Tungsten: Properties, Chemistry, Technology of the Element, Alloys, and Chemical Compounds

447 Pages·1999·22.22 MB·English

by  Erik Lassner

Tungsten
Properties, Chemistry, Technology of the
Element, Alloys, and Chemical Compounds
Erik Lassner and
Wolf-Dieter Schubert
Vienna University of Technology
Vienna, Austria
Kluwer Academic / Plenum Publishers
New York, Boston, Dordrecht, London, Moscow
Library of Congress Cataloging-in-Publication Data
Lassner, Erik.
Tungsten .- properties, chemistry, technology of the element,
alloys, and chemical compounds / Erik Lassner and Wolf-Dieter
Schubert.
p. cm.
Includes bibliographical references and index.
ISBN 0-306-15Q53-4
1. Tungsten. I. Schubert, Wolf-Dieter. II. Title.
QD181.W1L37 1998
620 . 1 ' 8934—dc21 98-45787
CIP
ISBN 0-306-45053-4
© 1999 Kluwer Academic / Plenum Publishers, New York
233 Spring Street, New York, N.Y. 10013
10987654321
A C.I.P. record for this book is available from the Library of Congress.
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any
means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written
permission from the Publisher
Printed in the United States of America
To a group of pioneers in the field of Power Metallurgy and Tungsten
Science: Friedrich Benesovsky, Gustav F. Hiittig, Richard Kieffer,
Tivadar Millner, Hans Novotny, Paul Schwarzkopf, and
Karl Sedlatschek. They educated a generation of scientists and
technicians who spread their knowledge throughout the world.
And to our friend, the late Bernhard F. Kieffer.
Preface
Why does someone write a book about Tungsten? There are several reasons and precedents
for this, the most important of which is that the last book on tungsten was written more
than 20 years ago, in 1977, by St. W. H. Yih and Ch T. Wang. During the intervening
period there have been many new scientific and technological developments and innova-
tions, so it was not only our opinion but the view of many other members of the "tungsten
family" that it was time to start writing a new book about tungsten. Preparations of the new
book began in 1994.
Further impetus to the project was provided by the realization that in spite of this new
knowledge having been presented at seminars or published in the technical press, a general
acknowledgement of it by the majority of technicians and scientists is still far from being
realized. It is our hope that this book will significantly contribute to a broader acceptance
of recent scientific and technological innovations.
An important prerequisite for such a project is the availability of a recently retired,
experienced person willing to devote his time and talents to the tedious part of the exercise.
Erik, who retired in 1993, was both highly motivated and eager to start; and it was a
relatively easy task for Erik to persuade Wolf-Dieter to participate in the project. The fact
that both of us have for many years enjoyed a close cooperation in tungsten-related
research projects leading to the publication of several joint papers only facilitated the
decision. Moreover, as authors of "Tungsten, Tungsten Alloys, and Tungsten Compounds"
in the latest edition of Ullmann s Encyclopedia of Industrial Chemistry, we have also had
some common experience in writing.
Another important prerequisite was that we both had extensive experience in
tungsten-related research and technology during our professional work. Wolf-Dieter's
scientific career and extensive research activities combined with Erik's long-term industrial
and development knowledge contributed to a fruitful cooperation in preparing the manu-
script for this book.
Nevertheless, in the writing of this book we also learned a lot more about tungsten.
Richard Kieffer (the father of Bernhard Kieffer and for many years one of the leading
experts on tungsten) always said: "If you want to inform yourself only roughly about
something, present a paper about the subject; but, if you want to gain an in-depth
knowledge about it — you have to write a book." So it seems that during the writing of this
book (it is now February 1998) we grew into experts.
Encouragement, a very important aid in a project of this kind, was given to us first of
all by Bernhard F. Kieffer, who unfortunately passed away prematurely. Bernhard not only
encouraged us to write this book, but also encouraged Plenum Publishing Corporation to
publish it.
Sometimes it was not easy to decide what should be included and what should be
omitted; or the extent of detail to which each item should be discussed. We decided in
general to emphasize the technologically related matters and to refrain from discussing
purely scientific principles. Naturally, these decisions are always subjective and chapters
dealing with those subjects with which we are more familiar are undoubtedly treated more
precisely than others. This is natural, because otherwise the individual chapters should
each have been written by an expert on that particular topic. As our original manuscript
already exceeded the maximum allowed by the publisher, such an expert treatise would
have exceeded the publisher's maximum several times over. Nevertheless, we hope that our
book gets a good reception from the reader.
Returning once again to the original question: "Why write a book?" somebody once
said it is to establish a "monument" to the author(s). If this should be the truth, we want
many people to come and glance at it. However, besides constructing a monument, it is our
intention to summarize the current status of the science and technology of tungsten for
those interested in extending their knowledge of this subject. A book always provides for
easier and more efficient learning than searching for a large number of original publica-
tions, which must first of all be identified.
The preparation of this manuscript has sometimes exacted its toll on our families, we
want to especially thank our wives for their patience and understanding.
Vienna and Graz, February 1998
Acknowledgments
Without the support and help of numerous colleagues and friends as well as companies, it
would not have been possible to write the book in its present form.
For valuable information, literature, photographs, data sheets, etc., we are kindly
indebted to many people in many countries:
Austria
K. Voigt and R. Cantz, Bohlerit, Kapfenberg
M. Schwarzkopf, G. Leichtfried, A. Singer, and R. Piircher, Plansee, Reutte
H. Wohrle, Plansee Tizit, Reutte
P. Putz, Sandvik Austria, Vienna
F. Sattler, Tamrock Voest-Alpine Bergtechnik, Zeltweg
M. Spross, B. Zeiler, O. Grau, and E. Moos,
Wolfram Bergbau-und Huttenges., St. Peter i.S
I. Begsteiger, Porzellanfabrik Frauenthal GmbH
Th. Nagl, Austrian Energy and Environment
F. Koch, Bohler Edelstahl GmbH, Kapfenberg
G. Groboth, Austrian Research Center Seibersdorf
E. Hengge, Technical University Graz
B. Lux, P. Ettmayer, H. Danninger, and R. Haubner, Vienna University of Technology
Belgium
D. Lison, University of Louvain, Brussels
China
Zhao Quinsheng and Zou Zhiqiang, Central South University of Technology, Changsha
Czech Republic
V. Dufek, Prague
D. Rafaja, Charles University Prague
Germany
K. Dreyer, Widia, Essen
D. Ermel, ALD Vacuum Technologies, Erlensee
H. Frick, Kemmer Prazision, Schwabisch Gmiind
J. HoIz, Industrievertretungen GmbH., Wachtersbach
H. Kolaska, Fachverband Pulvermetallurgie, Hagen
E. Kubel, WI Hartmetall, Miinsingen
G. Marsen, Osram, Schwabmiinchen
H. Palme, University of Cologne
D. Pratschke, Gebr. Leitz, Oberkochen
G. Gille, Starck, Goslar
H. Westermann, United Hardmetal, Horb;
Elino Industrieofenbau, Diiren
Hungary
L. Bartha, O. Horacsek, and J. Neugebauer, Hungarian Academy of Science, Budapest
Israel
R. Gero, Ashot Ashkelon, Ashkelon
R. Porat and M. Leiderman, ISCAR; Tefen
Japan
T. Tanase, Mitsubishi Materials Corporation, Omiya
T. Nomura, Sumitomo Electric Industries, Itami
Y. Yamamoto, Tokyo Tungsten, Toyamaken
K. Kitamura, Toshiba Tungaloy, Iwaki City
Luxemburg
J. P. Lanners, Cerametal, Mamer
Principality of Liechtenstein
Th. Kraus, Triesen
Sweden
L. Rohlin, AB Sandvik Coromant, Stockholm
U. Fischer, AB Sandvik Rock Tools, Sandviken
B. Uhrenius, Sandvik Hard Materials, Stockholm
C. G. Granquist, University of Uppsala
The Netherlands
F. Mertens and G.vd. Kerkhof, Philips Lighting, Maarheeze
UK
B. Williams, EPMA, Shrewsbury
S. Jones, Royal Ordnance Speciality Metals, Wolverhampton
M. Maby, Secretary General, International Tungsten Industry Association, London
USA
B. North, M. Greenfield, and G. J. Wolfe, Kennametal, Latrobe
B. F. Kieffer, M. Ostermann, J. Oakes, and K. Horten,
Teledyne Advanced Materials, Huntsville
E. Rudy, SINTEX, Oregon
C. L. Conner, The Dow Chemical Company, Midland
E. A. Amey, USBM
J. Stone, Denver
Ch. W. Miller, Jr., Harper International, Lancaster
We gratefully acknowledge the critical reading of various parts of the manuscript by
the following people:
M. Spross and B. Zeiler, Wolfram Bergbau- und Hiittenges., St. Peter i.S., Austria
G. Leichtfried, Plansee, Reutte, Austria
K. Mereiter, E. Zobetz, H. Mayer, P. Mohn, and J. Redinger, Vienna University of
Technology, Austria
W. Kiesl, R. Stickler, and R. Podloucky, University of Vienna, Austria
M. Shale, William Rowland, Sheffield, UK
E. Bennett, NPL, Teddington, UK
H. C. Starck, Goslar, Germany
O. Foglar, Schladming, Austria
A particular vote of thanks is due to A. Bartl and W. Prohaska (Institute for Chemical
Technology of Inorganic Materials, Vienna, Austria) for the preparation of numerous
drawings, tables, copies, and photographs.
We owe special thanks to Mrs. Ann Stanly of Teledyne Metalworking Products for
correcting the manuscript in regard to the English, which is not our mother tongue.
We gratefully acknowledge the financial support of Teledyne Advanced Materials^
Huntsville, AL, USA
Contents
Preface ...................................................................................... vii
Acknowledgments ..................................................................... ix
1. The Element Tungsten: Its Properties ............................. 1
1.1 Analogous to Atom Related Physical Properties ................... 1
1.1.1 Nucleus ................................................................. 2
1.1.2 Electron Configuration .......................................... 2
1.1.3 Spectra ................................................................. 3
1.1.4 Thermodynamic Functions .................................... 6
1.2 Bulk Tungsten Metal Related Physical Properties ................ 7
1.2.1 Electronic Structure and Bonding .......................... 7
1.2.2 Structural Properties ............................................. 11
1.2.3 Mechanical Properties .......................................... 16
1.2.4 Thermal Properties ............................................... 30
1.2.5 Electromagnetic Properties ................................... 34
1.2.6 Optical Properties ................................................. 36
1.2.7 Electron Emission ................................................. 40
1.2.8 Acoustic Properties ............................................... 42
1.3 Chemical Properties of Tungsten Metal ................................ 42
1.3.1 General Remarks .................................................. 42
1.3.2 Reactions with Nonmetals .................................... 46
1.3.3 Reactions with Metals ........................................... 46
1.3.4 Reactions with Compounds .................................. 50
1.3.5 Reactions with Aqueous Solutions ........................ 53
1.3.6 Miscellaneous ....................................................... 55
1.3.7 Reactions with Organic Compounds ..................... 56
References for Chapter 1 ................................................................ 56

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xiv Contents

2. Tungsten History: From Genesis to the 20th
Century Products .............................................................. 61
2.1 The Formation of Tungsten Atoms ........................................ 61
2.2 How Tungsten Atoms Came on Earth ................................... 63
2.3 Average Abundance .............................................................. 64
2.4 Geology: Formation of Ore Deposits ..................................... 65
2.5 Minerals .................................................................................. 69
2.6 Ore Deposits and Reserves ................................................... 70
2.7 Early Discoveries of Ores, Compounds, and of the
Element .................................................................................. 77
2.8 Technically Important Discoveries ......................................... 79
2.9 Industrial Evolution ................................................................. 80
References for Chapter 2 ................................................................ 83
3. Important Aspects of Tungsten Chemistry ..................... 85
3.1 Oxidation of Tungsten Metal by Air or Oxygen ...................... 85
3.2 Reaction of Tungsten with Water ........................................... 86
3.3 Reduction of Tungsten Oxides by Hydrogen ......................... 88
3.3.1 Introduction ........................................................... 88
3.3.2 Thermodynamic Considerations ............................ 89
3.3.3 Formation of a Volatile Tungsten Oxide
Hydrate [WO (OH) ] .............................................. 91
2 2
3.3.4 Kinetic Considerations .......................................... 91
3.3.5 Influence of Foreign Elements .............................. 103
3.4 Reduction of Tungsten Oxides by Carbon or Carbon-
Containing Compounds ......................................................... 107
3.5 Reduction of Tungsten Halides .............................................. 110
3.5.1 Introduction ........................................................... 110
3.5.2 Reduction of WF .................................................. 111
6
3.5.3 Reduction of WCl by Hydrogen ............................ 113
6
3.5.4 Reduction of WCl by Carbon-Containing
6
Reagents .............................................................. 113

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