Thermal Analysis in the Geosciences

375 Pages·1991·7.203 MB·English

by  R. C. Mackenzie (auth.), Prof Werner Smykatz-Kloss, Prof. Slade St. J. Warne (eds.)

Lecture Notes ni
Earth Sciences
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Editors
Prof Werner Smykatz-Kloss
Mineraloglsches Instltut, University of Karlsruhe
Kalserstr. 12, D-?500 Karlsruhe
Prof. Slade St. J Warne
Department of Geology, University of Newcastle
NSW, Australia
ISBN 3-540-54520-4 Sprlnger-Verlag Berlin Heidelberg NewYork
ISBN 0-387-54520-4 Sprlnger-Verlag NewYork Berlin Heidelberg
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Preface
The application of thermal analysis to earth science has a long history. This
is evidenced by the extensive coverages by Mackenzie (1957, 1970),
Langier-Kuzniarowa (1967), Schultze (1971), Liptay (t973), Smykatz-
Kloss (1974), Todor (1976) and Heide (1982). The chief thermal method
has been differential thermal analysis (DTA). Additionally,
thermogravimetry (TG; Duval, 1963; Keattch, 1969; Earnest, 1988) and
thermodilatometry (Schomburg & Str6~, 1984) have gained some
importance. All these methods are still widely ltsed. But recently several
new techniques have gained attention, such as thermomagnetometry,
thermomechanical analysis and thermosonimetry. Improved equipment
made possible the application of thermal methods to problems in
thermodynamics and kinetics (e.g. by means of differential scanning
calorimetry, DSC). This progress in the construction ofn ew instruments as
well as the combination of existing methods to enable simultaneous
determinations (e.g. TG/~TA; TGflR spectroscopy; DTA/mass
spectrometry; DTA/microscopy; high-pressure DTA) have led to a
resurgence in the use and application of thermal analysis in the earth
sciences. Here the applications cover such diverse areas as the examination
of individual minerals, mineral mixtures, rocks, soils, ceramics, cements,
raw materials as well as their industrial evaluation, performance assessment
and quality control. In the field of solid fossil fuels thermal determinations
range from proximate analysis of inorganic constituents and the
measurement of calorific values to the assessment of the environmental
aspects of fly ashes and mineral residues.
To support this tendency, the International Confederation for Thermal
Analysis (ICTA) has recently founded a "Committee for Thermal Analysis
in Geosciences". The aim of this committee shall be to discuss, improve
and distribute the knowledge about the possibilities of solving geoscientific
questions by means of thermal analytic methods.
III
On a joint scientific meeting with the German Society for Thermal
Analysis (GEFrA) in Berghausen/Karlsruhe (October 2nd to 5th, 1990)
the members of the committee met for a round-table discussion, to review
the application of thermal analysis in the different fields of the geoseiences.
The session was introduced by the Doyen of the group, Robert C.
Mackenzie from Aberdeen, Scotland, who illustrated the development of
thermal analysis in earth sciences. It continued with papers on the use of
DSC and DTA in measuring thermodynamic parameters of minerals and
melts (J. V. Dubrawski, W. Eysel), in studying the kinetics of mineral and
melting reactions (K. Heide, J. Rouquerol) , and in characterizing the
different water species in minerals and rocks (M. F61dvari, C. August, E. T.
Stepkowska). A number of papers was concerned with clays and clay
minerals, their exact determination and use (A. Langier-Kuzniarowa, Ch.
Earnest) and their special importance in environmental studies (S. Yariv,
W. Smykatz-Kloss). The lectures of L. Stoch, J. V. Dubrawski, J.
Rouquerol and S. Wame included the basic principles of refined methods
such as "variable atmosphere thermal analysis" (S. Warne) and "controlled
transformation rate thermal analysis" (J. Rouquerol). A. M. Abdel Rehim,
J. Schomburg and S. Starck reported the use of thermal methods in applied
and technical mineralogy, e.g. for the study of raw materials and the control
of technological processes.
Of course, the above-mentioned lectures may not cover all fields of
geosciences in which thermal analytical methods can be profitably applied,
but theyh elp to envisage the scope of possible applications.
We have to thank many persons, institutions and companies for making the
conference and this publication possible. Drs. H. Schubert, N. Eisenreich,
W. Engel and H. Schmid from the "Institute for Chemical Technology
(ICT)" of the Fraunhofer Society offered the place and the facilities for the
conference in Berghausen. For financial support we are grateful to:
Deutsche Forschungsgemeinschaft, Bonn
Dorfner-Analysenzentrum, Hirschau
Gesellschaft ffir Thermisehe Analyse (GEFrA)
IV
Fa. G6decke, Freiburg/Br.
Heraeus Feinchemikalien, Karlsruhe
Fa. Madaus AG, K61n
Fa. Marx-Bergbau, Ruppach-Goldhausen
Netzsch-Ger~itebau, Selb
Oertikon- Schweigtechnik, Eisenberg]Pfalz
Polymer Laboratories, Heidelberg
Fa. Riedhanuner, Niimberg
Ing.-Bfiro Roth, Karlsruhe
Chr. Seltmann GmbH, Weiden
SonderabfalI-Entsorgun'g Saar, Saarbriicken
S/id-Chemie AG, M/inchen
Also, we are grateful to our co-workers Anke Brannath, Lutz Kaeding,
Jiirgen Reichelt, Eva Roller, Sabine Wenigwieser and especially to Andreas
Heil and Wolfgang Klinke for their assistance. Our colleague Egon Althaus
gave an exciting invited lecture on the German continental deep drilling
project. Last but not least: thanks to W. S.-K.'s daughter Bettina for acting
as hostess and travel guide during thec onference.
Karlsruhe and Newcastle/NSW,
July 1991 Wemer Smykatz-Kloss, Slade .tS J. Wame
References
LAVUD C. (1963) - Inorganic thermogmvimetric analysis.- 2nd ed., Elsevier Publ. Co.,
Amsterdam.
HCTTAEK C. (1969) - An introduction to thermogravimetry.- Heyden and Sons, London.
(for the other citedp apers see the references of the special lectures)
V
Contents
Introductory serutceL
EIZNEKCAM R. C., Aberdeen
Geosciences in Thermal Analysis Development ......... 2
IKSWARBUD J. V., Newcastle/NSW
Differential Scanning Calorimetry and its Applications to
Mineralogy and the Geoseiences ......... . 16
. . . . . . . . . . . .
II Petrography
WARNE S. .TS J., NewcastleflqSW
Variable Atmosphere Thermal Analysis - Methods, Gas
Atmospheres and Applications to Geoscience Materials .... 62
IRAVDL3IF M., Budapest
Measurement of Different Water Species in Minerals by
Means of Thermal Derivatography .................. 84
TSUGUA C., Wroclaw
The Determination of Hydrated Sulphates in the Weathered
Crystalline Rocks by Means of Thermal Analysis ........ 102
!II lacimehC-ocisyhP ygolareniM
HCOTS L., Krakow
Internal Thermal Reactions of Minerals ............... 118
LOREUQUOR J., ER~IDROB S. & LOREUQUOR F., Marseille
Kinetical Study of Mineral Reactions by Means of
"Controlled transformation Rate Thermal Analysis
(CRTA)". ................................... 134
VII
LESYE W., Heidelberg
Thermoanalytical Investigations of Binary Oxide
Systems ..................................... 152
EDIEH K., Jena
Kinetic Analysis of the Crystallization of Silicate Melts by
Means of DSC, DTA and Thermal Optical Methods ...... 172
VI Technical Mineralogy
LEDBA MIHER A. M., AIexandria
Application of Thermal Analysis in Mineral Technology... 188
SCHOMBURG J., Neubrandenburg
Thermal Investigations in Technical Mineralogy ......... 224
KCRATS S., Eisenberg/Pfatz
Application of Thermal Methods in Raw Material Control
and During the Production Process .................. 234
V Mineralogy Clay dna Geology Applied
AKSWOKPETS E. T., KELUS Z., ZEUGIRDOR-ZEREP J. L.,
ADEUQAM C. & OTSUJ A., Gdansk and Sevilla
A Study of the Thermal Behaviour and Geotechnical
Properties of a Marine Clay and Its Composites ......... 246
TSENRAE C. M., Rome/Georgia
Thermal Analysis of Selected Illite and Smectite Clay
Minerals.
Part I. Illite Clay Specimens ....................... 270
Part II. SmectiteC lay Minerals ..................... 288
VIII
LANGIER-KUZNIAROWA A., Warszawa
Remarks on the Applicability of Thermal Analysis for the
Investigations of Clays and Related Materials ........... 314
VIRAY S., Jerusalem
Differential Thermal Analysis (DTA) of Organo-Clay
Complexes ................................... 328
SSOLK-ZTAKYMS W., HEIL A., GNIDEAK L. & RELLOR E.,
Kartsruhe
Thermal Analysis in Environmental Studies ............ 352
Subject Index ................................. 368
IX
Lecturers
Abdel Rehim, Prof. Dr. Ali Mohammed, Head of the Department of
Geology, Fac. of Science, Alexandria Univ., Egypt.
August, Docent Dr. Czes{aw, Inst. of Geological Sciences, University of
Wroc|aw, Poland.
Dubrawski, Dr. Jules V., BHP Research Laboratories, Shortland NSW,
Australia.
Earnest, Prof. Dr. Charles M., Berry College, Rome, Georgia/USA.
President of NATAS, North Amer. Thermal Anal. Society.
Eysel, Prof. Dr. Walter, Mineralogisch-Petrographisches Institut der
Universifiit, Heidelberg, Germany.
F61dvari, Dr. Maria, Geolog. Survey of Hungary, Budapest
Heide, Docent Dr. Klaus, Abt. fiir Glaschemie der Universit~it, Jena,
Germany.
Langier-Kuzniarowa, Prof. Dr. Anna, Geolog. Inst. of the University,
Warszawa, Poland.
Vice-Chairperson of the ICTA-Committee for "Thermal
Analysis in Geosciences'.
Mackenzie, Dr. Robert C., Retired Director of the Inst. for Soil Science,
AberdeenU,. K.
Rouquerol, Dr. Jean, Centre de Thermodynamique et de Microcalorimetrie
du CNRS, Marseille, France.
Chairman of the ICTA-Committee for Science.
Schomburg, Docent Dr. Joachim, Durtec-Ges., Neubrandenburg, Germany.
XI
Smykatz-Kloss, Prof. Dr. Werner, Mineralogisches Iustitut der Universit~t
Karlsruhe, Germany.
Chairman of the ICTA-Committee for "Thermal Analysis in
Geosciences'.
Starck, Dipl. Mineral. Stefan, Oerlikon-SchweiBtechnik, Eisenberg]Pfalz,
Germany.
Stepkowska, Prof. Dr. Ewa T., Inst. of Hydroengineering, Polish Academy
of Sciences, Gdansk, Poland.
Stoch, Prof. Dr. Leszek, Academy of Mining and Metallurgy, Krakow,
Poland.
Warne, Prof. Dr. Slade .tS J., Geological Department, University of
Newcastle, New South Wales, Australia.
President of the ICTA (International Confederation for
Thermal Analysis).
Yariv, Prof. Dr. Shmuel, Dept. of Inorganic and Analytical Chemistry, The
Hebrew University of Jerusalem, Israel.
IIX