-
Contents of the section: Citation records and selection of
useful citations CITATION RECORDS AND SOME FORGOTTEN ANNIVERSARIES
IN THERMAL ANALYSIS Jaroslav Šesták J Thermal Anal Calor, 2012;
109: 1-5 TEN YEARS SINCE ROBERT C. MACKENZIE’S DEATH. A TRIBUTE TO
THE ICTA FOUNDER Gianni Lombardi , Jaroslav Šesták Journal of
Thermal Analysis and Calorimetry, Vol. 105 (2011) 783-701 PREFACE
FOR THE BOOK „THERMAL ANALYSIS OF MICRO-, NANO- AMD NONCRYSTALLINE
MATERIALS“ Jaroslav Šesták Springer 2013, ISBN 978-90-481-3149-5.
IMAPACT OF CZECH AND SLOVAK THERMOANALYSTS TOWARD THE EARLY
PROMOTION OF THERMOMETRY, CALORIMETRY AND THERMAL PHYSICS Jaroslav
Šesták, Pavel Holba International calorimetry seminary in Harrachov
2012, proceedings by Pardubice University 2012 DISTINCTIVE
ANNIVERSARIES, PAPERS AND CITATION RECORDS IN THE TOPIC OF GLASS
CRYSTALLIZATION Jaroslav Šesták, Sklář a keramik 11–12 / 2011 – 265
(published in Prague)
DATABASES IN MATERIALS SCIENCE: CONTEMPORARY STATE AND
FUTURE
J. Fiala and J. Šesták Journal of Thermal Analysis and
Calorimetry 60 (2000) 1101-1110.
-
Citation records and some forgotten anniversaries in
thermalanalysis
Jaroslav Šesták
Received: 29 April 2011 / Accepted: 2 May 2011
� Akadémiai Kiadó, Budapest, Hungary 2011
Abstract Extent of citation is analysed and the best citied
papers mentioned accentuating Journal of Thermal analysis
and Thermochimica Acta. The relevant scope of papers is
uncovered and some viewpoints are shown. The sphere of
kinetics appears the most cited subject matter.
Keywords Impact factor � Quotation responses � Bestcited papers
� Thermoanalytical journals � Kinetics
Preface
Ten years ago we published an assay describing the storage
and citation manners utilized in the sphere of scientific
literature [1] noting if the aim of science is pursuit of
truth,
then the pursuit of information may even drive people from
science. In 1978, American E. Garfield became a founder
of the Institute for Scientific Information (ISI) and insti-
gated an associated launching the citation and co-citation
(‘scientometric’) databasing. Since that the demand for a
more extensive data dissemination accelerated because
most scientific evaluations account on ‘publicability’,
which is rated according to the so-called journals’ impact
factors (IF) and the authors’ citation feedback (respon-
siveness).1 Specific databases have been established and
the available records are attentively followed to provide
basis for a more unprejudiced scientific appraisal though
the absolutely objective assessment is yet unreachable.
Most common is the ISI Web of Science (WOS) which is
standard in providing easy accessible data on a searched
journal, paper, and/or author yielding figures on the total
citation and annual citation record as well as partial data
on
the yearly mean responsiveness (including IF and
H-index). However, for older data (\1972) WOS
requestsapplication of a more specific search. In addition there
is
another database SCOPUS which needs somehow more
concern in the process of searching and is mostly preferred
when exploring more recant data ([1990). SCOPUS wasfactually
used for finding the theme citation responsiveness
in the sisters’ journal [2]. For the below ascertainment of
citation responses we used a caring service of the Docu-
mentation Department of the Prague Institute of Physics
and its well-established links to various databases giving,
nevertheless, the preference to the certificated WOS (tun-
ing disqualification of so-called self-citations).
Written on the occasion of the April 2011 death of Joseph H
Flynn, a
great pioneer in the field of nonisothermal kinetics, to whom
this
paper is dedicated.
J. Šesták (&)New Technology—Research Centre in the
Westbohemian
Region, West Bohemian University, Universitnı́ 8, 30114
Pilsen,
Czech Republic
e-mail: [email protected]
1 Journal IF is from Journal Citation Report (JCR), being a
product
of Thomson ISI providing thus quantitative tools for
evaluating
journals. The IF is a measure of the frequency with which the
so
called ‘average article’ in a given journal has been cited
within an
agreed period of time (a three-year interval). Thus, IF can
be
considered to be the average number of times published papers
are
cited up to 2 years after publication (and in the below account
we
show the contemporary last year IF). The newly introduced
H-index
(by American physicists J. Hirsch at 2005) is used to measure
the
productivity of an individual (or group or institution) and is
calculated
by taking into account the balance between the number of
publica-
tions and the number of citations per publication. For example,
the
author’s H-index of 22 tells us that he has 22 publications
which
received 22 citations on each paper or more. One can trace a
certain
regularity that the larger number of a paper co-authors often
generate
improved IF increasing subsequently H-index so that the single
and
double authored papers are herewith more respected.
123
J Therm Anal Calorim
DOI 10.1007/s10973-011-1625-3
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In the contribution we also took in account that in the
meantime some anniversaries have taken place occurring
roughly within similar years such as was the foundation of
two thermoanalytical periodicals, i.e., Journal of Thermal
Analysis and Calorimetry (JTA-1969, JTAC-1998) and
Thermochimica Acta (TCA-1970) as well as the institu-
tionalization of thermoanalytical confederation (ICTA-
1968 and ICTAC-1994) [3–5]. Similar anniversaries are
associated with the two most highly cited papers [6, 7]
published in the respective journal which are the basis of
following citation analysis and theme correlativeness. As a
matter of curiosity the most best cited papers were related
to the topic of reaction kinetics studied by means of ther-
mal analysis.
Some tangible data and comparisons
For the JTAC (IF = 1.59) the outmost quotation reveals
the paper by T. Ozawa [7] with as many as 1,053 citations,
which is comparable with his other papers in the Bulletin of
Chemical Society of Japan (IF = 1.63) [8] with 2096
citations or in Polymer (IF = 3.57) [9] with 1,097 cita-
tions. This is still far below the responses to the famous
kinetic paper by H. E. Kissinger [10] with as many as 4,461
citations or M. Avrami [11] with 5223 citations published,
respectively, in the renowned Analytical Chemistry
(IF = 5.63) and Journal of Chemical Physics (IF = 3.1).
The kinetic theme is followed in JTAC by the second best
cited paper [12] with 444 citations, which is one of hun-
dreds papers modifying the Kissinger method (e.g., [13]).
Only the third position keeps the paper from a different
area of novel techniques [14] with 301 citations (becoming
widely functional, e.g., [15]), but encompassing only third
time of its comparable quotation existence. Certainly we
should not forget another in that time inventive instru-
mental paper by the brothers F. Paulik (1922–2005) and J.
Paulik (1927–1988) [16] with 151 citations.
These citation figures are comparable with the output of
TCA (IF = 1.74), namely with the so-called SB equation
[6] exhibiting uppermost 562 responses followed by
methodically oriented papers on thermoporometry [17]
with 345 citations which is comparable with papers [18]
and [19] with 530 and 626 citations, respectively. The third
TCA place holds modulated DSC [20] with 336 citations
(see also [15] with 231 citations) authored by B. Wun-
derlich (1932-), who is one of the most influential authors
in wide spectrum of interests mostly within amorphous
polymers (e.g. [21] with 317 citations). His total record of
*16000 citations and H-index *67 is comparable withanother
American glass-physicists C.A. Angel (1933-) with
*21000 citations and H-index *80.
The above two kinetic-like feedbacks [6, 7] correlate, for
example, with the quotation of the widespread Jander dif-
fusion equation [22] from Zeitschrift für anorg, Chemie
(IF = 1.23) revealing 550 citations. It follows that the
best
cited kinetic-oriented articles [6–9, 12] have formed a rea-
sonable basis for creation of certain kinetic school within
the
field of thermal analysis as showed in respective journals,
e.g., JTAC [23–28] and TCA [29–33] (cited *1009 andassociated
with high H-factors). Moreover it reveals that
Takeo Ozawa (1932-) is likely the best cited personality
within the field of thermal analysis kinetics (when also
accounting his wide-ranging activity in material sciences,
providing his total citation record approaching ten thou-
sand). Certainly the above figures should be correlated to
the
time lapse since the paper publication (i.e., early papers
published before 1985) as well as with the number of overall
publications, i.e., JTAC-5769 and TCA-21557 and partici-
pation of kinetic oriented articles (JTAC-1248 and TCA-
1838) as well as with the mutual impact factors.
Nonetheless,
the entire IF values do not seemingly play a more
significant
function in the inherent papers’ responsiveness.
For a comparison we can adopt data from another
journal with a matching impact factor (IF = 1.43) and
overall number of publications (17,043), which is the
Journal of Non-crystalline Solids. This JNCS has also been
subjecting lot of data related to reaction kinetics (equiva-
lent portion 1033), namely to the thermal processes on
nucleation and crystal growth. Here, however, the best
cited paper authored by famous N. F. Mott (1906–1995)
[34] was related to glass conductivity with 1,396 citations
followed by structural studies [35] with 602 citations and
only the third paper was related to the study of thermal
properties [36] with 593 citations. This again is comparable
with the early findings by the Czech-American author J.
Tauc (1922-2010) [37] related to the structural subject of
optical band in tetrahedral semiconductors being again one
of the best cited papers of Physica Status Solids
(IF = 1.15) with 1375 citations. Thermal conductivity
oriented papers [34] were also revealed in the thematically
related journal Physics and Chemistry of Glasses
(IF = 0.58) such as the best cited papers [38, 39] with 771
and 582 citations, respectively. This PCG provided, how-
ever, highly cited papers on crystallization kinetics, for
example [40–43] with 291, 243, 199, and 155 citations,
respectively as well as similarly related papers in JNCS
[13, 44–46] with 231, 288, 417, and 445 citations,
respectively. Temperature plaid a specific role in the best
cited articles in Journal of American Ceramic Society
(IF = 1.94) with the historical record by the paper on
viscosity [47] by Fulcher (1884–1959) exhibiting as many
as 1,798 citations. In JACS there are worth noting ther-
moanalytically influential papers [48, 49] with 609 and 109
citations, respectively.
J. Šesták
123
-
Thermal analysis became also the topic for utmost
quotations in some leading national journals such the
Czechoslovak Journal of Physics (IF = 0.57) exhibiting
another record of 372 citations for the paper by A. Hrubý
(1919-) [50] who applied characteristic temperatures
determined by DTA for the specification of glass-forming
capability of various materials. Curiously, this criterion
was subjected to various modification (e.g. [51]) showing,
however, their fewer correctness than the original form
[50]. J. Šesták (1938-) [52] analyzed various methods of
kinetic data evaluation in another local Czech journal Sil-
ikaty-Ceramics (IF = 0.66) which received another his-
torical citation record of 61 responses and befall the basis
of the consequent paper [6] becoming thus the target of
various evaluations [28–32]. Another paper by M.
C. Weinberg (1941–2002) [53] published in the Serbian
Journal of Mining and Metallurgy (IF = 0.55) was dealing
with transient nucleation and its overlapping with growth
curves and exhibited maximum of 27 citations.
There are some other journals that cared to publish
papers on thermoanalytical kinetics, such as in Talanta [54]
(IF = 3.29 with 119 citations), Solid State Ionics [55]
(IF = 2.16 with 141 citations), Journal of Computational
Chemistry [56] (IF = 3.77, with 263 citations], Annual
Review of Physical Chemistry [57] (IF = 17.4 with 158
citations), Nature [58] (IF = 34.48 with 161 citations),
Science [59] (IF = 29.7 with 479 citations), Acta Metal-
lurgica [60] with 471 citations) and historically famous
paper by J. H. Flynn (1922–2011) in Journal of Research of
the National Bureau of Standards [61] (with 769 citations).
In order to have a comparison with other level of citation
responses while completing this overview on the best cited
papers we include some selected journals of a related
scope, for example [62] (IF = 0.69), [63] (IF = 0.7), [64]
(IF = 1.97), [65] (IF = 1.77), [66] (IF = 1.23), [67] (IF =
1.62), [68] (IF = 0.8), [69] (IF = 1.63) [70] (IF = 2.34)
and [71] (IF = 4.39) with 319, 136, 397, 180, 274, 323, 785,
317, 571 and 243 citations, respectively.
Such citation records would be unthinkable without the
diligent exertion of the editors-in-chief of
thermoanalytical
journals, being sorry that the society has somehow forgotten
their anniversaries. The originator and long-lasting editor
of
Thermochimica Acta, W. W. Wendlandt (1927–2000) [72],
the founder of the European Symposia on Thermal Analysis
and Calorimetry and associated proceeding books ‘‘Thermal
Analysis’’, D. Dollimore (1927–2000) as well as the early
thermoanalytical ground-worker P. D. Garn (1920–1999)
[73] are worth of a particular noting. They and many others
[5] also contributed good reputation of the Journal of
Thermal Analysis orchestrated by its lifelong editor Judit
Simon (1937-). Alternatively, we did not care to seek the
extreme number of citations (e.g., [74] with as many as
30,606 citations) as well as we did not try to enumerate all
doyens of reaction kinetics (such as V. Šatava,1922-, C.
Várhelyi, 1925-, Z. Adonyi, 1926-, V. V. Boldyrev, 1927-,
H. Suga, 1930-, B. V. L’vov, L. Stoch, 1931-, E. Segal,
1932-, E. Koch, J. R. MacCallum, R. K. Agrawal, A.
K. Galway, or J. Pysiak, 1933-). However, special compli-
ments are due to the middle age generation of thermoana-
lysts who achieved the captivating level of 200 citation per
a
single paper published not more than 20 years ago (e.g., A.
K. Burnham (USA), 1951- [71] (3,696 citations, Hindex =
31), M. Reading (UK), 1956- [15] (2,314 citations, H-index
= 24), J. Málek (Czechia), 1959- [32] (2,166 citations,
Hindex = 25), S. Vyazovkin (USA), 1960- [56] (4,350
citations, H-index = 35) or forthcoming N. Koga (Japan),
1963- [30] (*1000 citations, H-index *17).Curiously one of
highly quoted paper [45] dealing with
the application of nonisothermal kinetics to crystallization
(priced by as many as 417 citations] is unfortunately
revealing a misinterpretation toward the dominant respon-
sibility of partial derivatives of rate equation and
resultant
kinetic constitutiveness (already beforehand discussed
comprehensively in JTAC [75]). Article’s rightness would
also generate a question what would be a best approach in
achieving a highest citation response. Even assuming a
well-done manuscript matching passable for referees it, in
many cases, becomes sensitive to various unwritten factors
(such as interior rules, mutual reverence between the
authors and referees, instantaneous actuality and perspec-
tives of the subject, its impact and understandability,
etc.).
In most journals there is a large excess of manuscripts
supply over their demand, which is far overcoming the
journals’ capability to absorb all what is offered so that
some genius ideas may be overlooked. Publication boom is
driven by the pressure on the authors to publish as much as
possible in order to survive the competition due to assorted
financing. A possibility is presumed as to create an alter-
native publication forum for (often refused) articles in,
e.g.,
framework of internet, which might be likewise to a curi-
ous state of the so-called dissident physics. This unusual
forum for distributing physical theories often impassable
for publication in the regular journals (most common
‘Physica’) are consequently publishable on internet and
even printed in a somehow unofficial journal such as A-
peiron, Galilean Electrodynamics, Tired Light, Physics
Assays, etc.
It again calls attention in the direction of the most
attractive topics within the frame of thermal analysis,
which besides kinetics [76] may be novel, but already well-
developing special techniques [14, 15, 20]. Though diffi-
cult to predict, we can meet on the road toward new
interdisciplinary targets and thus across-boundary issues
somewhat inquisitive new endeavors such as thermal
quantum diffusion [77, 78] or alternative caloric-based
innovative thermodynamics [79, 80] which, however, not
Citation records and some forgotten anniversaries
123
-
yet digested are used not to bring any citation responses so
far. In this light we may be thankful to the journals
editors
to challenge the publications of special journal issues to
exclusively devoted to the burning themes such boundless
topic of thermoanalytical studies of glass crystallization
[81, 82] or the book series made available by publication
house Springer, such as the hot topics in thermal analysis
(edited by J. Simon) [83, 84].
The above reviewed papers represent, however, a neg-
ligible portion of overall published papers in the field of
thermal analysis, which in its broader view covers other
thermophysical measurements (such as conductivity [34,
38, 39], viscosity [47, 49], and relaxation [36]) so that
this
short communication should be merely accepted as brief
data revelation approached under a certain personal rec-
ollection and vision for better thermal science [85].
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.
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Citation records and some forgotten anniversaries
123
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Ten years since Robert C. Mackenzie’s death. A tributeto the
ICTA founder
Gianni Lombardi • Jaroslav Šesták
ESTAC2010 Conference Special Issue
� Akadémiai Kiadó, Budapest, Hungary 2010
Abstract Dr. Robert Cameron Mackenzie was an emi-
nent scientist who gave a major contribution to the progress
of science in the fields of thermal analysis and clay min-
erals. He was a leading figure in the East–West cooperation
at times when these relations were politically very
difficult.
The authors give an outline of his achievements and some
personal recollections of his activity.
Keywords Thermal analysis � Clay minerals � ICTA �DTA
‘‘whoever desires to build a future may not neglect the past’’
[1].
Fig. 1
Introduction
Robert Cameron Mackenzie was a pioneer in establishing
thermal analysis as a novel and accepted technique applied
to a wide array of materials in many different areas [1–4].
He was a leader in the establishment of the ICTA organi-
zation and always upfront in its development. He was also
internationally recognized as an outstanding figure in the
clay minerals world.
Shortly after his passing away in 2000, obituaries
describing his activity were published [5, 6]. The authors
of
this tribute are two old friends of him, who are thankful
for
all what they learnt from his example and scientific per-
sonality and who wish to remind the young generations of
thermoanalysts of his achievements, of his former co-
workers and of some less-known aspects of his life (Fig. 2).
Robert and the world of clay minerals
His impact on thermal analysis is well known, but it should
be stressed that he also gave a substantial contribution to
the international clay minerals community. Robert’s
investigations in the 1950s dealt with the pre-treatments
and thermal behaviour of clays and their products [7–14].
He applied what was then an uncommon technique, Dif-
ferential thermal analysis (DTA), and X-ray diffraction
(XRD) in the study of dehydration and rehydration of
thermally treated raw materials, sesquioxides and amor-
phous components. He was a groundbreaker in the inves-
tigation of the effect of temperature on water adsorption by
organo-clays (e.g. ethylene glycol complexes with mont-
morillonite or saponite). He also worked on thermo-
chemical reactions of clay minerals with other components
(e.g. clays with carbonates), while cooperating with B.
D. Mitchell, R. Glentworth (a first-class agricultural sur-
veyor in NE Scotland) and A. A. Milne.
Robert was very good at instrumentation and, for his
laboratory, he built a DTA apparatus working under con-
trolled atmosphere [15]. He applied this technique to the
G. Lombardi (&)Former Sapienza Università di Roma, Via D.
Chelini 5,
00197 Rome, Italy
e-mail: [email protected]
J. Šesták
New Technology—Research Centre in the West Bohemian
Region, West Bohemian University, Universitnı́ 8,
30114 Pilsen, Czech Republic
e-mail: [email protected]
J. Šesták
Institute of Physics, Cukrovarnicka 10, 16200 Praha,
Czech Republic
123
J Therm Anal Calorim (2011) 105:783–791
DOI 10.1007/s10973-010-1215-9
-
study of soils, where the organic matter is so closely bound
to the clay fraction that it is hard to separate them com-
pletely and with simple methods. He also used an oxygen
flow to study oxidation and combustion reactions and this
method became applicable to a much broader range of
materials. In 1959, he described his apparatus in a paper,
which inspired further instrumental developments in sev-
eral countries [16–18]. Later, it was commercially pro-
duced and used in many British laboratories.
The results of Robert’s leading-edge mineralogical
investigations were the source for significant papers and
stimulated the publication (in 1957, when he was only in
his 30s) of ‘The differential thermal investigation of
clays’
[19]. Robert wrote three of the 17 chapters of the book:
‘Thermal methods’, ‘Apparatus and technique for differ-
ential thermal analysis’ (jointly with B. D. Mitchell) and
‘The oxides of iron, aluminium and manganese’. Despite
its age, the book is still used all over the world by clay
mineralogists.
Robert not only opened new ground in thermal evalua-
tion of clays, but also stands as a maestro in cooperating
with and providing guidance to many foreign scientists,
who attended his Macaulay Institute for Soil Research to
learn and make progress in the field of clays and thermal
analysis, among them, G. Berggrenn from Sweden, S.
Yariv from Israel, S. Warne from Australia, N. Yoshinaga
from Japan, G. Lombardi, N. Morandi and A. Negro from
Italy.
In the 1950s, supported by his knowledge of Russian
and German, Robert became aware of the progress made in
the eastern countries in the field of clay mineralogy and
thermal analysis. He knew the work of Prague O. Kallauner
and J. Matějka [20, 21], who conducted an extensive
investigation on kaolinite transformations under heating.
Their study was influenced by the results of the French H.
Le Chatelier and their interactions with K. Friedrich and B.
Wohlin (Polish Royal Technical University of Wroclaw),
who were investigating the thermal behaviour of bauxitic
soils and also built their own apparatus for thermal
analysis.
In the early 1960s, contacts between western and eastern
scientists were impaired by restrictions not only on travel,
but also on correspondence and telephones. Nevertheless,
Robert managed to keep in touch with Prague R. Bárta and
Polish clay scientists such as A. Kuźniarowa. In 1961,
Robert was invited to give a lecture at the Prague Geology
Conference and awarded with the distinguished Centenary
Medal of the historical Charles University. Then, in 1983,
he received the Emanuel Boricky Medal from the Faculty
of Science of the Charles University during one of the
meetings of the European Clay Groups.
Robert’s work on clays was well known at international
scale. He was instrumental in the organisation of AIPEA
(Association Internationale pour l’Étude des Argiles), its
President in 1980–1984 and founder of the Clay Mineral
Bulletin (today named Clay minerals, the Journal of the
European Clay Society). In 1972, he was elected Chairman
of the British Clay Minerals Group and, in 1983, he was
appointed Distinguished Member. In 1978, he was the
convenor of the scientific committee for the 1978 Sixth
International Clay Conference and in 1987 Honorary
Member of the Sociedad Española de Arcillas.
Fig. 2 Personalities with whom Robert (first from the left)
collaborated in various areas: Canadian H. G. Mc Adie, Scottish B.
D. Mitchell,Swedish G. Berggrenn, English J. P. Redfern, Hungarians
L. Erdey and G. Liptay and Czechoslovak I. Proks
Fig. 1 *Geologist Gianni Lombardi and thermodynamist
JaroslavŠesták were Robert’s friends until his last days. They
have similar
stories in ICTA. Lombardi (*1939), early member of ICTA (1965),
of its
Standardization Committee (1968–1976), of the editorial board of
J.
Thermal Analysis (1969) and of Thermal Analysis Abstracts
(1970);
ICTA Council (1968–1971), Secretary (1971–1977), Vice and
President
(1977–1982); Editor ‘For Better TA’ (1977–1980); ICTA Award
(1980);
discontinued ICTA 1985. Šesták (*1938), groundwork for ICTA
(1965),
co-founder of Thermochimica Acta (1970), ICTA
Councillor-at-large
(1977–1982), member of ICTA Nomenclature and Kinetic
Committees
and the chair of Advanced Inorganic Materials (1984–1996),
ICTA
Program Chairman (Bratislava 1985), ICTA Award (1992),
Affiliated
Councillor (1992–2000), discontinued ICTAC 2006
784 G. Lombardi, J. Šesták
123
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Impact on thermal analysis
In the early 1960s, many western and eastern laboratories
used thermal methods for the analysis of both inorganic
and organic materials. Based on his international contacts
and on the experience gained with the 1957 book on DTA
of clays, Robert thought that it would be a great scientific
advance if investigators in many fields of thermal analysis
could share their experiences within the framework of a
multidisciplinary society. His foresight gave birth to ICTA.
Robert was in contact with thermoanalysts L. Erdey and
the Paulik brothers in Budapest, the Russian L. G. Berg, the
Polish W. Świętosławski and Czech R. Bárta of the Prague
Institute of Chemical Technology. Already in the early
1950s, Bárta had organised conferences on thermal anal-
ysis, namely Thermography discussions (Prague 1955), the
first Thermography day (Prague 1956) and the second
conference on Thermography (Prague 1958). After that,
Robert was an invited speaker at the 1961 third conference
on thermal analysis. He was impressed by the quantity and
quality of the results presented at the meetings and got to
know the work of Bárta’s co-workers, e.g. V. Šatava, S.
Procházka, I. Proks and postgraduate student J. Šesták.
He
also co-authored Bárta’s obituary [22].
In the early 1960s, Robert visited the United States and
his friend C. B. Murphy (an internationally renowned
personality in the field of thermal analysis [23]) encour-
aged him to organise a large-scale international conference
on thermal analysis. Robert began to work on the project,
assisted by the Russian L. G. Berg, author of two books on
thermal analysis [24, 25], the Hungarian L. Erdey, the
Czech R. Bárta, the Japanese T. Sudo, the Canadian H.
McAdie and the Swedish G. Berggrenn of Studsvik Ac-
tiobolaget Atomenergi (who suggested Sweden as the
venue of the first ICTA).
A first Symposium on thermal analysis with scientists
from various countries was held at the Northern Poly-
technic in London in April 1965. It was organized by B.
R. Currell and participants included R. C. Mackenzie, the
British D. A. Smith, J. P. Redfern, W. Gerrard, P. D. Garn
[26] and W. W. Wendlandt [27] from the US, as well as the
Swedish G. Berggrenn. F. Paulik from Hungary and J.
Šesták from Czechoslovakia were invited to give plenary
lectures, a way to introduce eastern scientists to the
inter-
national scientific community. The program is a witness of
the state of the art of the instrumentation and applications
of thermal analysis (Fig. 3).
Soon after there followed a great success. Robert, J.
P. Redfern and B. D. Mitchell undertook the organisation
of the first International Conference on Thermal Analysis,
which was held in Scotland, at Aberdeen, in September
1965 [28] (the registration fees was as low as 15 US $!).
Almost 3,000 copies of the First Announcement were
distributed, with a final attendance of 300 scientists from
29 countries, including Czechoslovakia, Hungary, Poland
and USSR.
Robert’s merits for the subsequent creation and further
development of ICTA are invaluable. The Aberdeen
meeting opened the way to the formal establishment of
ICTA in 1968 (Fig. 4), during the Business meeting held at
the second ICTA in Worcester, Massachussets (USA).
Several ICTAs followed at regular four-year intervals with
a large number of attendees and, beginning 1980, inter-
mediate European meetings (ESTAC), promoted by D.
D. Dollimore, were also held.
The authors would like to recall two anecdotes which
occurred 17 years apart, both with Robert’s involvement.
At the 1968 Worcester second ICTA, in the evening of 20
August, several delegates were watching the TV news.
Suddenly, images of Soviet armoured trucks invading
Prague appeared. The three Czech delegates R. Bárta, P.
Kralik and J. Šesták were shocked and furious. Šesták
attacked the Russian delegate E. I. Yarembash, who was
saying that the images were old ones, taken during the
1945 liberation. Robert had to use all his weight and
diplomacy to solve a very difficult situation, though
tension
pervaded the last days of the conference.
In 1985, the eight ICTA was held in Bratislava. The
participants were over 400 from 33 countries (and the
registration fee had already reached 200 US $). Robert was
invited to give a plenary lecture, together with the Slovak
I.
Proks, regarding the life of the Czech thinker Comenius
and the Scottish scientist Black, two precursors of thermal
analysis who lived between the sixteenth and seventeenth
century. He not only gave an important scientific contri-
bution, but also helped the conference acting chairman V.
Balek and scientific chairman J. Šesták to solve a
sensitive
political problem. The Czech police had refused the visa to
the ICTA Secretary, the Israeli S. Yariv, and to the South
African M. E. Brown, because of their ‘unfriendly’
nationality. US participants were ready to boycott the
Conference if the visa was not granted. The result of
Robert’s diplomatic efforts was that, for the first time in
many years, two citizens from the ‘hostile capitalist
countries’, Israel and South Africa, were allowed to visit
communist-ruled Czechoslovakia.
A rare case among the British, Robert had not only a
splendid command of English, but also reading and
speaking skills in Gaelic, French, Italian, Spanish, German
and Russian. In 1965, he made the introductory welcome to
the International Conference in Aberdeen in English and
Russian and, in the same way, he surprised the audience in
1985 with his acceptance speech for a USSR award
(Fig. 5).
He never became ICTA president, but until retirement
he remained a very active and influential member of ICTA
A tribute to the ICTA founder 785
123
-
and a basic point of reference for all Council and ordinary
members. Treasurer more than 15 years, he created a sound
financial basis for ICTA and gave a great scientific con-
tribution as chairman of the Nomenclature and member of
the Publication and Standardization Committees. From
1986 to 1997, he was editor of ICTA News.
Though not many were aware of it, the Scottish and Irish
‘mafia’ occupied the dominant ICTA positions for a long
period. In addition to the obvious Mackenzie and McAdie,
there were others (Fig. 6). Gallagher and Murphy were
members of well known Irish Clans and Lombardi has
solid roots in the Clan McGillivray (Fig. 9).
Robert’s major contribution to thermal analysis was
scientific, with over 100 papers and review articles [2], as
well as the editorship of three books, which stand as
milestones in their field. He was particularly concerned
with the improvement of thermoanalytical techniques and
theory and their wider applications. In later years, the
nomenclature and history of thermal analysis became his
main interests. In a fundamental paper of 1974 [1], he
summarised his ideas about the future development and the
classification of thermal analysis methods, a subject cov-
ered in other papers.
The first book that he edited, ‘The differential thermal
investigation of clays’, leads back to 1957 [19]. The second
was ‘A handbook on DTA’ in 1966 [29]. The two volumes
of his third book, ‘Differential Thermal Analysis’, were
published by Academic Press in 1970 and 1972 [30]. There
are 25 chapters and he is the author of four of them:
‘Simple phyllosilicates based on gibbsite- and brucite-like
sheets’, ‘Oxides and hydroxides of higher-valence ele-
ments’ (with G. Berggrren), ‘Basic principles and historical
development’ and ‘Instrumentation’ (with B. D. Mitchell).
The book still represents a bible on DTA applications,
dealing with different problems such as theory, experi-
ments, geosciences, nomenclature and history.
Fig. 3 The program of theLondon International
symposium on thermal analysis,
held in April 1965, the first
meeting on the subject with
scientists from western and
eastern Countries. On the left,
B. R. Currell, on the right P.
D. Garn
786 G. Lombardi, J. Šesták
123
-
He helped to improve the DTA theory [30–34] and his
fine usage of English, together with extreme care for
details
and forward-looking considerations, made him a prominent
figure in the nomenclature field. For many years, he was
the soul of the nomenclature activity of both AIPEA and
ICTA and strongly influenced the preparation of widely
accepted complex documents on the subject [e.g. 35–41].
He had the great merit of creating derived nomenclatures,
even in different languages [42, 43].
The vast knowledge of the field led him to devote the
last part of his scientific life to the many aspects of the
history of thermal analysis [44–50]. He is credited with
new findings on the impact of G. Martine as a very early
thermoanalyst, on the responsibility of J. Comenius in the
earliest use of the term ‘caloric’ and on the role of G.
A. Charpy in the development of electric furnaces. These
studies produced an excellent compendium of thermoana-
lytical history [45], a source for many subsequent studies.
He kept close contacts with the Slovak I. Proks from
Bratislava and inspired his work, which resulted into var-
ious papers on the history of thermodynamics [51–55].
With J. Šesták, he prepared an article on a
thermoanalytical
Fig. 4 The composition ofICTA Council in the first
12 years of its life. In the
photos, from the left: R.
C. Mackenzie, L. G. Berg, C.
B. Murphy, R. Bárta and H.
Kambe
Fig. 5 Bratislava 1985. Dr. Mackenzie receives the USSR
KurnakovMedal from the hands of Prof. V. B. Lazarev
A tribute to the ICTA founder 787
123
-
journey from prehistory to the third millennium; its com-
pletion was interrupted by his death, but anyhow it was
published in JTAC [56].
Robert was very much aware of the need to have an easy
access to the thermoanalytical data dispersed in the litera-
ture. As early as 1965, he collected and ordered the results
of
DTA of minerals and other substances and prepared a pun-
ched-card data index named SCIFAX, published by Cleaver-
Hume Press. The index was based on the temperatures of the
DTA peaks and with its help it was much easier to identify
the products obtained during the decomposition processes.
Jointly with J. P. Redfern, in 1972 he then started
Thermal Analysis Abstracts (TAA), a periodical with
abstracts of papers dealing with thermal analysis and cal-
orimetry prepared by a team of reviewers covering eastern
and western countries. There was a 25% contribution from
abstractors of periodicals from the eastern countries (Bul-
garia, Czechoslovakia, German Democratic Republic,
Hungary, Poland, Romania, USSR and Yugoslavia) and
their payment in foreign currency was a great help to them.
They could travel abroad to participate in conferences
organized by western countries, in times when scientists of
the countries behind the iron curtain could get only a very
limited amount of money in foreign currency. For all the
TAA life (1972–1991), the regional editor for eastern
European territories was G. Liptay, the author of the five-
volume Atlas of Thermal Analysis Curves [57]. After
20 years, TAA was stopped in 1991, due to the spread of
computers.
Robert contributed to the launching of the Journal of
Thermal Analysis (JTA), the first journal devoted to the
subject. It was started in 1969 with Judit Simon as editor
(still nowadays its editor-in-chief), under the supervision
of
the Hungarian Academy of Sciences (Académia Kiadó)
and the support of the F. and J. Paulik brothers, G. Liptay,
L. Erdey and E. Buzagh. Since the beginning, it had a truly
international editorial board and was published jointly with
the British Heyden and Son. It was a good example of
western–eastern countries cooperation in a difficult politi-
cal period. Soon after, in 1970, Elsevier put on the market
Thermochimica Acta (TCA), for a long time edited by W.
W. Wendlandt [58] assisted by a wide-ranging interna-
tional board including J. Šesták (Fig. 7).
Fig. 6 July 1977. ICTA executives at the fifth ICTA of
Kyoto(Japan). Upper row H. R. Oswald, P. K. Gallagher, H. G.
McAdie, S.St. J. Warne, J. P. Redfern, R. C. Mackenzie and F.
Paulik. Middlerow C. B. Murphy, S. Seki, W. D. Emmerich, G.
Lombardi and H.Kambe. Lower row P. D. Garn, Mrs. Kambe, Mrs.
Lombardi, Mrs.Murphy, Mrs. Warne and Mrs. Gallagher. In the long
period when
Robert was ICTA treasurer, Murphy and Gallagher (US with
Irish
roots), Canadian McAdie and Italian Lombardi (Scot roots)
were
elected ICTA Presidents
Fig. 7 The internationaleditorial board in the first years
of Journal of Thermal Analysis
and Thermochimica Acta.
Photos of W. W. Wendlandt and
J. Simon
788 G. Lombardi, J. Šesták
123
-
Many people are indebted to Robert for all what he
contributed to the many fields of thermal analysis. He also
received official recognitions for his activity, e.g.:
Fellow
of the Royal Society of Edinburgh (1961), Fellow of the
Royal Society of Chemistry (1961), Mettler NATAS
Award (1968), SAC Gold Medal Royal Society (1980),
Netzsch GEFTA Award (1982), ICTA/TA Award (1985),
NATAS Fellow (USA 1985), Kurnakov medal (USSR
1985) and First Honorary Member of ICTA (1988).
Some personal notes
Robert was born on 7 May 1920 from a family of farmers
living in the Portmahomack area, a lovely small village on
the eastern coast of Northern Scotland, beautifully pre-
served. He attended first the Tain Royal Academy and then
the Edinburgh University. In 1942, he obtained a B.Sc.
with First Class Honours in Chemistry and, in 1944, he
completed his Ph.D. thesis dealing with gas-phase reaction
kinetics. In the same year, he joined the Aberdeen
Macaulay Institute for Soil Research, where he remained
throughout his scientific life, becoming the head of the
Physical Chemistry Section and then of the Department of
Pedology, until his retirement in 1983.
In 1950, he married Hilda Bruce, a fellow member of
the Macaulay, and it was a very happy marriage. They were
always very close to each other, though she seldom trav-
elled with him to professional commitments. They had a
son, Bruce, now a retired reservoir engineer and consultant
in the oil industry, living in Edinburgh, and a daughter,
Morag, married with a farmer and living on a large estate
close to the Aberdeen airport with a son and a daughter
(Fig. 8).
He liked to travel and had many experiences abroad as
visiting professor, or for lectures and meetings. He was a
keen and fast driver and for many years, in the 1960s and
1970s, he used to drive his Bentley to Positano (southern
Italy) for a family holiday.
No better words can be used to describe his personality
than those in the obituary written by J. Wilson, a colleague
of him at the Macaulay [6]: ‘To many, he embodied the
very essence of the ‘‘English’’ gentleman (despite being a
true Highland Scot), unfailingly courteous and fair-minded,
but with a patrician demeanour which invested his lectures
and pronouncements with an aura of authority’.
The Macaulay was attended by visitors from all over the
world and Robert was always very, very polite, though
often shuddering at the quality of the English language
spoken by some foreigners. Many Italians worked at the
Macaulay with him and one of them (F. Palmieri) was sent
to the ceremony for his retirement. He handed him a set of
tiles (Fig. 9) with a dedication which well expresses the
feeling of the many Macaulay visitors:
On the occasion of the retirement of Dr. Robert C.
Mackenzie, the Italian visitors to the Macaulay
Institute for Soil Research present this plaque to
‘‘Mac’’, with heartfelt thanks for all what he con-
tributed to their professional background. We join all
those who admire his stature in the field of thermal
analysis, clay mineralogy and soil science, but we are
also very grateful for his interest in our scientific and
personal problems, that he shared with us throughout
the years and for his stoic patience in bearing with
Fig. 8 Dr. Mackenzie in a picture of August 1999 with his
daughter,grandchildren, G. Lombardi and his wife
Fig. 9 Handmade tiles given to Dr. Mackenzie on his retirement
bythe Italian visitors of the Macaulay and G. McGillivray Lombardi
(onthe right) at a 2009 party in Inverness
A tribute to the ICTA founder 789
123
-
our continuous murdering of the English language,
for which we publicly apologise. We went to the
Macaulay as young researchers, we have grown to
become Professors, but we will never forget the
stimulating periods of research and study we had in
lovely Aberdeen. Thanks Mac and arrivederci a pre-
sto. Gianni Lombardi, Noris Morandi, Alfredo Negro,
Francesco Palmieri, Pietro Violante, November 1983.
After leaving the Macaulay, Robert continued to work
and keep a keen interest in the history of thermal analysis,
maintaining pen contact with his many friends. Then, his
wife’s health declined and he patiently assisted her for
many difficult years, always in the same home in Aber-
deen, up to when she died in 1998.
Robert’s funeral was held in Aberdeen on a Monday, a
few days after his death in July 2000. There were his old
Macaulay colleagues and many friends of the family. One
of the authors (G. L.) was the only ICTA representative.
Together with the family, he went north to Portmahomack
and had the moving privilege to help him lie down in his
grave (Fig. 10). Still visiting Scotland every one or two
years, Gianni feels a duty to bring a flower to the grave,
on
behalf of his many friends and in memory of a gentleman
who gave so much to the world of science.
Acknowledgements The authors thank Brian Currell, Georgy
Lip-tay, Morag Mackenzie, Judit Simon and Shmuel Yariv for their
col-
laboration in preparing this article. The grant support in the
field of
geopolymers No FR-TI 1/335 is appreciated.
References
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J Therm Anal. 2000;62:595–7.
6. Wilson MJ. Obituary. Robert Cameron Mackenzie 1920–2000.
Clay Miner. 2000;35:859–60.
7. Mackenzie RC. Investigations on soil clays at the
Macaulay
Institute for Soil Research. Clay Miner Bull. 1947;1:8–9.
8. Mackenzie RC. DTA and its use in soil-clay mineralogy.
Geol
Fören Stockh. 1956;78:508–25.
9. Mackenzie RC, Milne AA. The effect of grinding on micas.
Clay
Miner Bull. 1953;2:57–62.
10. Mackenzie RC. Free iron-oxide removal from soils. J Soil
Sci.
1954;5:167–72.
11. Mackenzie RC. The thermal investigation of soil clays.
Agro-
chimica. 1956;1:1–22.
12. Mackenzie RC. Some unsolved problems in clay mineralogy.
Geol Fören Stockh. 1956;78:558–60.
13. Mackenzie RC. Modern methods for studying clays.
Agrochi-
mica. 1957;1:305–7.
14. Mackenzie RC. Hydration and hydroxylation with special
refer-
ence to montmorillonite. Geol Fören Stockh. 1957;79:58–60.
15. Mitchell BD, Mackenzie RC. An apparatus for differential
ther-
mal analysis under controlled atmosphere conditions. Clay
Miner
Bull. 1959;4:31–4.
16. Šesták J, Burda E, Holba P, Bergstein A. Apparatus for DTA
in
controlled atmospheres. Chemické listy. 1969;63:785.
17. Brown A, Šesták J, Kronberg A. Vertical tungsten furnace
for
thermal studies up to 2700 �C. Czech J Phys. 1973;A23:612.18.
Mackenzie RC. An early Swiss commercial instrument. Ther-
mochim Acta. 1985;85:251–4.
19. Mackenzie RC, editor. The differential thermal investigation
of
clays. London: Mineral Society; 1957.
20. Kallauner O, Matějka J. Beitrag zu der rationellen
analyse.
Sprechsaal. 1914;47:423.
21. Matějka J. Chemical changes of kaolinite on firing.
Chemické
listy 1919;13:164–166 and 182–185.
22. Šesták J, Mackenzie RC. Rudolf Bàrta (1897–1985). J
Therm
Anal. 1986;31:3–4.
23. Murphy CB. Thermal analysis progress. Anal Chem.
1958;30:867, 1960;32:168R, 1962;34:298R.
24. Berg LA. Introduction to thermography. Moscow: Nauka;
1964.
(in Russian).
25. Berg LA. Introduction to thermal analysis. Moscow: Akad
Nauk
USSR; 1961. (in Russian).
26. Garn PD. Thermoanalytical methods of investigation. New
York:
Academic Press; 1962.
27. Wendlandt WW. Thermal methods of analysis. New York:
Wiley; 1964.
28. Mackenzie RC. Origin and development of the
international
conference for thermal analysis (ICTA). J Therm Anal.
1993;40:5–28.
29. Mackenzie RC, editor. Handbook of DTA. New York:
Chemical
Publishing; 1966.
30. Mackenzie RC, editor. Differential thermal analysis.
London:
Academic Press, 1970 vol. 1, 1972 vol. 2.
31. Mackenzie RC. Differential Thermoanalyse und ihre
Anwendung
auf technische Stäube. Tonindustr Ztg. 1951;75:334–40.
32. Mackenzie RC, Farmer VC. Some notes on Arens’ theory of
differential thermal analysis. Clay Miner Bull.
1952;1:262–5.
33. Šesták J. Thermophysical properties of solids: theoretical
thermal
analysis. Amsterdam: Elsevier; 1984.
34. Šesták J. Těoretičeskij těrmičeskij analyz. Moscow:
Mir; 1988.
(in Russian).
Fig. 10 On the right Dr. Mackenzie’s family grave in the
cemeteryof the Portmahomack church and his tombstone
790 G. Lombardi, J. Šesták
123
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35. Mackenzie RC. Nomenclature in thermal analysis. In: Kolthoff
IM,
Elving PJ, Murphy CB, editors. Treatise on analytical
chemistry.
2nd ed. New York: Wiley 1983. Part I, vol. 12. p. 1–16.
36. Mackenzie RC, Keattch CJ, Hodgson AA, Redfern JE. Abbre-
viations in thermal analysis. Chem Ind. 1970;272–275.
37. Mackenzie RC. Recommendations for nomenclature in
thermal
analysis. In: Schwenker RE, Garn ED, editors. Thermal
analysis.
New York: Academic Press; 1969. p. 685–91.
38. Mackenzie RC. Nomenclature in thermal analysis. Talanta.
1969;
16:1227–30.
39. Mackenzie RC. How is an acceptable nomenclature system
achieved? J Thermal Anal. 1972;4:215–21.
40. Mackenzie RC. Nomenclature in thermal analysis. Part IV.
Thermochim Acta. 1979;28:1–6.
41. Mackenzie RC, et al. Nomenclature in thermal analysis. Part
V.
Symbols. Thermochim Acta. 1981;46:333–5.
42. Šesták J, Holba P, Fajnor V. Proposal of the
Czech-Slovak
nomenclature in thermal analysis. Chemické listy. 1983;77:
1292–308. (published under the supervision of RC Mackenzie).
43. Šesták J, Holba P, Fajnor V, Kuzniarová A, Logviněnko
VA,
Metlin JuG, Pelovský Y, Živkovič Z., Mackenzie RC.
Proposition
for English based thermoanalytical terminology in Bulgarian,
Czech, Polish, Russian, Serbian and Slovak languages. ICTA
report completed under the Slavic international cooperation.
44. Mackenzie RC. The story of the platimun-wounded electric
resistance furnace. Platinum Met Rev. 1982;26:175–83.
45. Mackenzie RC. De Calore: prelude to thermal analysis.
Ther-
mochim Acta. 1984;73:251–306.
46. Mackenzie RC. Origin and development of thermal
analysis.
Thermochim Acta. 1984;73:307–67.
47. Mackenzie RC, Proks I. Comenius and Black: progenitors
of
thermal analysis. Thermochim Acta. 1985;92:3–14.
48. Mackenzie RC. George Martine, M.D., F.R.S. (1700–1741):
an
early thermal analyst? J Thermal Anal. 1989;95:1823–36.
49. Mackenzie RC. Early thermometry and differential
thermometry.
Thermochim Acta. 1989;148:57–62.
50. Mackenzie RC. The first quarter century. J Thermal Anal.
1994;
42:295–9.
51. Šesták J. Some historical aspects of thermal analysis:
origins of
Termanal, CalCon and ICTA. In: Klein E, Smrčková E, Šimon
P,
editors. Proceedings of the International Conference on
Thermal
Analysis ‘‘Termanal’’. Bratislava: Publishing House of the
Slovak
Technical University; 2005. p. 3–11.
52. Proks I. Evaluation of the knowledge of phase equilibria.
In:
Chvoj Z, Šesták J, Třı́ska A, editors. Kinetic phase
diagrams.
Amsterdam: Elsevier; 1991. p. 1–53.
53. Proks I. Celok je jednoduššı́ než jeho části. (Whole is
simpler
than its parts). Bratislava: Publishing House of Slovak
Academy
of Sciences; 2010 (in Slovak).
54. Šesták J, Proks I, Šatava V, Habersberger K, Brandštetr
J, Koráb
O, Pekárek V, Rosický J, Vaniš M, Velı́šek J. The history
of
thermoanalytical and related methods in the territory of
present-
day Czechoslovakia. Thermochim Acta. 1986;100:255–70.
55. Šesták J, Hubı́k P, Mareš JJ. Historical roots and
development of
thermal analysis and calorimetry. In: Šesták J, Mareš JJ,
Hubı́k P,
editors. Glassy, amorphous and nano-crystalline materials.
Ber-
lin: Springer; 2011. p. 347–70.
56. Šesták J, Mackenzie RC. The heat/fire concept and its
journey
from prehistoric time into the third millennium. J Therm
Anal
Calorim. 2001;64:129–47.
57. Liptay G, editor. Atlas of thermoanalytical curves: (TG,
DTG,
DTA curves measured simultaneously). London, New York:
Heyden and Son; 1971.
58. Wendlandt WW. How Thermochmica Acta began: some recol-
lections. Thermochim Acta. 1981;50:1–5.
A tribute to the ICTA founder 791
123
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Jaroslav Šesták - Peter Šimon
Thermal analysis
of micro-, nano- and non-crystalline materials
Transformation, crystallization, kinetics and thermodynamics
Springer
-
Preface Nucleation, glass crystallization and nonisothermal
kinetics There are thousands of worth mentioning researches,
scientists and engineers who contributed to better understanding of
the glass science; we are able to present only some. Already in
1830 M. Faraday noted that “glass is a solution of different
substances one in another rather than a strong chemical compound”.
S. Arrhenius (1889) and then H. Eyring (1935) gave the requisite
meaning to the reaction rate constant. Among significant scientific
achievements worth mentioning are Griffith's theory of the strength
of brittle materials (1921) and X-ray diffraction analysis showing
the way for W.H. Zachariesen (1932) to consider his principles how
the nearest neighbor coordination was maintained without imposing
an exact long range order so far common for crystalline materials.
Not less important were studies pertaining to vitrification and
crystallization studies the inspiration of which can be found in
the early books by G. Tammann (States of Aggregation, 1925) or G.O.
Jones (Glass, 1956) and assorted fundamental research impacts by
e.g. D.H. Vogel, S. Fulcher, W. Kauzman, A.Q. Tool, E.A. DiMarzio,
D. Turnbull, W.E.S. Turner, J. Frenkel, R.O. Davis, H.A. Davies,
J.H. Gibbs , M. Cohen, R.W. Douglas, M. Cable, P. F. McMillan, C.A.
Angel, J.C. Fisher, J. Tauc, B.T. Kolomiets, N.F. Mott, A. Hruby,
L.L. Hench, N.J. Kreidl, H. Schaeffer, G. Frischat, J.C. Maxwell,
H. Rawson, R.S. Elliot, R. Roy, P.K. Gupta, J. E. Shelby, O.V.
Mazurin, E.A. Porai-Koshitz, S.V. Nemilov, G.P. Johari, W. Götze,
C.T. Moynihan, E. Donth, A.R. Cooper, G.N. Greaves, A.L. Greer,
K.F. Kelton, A. Feltz, D.R. Uhlmann, J.D. Mackenzie, R.E. Moore,
R.K. Brow, P.C. Schultz, E.N. Boulos, C.R. Kurkjan, C. Rüssel, R.H.
Doremus, F.I. Gutzow, I. Avramov, W. Vogel, J.C. Philips, C.G.
Pantano, C.A. Wright, M. Tatsumisago, F. Speapan, R. Conrat, A.
Inoue, P.K. Gupta, K. Hirao, D.E. Day, W. Höland, M. Poulain, P.F.
James, W.P.J. Schmelzer, B.P. Macedo, M.C. Weinberg, H. Suga, S.L.
Simon, B. Wunderlich, L.D. Pye, M.D. Ingraham, A.V. Tobolsky, K.J.
Rao, M.H. Fernandes, A.K. Varshneya, K.A. Jackson, W.A. Philips,
M.E. Glicksman, F.E. Luborski, J.H. Simmons and many others . It is
c1ear that a considerable amount of rapidly expanding data on
glass-formation as a result of enhanced understanding of (often
controlled) melt enhanced cooling and consequent re-crystallization
of glasses has required certain taxonomy leading to the early
foundation of specific journals and symposia. Associated
theoretical studies on nucleation, crystallization and crystal
growth have also escalated being viewed from both limiting sides:
on the one hand it was the solidification upon a slow
(self-cooling) of melts and on the other hand the purposefully
suppressed crystallization of quenched (freeze-in) melts. Thermal
analysis, particularly differential thermal analysis (DTA), became
effectively involved from the very beginning, simply
discriminating, e.g., bulk and surface nucleation by mere comparing
thermal behavior of the as-cast and subsequently powdered samples
(already R.L. Thakur in the 1960s). Some other fundamental and
complementary methods of thermal physics arrived at sophisticated
levels of research as was exposed in the previous volume entitled
“Glassy, amorphous and nanocrystalline materials: thermal physics,
analysis, structure and properties” published by Springer, 2011
(ISBN 978-90-481-2881-5 and DOI 10.1007/978-90-481-2882-2)
containing 21 chapters with 380 pp. The best theoretical endeavor,
however, was made in the field of oxide glasses where the
traditional symposia on advances in nucleation and crystal growth
were originally held every ten years resulting in the valuable
proceedings, beginning the early seventies by compendium "Advances
in nuc1eation and crystallization of glasses" edited by L.L. Hench
and S.W. Freiman and published by the American Ceramic Society
(Columbus, Ohio 1972) and followed by "Nuc1eation and
crystallization of glasses" edited by J.H. Simmons, D.R. Uhlmann
and G.H. Beall and published in "Advances of Ceramics" (Amer. Cer.
Soc.,
-
Columbus, Ohio 1982) as well as by "Nuc1eation and
crystallization in liquids and glasses" edited by M.C. Weinberg and
published in "Ceramic Transactions" (Amer. Cer. Soc., Westerville,
Ohio 1993) and finally by “Crystallization in glasses and liquids”
(the symposium in Vaduz, Liechtenstein 2000), edited by W. Höland,
M. Schweiger and V. Rheinberger and published in Glastech. Ber.
Glass. Sci. Tech. 73 C, 2000 (with 425 pp.). In this respect, the
presented book is supposed to portray a certain continuation of
such a traditional publication activity particularly mentioning our
previous monograph, which received abundant citation feedback
responses. Namely, it was a 1996 special issue of the journal
Thermochimica Acta (Vol. 280/281) entitled ”Vitrification,
transformation and crystallization of glasses” (Elsevier,
Amsterdam), edited by J. Šesták (and dedicated to the life
anniversaries of H. Suga, V. Šatava and D.R. Uhlmann). Compendium
arrangement was initiated upon the cooperation with N.J. Kreidl,
D.R. Uhlmann and M.C. Weinberg during the Šesták´s 1993 visiting
professorship at the University of Arizona in Tucson (see the end
photo). The final book compilation was made possible by help of the
most renowned US glass scientist such as C.A. Angel, D.E. Day, L.L.
Hench, P.M. Mehl, C.T. Moynihan, C.S. Ray, J.H. Flynn and S.H.
Risbud who considered contributing the inherent text. The resulted
softbound book contained as many as 40 chapters on 533 pp.
coauthored by other recognized scientists, such as Argentinean
C.J.R. Gonzales-Oliver, O.F. Martinez; Brazilian E.D. Zanotto;
Czech Z. Kožíšek, Z. Chvoj, B. Hlaváček, J. Málek, P. Demo; British
P.F. James, M.J. Richardson; Bulgarian I. Avramov, A. Dobreva, I.B.
Gugov, I. Gutzov; Canadiend H.D. Gollf; French M. Poulain; German
K. Heide, R. Müller; Hungarian L. Granasy; Indian K.S. Dubey, P.
Ramachandrarao; Italian A. Buri, F. Branda; Liechtenstein W.
Höland, V. Rheinberger; Japanese T. Kokubo, T. Komatsu, M.
Matusita, M. Tatsumisago, M. Koide, Y.Masaki; Liechtenstein W.
Hölland; Russian V. Filipovich, V. Fokin, G. Moiseev, A. Kalinina,
I. Tomilin or Spanish J.M. Barandiarán and I. Tellería. Recently
this tradition has been followed by a similarly anticipated
compendium entitled "Interplay between nucleation, crystallization
and the glass transition" with almost 30 contributed papers
published as a special issue of Thermochimica Acta (Vol. 503, 2011)
under the editorial care of C. Schick and C.W. Höhne. The idea of
collecting broader viewpoints toward the formation and
devitrification of glasses, particular1y aimed at the confrontation
of various aspects of descriptive theories, evaluative treatments
and applied technologies were repetitively the entire subject
during the series of renowned Kreidl’s memorial conferences. The
one on “Advances of glasses” was held in Liechtenstein 1994
(proceedings edited D.R. Uhlmann and W. Hölland). The subsequent
(last) meeting “Building the bridges between glass science and
glass technology” was held in Slovak Trenčín 2004 (proceedings
published in Glass. Ber. Glass. Sci. Tech. 77C, 2004, and edited by
J. Šesták and M. Liška). Worth noting is the compendium “Reaction
kinetics by thermal analysis” published as a special issue of
Thermochimica Acta (Volume 203, 1992, with 530 pp., edited by J.
Šesták and dedicated to the chairman of Kinetic Committee of ICTAC,
late J.H. Flynn at the occasion of his seventies). Another
collection, entitled “Thermal studies beyond 2000”, is also
noteworthy as published as a special issue of the Journal of
Thermal Analysis and Calorimetry (Volume 60, 2000 by Kiado,
Budapest and Kluwer, Dordrecht with 402 pp) and edited by M.E.
Brown, J. Málek, N. Koga and J. Mimkes (and dedicated to the J.
Šesták’s sixties). There are also two recent monographs: “Glass:
the challenge for the 21st century” (published by Trans Tech
Publications, Switzerland 2008, 692 pp. and edited by M. Liška, D.
Galusek, R. Klement as the proceedings of the international IX.
ESG/ICG conference held in Trenčín, Slovakia 2008) and “Some
thermodynamic, structural and behavioral aspects of materials
accentuating non-crystalline states” (published as a university
internal booklet by
-
the Public Weal Society. OPS, at the West Bohemian University -
ZČU Pilsen 2009 and 2011, with 620 pp. and edited by J. Šesták, J.
Málek and M. Holeček). The are quite a few recent books on the
topic among others quoting those responsive to nucleation, such as
by S. Kaschiev “Nucleation: basic theory with application”
(Butterworth 2000), D. Jürn, J.W.P. Schmelzer: “Nucleation: theory
and application” (Wiley 2005), H. Vehkamäki „Classical Nucleation
Theory in Multicomponent Systems“ (Springer 2006), K.F. Kelton,
A.L. Greer „Nucleation in Condensed Matter: applications in
materials and biology” (Elsevier 2010) or V.I. Kalikhmanov
“Nucleation Theory” (Springer 2011). Other influential are books on
glass formation such as Donth E.J: Glass Transition, Relaxation
Dynamics and Disordered States, Springer, Berlin (2001); Egami T,
Greer A. L, Inoue A, Ranganathan S, (eds): Supercooled Liquids,
Glass Transition and Bulk Metallic Glasses, Cambridge (2003);
Wunderlich B: Thermal Analysis of Polymeric Materials, Springer,
Berlin (2005); Henkel M,; Pleimling M, Sanctuary R, (eds): Ageing
and the Glass Transition, Springer, Berlin (2007); Schmelzer J. W.
P, Gutzow I.S, Mazurin O. V, Priven A. I, Todorova S. V, Petroff B.
P, (eds): Glasses and the glass transition, Wiley, New York (2011).
Concerning the field continuous upgrading a particular attention
should be paid to the Committee on Glass Nucleation and
Crystallization (abbreviated ‘CT 7’) as a part of the ICG
(International Commission on Glass) cf. Fig 1.
Fig. 1. The 2001 composition of TC7 committee (of ICG) working
in the historical configuration (from right) G. Völksch (Germany),
V.M. Fokin (Russia), M. Davis (USA), R. Müller (Germany), late P.
James (UK), kneeing E. Zanotto (present chairman,, Brazil), late
M.C. Weinberg (USA), W. Hölland (past chairman, Liechtenstein), T.
Kokubo (Japon), late I. Szabo (Hungary), I. Donald (UK), L.
Pinckney (USA), W. Panhorst (former chairman, Germany) and J.
Šesták (Czech Republic). Notable element of randomness is the
variation of bond angles sometime assumed to be crucial in
auxiliary distinguishing of constrained states of glassy and
amorphous materials. The flexibility of covalent bond is largest
for the two-fold coordination groups of VI-elements and is lowest
for the tetrahedrally coordinated groups of IV-elements. For
instance, in the SiO2 glasses the oxygen atoms are bridging the
Si-tetrahedral providing the essential flexibility, which is
considered necessary to form a random covalent network (without
exhibiting excess of strain). However, if such a covalent random
network is formed without the flexing bridges of the group
VI-elements, the structure becomes amorphous (as the deposited
strain-confined films of, e.g., As2S3), which can exist in many
various forms of non-crystalline configurations (often
experimentally irreproducible). The glass-forming tendency
-
occurs greatest when the short-range order imposed by bond
stretching and bending forces is just sufficient to exhaust the
local degrees of freedom. The internal strain increases with the
average coordination number, m, while the entropy follows the
opposite trend because the non-crystalline state becomes
insufficiently interconnected (i.e., ‘cross-linked’). Therefore,
the conventionally “stable” state of chalcogenide glasses is
typically restricted to lie in the region ~3.3 > m > 2; while
with m > 3.3 glass becomes over-constrained amorphous (shown by
J.C. Phillips already in 1970s); yet higher, with m > 4.3,
associates with unusual state of non-crystalline metals obtained by
ultrafast quenching. On the other hand, those having the lower
connectivity (m < 2) are assumed to be under-cross-linked
amorphous materials, such as typically thin films. The highly
constrained nature of variously obtained amorphous films suggests
that defects might not be randomly distributed but could be
predominantly located as internal blocks, voids and strain-relief
interfaces between low-strain regions. In contrast to glasses, the
amorphous films can thus exist in many non-crystalline
configurational states the thermal annealing of which can lower
their tense energy, however, cannot transform the over-constrained
amorphous configuration from one ranking to another. A drastic
atomic rearrangement would be enforced as to accomplish such an
‘unstructured’ reconstruction, which would, instead, materialize
overlapping by more pertinent as well as unprompted
crystallization. However, a possible interference of so the called
‘medium-range order’ (or ‘modulated structures’) becomes
particularly common in resolving various non-crystalline materials,
pertinent typically semiconductors, where the concept of
homogeneously random network and its heterogeneity was most
extensively studied. It is closely connected with the fashionable
use of adjective ‘nano’ (nano-technology or nano-materials)
touching the limits where the ordered and disordered states
transpire factually a guaranteed threshold (‘delimitability’). The
standard observations, based on measuring crystallographic
characteristics and the amount of crystalline phases (such as
typical XRD) are capable to detect the crystalline phase down to
about 2 % within the glassy matrix, certainly under certain
crystal-size discrimination (‘detectability’). If not assuming here
the capability to distinguish a minimum of neither
‘yet-crystal-magnitude’ nor we account for a specialized
diffraction measurement at low diffraction angles (radial
distribution function); we can concentrate toward the critical
amount of crystalline phase in the glassy sample. This issue is yet
befitting the crucial question of how to relevantly define the
limit of yet ‘true glassiness’ and already ‘nano-crystallinity’. A
few proposals became known but the generally accepted figure is,
for long, the value of 10-6 vol. % (less common 10-3 %), of
crystallites to exist within glass matrix not yet disturbing its
non-crystalline portrayal and consequent characterization of
glassines. The appropriateness of this value, however, is difficult
to authorize persisting in its maintenance on the basis of acute
convenience and reiteration. Regarding the process of
crystallization the early theories of solid-state reactions (D.A.
Young, K. Haufe, H. Schmelzried, J.P. Tretyakov, C.S. Smith, F.C.
Tompkins, R.F. Mehl, V.V. Boldyrev, E.A. Prodan, B.V. L’vov, S.F.
Hulbert , A.K. Galwey, D. Dollimore, M.E. Brown) should be
mentioned performing an important grounding for generalized kinetic
studies. It was preceded by diffusion controlled kinetics (E.
Kirkendall, W. Jander. C. Kroger, V.F. Zhuravlev, A.M. Ginstling,
B.I.Brounshtein,R.E. Carter, W. Komatsu, M.E. Fine). A specific
role played the methods of kinetic evaluation by means of thermal
analysis, specifically DTA, which was inaugurated to the study of
reaction kinetics by H.J. Borchard and F. Daniels (1950) and H.E.
Kissiner (1957) and introduced in the practice of solid-state
reactions in1960s (L. Reich, C.D. Doyle, E.S. Freeman, H.L.
Friedman, J. Zsako, P.D. Garn, J.H. Flynn, T. Ozawa, E. Segal, V.
Šatava or J. Šesták). It was preceded by the traditionally
calculated mode of so called “isothermal” crystallization kinetics
using the comprehensive form of
Johnson-Mehl-Avrami-Yerofeeyev-Kolmogorov equation (abbreviated as
JMAYK
-
and pioneered in the turn of the forties). Its validity
extension came by means of its derivation mode under a more general
(“non-isothermal”) conditions respecting thus the standardized
thermal regime of the temperature linear increase (common, e.g.,
during DTA measurements). It was necessary to introduce the
temperature-dependent integration (D.W. Henderson, T.J.W. DeBroijn,
W.A. DeJong, T. Kemeny, J. Šesták) yielding the concealed but
anticipated fact that that the non-isothermal equivalent of the
isothermally derived JMAYK relation is almost indistinguishable. It
enabled one to simplify the kinetic rate equation to all types of
interface-controlled and/or diffusion-controlled crystallization in
a comprehensive form of ln (1-α) = - kT tr where the general
exponent, r, can be seen as a multipart number of a robust analysis
of the basic JMAYK equation effortlessly analyzable in terms of DTA
measurements. It reveals that the apparent (overall) values of
activation energies, Eapp is frequently correlated to the partial
activation energies of nucleation, EN, growth, EG and/or diffusion,
ED (J. Šesták, M.C. Weinberg, C.T. Moynihan, J.W. Christian). In a
brief wrapping up it should be stressed out that numerous variously
adapted methods of kinetic analysis and evaluation cannot be easily
covered in a single communication. These manners have been treated
repeatedly yielding thus plentiful publications, which were dealt
with by a range of well known kineticists, cf. Fig. 2. The editors
and authors are optimistic that this compendium of distinctive
chapters would facilitate kinetic proficiency of readers enhancing
associated citation feedback, which became important in the
appraisal of scientific work. Let us point out that the topic of
nucleation-crystallization kinetics has been extensively quoted in
the literature, for example (according to WOS 2011); Avrami
fundamental paper on general kinetics of phase changes (1939)
received 5368, Kissinger’s reaction kinetics by DTA (1957) 4461 and
Ozawa’s kinetic method of analyzing thermogravimetry data (1965)
2096 respective responses. Correspondingly the renowned kinetic
equations by Jander (1927) on diffusion received 551, that by
Šesták-Berggrenn (1971) on fractal (autocatalytic) kinetics 566
responses, mentioning also the Uhlmann kinetic treatment (1972)
with 473 responses. These figures are comparable with 1913 and 1396
citations for the basic papers on glass behavior by Fulcher
(viscosity 1925) and Mott (conduction 1968), respectively. The
citation data illustrates that the theme of reaction kinetics is
one of the best denoted focuses within the literature on
solid-state reactions, which is the reason why this subject was
chosen to prevail in the text of following chapters. Fig. 2.
Numerous researches have been involved in studying reaction
kinetics and particularly in the development of nucleation theory
and associated nonisothermal evaluations, some of them are listed
below which is, certainly, restricted by the availability of
individual portraits. First raw: Svante A. Arrhenius, Henry Eyring,
Andrey N. Kolmogorov, Robert F. Mehl, Raoul Kopelman, Andrew K.
Galwey, Paul D. Garn; below Erwad M.D. Karhanavala, Joseph H.
Flynn, David Dollimore, Vladimir V. Boldyrev, Janus Zsako, Boris L.
L'vov, Vladimír Šatava; below Eugene Segal, Ari Varschavski, Viktor
Jesenák, Delbert D. Day, Cornelius T. Moynihan, Takeo Ozawa, Donald
R. Uhlmann; below Julia Sempere, Rosa Nomen, Judith Simon, Barbara
Malecka, Andrzej L. Malecki, Alan K. Burnham, Michael E. Brown;
below Marek Maciejewski, Zdeněk Kožíšek, Jerzy Czarnecki, Nobuyoshi
Koga, Petru Budrugeac, Nae-Lih Wu, Emília Illeková; below Peter
Šimon, Jaroslav Šesták, Jiří Málek, Vladimir M. Fokin, José M.
Criado, Sergey Vyazovkin, Bertrand Roduit; below John M.
Hutchinson, Klaus Heide, Isaac Avramov, Lindsay A. Greer, Kenneth
F. Kelton, Edgar D. Zanotto, Takayuki Komatsu; bottom raw Živan
Živkovič, Jurn W.P. Schmelzer, Pavel Hrma, Pavel Holba, Paul S.
Thomas, Pavel Demo, Vladimir A. Logvinenko.
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Jaroslav Šesták Emeritus scientist of the Academy of Science of
the Czech Republic; Program auspice of the West Bohemian University
in Pilsen and ‘Doctor Honoris Causa’ of Pardubice University. He is
a co-founding professor of both the School of Energy Science of the
Kyoto University in Japan, the Faculty of Humanities of the Charles
University in Prague and the New York University, branch in Prague
authoring numerous books (the most cited “Thermophysical Properties
of Solids”); shown (upper left) with th