 (1979).
153. holba p.: Enthalpy and phase relations at melting in heterogeneous systems; Silikáty 23, 289 (1979).
156. nevřiva m., Šesták J.: On the study of solid-liquid stable-metastable phase equilibria; thermochim. acta 92, 623 (1985).
157. Šatava v.: Determination of standard enthalpies, Gibbs energies and entropies of formation of hydrated calcium sulphoaluminates; Silikáty 30, 319 (1986).
158. majling J., Jesenák v.: Algorithmizing the calculation of equilibria phase composition of multicomponent systems; Silikáty 30, 319 (1986)
160. Šesták J., Chvoj z.: Thermodynamics and thermochemistry of kinetic (real) phase diagrams involving solids; J. thermal anal. 32, 1645 (1987).
161. Šatava, v.: Direct determination of standard enthalpies and Gibbs energies of formation and absolute entropies of hydrated calcium sulphoaluminates and carboaluminates;
thermochim. acta 132, 285 (1988).162. liška m., daněk v.: Computer calculation of the phase
diagrams of silicate systems. Ceramics-Silikaty 34, 215 (1990).
Kinetics
163. Šatava v., körbel J.: Kinetics of thermal decomposition of silver permanganate; Collect. Czech. Chem. Com. 22, 1380 (1957).
164. Šatava v.: Reactions of solids; Silikáty 4, 67 (1960).165. Šatava v.: Reaction of solids with liquids; Silikáty 5, 171
(1961).166. Šatava v., marek J., matoušek J.: Dehydration kinetics
of α- a β- calcium sulphate hemihydrates in suspension; Silikáty 5, 309 (1961).
170. Šesták J.: Review of kinetic data evaluation from nonisothermal and isothermal TG data; Silikáty 11, 153 (1967).
171. Šesták J., Šatava v., Řihák v.: Algorithm for kinetic data computation from thermogravimetric data obtained at increasing temperature; Silikáty 11, 153 (1967).
172. procházka S.: Surface area changes during sintering; amer. Cer. Soc. bull. 47, 753 (1968).
173. vašková l, hlaváč J. Crystallization of quartz glass; Silikáty 13, 211 (1969).
174. Šatava v., Škvára f.: Mechanism and kinetics of solid-state reactions; J. am. Ceram. Soc. 52, 591 (1969).
175. Šatava v.: Mechanism and kinetics of crystallization from nonisothermal measurements; thermochim. acta 2, 423 (1971)
176. vachuška J., vobořil m.: Kinetic data computation from non-isothermal thermogravimetric curves of non-uniform heating rate; thermochim. acta 2, 379 (1971).
177. Šesták J., berggren G.: Study of the kinetics of the mecha-nism of solid-state reactions at increasing temperatures; thermochim. acta 3, 1 (1971).
178. Šimon p.: Fourty years of the Sestak-Berggren equation; thermochim. acta 520, 156 (2011).
179. holba p., Šesták J.: Kinetics with regard to the equilibrium of processes studied by non-isothermal techniques; zeit. physik. Chem. n.f. 80, 1 (1972).
180. mianowski a.: Consenquences of Holba-Sestak equation; J. thermal anal. Calor. 96, 507 (2009).
181. Šesták J., kratochvil J.: The role of state constitutive equations in chemical kinetics; thermochim. acta 7, 330 (1973).
182. Šatava v., Šesták J.: Kinetics and mechanism of thermal decomposition at iso- and non-iso- thermogravimetry; anal. Chem. 45, 153 (1973).
183. Šatava v.: Fundamental principles of kinetic data eva-luation from TA curves; J. thermal anal. 5, 217 (1973).
184. kratochvíl J., Šesták J.: Rational approach to thermo-dynamic processes and constitutive equations in iso- and non-isothermal kinetics; J. thermal anal. 5, 193 (1973).
185. Šesták J.: Applicability of DTA to the study of crystallization kinetics; phys. Chem. Glasses 15, 137 (1974).
186. matuchová m., nývlt J.: Theory of crystallization rate;
Czechoslovak footprints in the development of methods of thermometry, calorimetry and thermal analysis
Ceramics – Silikáty 56 (2) 159-167 (2012) 167
Chem. listy 69, 1 (1975).187. holba p., nevřiva m., Šesták J.: Analysis of DTA curve
and related calculation of kinetic data using computer technique; thermochim. acta 23, 223 (1978).
188. kubíček p., leško J.: Determination of the kinetic para-meters from non-isothermal measurements with a general temperature program; Thermochim. Acta 31, 21 (1979).
189. Šesták J.: Philosophy of nonisothermal kinetics; J. ther-mal anal. 16, 503 (1979).
190. Šimon p., valko l.: Autocatalytic effect of hydrogen chloride on the thermal dehydrochlorination of polyvinyl chloride; Chemické zvesti 37, 581 (1983).
191. illeková e.: On the Various Activation Energies at Crystallization of Amorphous Metallic Materials; J. non-Cryst. Solids 68, 153 (1984).
195. kemény t., Šesták J.: Comparison of crystallization kinetics determined by isothermal and non-isothermal methods; thermochim. acta 110, 113 (1987).
196. málek J.: The crystallization of Ge40S60 glass. Thermochim. Acta 129, 293 (1988).
197. militký J., málek J., Šesták J.: Parameter distortion by unappropriate nonisothermal treatment; J. thermal anal. 35, 1837 (1989).
198. Chvoj z., kožíšek z., Šesták J.: Nonequilibrium processes of melt solidification during programmed temperature changes and the metastable phases formation; thermochim. acta 153, 349 (1989).
199. Šimon p.: Kinetics of polymer degradation involving the splitting-off of small molecules; polym. degrad. Sta. 29, 155 (1990).
Mechanical and transport properties200. bárta R., Šatava v, procházka S, hlaváč J: Základní
výzkum silikátů; (basic Research of Silicates), Sntl praha 1957.
201. Šatava v., Šesták J.: Influence of setting temperature on the structure and strength of the plaster of Paris; Silikáty 6, 178 (1962).
202. hrubý a., kubelík i.: Electrical conductivity and thermo-electric power in semiconductors; Czech. J. phys. b 15, 740 (1965).
203. hrma p.: Corrosion of refractory materials by molten glass; Silikáty 13, 165 (1969).
205. matoušek J., hlaváč J.: Study of volatilization of lead glasses; Glass technol. 12, 103 (1971).
206. kaščejev i., matěj J., bartuška m.: Corrosion of mullite ceramics by binary glass under free convection; Silikáty 16, 25 (1972).
207. němec l.: Dissolution and diffusion of technologically significant gases in glass; Silikáty 16, 347 (1972).
208. hrma p., Šatava v.: Model for strength of brittle porous materials; J. am. Ceram. Soc. 57, 71 (1974).
209. hrma p.: Diffusion theory of ceramic body growth; Silikáty 22, 357 (1978).
210. kubíček p., Wozniaková b., leško J.: Determination of diffusion coefficients with a general temperature program using DTA; thermochim. acta 64, 229 (1983).
211. illeková e.: Model of mass transport in amorphous metallic materials; acta phys. Slov. 34, 255 (1984).
212. Šajgalík p, haviár m, pánek z, Contribution to the sintering diagrams; zeits. metall. 77, 193 (1986).
213. liška m., hamlík l., kanclíř e.: Enamel viscosity depen-dence on modeling compositional and thermal relations; Silikáty 31, 43 (1987).
214. málek J., klikorka J., tichý l.: Conductivity measurements during crystallization of glasses; mater. Sci. let. 5, 183 (1986).
215. mareš J., krištofík J., Šmíd v.: On the conductivity in semiinsulating semiconductors; Sol. State Com. 60, 275 (1986).
216. málek J., klikorka J., Šesták J., tříska a.: Thermoelectrical conductivity as a complementary method to DTA; thermochim. acta 110, 281 (1987).
217. helebrant a., matoušek J.: Mathematical models of the interaction of glass with water and with aqueous solutions; Silikáty 32, 173 (1986).
218. Šatava v.: Strength and microstructure of cast gypsum; Ceramics-Silikáty 40, 72 (1996).
History and nomenclature
219. holba, p., Šesták J.: On the nomenclature of thermo-analytical methods associated with energy changes; thermochim. acta 13, 471 (1975).
220. Šesták J., holba p., fajnor v.: System of Czech and Slovak terms used in thermal analysis; Chem. listy 77, 1292 (1983).
221. hlaváč J.: The present state and perspective view of the material research; Silikáty 29, 169 (1985).
222. mackenzie R., proks i.: Comenius and Black as proge-nitors of thermal analysis; thermochim. acta 92, 3 (1985).
223. Šesták J., mackenzie R.C.: Bárta Rudolf (1897-1985); J. thermal anal. 31, 3 (1986).
224. nevřiva m , Rosický J, proks i, kanclíř e.: Pioneers of thermal analysis in Czechoslovakia; thermochim. acta 110, 553 (1987).
225. bartuška m., Götz J.: The Silikáty periodical in future; Silikáty 33, 289 (1989).
226. proks i.: Evaluation of the Knowledge of Phase Equilibria; in book “kinetic phase diagrams: nonequilibrium phase transitions” (z. Chvoj, J. Šesták, a. tříska, eds.), p.1-49, elsevier, amsterdam 1991.
227. proks i. Celok je jednoduchší ako jeho časti; (Whole is simpler than its parts), publ. house of Slovak academy of Sciences, bratislava 2012.
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