Microweighing in Vacuum and Controlled Environments

404 Pages·1980·48.51 MB·English

by  A.W. CZANDERNA and S.P. WOLSKY (Eds.)

METHODS AND PHENOMENA
THEIR APPLICATIONS IN SCIENCE AND TECHNOLOGY
Series Editors
S.P. Wolsky
Vice President, Research & Development
P.R. Mallory & Co., Inc.
Burlington, MA 01803, U.S.A.
and
A.W. Czanderna
Editor, Methods and Phenomena
P.O. Box 27209
Denver, CO 80227, U.S.A.
Volume 1. A.W. Czanderna (Ed.), Methods of Surface Analysis
Volume 2. H. Kressel (Ed.), Characterization of Epitaxial Semiconductor Films
Volume 3. FJ. Fry (Ed.), Ultrasound: Its Applications in Medicine and Biology
Volume 4. A.W. Czanderna and S.P. Wolsky (Eds.), Microweighing in Vacuum and
Controlled Environments
In preparation
R.C. Laible (Ed.), Ballistic Materials and Penetration Mechanics
K. Moorjani and J.M.D. Coey, Disordered Solids
A.N. Dey, Lithium Batteries
Edited by
A.W. CZANDERNA
Editor, Methods and Phenomena
P.O. Box 27209,
Denver, CO 80227, U.S.A.
S.P.WOLSKY
Vice President, Research and Development
P.R. Ma/lory and Co., Inc.
Burlington, MA 01803, U.S.A.
Volume 4 of
METHODS AND PHENOMENA
THEIR APPLICATIONS IN SCIENCE AND TECHNOLOGY
ELSEVIER SCIENTIFIC PUBLISHING COMPANY
Amsterdam - Oxford - New York 1980
ELSEVIER SCIENTIFIC PUBLISHING COMPANY
335 Jan van Galenstraat
P.O. Box 211, 1000 AE Amsterdam, The Netherlands
Distributors for the United States and Canada:
ELSEVIER/NORTH-HOLLAND INC.
52, Vanderbilt Avenue
New York, N.Y. 10017
Library of Congress Cataloging in Publication Data
Main entry under title:
Microweighing in vacuum and controlled environments.
(Methods and phenomena, their applications in
science and technology ; v. k)
An expansion of the 1969 ed. entitled, Ultra
micro weight determination in controlled environ­
ments entered under S. P. Wolsky.
Includes bibliographies and index.
1. Microbalance. I. Czanderna, Alvin
Warren, 1950- II. Wolsky, S. P., 1926-
Ultra micro weight determination in controlled
environments. III. Series.
QC107.W6 1980 530».7 80-1062*4-
ISBN 0-kkk-kl86Q-7
ISBN 0-444-41868-7 (Vol. 4)
ISBN 0-444-41640-4 (Series)
© Elsevier Scientific Publishing Company, 1980
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or
transmitted in any form or by any means, electronic, mechanical, photocopying, recording or other­
wise, without the prior written permission of the publisher, Elsevier Scientific Publishing Company,
P.O. Box 330, 1000 AH Amsterdam, The Netherlands
Printed in The Netherlands
V
CONTRIBUTORS TO VOLUME 4
C.L. Angell Union Carbide Corporation, Tarrytown Techni­
cal Center, P.O. Box 278, Tarrytown, NY 10591
F.A. Brassart Westinghouse Advanced Reactors Division, P.O.
Box 158, Madison, PA 15663
A.W. Czanderna Solar Energy Research Institute, Materials
Branch, 1617 Cole Boulevard, Golden, CO
80401
E.L. Fuller, Jr. Oak Ridge National Laboratory, P.O. Box X,
Oak Ridge, TN 37830
Th. Gast Technishe Universitat Berlin, Institut fur
Me3-u. Regelungstechnik, 1000 Berlin 15, W.
Germany
E.A. Gulbransen University of Pittsburgh, Department of Metal­
lurgical and Materials Engineering, Pittsburgh,
PA 15261
W. Kollen Owens-Illinois Technical Center, P.O. Box
1035, Toledo, OH 43601
C.H. Massen Technische Hogeschool te Eindhoven, Postbus
513, Eindhoven, The Netherlands
J.A. Poulis Technische Hogeschool te Eindhoven, Postbus
513, Eindhoven, The Netherlands
E. Robens Battelle-Institut e.V., 6 Frankfurt/Main-90,
Wiesbadener Strasse, Postfach 900 160, W.
Germany
R.L. Schwoebel Sandia Laboratories, Research Department
5110, Albuquerque, NM 87115
R. Vasofsky Rome Air Development Center, RBRM, Griffiss
AFB, NY 13441
S.P. Wolsky P.R. Mallory and Co., Inc., Northwest Industrial
Park, Burlington, MA 01803
VI
METHODS AND PHENOMENA
Editorial Advisory Board
Prof. Dr. J. Block Fritz Haber Institut, Berlin, W. Germany
Dr. S. Davison University of Waterloo, Waterloo, Ont., Canada
Prof. F.J. Fry Interscience Research Division, Indianapolis,
IN, U.S.A.
Dr. J.P. Kratohvil Clarkson College of Technology, Potsdam, NY,
U.S.A.
Dr. R.H. Krock P.R. Mallory and Co., Inc., Burlington, MA,
U.S.A.
Dr. R. Schwoebel Sandia Laboratories, Albuquerque, NM, U.S.A.
Mr. G. Siddall University of Strathclyde, Glasgow, Gt. Britain
Prof. J.N. Zemel University of Pennsylvania, Philadelphia, PA,
U.S.A.
vii
PREFACE
The editors are privileged to dedicate this book to the memory
of E.J. Zdanuk, who was not only a long time co-worker and
colleague, but also carried out superb pioneering work on sputtering
phenomena using microgravimetric techniques. As detailed below,
a major fraction of this book can be related back to his efforts
as a co-editor of the only previous treatise in the field. We are
confident those in the microbalanee community who knew Ed
Zdanuk as a person, as well as a scientist, will be supportive of
our decision.
This book is both a consolidation and expansion of the first
treatise on micro mass measurements, entitled, MUltra Micro Weight
Determination in Controlled Environments," edited by S.P. Wolsky
and E.J. Zdanuk, (Wiley, Interscience, 1969), which is now out-of-
print. The use of the microbalanee has continued to develop
dynamically since then. The concept of micro mass determination
has widened markedly with the development of the quartz crystal
oscillator. Hence, the subject material of the book by Wolsky and
Zdanuk has been divided into two parts. This book deals with beam
microbalances; crystal oscillators will be treated in a future vol­
ume. Mass is measured directly with the beam microbalanee and
indirectly through its effect on oscillator frequency with the quartz
crystal. The two methods possess their own peculiar advantages and
problems and do not usually compete with each other for utility,
but rather often are used in a complementary fashion. If there is
strict environmental control, the oscillator is particularly attractive
for its potential sensitivity, which is several orders of magnitude
greater than the beam microbalanee. Where temperature dependent
measurements are desired on samples of varied configuration and
composition, the beam balance is greatly superior.
The utilization of microbalances has been very imaginative and
varied. Because the microbalanee has been applied so broadly, the
details of theory, design and applications are scattered throughout
the literature; in the case of applications, it is even rare to find the
word microbalanee mentioned in the abstract. It is the prime objec­
tive of this book, therefore, to provide a single effective source
on the theory, design, artifacts, and varied applications of the
beam microbalanee. Sufficient information is included to allow the
reader to practice these techniques in a TTdo-it-yourselfTT manner.
viii
We are pleased to acknowledge the encouragement and assistance
of many of our colleagues in the conception and preparation of this
book. We are particularly indebted to the participants of the
sixteen Conferences on Vacuum Microbalance Techniques, initiated
in 1960, who have helped show this area of activity is broad, vibrant
and creative. It is fitting to remember the promotional, organiza­
tional and dedicated zeal of Mr. Lee Cahn, Dr. K.H. Behrndt and
Mr. E.J. Zdanuk, now deceased, along with Drs. E.A. Gulbransen,
Th. Gast and T.N. Rhodin, who were early pioneers in this field. Dr.
Gulbransen and Professor Dr. Gast are still contributing consistently
as evidenced by the last two chapters in this book.
We are also pleased to acknowledge the contributions of many
individuals to our own efforts at applying the microbalance to solve
fundamental and technological problems. For A.W. Czanderna,
thanks are due to Prof. J.M. Honig, who introduced him to the idea
of a pivotal beam microbalance in 1954, along with Drs. P.A. Faeth,
A.N. Gerritsen, D.H. Damon, and Mr. J. Richlin at Purdue Univer­
sity and Dr. H. Wieder, Mr. C.W. Nezbeda, Miss L.I. Forrest, Mr.
P.A. Given, Dr. F.G. Young, and Dr. H.C. Chitwood of Union
Carbide Corporation. Special praises are due my former students,
Dr. W. Kollen, Dr. J. Biegen, Dr. E.G. Clarke, Jr., Mr. S.C. Chen,
and my current associates, Mr. J. Rodder of Rodder Instrument, and
Dr. R. Vasofsky and Mr. E. Prince for their contributions at
Clarkson College of Technology. Finally, Mr. D. Shipley and Mr. B.
Doran are thanked for their expert glassblowing. For S.P. Wolsky,
who started his microbalance efforts at the Raytheon Co., Mr. E.J.
Zdanuk, Mr. R. Chase, Dr. W.C. Dunlap, Dr. A.B. Fowler, Mr. G.
Freedman, Dr. L. Guildner, Dr. T.H. Johnson, Dr. J. Hawkes and Dr.
H.A. Papazian, all have contributed, along with the special technical
assistance of Mr. L. Rubin, Mr. J. Gage, Mr. J. Silva and Mrs. P.
Rodriguez.
Finally, we are grateful to those who have assisted us in the
preparation of this book. First and foremost, we appreciate the
enthusiastic and cooperative efforts of the authors of the various
chapters, and especially Mrs. Lucile D. Czanderna who prepared the
camera-ready copy for this volume.
Lakewood, Colorado A.W. Czanderna
Burlington, Massachusetts S.P. Wolsky
August, 1979
Chapter 1
INTRODUCTION AND MICROBALANCE REVIEW
A.W. Czanderna and S.P. Wolsky
I. INTRODUCTION
The subject matter of this book and this chapter will be discussed
briefly to provide an overview. The progress of many important
physical processes can be followed through observation of associated
mass changes. Adsorption, desorption, oxidation, reduction, and
evaporation are only a few of the more common phenomena that fall
into this category. Although the phenomena can be studied by
measuring other physical and/or chemical changes, the simple,
direct, and absolute nature of gravimetric measurements is very
attractive.
The increased interest in the mierobalance has resulted, in part,
from the recent rapid progress in scientific instrumentation. From
a current view, it is difficult to realize that as recently as 1960 the
ranks of mierobalance experts were limited to those few with the
resources and ability to fabricate their own instruments. Today,
highly sophisticated automatic recording devices adequate to satisfy
most requirements are available commercially. Parallel progress in
vacuum science and technology has provided a means for careful
environmental control required for many microgravimetric experi­
ments.
Access to the literature on applications of the mierobalance was
relatively simple until the last few years. In the last two decades,
studies with microgravimetric techniques graduated from using
custom-made apparatus, designed and constructed by pioneers in the
field to solve specific problems, to wide use of commercially
available microbalances. As summarized in the only treatise in the
field [1], usage of commercially available units dominated applica­
tions of the mierobalance by 1969 [2]. Until 1971, the bulk of the
development of mierobalance technology has been tidily covered in
ref. 1, the reviews cited in ref. 2, and in the proceedings of the first
eight conferences under the title Vacuum Mierobalance Techniques
[3-10]. In recent years, the mierobalance has been increasingly
employed as a routine analytical instrument. As a result, abstracts
2 A. W. CZANDERNA AND S. P. WOLSKY
only infrequently mention using a microbalance, and even in the
experimental section it may be referenced as a gravimetric method.
Considerable access to the recent literature on microbalance tech­
nology and applications can still be gained from the proceedings of
the ninth, tenth, and twelfth conferences on microbalance tech­
niques under the title Progress in Vacuum Microbalance Techniques
[11-13], of the fourteenth and sixteenth conferences in Thermo-
chimica Ada [14], and of the eleventh, thirteenth, and fifteenth
conferences in The Journal of Vacuum Science and Technology
[15-17]. However, coverage in these three sources now needs to be
supplemented by direct contact with appropriate journals because of
the difficulty in finding pertinent articles from citation indices
which are based on abstracts in the various journals. It is the prime
purpose of this book to provide a single reference source for
detailed and critical discussions of the important features, limita­
tions, and applications of the beam microbalance. The contributors
to this volume are recognized internationally for specific contribu­
tions, and many have pioneered some aspect of the development and
application of the microbalance.
This book has been designed to be practical. Detailed discussions
are deliberately included on classifications, auxiliary equipment,
design, fabrication, artifacts, theory, operation, and applications of
beam microbalances. This information is sufficient to allow the
reader to evaluate the microbalance before initiating his own effort.
The first three chapters deal with an overview, theory, design, and
artifacts. The last seven chapters consider various applications.
Each chapter is a separate entity and can be read by a knowledge­
able worker. Cross referencing has also been used to integrate the
entire treatise.
In this chapter, a review of the microbalance literature provides a
current assessment of the field. Details of microbalance theory,
design, and fabrication in the second chapter will assist those willing
to build their own or to modify commercially available apparatus.
The third chapter provides insight into instrumental and environ­
mental factors affecting the sensitivity of beam balances.
The applications considered in the last seven chapters were
chosen from the mainstream of problems being addressed with the
vacuum microbalance. The physical and chemical adsorption and
desorption of gases, the study of oxidation and catalytic reactions,
the simultaneous measurement of mass and infrared or residual
gases present covers the vast bulk of current applications of
microgravimetry in controlled environments. Using beam micro-
balances for studying reduction reactions, decomposition, dehydra­
tion, evaporation, condensation, surface pressure, surface tension,
and magnetic susceptibility was addressed in a recent noncritical
MICROBALANCE REVIEW 3
review [18]. The readers imagination should be stimulated by the
various applications cited, especially those presented in the final
chapter.
Thermogravimetry has not been considered in this book, as a
deliberate omission. Using balances for thermogravimetric studies
has been well covered in other texts starting with the treatise by
Wendlandt [19], successor books, and related journals such as J.
Thermal Analysis and Thermochimica Ada.
The subject matter in this chapter provides a broad introductory
review for this volume. The intent of this chapter is to summarize
the historical development of the various types of balances, to cite
references to the significant complexities that may be introduced in
the measurements, and to reference the most important groups of
microbalance applications. It is hoped that this discussion will aid
the new host of microbalance experimentalists in avoiding needless
repetitious studies of the undesirable mass and force changes that
accompany the application categories.
The detection of changes in mass (or weight) is one of the
fundamental measurements in the physical sciences. As a result,
considerable effort has been expended in the design, construction,
and use of ultrasensitive weighing apparatus. The advent of the
simple precision microbalance is generally attributed to Warburg
and Ihmori in 1886 [20]. The steady progress in this field has been
discussed in review articles [21-34] and the published proceedings of
a series of conferences on vacuum microbalance techniques [3-17].
Since extensive references are available in these articles and
volumes, no attempt will be made to produce a complete bibliogra­
phy of the microbalance literature in this chapter. Rather, refer­
ences will be used for illustrative purposes and to provide a more
detailed account of some important topics that were left somewhat
incomplete in the most recent reviews [29,31-34]. These topics will
include classification of microbalances based on the response to an
applied force, on the method used for monitoring the response, and
on the method of automatic operation. Then, an account of various
types of auxiliary equipment required to operate a microbalance will
be presented. This will be followed by a discussion of the undesir­
able disturbances encountered in vacuum microgravimetry. Here,
the radiometric forces that result from the thermomolecular flow of
gases will be reviewed in some detail because they represent the
greatest constraint to precise measurement of mass changes uncov­
ered in the last two decades. Finally, the use of different types of
microbalances for various applications will be cited.
Only brief mention will be made of the materials used for the
construction of microbalances and of the techniques of calibration
since these will be covered in detail by Schwoebel in Chapter 2.