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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
J aroslav estk
Journal of Thermal Analysis and Calorimetry - 2013, DOI 10.1007/s10973-
012-2848-7
HISTORICAL ROOTS AND DEVELOPMENT OF THERMAL
ANALYSIS AND CALORIMETRY,
J aroslav estk, Pavel Hubk, J i J Mare
Book chapter
SOME HISTORICAL ASPECTS OF THERMAL ANALYSIS:
ORIGINS OF TERMANAL, CalCon AND ICTA
J aroslav estk
TERMANAL 2005 - published in Bratislava
FROM CALORIC TO STATHMOGRAPH AND POLAROGRAPHY
J aroslav estk, J i J Mare
Journal of Thermal Analysis and Calorimetry, Vol. 88 (2007)
CZECHOSLOVAK FOOTPRINTS IN THE DEVELOPMENT OF
METHODS OF THERMOMETRY, CALORIMETRY AND THERMAL
ANALYSIS
Pavel Holba, J aroslav estk
Ceramics Silikty (Prague) 56 (2) 159-167 (2012)
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Thermal science and analysis
Terms connotation, history, development, and the role of personalities
J. S

estak
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
efciency is discussed. The meaning of idiomatic terms
thermal physics, thermodynamics, thermostatics, thermot-
ics, and thermal analysisis specied and revealed within
two parallel developed branches of thermal science. Item-
ized 105 references with titles.
Keywords Thermometry Thermodynamics
Thermostatics Thermotics Thermal physics
Natural laws Temperature scales H.Suga T.Ozawa
Introduction
A plentiful literature about thermal science [15] and its
precedent thermometry [611], as well as historic thermal
analysis [1221], is available through various sources easy
accessible even from internet. Therefore, we do not want to
repeat available gures, but prefer mentioning some hidden
aspects responsive to the record of accessible citations,
while not claiming completeness. All history records reach
back to the early concept of hotness [22] as the scientic
principle on which temperature measurement is based and
evolved as a part of the development of thermal science.
Thermoscope, thermometer, thermometry,
and temperature scales
The ancient Greek discerned the expansion of air by heat
long time ago. The earliest writings concerned that the
phenomena were the Works of Philo of Byzantium and
Heron of Alexandria (II Century B.C.). The Greeks made
simple thermometers in the rst century BC, but there was
no way to quantify heat with hot and cold still following
the Aristotelian tradition of being treated as fundamental
qualities of the universe. The ideas of Aristotle were
adopted by Galen (A.D. 130200), who was the rst
describing the heat and cold by a number about fteen
hundred years ago. And, the word temperature originated
from temper, after Galen determined the complexion
of a person by the proportion in which four human
qualities were tempered [68]. It is known that by the
16th Century, knowledge of the weatherglass (the other
common name for thermoscope) became widely spread
among educated people either due to the new edition of
Herons papers or upon the accessibility of excerpts of
Arabian alchemistic manuscripts.
One of the rst modern-times considerations on active
principles (heat and cold) acting on a passive matter can be
found in the treatise published in 1563 by Italian Bernar-
dino Telesio (15091588) and perceived by Francesco
Patricio (15291597) and Giordano Bruno (15481600).
The rst air thermoscope appeared in 1594 through Galileo
Galilei (15641542), but the Englishman Robert Fludd
(15741651) was also regarded as one independent
inventor around 1617. Yet, another originator was
Dedicated to Prof. Hiroshi Suga and Prof. Takeo Ozawa (recently
passed away), pioneers of the advanced thermal science and the
honorary chairmen of the ICTAC15 in Osaka2012.
J. S

estak (&)
New TechnologiesResearch Centre of the Westbohemian
Region, University of West Bohemia in Pilsen (NTC-ZC

U),
Universitn 8, 301 14 Plzen, Czech Republic
e-mail: sestak@fzu.cz
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J Therm Anal Calorim
DOI 10.1007/s10973-012-2848-7
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indicated Cornelis J. Drebbel (15721633) who made a
two-bulbed J-shaped thermometer between 1598 and 1622.
In 1626, the factual word thermometer was initially used
to describe thermoscope equipped with a scale marked with
eight degrees by Jean Leurechon (15911670) in his book
[23]. Shortly after, the world-known Czech educator Jan
Amos Comenius (15921670) inserted reections on the
role of heat and cold in nature into his book work [24] and
then, in 1659, published another worth noting book [25] on
the nature of heat and cold. In 1665, Christian Huygens
(16291695) had a brilliant idea to use the melting and
boiling points of water as a standard gauge.
The rst quantitative thermal law expressing the depen-
dence of temperature of a cooling body (expressed in 8
degrees) on the time was published in 1701 by Isaac Newton
(16431727). Such a forgotten attempt to put high temper-
atures on a mathematical scale described a thermometer on
the basis of oil and calibrated it by taking the heat of the air
in winter when water begins to freeze as 0 and blood heat
as 12 on this scale water boils at 34. The melting points of
alloys were determined by an extrapolation and logarithmic
temperature scale that was proposed for high experimental
temperatures on the basis of the equation, h = 12{2
(x-1)
},
where h was the temperature in units of the above scale and
x represented the logarithmic temperature [2628].
One of the earliest challenges at calibration and stan-
dardization between thermometers was attempted in 1663 by
the members of Royal Society in London, who agreed to use
one of several thermometers made by Robert Hooke
(16351703) as the standard so that the reading of others
could be adjusted to it. Non-Euclidean mathematician
Johann H. Lambert (17281777) revealed in his less familiar
book Pyrometria as many as nineteen temperature scales.
Differential air thermometer was invented, almost simulta-
neously, by John Leslie (17661832) of Edinburgh and by
Benjamin Thompson, Count Rumford (17531814) and
consequently James Clerk Maxwell (18311879) recognized
that for thermometry (to be a logically closed system) it is
necessary to add a concept of thermal equilibrium.
Daniel G. Fahrenheit (16861736) proposed in 1724 a
temperature scale of 100 degrees from 0 F (at the tem-
perature of mixture of ammonium chloride, water, and ice)
and 100 F at the human body temperature and invented
the rst mercury thermometer. A year later, Joseph-Nicolas
Delisle (16881768) introduced an exotic scale with
240 degrees, which was later (1738) modied and adjusted
to 150D corresponding to the melting point of water and
to 0D at boiling point of water (240D = 60 C), and this
scale was being used in Russia for the whole hundred
years. The story of different scales, from Fahrenheit and
Celsius degrees to the now-forgotten Rankine, Rmer,
Desliste, Reaumur, Lime, or Amontons scales, and the
history of the gradual scientic then popular understanding
of the concept of temperature are familiar and thus not
herewith reiterated [1822, 26].
Worth of a special attention would be 1848 Thomsons
approach based on thermal efciency g (originated [29, 30]
by Nicolas Leonard Sadi Carnot (17961832)) introducing
thus a logarithmic temperature scale, h, in the form of
dh & dT/T. After integration, it follows that h = const
1
lnT ? const
2
, where both constants can be determined using
the traditionally xed points of the melting and boiling of
water. This more natural scale, however, would dramatically
change the customary concept of thermodynamics [26, 28]
easing the interpretation of the third law of thermodynamics
replacing the traditional zero temperature by innity (T =
-?). However, the conventional degree of freedom,
*1/2 kT, would revolutionize to embarrassing proportion-
ality, T * exp{(h-const
2
)/const
1
}, etc. On the other hand,
the simple interpretation of heat conduction and the cus-
tomary evaluation of efciency for steamengines necessitate
the temperature to behave like the potential of a heated uid
and the traditional linear scale, equivalent to the contempo-
rary Kelvins international scale, manage to survive as the
most opportune one. There can be seen various attempts
introducing so far inconvenient thermodynamics concepts
based, for example on the Carnot use of caloric [31, 32].
Thermal physics, thermodynamics, thermotics,
and thermal analysis
Early attempts to create a common scientic language can
be associated with the early work by Comenius emerging
from his effort to portray heat [25]. However, equally
important was his challenge to articulate his own idea of
universal language [33] and its relation to the encyclopedic
knowledge concept of the pansophia having a profound
inuence on the discussion on an exploitation of such a
universal language in England. Inquisitively it resulted to
his invitation offered by John Winthrop (15881649) a
governor of Massachusetts to become a rector of a new
US university founded by preacher John Harvard. Later,
the Comenius younger follower Gottfried W. Leibnitz
(16481716) used his idea of lingua catholica in an
attempt to formulate mathematical, scientic, and meta-
physical concepts more effective. He introduced charac-
teristica universali hopeful to create a language usable
within the framework of a universal logical calculation
[34, 35] or calculus ratiocinator convincingly affected
by Rene Descartes (15961650) through his correspon-
dence with Comenius [21]. Descartes [36] became
responsible for the formulation of conservation law applied
to the amount of movement (momentum-mv) later cor-
rected by Leibnitz as vis viva (mv
2
). On the other hand,
it is worth mentioning that the law of conservation was
J. S

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foreseen by another Czech mastermind Jan Marcus Marci
(15951667) [37].
Another signicant impact to generalized understanding of
nature was brought by Pierre de Fermat (16011655) when
introducing the principle of least time [38]: the Nature acts via
the easiest and the most accessible way reached within the
shortest time. A century later it was resumed by Pierre-Louis
M. de Maupertuis (16981759) whoin1744envisagedtheleast
action premise noting [39]: when some change takes place in
nature, the quantity of action necessary for the change is the
smallest possible. The quantity of action is the product
obtained by multiplying the mass of the bodies (m) with their
velocity (v) and the distance travelled (k), which interestingly
correlates withthePlanckconstant h (=mvk). It recentlybecame
the basis to explain the inborn self-periodicity of many natural
processes [4042]. These fundamental laws of motion became
equally crucial as the Carnot temperature limits for the thermal
efciency of heat engines [20, 29, 31, 32].
The decisive experimental studies, thanks to which tem-
perature became a clearly measurable physical quantity,
contributed the formation of a contemporary discipline lan-
guage. In the 1840s, a thermodynamic discourse was worked
up by Henri Victor Regnault (18101878) whose attitude,
however, turned out long after Joseph Black (17281799)
[15, 17, 26, 43] distinguishing between the specic heat (heat
capacity) and the latent heat [19, 30]. Curiously, his less
known correspondence [21] with James Watt (17361819,
who invented steam engine in 1776) remained unmentioned.
Consequently, Pierre Simon de Laplace (17491827) and
Antoine Lavoisier (17431794) performed in 1786 their rst
calorimetric measurements [25, 4450]. Yet, after the detailed
results of 1842 Regnaults dilatometric and heat capacity
measurements, and together with 1824 theorem of Carnot
[29, 32] and its 1834 interpretation by Benoit-Paule E. Cla-
peyron (17991864) it provided the basis for the 1848 intro-
ducing of absolute temperature scale by William Thomson
(baron Kelvin of Larges) (18241907) and for the factual
inception of thermodynamic language [15, 5153] as a new
science, not forgetting the work of Josiah Willard Gibbs
(18391903) [15, 21, 51]. Literally, this new science would be
optimally associable with the term thermostatics by way of
thermallyequilibratedstates anddevelopedthroughthe Carnot,
Clapeyron, Clausius, and/or Gibbs work as a branch of dis-
sipationless work understanding of the science of heat [2, 26].
Complementary approach involving the concept of
workless dissipation comprise, however, temperature
gradients (existing everywhere and in thermostatic concepts
often neglected due to necessary simplications) which was
developed in the course of studies by Newton, Fourier,
Stokes and/or Onsager framing thus the new eld of true
thermodynamics involving irreversible processes [13, 54].
Most remarkable personalities became Joseph Baptiste
Fourier (17681830) while publishing the laws of heat
transfer 1822 [55] and Lars Onsager (19031976) [56]
while depicting the equations of irreversible processes (later
rooting the eld of extended thermodynamics [57, 58]).
So far, the enduring term of thermodynamics subsists the
energetic concepts [5963] of temperature and heat based
upon the Greek word therme (= heat); however, it is worth
noting that it also involves a Greek concoction for the motive
power of heat, i.e., thermodynamics factually means heat-
engine science. It is concerned with heat and its relation to
other forms of energy and work dening macroscopic vari-
ables which describe average properties of material bodies,
and explains how they are related and by which laws they
change with equilibrating [5971]. There are many grand-
fathers such as a UKprofessor Edward Armand Guggenheim
(19011970) [3, 69].
Yet, more general terms thermal science or science
of heat [2] sustain for a shared study of thermodynamics,
uid mechanics, heat transfer, thermal investigation,
combustion, and thermokinetics while more restricted
terms thermal physics [44, 7274] involve the combined
study of thermodynamics, statistical mechanics, and kinetic
theories providing thus an umbrella subject which is typi-
cally designed to provide a general introduction to each of
core heat-related subjects.
There is yet another a more unfamiliar term thermotics
(alike the term mathematics) staying also behind the gen-
eralized science of heat (and also based on its Greek origin),
apparently used as early as in 1837 [75]. In 1967, American
physical chemist Ralph Tykodi (1925) made an attempt to
revive thermotics [76, 77] as an idiom which, he said, should
be equal in usage to 1946 version of energetics provided by
the Danish physical chemist Johannes Nicolaus Brnsted
(18791947) [59, 60]. In this view, thermotics subsist a ther-
mal science comprised of three sub-branches: thermo-stat-
ics pertaining to the ordinary classical equilibriumaspects of
heat, thermo-dynamics relevant to those aspects for which
time variation is important, and thermo-staedics concern-
ing the aspects that are temporally steady or stationary. The
focus of latter term may be seen more suitable to envelop the
eld of thermal analysis [1, 1421, 26, 78] the true meaning
of whichwas never appropriatelylocatedwithinthe spheres of
thermal sciences [2, 26, 30].
The entire term thermal analysis was coined by Gustav
Heinrich J.A. Tammann, (18611938) [79, 80], further
accredited in [12, 13] and then particularized in our previous
papers [2, 14, 1719]. Seemingly the inherent thermoana-
lytical theory is historically based [12, 81] on equilibrated
(i.e., thermostatic) states often omitting the non-equilibrium
(ux) character of its measurements, which seems be a most
crucial source of inaccuracy in the existing theoretic evalu-
ation of DTA (= differential thermal analysis) [2, 13] where
thermal gradients are habitually not incorporated in the
evaluation (with few exceptions [8285]).
Development and the role of personalities
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A tribute paid to Japanese personalities: Hiroshi Suga
and Takeo Ozawa
The eld of thermal analysis became a starting point for
expanded cooperative studies under the umbrella of the
International Confederation (ICTA/ICTAC) [86, 87] which
benets from its over 40 years running established under
the protable impact of many foremost personalities [88]
such as the distinguished celebrities of Hiroshi Suga (1930)
and Takeo Ozawa (19322012) with whom the author has
the honor to publish joint studies [8991] being also the
guarantee of the 1996 foundation of the School of Energy
Science at the Kyoto University. Both of these Japanese
famous persons are accountable for the augmentation of
thermoanalytical societies as well as the development of
the theory of processes carried out under non-isothermal
conditions. Though the work of Ozawa (e.g., [9299])
received a wider recognition (H-index = 81, total citation
record = 38,580 with 2,316 feedback for his best cited
paper) because attentive to a more fashionable subject of
thermoanalytical kinetics, the work of Suga (H-index = 40,
total citation record = 5,582 with 316 feedback for his best
cited paper) enveloped a more fundamental subject of gen-
eralized behavior and characterization of noncrystalline
solids (e.g., [91, 100105]). Their worldwide impact has
positively affected the international cooperation, which is
well illustrated by the group photos (above Figs. 1 and 2).
We all are very grateful for their fruitful guidance and affable
dissemination of knowledge.
Acknowledgements The results were developed within the CEN-
TEM project, reg. no. CZ.1.05/2.1.00/03.0088 that is co-funded from
the ERDF within the OP RDI program of the Ministry of Education,
Youth and Sports. The author feels also indebted to his scientic
friends, coworkers, and uppermost thermodynamists Pavel Holba
(Pilsen), Gyorgy Liptay (Budapest), Jiri. J. Mares (Prague), Jir Malek
(Pardubice), Nobuyoshi Koga (Hiroshima), late German K. Moiseev
(Jekaterinburg), Ingo Muller (Berlin), late Tooru Atake (Tokyo), late
Ivo Proks (Bratislava), Vladim r S

atava (Prague), Peter S

imon (Bra-
tislava), late Bernhard Wunderlich (Knoxville), Harumi Yokokawa
(Tsukuba), and Shmuel Yariv (Jerusalem). The author, however, was
disappointed that this tribute lecture was suspended by the conference
secretary (Riko Ozao) out from the Commemorate Special Session
(crediting the conference honorary chairmen) to general session only.
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J. S

estak
1 3
21 Historical roots and development of thermal
analysis and calorimetry
Jaroslav estk
1
, Pavel Hubk
2
, Ji J. Mare
2
1
New Technology Research Centre, University of West Bohemia, Univerzitn 8, CZ-30614
Plze, Czech Republic
2
Institute of Physics ASCR, v.v.i., Cukrovarnick 10, 162 00 Praha 6, Czech Republic
e-mail: sestak@fzu.cz
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 (J an Amos Komensk,
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
2
and almost correctly explained the function of a thermoscope (vitrum caldarium)
and introduced his own qualitative scale with three degrees of heat above and three
degrees of cold below the ambient temperature launching thus a concept of 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].
Blacks 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, Simon 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 Rumfords 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 Torricellis vacuum over mer-
cury by Gay-Lussac) and in spite of that Thompson (1798) showed that the heat
3
could be produced by friction ad infinitum, the caloric theory survived many de-
feats and its mathematical scheme is in fact applied for the description of heat
flow until today. The above customary unit was called calorie (cal) or small
calorie, whereas a large calorie corresponded to the later kilocalorie (kcal).
The word calorie was more widely introduced into the vocabulary of academic
physicists and chemists by Favre and Silbermann [14] in 1852. The expression of
one kilocalorie as 427 kilogram-meters was given by Mayer in the year 1845.
We should add that caloric differed from the foregoing concept of phlogiston
because, beside else, it could be measured with an apparatus called a calorimeter,
however, it is not clear who was the first using such an instrument. If we follow
the studies of Brush [8], Mackenzie [15] and Thenard [16] they assigned it to
Wilcke. It, however, contradicts to the opinion presented in the study by McKie
and Heathcote [17] who consider it just a legend and assume that the priority of
familiarity of ice calorimeter belongs to Laplace who was most likely the 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
Mmoire 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 Blacks employment of the calorimeter seems to appear firstly almost a century
later in the Jamins 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
4
for all gases, anticipating thus the Mayers relation for ideal gas: c
p
c
v
=R. Sadi
also introduced the Carnots 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, Sadis 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 Carnots intuitive thinking [26,27], the small amount of
work done dL (motive power in Carnots terms) is performed by caloric literarly
falling over an infinitesimal temperature difference dT [11,16,26], dL = F(T)
dT. The function F(T) here is the Carnots function, which has to be determined
experimentally, certainly, with respect to the operative definitions of quantities
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 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 must be independent of temperature and, consequently, Carnots 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 = 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 J oules 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 d =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
5
J oule (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 Carnots theory of heat engines is the evalu-
ation of engine efficiency. The amount of caloric which is entering the complete-
ly reversible and continuously working heat engine at temperature T
1
and leaving
it at temperature T
2
will produce a motive power of amount L. Carnots efficiency
q
C
defined as a ratio L/

is then given by a plain temperature drop AT =(T
1
T
2
)
(as measured in the ideal gas temperature scale). Transforming the incoming ca-
loric into thermal energy T
1
, we obtain immediately Kelvins dimensionless effi-
ciency q
K
of the ideal reversible heat engine, q
K
={1(T
2
/T
1
)}, which is well-
known from textbooks of thermodynamics [3,29].
However, q
K
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 , taken from the boiler
kept at temperature T
1
, increases, by passing across a thermal resistance, to the
new quantity equal to + A , entering than the ideal heat engine at temperature
T<T
1
, and leaving it temperature T
2
. If we relate the quantities L and to an arbi-
trary time unit (we conveniently use for this purpose a superscript u), it follows L
u
= (T
1
T)(TT
2
)/T , where for the evaluation of temperature drop across the ther-
mal resistance we can apply the Fourier law [12]
u
T
1
= (T
1
T), where 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 dL
u
/dT =0,
from which we obtain T =\(T
1
T
2
) [26]. Consequently, the Carnots true efficien-
cy of such a system with optimized output power is thus given by a formula, q
C
=
T
1
{1 \(T
2
/T
1
)}. Such a root square dependence, which is the direct consequence
of linearity of Fouriers law, is also obviously repeated for the above mentioned
dimensionless Kelvins efficiency, q
K
. 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
(16421727) who published his temperature scale in 1701 the significance of
which lies both in its range of temperature and in its instrumentation presenting
6
also the famous Newton's Law of Cooling [36]. First cornerstone of the theory of
warmth propagation was provided by J.-B. J. Fourier who initiated the 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.
7
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
Gertebau 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 J upiter (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).
8
toward the modern solid state physics was induction of the notion of diffusion by
Adolf E. Fick (1829-1901) and its improved understanding by Ernest Kirkendall
(1914-2005) as well as the introduction of the concept of disorder by Jakob I.
Frenkel (1894-1952) [45] and models of glasses by Tammann [46].
By 1908, knowledge of the heating or cooling curves, along with their rate 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 Newtons law
while Berg gave the early bases of DTA theory [49,50], which was independently
simplified by Speil. In 1939 Norton published his classical paper on differential
thermal techniques where he made rather excessive claims for their value both in
the identification and quantitative analysis exemplifying clay mixtures [51]. Vold
(1948) [52] and Smyth (1951) [53] proposed a more advanced DTA theory, but the
first detailed theories and applicability fashions, free from restrictions, became
9
accessible by followers in fifties [3,50,54-58], e.g., Keer, Kulp, Evans, Blumberg,
Erikson,Soule, Boersma, Borchard, Damiels, Deeg, Nagasawa, Tsuzuki, Barshad,
Strum, Lukaszewski, etc.
In general, the thermoanalytical methods gained theoretical description early
sixties [59-61]. The resulting thermal effects, explicitly temperature disparity
(AT), 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-
10
terface between the sample-block, B, and the surrounding jacket, J. The tempera-
ture difference [3] , T
B
T
J
, is used to classify calorimeters, i.e., diathermal (T
B
=
T
J
), isodiathermal (T
B
T
J
) = constant and d(T
B
T
J
)0, adiabatic (T
B
= T
J
), iso-
thermal (T
B
= T
J
= const.) and isoberobolic (T
B
T
J
)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 ONeil [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-
11
ments. In order to cancel the heat losses between two symmetric calorimeters were
used (e.g., twin calorimetry one cell with the sample and the other identical, but
empty or filled with a reference material), however presented control problems
were not easy to handle [3].
True DSC is monitoring the difference between the counterweighing heat 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 estk [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
12
thermal methods commonly exercised. Worth noting is the inertia term, which is a
particularity for DTA (as well as for heat-flux DSC) expressing a specific 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 (AT 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 Na
2
CO
3
-CaCO
3
or BaCO
3
-SrCO
3
or various sesquioxides mixtures like manga-
nese spinels) [3]. However, the use of the J oule 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., substances
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-
13
sibility and potential frequency-dependence of changes of the studied sample. The
heat capacity C
s
of the sample can be determined from the ratio of the heat-flow
response of the sample, represented by its amplitude A
HF
, to the product of the
amplitude of the sinusoidal sample-temperature modulation A
Tt
and the modula-
tion frequency e=2t/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 T
S
oscillates about the underlying temperature T
0

(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, c, is taken relative to a reference oscillation, T
S
=T
0
+A
Tt
sin (et
- c), 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: T
r
/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
) [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 Matjka (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
15
by digestion with sulphuric acid, which factually played in that time the role of the
contemporary X-ray diffraction. They were strongly affected by the work of H.
LeChatelier [38] and their visits at the Royal Technical University of Wroclaw (K.
Friedrich, B. Wohlin) where the thermal behavior of soils (bauxite) was investi-
gated during heating and related thermal instrumentation was elaborated. Calori-
metric proficiency was consequently gained from Polish Wojciech witosawski
(1881-1968). Much credit for further development of modern thermal analysis was
attributed with Rudolf Brta (1897-1985) who stimulated thermal analysis activity
at his coworkers (Vladimr atava, Svante Prochzka or Ivo Proks) and his stu-
dents (Jaroslav estk) at the Institute of Chemical Technology (domestic abbrev-
iation VChT) 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. Brta
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. estk (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. Brta, 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 2
nd
ICTA in Worcester (USA 1968). In particular it was Journal of Thermal
16
Analysis, which was brought into being by Judit Simon (1937-, who has been serv-
ing as the editor-in-chief until today) and launched under the supervision Hunga-
rian Academy of Sciences (Akadmiai Kiad) in Budapest 1969 (L. Erdey, E. Bu-
zagh, F. and J. Paulik brothers, G. Liptay, J.P. Redfern, R. Brta, 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. estk, 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. OHare, 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 kramovsk (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 Clment
Duval (1902-1976) or J apanese 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 1950s [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 limited
to age above 75. Upper from left: Cornelius B. Murphy (1918-1994), USA (TA theory); Robert
C. Mackenzie (1920-2000), Scotland (DTA, clay minerals, history); Sir William C.Roberts-Austen
(1843-1902), England (thermoelectric pyrometer); Gustav H.J. Tammann (1861-1938), Germany
(inventing the term thermal analysis) and Nikolaj S. Kurnakov (1860-1941), Russia (contriving
the first usable DTA); below: Lev G. Berg (1896-1974), Russia (TA theory); Rudolf Brta
(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 witosawski (1881-1968), Poland (calorimetry); enk Strouhal (1850-1922), Cze-
choslovakia (thermics, Strouhal numbers); yet below: Hans-J oachim Seifert (1930-), Germany
(phase diagrams); Takeo Ozawa (1932-), J apan (energetic materials, kinetics); Eugene Segal
(1933-), Romania (kinetics); Hiroshi Suga (1930-), J apan (calorimetry) andGiuseppe 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 Srensen (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) andPatrick 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) - Gerge Liptay
(1931-), left
Fig. 21.4 The photo from 28th conference of the
J apanese Society on Calorimetry and Thermal
Analysis (J SCTA) in Tokyo (Waseda University,
1992) shows (from left) M. Taniguchi (J apan),
late C.J . Keattch (GB), late R. Otsuka (J apan), S.
St. J . Warne (Australia, former ICTA president),
H. Suga (J apan), J . estk (Czechoslovakia) and
H. Tanaka (J apan). The regular J SCTA confe-
rences started in Osaka 1964 under the organiza-
tion of Prof. S. Seki who became the first presi-
dent when the J SCTA was officially established
in 1973. Since then, the J SCTA journal NETSU
SOKUTEI has been published periodically.


19
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IN:
http://www.springer.com/materials/special+types/book/978-90-481-
2881-5?detailsPage=free
Glassy, Amorphous and Nano-crystalline
Materials
Thermal Physics, Analysis, Structure and Properties
Series: Hot Topics in Thermal Analysis and Calorimetry, Vol. 8
estk, J aroslav; Mare, J iri J .; Hubik, Pavel (Eds.)
1st Edition., 2010, Approx. 350 p., Hardcover
ISBN: 978-90-481-2881-5
Due: October 2, 2010
1
SOME HISTORICAL ASPECTS OF THERMAL ANALYSIS:
ORIGINS OF TERMANAL AND ICTA
Jaroslav estk
Institute of Physics, Academy of Sciences
Cukrovarnicka 10, CZ-16253 Prague 6 and
Faculty of Applied Science, West Bohemian University,
Universitni 8, CZ-30614, Pilsen, Czech Republic
sestak@fzu.cz
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 140
th
Anniversary of the Czech-and-Slovak Chemical Society, 50
th

Anniversary of Czechoslovak and Slovak thermoanalytical conferences and 40
th
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 [122] 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
(15921670). 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 19
th
paragraphs of this chapter Comenius gave a
2
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 enk Strouhal (18501922) [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 18
th
Century, the notions of
heat and temperature (from temper or temperament first used by Avicenna in the 11
th
Century) were
not yet distinguished in-between. Blacks 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 bodys 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. Irvines
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.
Blacks 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 Rumfords 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 18
th
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
3
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 todays 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 Hannays 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 20 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
4
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 19031905 [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
5
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 Newtons
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 [413] 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 estk [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
6
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).
7
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 (18861972) and J. Matjka (18921960) [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, Matjka 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
500600 C associated with the formation of mineral Al
2
O
3
-2SiO
2
(dissolvable in acids) and its further
exothermic transformation to Al
8
Si
3
O
18
(~dumotierite) at 900 C and coexistence of SiO
2
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. kramovsk (19011983)
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. Brta (18971985) as he stimulated his coworkers (S. Prochzka, V. atava,
M. p, M. Vaek) 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. Brandtetr (Enthalpiometry [45]), J. Komrska
(Photometric TA [46]), A. Bergstein (Dielectric TA [47]), S. Chrom (Photometric TA [48]), V. atava
(Hydrothermal TA [49]), V. Balek (Emanation TA [50]) or M. Vani (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 9001900 K. V. Pekrek initiated the construction of a isoberobolic calorimeter for the
determination of hydrogenation heats in catalytic studies and V. Tydlidt 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. Kubir [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 Brtas 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 Brtas 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
Brta). 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.
Vani, O. Korb, V. Tomkov, . Svetk, P. Krlk, late A. Sopkov, S. Fajnor, E. Smrkov) and the
Czech Group on Thermal Analysis 1974 (V. Balek, J. estk, K. Habersberger, P. Holba, late J.
Rosick, J. Ederov, M. Bernek, M. Nevina) both acting under the roof of Czech-Slovak Chemical
Society.
5
th
Congress of Czech natural scientists and physicists, Prague 1914
(already involving some aspects of thermometric studies)
0
th
Discussion Meeting on Thermography, Prague 1955
1
st
Thermography Day, Prague 1956
2
nd
Conference on Thermography, Prague 1958
3
rd
Conference on Thermography, Prague 1961
4
th
Conference on DTA, Bratislava 1966
5
th
Conference on DTA, Smolenice 1970
6
th
Czechoslovak Conference on TA: TERMANAL, High Tatras 1973
7
th
, 8
th
and 9
th


TERMANALs, High Tatras 1976, 1979 and 1982
10
th
TERMANAL and 8
th
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 (19201999) and later, for the most part, Dr. R. C.
Mackenzie (19202000) paid personal visits to see Prof. R. Brta. Especially, during the 3
rd

Thermography Meeting in Prague, Dr. Mackenzie together with Drs atava, p, Vaek, Prochzka
(curiously including estk, 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 Termanal73: late M. Malinovsk and G. Lommbardi; Termanal76: V.
Tomkov, late V. Jesenk and V. atava; Budapest75: F. Paulik, D. Schultze and W. Hemminger; Bratislava85: A. Blaek,
P. Gallagher, M. Hucl or H. J. Seifert; Japan91: late C. J. Keattch, late R. Otsuka, S. Warne, H. Suga and H. Mitsuhashi;
and Zakopane87: H. Piekrasky, K. Wiczorek-Ciurowa, B. Pacewska and J. Pysiak.
10
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. Brta, 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. estk, M. A. Dudley, K. Heide,
W. L. Charsley, R. Otsuka, T. Sudo, G. Takeya, C. Duval, M. Vani, P. Imri, B. el, K. Melka,
J. Skaln, S. Yariv, J. J. Fripiat, S. K. Bhattacharyya, H. L. Friedman, K. Heide, V. atava, 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. Mller-Vonmoos, F. W. Wilburn, W. Bodenheimer, A. LaGinestra,
B. Dobroviek, D. Deli, A. Langier-Kuniarow, 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 20
th
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), Vladimr Balek (Czechia), late Viktor Jesenk (Slovakia), Milan Hucl
(Slovakia), Jaroslav estk (Czechia), late Jaroslav Rosick (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, Brta, 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
11
Eastern governments and partly due to the executives 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
8
th
ICTA in Bratislava, August 1923, 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 ICTA8 organizing committee that was bravely acting as follows
M. Hucl, Slovak Technical University, Bratislava, Chairman
V. Balek, Nuclear Research Institute, e, Vice-chairman
O. Korb, Slovak Technical University, Bratislava, Secretary
J. estk, Academy of Sciences, Prague, Scientific Program
M. Vani, Slovak Technical University, Bratislava, Exhibition
A. Blaek, Institute of Chemical Technology, Prague, Proceedings
V. Tomkov, Slovak Technical University, Bratislava, Executive
Secretary
K. Habersberger, Academy of Sciences, Prague, Conference Affairs
. Svetk, Slovak Technical University, Bratislava, Conference Affairs
P. Krlk, Technical University, Koice, 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. estk, 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 (Acadmia Kiad) in Budapest
1969 (L. Erdey, E. Buzagh, F. and J. Paulik brothers, G. Liptay, J. P. Redfern, R. Brta, 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.
12
Attentive support of the West Bohemian University (MSMT 4977751303) and Grant Agency of Czech
Republic (522/04/0384) is highly appreciated.

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13
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th
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32. M. J. Vold, Anal. Chem. 21, 1949, 683.
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34. M. M. Factor, R. Hanks, Trans. Farad. Soc. 63, 1959, 1129.
14
35. A. P. Grey in proc. 4
th
ICTA, Thermal Analysis, Akademia Kiado, Budapest 1974.
36. P. Holba, J. estk, Silikty 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. Zlatkovsk, Chem. Zvesti 23, 1969, 620 (in Slovak).
40. C. Kallauner, J. Matjka, Sprechsaal 47, 1914, 423.
41. J. Matjka, Chemicke listy 13, 1919, 164 and 182 (in Czech).
42. S. kramovsk, Chemick listy 26, 1932, 521 (in Czech).
43. R. Brta, Silikty (Prague) 5, 1962, 125 (in Czech).
44. A. Blaek, Silikty 1, 1957, 177 (in Czech).
45. J. Brandtetr, Z. Anal. Chem. 254, 1972, 34.
46. J. Komrska, Silikty (Prague) 11, 1967, 51 (in Czech).
47. A. Bergstein, Collect. Czech. Chem. Commun. 20, 1955, 1058.
48. J. Chrom, Amer. Mineral. 54, 1969, 549.
49. V. atava, O. Vepek, Silikty (Prague) 15, 197), 1 (in Czech), J. Amer. Cer. Soc. 58, 1975, 357.
50. V. Balek, Silikty (Prague) 13, 1969, 39 (in Czech), J. Mater. Sci. 4, 1969, 919, Anal. Chem. 42,
1970, 167.
51. M. Vani, O. Korb, Silikty (Prague) 4, 1960, 266 (in Slovak).
52. J. estk, Silikty (Prague) 7, 1963 (in Czech), Talanta 13, 1966, 567.
53. V. atava, Thermochim. Acta 2, 1971, 423.
54. J. estk, G. Berggren, Thermochim. Acta 3, 1971, 1.
55. V. Jesenak, Proc. TERMANAL 82, Publ. House SVT, Bratislava 1982, 13.
56. J. Velek, Chem. Listy (Prague) 72, 1978, 51 (in Czech)
57. M. Malinovsk, Chem. zvesti (Bratislava) 28, 1974, 489 (in Slovak).
58. M. Roubal, V. Landa, Strojrenstv (Prague) 25, 1975, 559 (in Czech).
59. V. Tydlidt, Czech. J. Phys. B 21, 1971, 817.
60. J. Velich, Chem. Listy (Prague) 79, 1985, 661 (in Czech).
61. L. Kubir, Czech. J. Phys. A 34, 1984, 153.

15
ICTAC 196568 196871 197174 197477
President L. G. Berg (USSR) C. B. Murphy
(USA)
H. R. Oswald
(Switzerland)
H. Kambe
(Japan)
Vice-President R. Brta
(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. Brta
(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. Srensen
(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. Srensen
(Denmark)
S. St. J. Warne
(Australia)
Chairmen of
Committees
R. Brta, 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. Mller Von
Moos (Switzerland)
F. Paulik
(Hungary)
S. Seki
(Japan)

Historical Prague and its famous Charles
University
One of the most important moments in the history of
old Bohemia was the foundation of Charles Univer-
sity in Prague, as the first European university north
of the Alps, by Emperor Charles the IV. One of its
first achievements was the introduction of medieval
kinematics, which was brought to Prague by Johannes
de 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. Later
Czech astronomer Jan indel (13751456) was study-
ing the planetary motion and his astronomical tables
were greatly appreciated by Tycho de Brahe while
staying in Prague at the end of the 16th century.
indel had also a share in designing the advanced as-
trolabe in the famous Pragues astronomical clock.
Little renown is Ioannes Marcus Marci (Jan
Marek Mark 15951667) who probably helped to re-
veal the fundamental properties of the spectral colors
that emerge when light passes through glass prism,
was already aware of their monochromatic properties,
i.e., any succeeding refraction or reflection did not
change colors. He also studied the color change in
rays when spectral colors are mixed and in the field of
spectral 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 foreshadowed
some laws. Besides the refraction of light he con-
ducted the first-ever systematic study of the impact of
bodies, he discovered the difference between elastic
and inelastic impacts intuitively moving his thoughts
within the reach of the conservation laws. Marci,
13886150/$20.00 Akadmiai Kiad, Budapest, Hungary
2007 Akadmiai Kiad, Budapest Springer, Dordrecht, The Netherlands
Journal of Thermal Analysis and Calorimetry, Vol. 88 (2007) 3, xx
FROM CALORIC TO STATHMOGRAPH AND POLAROGRAPHY
J. estk
1,2*
and J. J. Mare
1
1
Institute of Physics, Academy of Sciences, Cukrovarnick 10, 16253 Praha 6, Czech Republic
2
Faculty 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,
Tade Hjek, Marcus Marci, Jan A. Commenius (caloric), Prokop Divi, Bernard Bolzano, Christian Doppler, Ernst Mach, Albert
Einstein, Vclav imerka, Frantiek Zvika, enk Strouhal, Reinhold Frst or Stanislav kramovsk (statmograph) and Jaroslav
Heyrovsk (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 members
and associates, astronomer Kepler Johannes (15711630), rector and mathematician Marcus Marci Ioannes (from
Kronland, 15951667) and famous professor of mathematics and practical geometry Doppler Christian (18031853)
* Author for correspondence: sestak@fzu.cz
however, was strongly convinced that white light was
the simplest element (quinta essentia), which, inter-
estingly, was close to the subsequent concept of ele-
mentary waves propounded about fifty years later by
Huyghens in the wave theory of light. There, how-
ever, is incomplete information concerning Marci`s
educational activities. He was the rector of the famous
Charles University and, perhaps, introduced a word
first specialization called chimiatrie, which was
conceivably taught as an unusual subject with regards
the traditional university disciplines: major artes
liberales and minor artes mechanicae (i.e., learning
common crafts such as warfare, navigation, business,
agriculture, hunting, medicine or veterinary) but not
in artes incertae (that was a part of the habitually re-
jected equivocal arts associated with occultism,
which traditionally involved alchemy).
Some medivial alchemists and the
introduction of caloric
When Rudolph the II (15521612) became the Em-
peror of the Holy Roman Empire and the King of Bo-
hemia, he provided in Prague court a vital support to
alchemists, astronomers and physicists. Among the
most outstanding scientists were Tycho de Brahe
(15461601) and Johannes Kepler (15711630)
whose astronomical observations and calculations
were published in the well-known Rudolphine tables.
After the death of Tycho de Brahe, Johannes Kepler
replaced his position of a royal mathematician in
Prague in the year 1601. Using Tycho de Brahes
data, Kepler determined elliptic orbit of Venus. In his
1609 treatise Astronomia Nova Kepler published
his two first laws, controlling the motion of planets
and according to which the orbit of a planet/comet
about the Sun is an ellipse with the Suns center of
mass at one focus.
Foremost Czech physician and astronomer, Chef
Medical Supervisor of the Kingdom of Bohemia at
the court of Rudolph the II, was Thaddaeus Hagecius
ab Hagek (Tade Hjek z Hjk, 15251600) known
as an author of several astronomical tractates and
books on geodesy, botanics and medicine particularly
acknowledged for the first concise book on the
beer-making, De cerevisia (1585). He essentially
helped the flourishing period of alchemy and played a
significant role in persuading Rudolph the II to invite
Tycho de Brahe to come to Prague.
Special attention should be paid to the Czech
thinker and Bohemian educator, latter refugee Jan
Amos Comenius (Komensk 15921670). In his
Physicae 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 substance
gains in density and shrinks: the condensation of vapor
to liquid water is given as an example. Comenius also
determined, though very inaccurately, the volume in-
crease in the gas phase caused by the evaporation of a
unit volume of liquid water. In Amsterdam in 1659 he
published a treatise on the principles of heat and
cold [2], which was probably inspired by the works of
the Italian philosopher Bernardino Telesius. The third
chapter of Comenius book was devoted to the descrip-
tion of the influence of temperature changes on the
properties of substances. The aimand principles of ther-
mal analysis were literally given in the first paragraph of
this chapter: citing the English translation [3] 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 ef-
fects of heat and cold become apparent to our senses. In
the following 19 paragraphs of this chapter Comenius
gave a rather systematic description (and also a partially
2 J. Therm. Anal. Cal., 88, 2007
ESTK, MARE
Fig. 2 From left: Hjek Tade (from Hjk, 15261600), Komensk Jan Amos (Comenius, 15921670), Prokop Divi
(16961765) and Bolzano Bernard (17811848)
correct interpretation) of the effects of continuous heat-
ing and cooling of water and air, and also stressed the
reversibility of processes such as, for example, evapora-
tion and condensation, etc., anticipating somehow the
concept of latent heat. Comenius concludes this chapter
as follows: All shows therefore that both heat and cold
are a motion, which had to be proved. In the following
chapter Comenius described and almost correctly ex-
plained 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.
It is difficult to trace and thus hard to say if it was
possible (though likely) to disseminate the idea of calo-
ric fromAmsterdam(when Comenius mostly lived and
also 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 constituent
parts of a substance causing its expansion. Although
caloric differed from foregoing concept of phlogiston
(because it could be later measured with an apparatus
called a calorimeter) it is not clear who was the first us-
ing such an instrument. If we follow the studies of
Mackenzie and Brush [4, 5] and Thenard [6] they as-
signed it to Wilcke. It, however, contradicts to the
opinion presented in the study by McKie and
Heathcode [7] who consider it just a legend and as-
sume that the priority of familiarity of ice calorimeter
belongs 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 and
Laplace entitled the first chapter of their famous
Mmoire sur la Chaleur (Paris 1783) as Presentation
of a new means for measuring heat whereas the report
of calorimetric employment by Black seemed to first
appear almost a century later in the Jamins Course of
Physics (MalletBachelier, Paris 1868).
Caloric was seen as an imponderable element
with its own properties. Unfortunately, the great prop-
agator, Joseph Black (and his student Irvine), pub-
lished almost nothing in their own lifetimes [8] and
their attitudes were mostly reconstructed from con-
temporary comments and essays published after their
deaths. Black 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 accumulate heat
(~1761). Irvines account that the relative quantities
of heat contained in equal weights of different sub-
stances at any given temperature (i.e., their absolute
heats) were proportional to their capacities at that
temperature and it is worth noting that the term ca-
pacity was used by both Black and later also Irvine to
indicate specific heats [8]. Black also introduced the
term latent heat which meant the absorption of heat
as the consequence of the change of state.
Blacks elegant explanation of latent heat to the
young Watts became the source of the invention of
the businesslike steam engine as well as the inspira-
tion for the first research in theory related to the novel
domain of thermochemistry, which searched for gen-
eral laws that linked heat, with changes of state.
Rumford presented qualitative arguments for such a
fluid 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 by
Mayer and, in particular, by Joule, who also applied
Rumfords theory to the transformation of electrical
work. The use of customary units called calories
was coined by Clment, who was giving in 1824 the
following 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 (Favre
and Silbermann [9]) in 1845. The characterization of
one kilocalorie as 427 kilogram-meters was launched
by Mayer in the year 1845. The caloric-like descrip-
tion of heat as a fluid has survived, nevertheless, until
today being a convenient tool for easy mathematical
description of heat flows [3, 1014]. Recently we
tried to refresh the concept of caloric in the view of
entropy and its connection to information [15].
Worth noting is the theory of Prokop Divi
(Divisch 16961765), which belongs to early pioneer-
ing times. Accordingly, Light of the First Day of Cre-
ation is regarded to be identical with electricity, which
is an inherent quality of all things, permeating the
whole Universe and manifesting itself by electric and
thermal 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 College
of Clementinum and its famous library and observa-
tory (opened in the 1720s) where about 1780 Antonin
Strnad (17471799) laid the foundation to the oldest
known series of systematic metrological observa-
tions. Worth noting are physicists and mathemati-
cians Josef Stepling (17161778) and Jan Tesnek
(17281788) who published many original studies
and initiated publishing of Prague edition of New-
tons Principia supplemented with his own com-
mentaries, in that time best edition reasoned with
better mathematical background.
Renaissance of Prague physics
The first half of the 19
th
Century mathematical and
physical studies in Prague became again on a par with
J. Therm. Anal. Cal., 88, 2007 3
HISTORICAL SURVEY
the world science. Important role paid some scientists
such as Frantiek J. Gestner (17561832) who is also
known as a pioneer of the railway transport in Europe.
Excellent achievements are duly associated with the
name of Bernard Bolzano (17811848) particularly in
mathematical logic and analysis and with his friend
Christian Doppler (18031853) who came to Prague
from Vienna in 1829. His famous paper was inspired
by astronomical phenomenon: the components of
many 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 radial
velocities, the principle itself is correct, being veri-
fied, e.g., in acoustics and optics. In 1867 arrived to
Prague Ernest Mach (18381916) and spent there
nearly 30 years. He is known for his discussion of
Newtons Principia and critique of conceptual mon-
strosity of absolute space in his book The Science of
Mechanics (1883). Mach encouraged and inspired
one of his students (later professor of theoretical
physics) Jan Kolek (18511913) to study some of
his hypothesis later approving that the Machs theory
correctly describes the dispersion of light, dichroism
and circular birefringence. The Mach successor at
Prague German University was Ernst Lecher
(18561926) who is well known for his research on
electromagnetic waves (i.e. Lecher wires). Mach also
analyzed conceptual basis of calorimetry from more
general, almost philosophical, point of views [18].
His influence on the further development of physics
was tremendous and he established a mathematically
specialized 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
(17871869) internationally known for discoveries in
physiology. Another young assistant of Mach was
enk Strouhal (18501922), later first Czech profes-
sor appointed for experimental physics. His studies in
acoustic are well known and the Strouhals number
concerning friction tones (oscillation) is named after
him. He wrote and exceptional book on heat called
Thermics [19].
Czech priest (and, unfortunately, rather un-
known mathematician) Vclav imerka (18191887)
introduced quantitative evaluation in psychology
4 J. Therm. Anal. Cal., 88, 2007
ESTK, MARE
Fig. 3 From left: Vclav imerka (18191887), Friedrich Reinitzer (18571927), Ernest Mach (18381916), Albert Einstein
(18791955)
Fig. 4 From left: enk Strouhal (18501922), Frantiek Zvika (18791945), Jaroslav Heyrovsk (18901967), Stanislav
kramovsk (19011983)
(logarithmic connotation of feelings) providing early
basis for the theory of information [20]. Czech-born
Friedrich Reinitzer (18571927) is famous as the dis-
coverer of cholesterol (including its metamorphosis
and stoichiometry formulae C
27
H
46
O) and is also
known for his pioneering work in the field of liquid
crystals (latter widespread by O. Lehmann). Bohumil
Kuera (18741921) examined effect of electrical po-
larization on surface tension in the interface of two
liquids prompting the idea of a new technique latter
known as the drop-weight method, which provided
physical basis for a new, today widely utilized, ana-
lytical method called polarography [21] as introduced
by Jaroslav Heyrovsk (18901967), which was
awarded by Nobel price in 1959 [22].
An original development of weight measurements
is connected with the name Stanislav kramovsk
(19011983), who, at the Charles University, investi-
gated thermal decomposition of complex oxalates
which led him in 1932 to his own construction of an
apparatus named stathmograph (from Greek
stathmos=mass, weight) [23] that made it possible to
measure mass changes. Independently, in the same
time Duval used for his way of weight measurements
the Latin-based term thermogravimetry that later be-
came generally accepted in thermal analysis. As the
principle scheme of the stathmograph instrument is not
generally known, it is perhaps worth mentioning to de-
scribe the arrangement. kramovsk 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 the left arm
of an analytical balance. A mirror attached to the beam
was 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 rod
immersed into paraffin oil and temperature was regis-
tered automatically by means of a mercury thermome-
ter provided by platinum contacts distributed along the
whole length of capillary.
A most prominent personality, which spent fruit-
ful time in Prague was Albert Einstein (18791955)
[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 of
photoelectric effect, theory of specific heats,
Brownian motion, etc. (see the book Builders of the
Universe 1932). In 1911 he obtained his first profes-
sorship at theoretical physics at the German Univer-
sity of Prague where he closely cooperated with his
friend professor of mathematics, Georg Pick
(18591942). While in Prague he published 11 pa-
pers, most extensive being the survey of the theory of
specific heats and very important were studies related
with his favorite problem the interaction of radia-
tion with matter and effort to construct a relativistic
theory of gravitation [25].
Worth noting is the so-called Planck-Einstein
transformation formula for temperature which reads
T=T
0
[ ( / ) ] 1
2
- v c [25] and is possibly related to the
previous dissertation work by K. von Mosengeil, post-
humously published in Ann. Physik 22 (1907) 867. It
means that the temperature of a body observed from
the system moving with a relative velocity, v, is lower
than the temperature in rest system. Basing on this idea
in 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. In
the year 1953, however, Einstein wrote a letter to M.
von Laue in which he doubts the correctness of this
formula and rather speculated about a formula used in-
verse (temperature as observed in moving system is
higher). This statement, which was later proved by H.
Ott [26], thus reads as T=T
0
[ ( / ) ] 1
2
- v c . In both these
cases information about the temperature is regarded to
be 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., by
means of digital coding, the temperature, in the con-
trast to both above formulae, must be considered as
ralativistically invariant.
Another distinguished, but unjustly not very ap-
preciated, savant born in Prague was Reinhold Frth
(18931979) who devoted his scientific life to the re-
search into the fundamentals of statistical phys-
ics [27]. Besides an extensive work concerning
Brownian motion and noise phenomena he is also au-
thor of stochastic interpretation of quantum mechan-
ics [28]. Accordingly to this theory, the Schrdinger
equation is nothing but the classical diffusion equa-
tion with complex diffusion constant ~j/2m. This
statement became later a cornerstone of so-called
stochastic electrodynamics, which provides an alter-
native to quantum mechanics [29].
One of the outstanding teachers, who earned
great merit for introducing modern theoretical physics
and thermodynamics to the curriculum of Charles
University, was Frantisek Zvika (18791945). One
of his textbooks was the first monograph on relativity
published in Czech and he is an author of excellent
books on thermodynamics [30]. He also concerned
waveguides and independently deduced relevant the-
ory early before the microwave technique became im-
portant. Other notable physicist was Augustin ek
(18861961) who studied damped electromagnetic
oscillations in vacuum electronic systems. His ex-
tended studies culminated at 1924 in the discovery of
the principle of magnetron, later becoming the basis
of radar systems.
J. Therm. Anal. Cal., 88, 2007 5
HISTORICAL SURVEY
The historical development and use of the meth-
ods of thermal analysis in the territory of former
Czechoslovakia is linked with the names Otto
Kallauner (18861972) and Jospeh Matjka
(18921960) who introduced thermal analysis as the
novel technique during the period of the socalled ra-
tional analysis of ceramic raw materials [31]. Much
credit for further development of modern thermal
analysis is attributed with Rudolph Barta
(18971985) who stimulated his coworkers (Vladimr
atava) and his students (Jaroslav estk) at the Insti-
tute of Chemical Technology in Prague (the latter
mentioned names became also initiators of the foun-
dation of the International Confederation for Thermal
Analysis in the year 1965 [32]).
Some other details were published elsewhere
[3134].
Acknowledgements
This study was supported by the grant No. A100100639 of the
Grant Agency of the Academy of Sciences of Czech Republic
and the Institutional FZU research plan No. AVOZ10100521
and the UWB project MSMT No. 4977751303.
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3 J. estk, Heat, Thermal Analysis and Society, Nucleus,
Hradec Krlov 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.
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6 L.Thenard, Treatise of Chemistry 6
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7 D. McKie and N. H. V. Heathcote, The Discovery of
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16 P. Divisch, Lngst verlangte Theorie von der
meteorologischen Electricite, Magiam Naturalem
benahmet, J. H. P. Schramm, Tbingen 1765.
17 M. Sparnaay, Historical Background of the Casimir
Effect in Physics in the Making (A. Sarlemijn,
M. Sparnaay, Eds), Elsevier, Amsterdam 1989.
18 E. Mach, Die Principien der Wrmelehre, Leipzig 1896.
19 . Strouhal, Thermika (Thermics), JMF, Praha 1908
(in Czech).
20 P. V. imerka, Sla pesvden: pokus v duchovn
mechanice (Strength of conviction, an attempt to mental
mechanics), asopis pro pstovn matemat. fyziky,
11 (1882) 75 (in Czech); A. Pnek, ivot a psoben
imerky (imerkas life and actuation), asopis pro
pstovn matemat. fyziky, 17 (1888) 253 as well as
J. 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, Chemick Listy, 26 (1932) 521 (in
Czech).
24 J. Bik, 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. estk, J. Stvek, H. evkov, J. Kritofik
and P. Hubk, Physica, E29 (2005) 145.
28 R. Frth, Z. Phys., 81 (1933) 143.
29 J. J. Mare, J. Stvek and J. estk, J. Chem. Phys.,
121 (2004) 1499.
30 F. Zvika, Termodynamika (Thermodynamics), JMF,
Praha 1943 (in Czech).
31 I. Proks, Evaluation of the Knowledge of Phase
Equilibria first chapter in the book Kinetic Phase
Diagrams (Z. Chvoj, J. estk, A. Tska, Eds), Elsevier,
Amsterdam 1991.
32 J. estk, Some historical aspects of thermal analysis:
origin of Termanal and ICTA in the proceedings of
Termanal 2005, p. 3 (Eds E. Klein, E. Smrkov,
P. imon).
33 P. Cardillo, J. Therm. Anal. Cal., 72 (2002) 7.
34 J. estk, Science of heat and Thermophysical Studies: a
generalized approach to thermal analysis, Elsevier,
Amsterdam 2005.
DOI: 10.1007/s10973-006-8210-1
6 J. Therm. Anal. Cal., 88, 2007
ESTK, MARE
Review papers
Ceramics Silikaty 56 (2) 159-167 (2012) 159
CZECHOSLOVAK FOOTPRINTS IN THE DEVELOPMENT
OF METHODS OF THERMOMETRY, CALORIMETRY
AND THERMAL ANALYSIS
A tribute to proIessor Vladimir Satava, DrSc, a mastermind oI theoretical basis oI thermal analysis, who celebrates
his 90
th
birthday dedicating also the 55
th
anniversary since he becomes the Editor oI the journal Ceramics-Silikaty
#
PAVEL HOLBA, JAROSLAV SESTAK
New Technologies - Research Centre of the Westbohemian region,
Universitv of West Bohemia in Pilsen, Universitni 8, 301 14 Pl:en, C:ech Republic
#
E-mail: holbapgmail.com
Submitted March 15, 2012; accepted May 16, 2012
Keywords: History, Thermal analysis, Calorimetry, Kinetics, DTA
A short historv on the development of thermometric methods are reviewed accentuating the role of Rudolf Barta in
underpinning special thermoanalvtical conferences and new fournal Silikatv in hfties as well as Jladimir Satava mentioning
his dutv in the creation of the C:ech school on thermoanalvtical kinetics. This review survevs the innovative papers dealing
with thermal analvsis and the related helds (e.g. calorimetrv, kinetics) which have been published bv noteworthv postwar
C:echoslovak scholars and scientists and bv their disciples in 1950-1980. Itemi:ed 227 references with titles show rich
scientihc productivitv revealing that manv of them were ahead of time even at international connotation.
Historical roots oI thermal sciences
- Irom thermoscopy to thermal analysis
One oI the frst modern-times considerations oI
heat and cold can be Iound in the treatise published in
1563 by B. Telesio. At the end oI the 16th century the
frst air thermoscope appeared (G. Galileo about 1597)
and in 1626 the word ,thermometer' was Ior the frst
time used to describe thermoscope equipped with scale
with eight degrees (Leurechon in book 'La Recreation
Mathematique). Shortly aIter, the world-known Czech
educator J. A. Comenius inserted refections on the
role oI 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 frst quantitative thermal law expressing the
dependence oI temperature oI a cooling body (expressed
in the scale oI 8 degrees) on the time was published by I.
Newton in 1701.
Meanwhile, other scientists had invented various
types oI the dilatation thermometers and had proposed
various temperature scales. Romer (1701) had flled
glass tube oI thermometer with red wine and proposed
a 60-degree scale. Fahrenheit (1724) proposed a tem-
perature scale oI 100 degrees Irom 0F (at the temperature
oI mixture oI ammonium chloride, water and ice) and
100F at the human body temperature. Reaumur (1731)
introduced the temperature scale with 80 degrees between
0Re at water melting point and 80Re at boiling point
oI water. A year later Delisle introduced an exotic scale
with 240 degrees, which was later (1738) modifed and
adjusted to 150D corresponding to the melting point oI
water and to 0D at boiling point oI water (240D -
60C), and this scale was being used in Russia Ior the
whole hundred years. Only then Celsius (1742) came
with its 100-degree scale (between the melting 100 and
boiling 0 points oI water, later switched to nowadays
0-100 by Linne).
The crucial experimental studies, thanks to which
temperature became a clearly measurable physical
quantity, was executed by Regnault in the 1840th, that
is long aIter the Black (1761) distinguished between
the specifc heat (heat capacity) and the latent heat,
Laplace and Lavoisier (1786) perIormed their frst
calorimetric measurements. In 1822 Fourier published
his laws oI heat transIer. Yet aIter detailed results oI
Regnault's dilatometric and heat capacity measurements
(1842), together with Carnot's theorem (1824) and its
consequent interpretation by Clapevron (1834) - the basis
was Iormed Ior the introducing oI absolute temperature
scale by W. Thomson (Kelvin 1848) and Ior the inception
oI thermodynamics as a new science.
Holba P., Sestak J.
160 Ceramics Silikaty 56 (2) 159-167 (2012)
The frst noted use oI thermometry as a method oI
thermal analysis took place in Uppsala in 1829 where
F. Rudberg (1800-1839) recorded inverse cooling-rate
data Ior various alloys. |1,2|. In 1883, H. L. Le Chatelier
(1850-1936) adopted a somehow more IruitIul approach
plotting the time vs. temperature curves easily convertible
to the relation oI sample temperature vs. environmental
temperature.
Several years later Le Chatelier (1887) had used
Pt/PtRh thermocouple and the new era oI thermometry
as well as oI calorimetry has arrived. In 1891, W.
C. Roberts-Austen (1843-1902) |3| became known
to construct a device to give a continuous record oI
the output Irom thermocouple and he termed it as
'thermoelectric pyrometer. Later with his assistant
A. Stanheld published in 1899 heating curves Ior
gold, which almost stumbled upon the idea oI DTA
('DiIIerential Thermal Analysis). They improved
the sensitivity by maintaining the thermocouple cold`
junction at a constant temperature and by measuring the
diIIerences between two high temperatures |4|. Among
other well-known inventors was Russian N. S. Kurnakov
(1860-1941) improving registration oI 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 signifcance oI cooling curves in phase-equilibrium
studies oI binary systems.
The frst Czech university textbook on the physics
oI heat was 'Thermika by C. Strouhal (1850-1922)
published in 1908 |7| maintaining its inIormative value
until today`s. The historical development and practical
use oI DTA in the territory oI Iormer Czechoslovakia |1,
2, 8| was linked with the names J. Burian (1873-1942),
O. Kallauner (1886-1972) and J. Matfka (1892-1960)
who introduced thermal analysis as the novel technique
during the period oI the so called 'rational analysis oI
ceramic raw materials |9| in order to investigate behavior
oI kaolinite |10, 11| at heating.
Worth a special attention is an original development
oI weight measurements that is connected with the
name S. Skramovskv (1901-1983), who, at the Charles
University, investigated thermal decomposition oI
complex oxalates which led him in 1932 to his own
construction oI an apparatus named 'stathmograph
(Irom Greek 'stathmos mass, weight) |12| that made
it possible to measure mass changes. Independently
(twenty years later), C. Duval used Ior his way oI weight
measurements the Latin-based term 'thermogravimetry
that later became generally accepted in thermal analysis
|13|. As the principle scheme oI the stathmograph
instrument is not generally known, it is perhaps
worth mentioning to describe this early arrangement.
Skramovsky placed a weighted sample into the drying
oven on a dish suspended on a long flament passing
through a hole in its upper wall (Iorming the balance
case) and hooked to an arm oI an analytical balance.
A mirror attached to the beam was refecting the image
oI alight slit into a slowly rotating drum lined with
photosensitive paper. The unwanted vibration was
reduced by an attached glass rod immersed into paraIfn
oil and temperature was registered automatically by
means oI a mercury thermometer provided by platinum
contacts distributed along the whole length oI capillary.
In the frst years aIter 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 oI DTA |17| was also published.
At the end oI 1950th a commercial device combining
DTA and TG appeared under the name 'Derivatograph
|18| Ior long providing a useIul service to the Eastern
scientists.
Much credit Ior the Iurther development oI modern
thermal analysis was attributed with Rudolf Barta
(1897-1985) who stimulated thermal analysis activity at
his Iellow workers (J. Satava, S. Procha:ka, J. Jasicek, M.
Cap or I. Proks) at the Institute oI Chemical Technology
Prague (abbreviated as VSChT) |19, 20, 21, 22|. Barta
organized premature thermoanalytical meetings, the
earliest was the 1
st
ConIerence on DTA (Prague
1956), the 2
nd
(Prague 1958) and the 3
rd
ConIerence
on Thermography (Prague 1961) Iollowed by the 4
th

ConIerence on DTA (Bratislava 1966). His Iriend R. C.
Macken:ie (1920-2000) |23, 24| Irom Scotland was an
invited guest at the 1961 meeting who was also one oI
the pioneers oI applied DTA |23, 24|. Upon the previous
communication with Russian L.G. Berg, Americans P. D.
Garn and C. B. Murphv as well as Hungarian L. Erdev
an idea Ior the creation an international society ICTA
was cultivated and realized during the frst international
thermoanalytical conIerence in London 1965 |24|
(where one oI 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 signifcance oI the early Czech-written books
on thermal science |7, 26|, which appeared beIore and/or
simultaneously with the credited international literature
|8, 22| the indispensable fgure in the Czechoslovak
development oI thermal analysis was undoubtedly
Jladimir Satava (*1922) |27-31|. He brought to the
Czech scientifc circles necessary theoretical basis on
solid-state chemistry and physics |29, 30|, pioneered
methods oI thermal analysis |18, 19, 27, 26|, educating
his students who thus Iollowed his proIessional guidance
and published esteemed books |27-33| completing thus
the rich spectrum oI Czech thermoanalytical literature
|31-38|, cI. Fig. 1. The individual contributions and
innovative approaches have been aIfuent and Iocal which
is worth oI a more detailed portrayal, as exposed in the
next paragraph, especially accentuating Czechoslovak
source journals. UnIortunately, most oI these rather cru-
C:echoslovak footprints in the development of methods of thermometrv, calorimetrv and thermal analvsis
Ceramics Silikaty 56 (2) 159-167 (2012) 161
cial papers disappeared in the shadows oI time due to
the Czech written texts. Only consequently a supply
role started playing the novel thermoanalytical journals,
Thermochimica Acta, which was coIounded by one oI
the authors back in the year 1970 as well as Journal oI
Thermal Analysis instigated by R. Barta in 1969.
Less known book by J. A. Komensky 'Investigation
of the nature of heat and cold. (Amsterodam 1659) in
which the predicament oI heat and cold is well discussed;
'Thermics by C. Strouhal (1908) was an unique book
describing the early but elementary treaties on heat, the
almost unknown book on DTA (1957) was published
ahead oI time, basic book oI solid-state chemistry and
material thermal behavior was also published (1965)
beIorehand oI international literature (unIortunately
never translated). Far right is the Russian translation
oI Czech original book on theoretical basis oI thermal
analysis (1988), which became curiously a scientifc
bestseller as whole 2000 issues were sold in the Iormer
USSR within one week.
Methodical Iootpath identifable
on the territory oI Iormer Czechoslovakia
The greatest promotion oI thermoanalytical methods
came aIter fIties when the methodical bases were Iormed
|39| and new techniques specifed. 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 feld oI TA
promoted in the Iormer Czechoslovakia are assorted into
several (but not very strict) categories. The reIerenced
papers are supplied by original titles (given in English)
and they are chronologically ordered within individual
categories. All reIerences were checked and corrected
according to database WOS (Web oI Science).
The frst category ,1A generally" consists oI artic-
les |42-57| deals mostly with thermal analysis in a ge-
neral way including papers published mainly in Czech
journals Silikaty and Chemicke listy, and in Slovak
journal Chemicke Zvesti.
The second category 'Special methods of 1A" 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 Iorerunner oI today`s tem-
perature modulated methods oI TA), diIIerential 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 oI radioactive
measurement called emanation thermal analysis (ETA)
which is connected mainly with authors J. Jesenak |64|,
J. Balek |67, 75, 76| and J. Tlgvessv |81|.
An explicit part oI the papers was devoted to the
description oI own constructions oI apparatuses Ior TA
measurement as a consequence oI at that time existing
inaccessibility oI commercial TA instruments. This type
oI articles is included into category Apparatuses of
1A |84-101|. Early instruments as were opportunely
produced by laboratory groundwork, such as DTA be-
long into this category. The production way oI latterly
produced TG apparatuses was paved by the development
oI a Czech thermogravimetric instrument named
'TEGRA and constructed by A. Blaek |37, 87|. Early
instruments were opportunely produced by laboratory
groundwork, such as DTA |84, 86, 91, 97|.
A rich sphere oI Czechoslovak research was
also Iormed by calorimetric contributions |103-127|
registered in category Calorimetry. Worth accentuating
is an initial classifcation oI calorimeters according to the
temperature diIIerence between the sample-block T
B
and
surrounding jacket T
J
as early suggested by J. Jelisek
|117|.
Consequent category 1heory of D1A/DCS is asso-
ciated with a gradual development oI theoretical basis
oI thermal measurements mostly Iocused on the DTA
|128-140| curiously noting early the associated eIIect
oI gradients |129, 130|. It involved problems oI
Figure 1. Some Iavored book related to the topic oI thermal science
Holba P., Sestak J.
162 Ceramics Silikaty 56 (2) 159-167 (2012)
calibration and standardization oI temperature and heat
measurements by employing solid solution |135, 140|,
application oI heat pulses |134|, conductivity issues
|138| as well as a detailed analysis oI the complex
composition oI a DTA peak including the eIIect oI heat
inertia |135, 137|. One oI the Irequently cited and widely
applied treaties was the Hruby glassIorming coeIfcient
|133| based on the DTA determination oI characteristic
temperatures during glass crystallization (inquisitively
becoming the best cited paper in the history oI Journal
Czechoslovak Physicists with 372 citations). Such
achievements were only possible by the impact oI
prosperous Czechoslovak school on thermodynamics
|27-34|. The other corresponding papers |141-162| are
included into category 1hermodynamics 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 oIIered by studies oI V. Satava whose kinetic
evaluation method |175| have been broadly exploited
and quoted by international resources (several hundreds
oI citations) and Irequently named as the 'Satava kinetic
method |31, 34, 35, 174, 183|. Such a popularity oI
theoretical works aimed to elucidate predicaments
oI reaction kinetics |34, 35, 183| became the heart oI
the so-called Czech school oI nonisothermal kinetics
recently continued both in Czech |195-198| and Slovak
republic |190, 191, 199|. Worth noting is the frst ever
published algorithm Ior the computer calculation oI
kinetic data |171| and the review paper |170| which
despite the Czech language became the best cited article
in the journal history. In Ieedback 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 aIter
the authors (i.e., the Sestak-Berggren |178| as well as
the Holba-Sestak |180| kinetic equations). Not less
important have been the contributions by recently
deceased Ivo Proks (1926-2011), who Iactually paved
the way to the development oI methods using the
modulated temperature modes |68|, early accounting on
temperature gradients and measurement accuracy |129,
132|, improved solution calorimetry |104, 113, 118|
thus signifcantly contributing the elementary attributes
oI thermochemistry and thermodynamics. Worth
mentioning are also his imperative studies on historical
root oI thermodynamics |8, 220, 222, 224, 225| as well
as the work by J. Brandstetr |93, 100, 108, 115, 120,
125| in the feld oI titrimetry.
Not less important were also the related articles
about mechanic properties (which was one oI Iavored oI
the Satava`s research topics |208, 217|), diIIusion studies
|203-212| and early measurements oI electrical and
heat conductivity |202, 214-217| inserted into category
Mechanical and transport properties |200-216|. The
last category oI Czechoslovak papers dealing with TA
is labeled as History and nomenclature. It contains
reviews oI historical aspects oI 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 misIortune to
allow their input to slip into oblivion. Clearly, one oI
the most important moments in the development oI
modern thermal analysis was the establishment oI the
journal Ceramics-Silikaty, launching 1956 by RudolI
Barta. Vladimir Satava was its chieI editor within
the years 1957-1967. This period was also credited
with creating the Ioundations oI thermal analysis and
physical chemistry in general |29-31|. Satava inspired
his students and coworkers, cI. photo, by continuously
broaden his own scientifc interest in elucidating solid-
state reactions which subsequently fourished into
publication oI various thermoanalytical books |34-39|.
Equally important was the introduction oI 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 oI 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 Iollowed by well cited Czechoslovak books
|31-38|. Solid grounds oI DTA were accomplished in
1976 by the consistent theory made up by Holba and
Sestak and published in Ceramics-Silikaty |135, 136|.
Fundamental contributions already appeared in the frst
issues oI the journal Silikaty, UnIortunately, they did
not get into a wider attention oI international public due
to the Czech language,. Nevertheless the Czech journal
Figure 2. Vladimir Satava between his Iormer students (gra-
duating VSChT in 1962 under his supervision) Jaroslav Sestak
(leIt) and Pavel Holba (right) when celebrating his 89
th
birthday.
C:echoslovak footprints in the development of methods of thermometrv, calorimetrv and thermal analvsis
Ceramics Silikaty 56 (2) 159-167 (2012) 163
Ceramics-Silikaty as well as its sister`s Chemicke Listy
and Czechoslovak Journal oI Physics has remained
important domestic as well as international sources
and platIorm oI many original ideas and we should be
thankIul to the eIIort oI their originators as well as their
current editors.
ReIerences
1. Sestak J., Mares J. J.: From caloric to statmograph and
polarographv; J. Thermal Anal. Calor. 88, 763 (2007).
2. Sestak J., Mares J. J., Hubik P.: Historical roots and
development of thermal analvsis and calorimetrv; chapter
21 in the book Glassv, amorphous and nano-crvstalline
materials, Sestak J., Mares J. J., Hubik P. (edts), Springer,
Berlin 2011, pp. 347-370 (ISBN 978-90-481-2881-5).
3. Roberts-Austen W. C.: Fifth report to the allovs research;
Nature 59, 566-567 (1899); and Proc. Inst. Mech. Eng. 35
(1899).
4. Stanfeld A.: On some improvements in the Roberts-
Austen recording pvrometer, with notes on thermo-electric
pvrometrv, Phil. Mag. 46, 59 (1898).
5. Kurnakov N. S.: Eine neue Form des Registrierpvrometers,
Z. anorg. Chemie 42, 184 (1904).
6. Tammann G.: ber die Anwendung der Thermische
Analvsen in abnormen Fllen, Z. anorg. Chem. 45,
24 (1905) and: ber die Anwendung der Thermische
Analvsen III,. Z. anorg. Chem. 45, 289 (1905).
7. Strouhal C.: Thermika; JCMF, Praha 1908.
8. Sestak J., Proks I., Satava V., Habersberger K., Brandstetr
J., Korab O., Pekarek V., Rosicky J., Vanis M., Velisek
J.: Historv of thermal analvsis on the territorv of former
C:echoslovakia, Thermochim. Acta 100, 255 (1986).
9. Kallauner O., Matjka J.: Beitrag :u der rationellen
Analvse, Sprechsaal 47, 423 (1914).
10. Matjka J.: Chemical changes of kaolinite on hring;
Chemicke listy 13, 164 (1919); and 182 (1919)
11. Matjka J.: Thermal analvsis as a tool for determination
of kaolinite in soils, Chem. Listy 16, 8 (1922).
12. Skramovsky S.: Apparatus for automatic registration of
dehvdration at rising temperature, Chemicke listy 26,
521 (1932).
13. Duval C.: Inorganic Thermogravimetric Aanalvsis, Else-
vier, Amsterdam 1953.
14. Swietoslawski W.: Microcalorimetrv, Reinhold, New
York 1946.
15. Vold M. J.: Differential thermal analvsis, Anal. Chem. 21,
683 (1949).
16. Berg L. G.: Cropocmuo ro.u:ecmeeuui qasoei
aua.us, (Rapid Quantitative Phase Analysis), Akad.
Nauk, Moscow 1952.
17. Boersma S. L.: A theorv of DTA and new methods of
measurement and interpretation; J. Amer. Cer. Soc. 38,
281 (1955).
18. Paulik F., Paulik J., Erdey, L.: Der Derivatograph; Z.
anal. Chem. 160, 241 (1958); and: Derivatographie,
Bergakademie 12, 413 (1960).
19. Barta R., Satava V.: DTA as a quick control and
investigative method in chemical industrv, Chem. prum.
3,113 (1953).
20. Satava V.: Signihcance of DTA in the industrv of cements,
Stavivo 31, 15 (1953).
21. Barta R.: International directions for thermal analvsis;
Chem. Listy 62, 454 (1968).
22. Satava V.: Rudolf Barta-Obituari, Silikaty 29, 289
(1985).
23. Mackenzie R. C. (ed.): The differential thermal
investigation of clavs, Mineral. Society, London 1957.
24. Lombardi G., Sestak J.: Ten vears since Robert C.
Macken:ies death. a tribute to the ICTA founder; J.
Thermal Anal. Calor. 105, 783 (2011).
25. Currell B. R.: Thermal Analvsis, Science 13, 765 (1965).
26. Elias M., Stovik M., Zahradnik L.: Diferencni termicka
analv:a, (DiIIerential Thermal Analysis), AVCR, Praha
1957.
27. Satava V.: Documentation on thermal analvsis; Silikaty 1,
240 (1957).
28. Satava V.: Utili:ation of thermographic methods for
studving reaction kinetics; Silikaty 5, 68 (1961).
29. Satava V.: Uvod do fv:ikalni chemie silikatu, (Introduction
to Physical Chemistry oI Silicates), SNTL, Praha 1965.
30. Satava V.: Fv:ikalni chemie heterogennich soustav -
:akladv klasicke a statisticke termodvnamikv, (Physical
chemistry oI heterogeneous systems Ioundation
oI classical and statistical thermodynamics), SNTL,
Praha 1977 and: Fv:ika pevnvch latek, (Solid state
physics), SNTL 1979 and: Fv:ikalni chemie silikatu na
ba:i racionalni termodvnamikv, (Physical chemistry
oI silicates based on rational thermodynamics), SNTL
1981 and: Fv:ikalni chemie silikatu kinetika, (Physical
chemistry oI silicates kinetics), SNTL 1982.
31. Sestak J., Satava V., Wendlandt W. W.: The Studv
of Heterogeneous Processes bv Thermal Analvsis;
Monography as a special issue oI Thermochimica Acta 7,
333 (1973).
32. Sestak J.: Mreni termofv:ikalnich vlastnosti pevnvch
latek. teoreticka termicka analv:a, Akademia, Praha 1982
and English translation: Thermophvsical Properties of
Solid. theoretical thermal analvsis; Elsevier Amsterdam
1984 and: Russian translation Mir, Moscow 1988.
33. Holba P.: Thermodvnamics and ceramic svstems; chapter
1 in book Structure and Properties of Ceramic Materials,
(A. Koller, ed.). Elsevier, Amsterdam 1994, pp. 17-113.
34. Sestak J.: Science of Heat and Thermophvsical Studies.
a Generali:ed Approach to Thermal Analvsis, Elsevier,
Amsterdam 2005.
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