VACUUM MICROBALANCE TECHNIQUESVOLUME 8

VACUUM MICROBALANCE TECHNIQUES

Volume 1Fort Monmouth Conference-1960

Edited by Max J. Katz

Volume 2Washington,D.C., Conference-1961

Edited by Raymond F . Walker

Volume 3Los Angeles Conference-1962

Edited by Klaus H. Behrndt

Volume 4Pittsburgh Conference - 1964

Edited by Paul M. Waters

Volume 5Princeton Conference-1965Edited by Klaus H. Behrndt

Volume 6Newport Beach Conference-1966

Edited by A. W. Czanderna

Volume 7Eindhoven Conference-1968

Edited by C. H. Massenand H. J . van Beckum

Volume 8Wakefield Conference-1969Edited by A. W. Czanderna

VACUUM MICROBALANCE TECHNIQUESVOLUME 8

Proceedings of the Wakefield ConferenceJune 12-13. 1969

Edited byA. W.Czanderna

Clarkson College of TechnologyPotsdam, New York

<:f? PLENUM PRESS • NEW YORK-LONDON • 1971

Library of Congress Catalog Card Number 61-8595

ISBN 978-1-4757-0135-7 ISBN 978-1-4757-0133-3 (eBook) DOl 10.1007/978-1-4757-0133-3

© 1971 Plenum Press, New York Soft cover reprint of the hardcover 1st edition 1971

A Division of Plenum Publishing Corporation 227 West 17th Street, New York, N.Y. 10011

United Kingdom edition published by Plenum Press, London A Division of Plenum Publishing Corporation, Ltd.

Da.vis House (4th Floor), 8 Scrubs Lane, Harlesden, NW10 6SE, England

All rights reserved

No part of this publication may be reproduced in any form without written permission from the publisher.

Introduction

This volume contains the proceedings of the Eighth Conference onVacuum Microbalance Techniques held at Wakefield, Massachusettson June 12 and 13, 1969. The tenth anniversary of the first confer­ence will be registered as this volume passes through the typeset­ting and proofreading stages. The eight volumes that have spawnedfrom this continuing series of conferences now contain a total of125 papers. Thus, these volumes serve as a major repository ofthe world's literature on vacuum microbalance techniques. TheNinth and Tenth Conferences will be held in West Germany in June1970 and in Texas in 1971.

Each of the eight meetings has served as a forum where newdevelopments in this rapidly advancing fie ld can be presented anddiscussed constructively within a conference atmosphere of cordialinformality. The interaction of the participants at the conferenceshas led to the first treatise on ultra mlcrogravtmetry;' edited byS. P. Wolsky and E. J. Zdanuk, with most of the fourteen chapterswritten by steady contributors to the volumes on Vacuum Micro­balance Techniques. The number of research investigations andpublished works in which a vacuum microbalance is utilized con­tinues to expand r apldly.f This is a direct result of several typesof automatic recording balances that are now available commercial­ly.3

The Eighth Conference was held to bring together again re­search scientists and engineers who exploit the measurement ofmass as a means of studying physical and chemical phenomena.

IS. P. Wolsky and E. J. Zda nuk, Ultra Mic ro Weight Determi nat ion in Controlled En­vironments. Intersci ence, New York, 1969.

2 A. W. Czanderna, "Utramicrobalance Review. " in: Wolsky and Zdanuk , op. cit••p. 7.

3 D. Fox and M. Katz. "The Availability of Commerci a l Microbalances and Quar tzCrystal Oscillators, " in: Wolsky and Zdanuk , op. cit• •p. 465.

v

vi INTRODUCTION

Support for the conference was provided by the Army Research Of­fice - Durham.! Clarkson College of Technology, P, R. Mallory andCo., Inc., and the Cahn Division of Ventron Instruments. Over 1500users of microbalances were contacted by mail announcing the con­ference. In addition, the meeting was announced in the Journal ofVacuum Science and Technology.! Chemical and Engineering News,6and Research/Development. 7

There were forty-six participants at the conference represent­ing Germany, Great Britain, and all regions of the United States.Roughly, two-thirds of the attendees from the United States camefrom the northeast, while the four scientists from Western Europeprovided an international character to the meeting. The attendeeswere welcomed by the Conference Chairman, A. W. Czanderna, whoprovided a brief historical sketch of the conferences and indicatedsome of the benefits derived by the participants of previous confer­ences. In the technical program which followed, J. W. Whalen, Th,Gast, E. J. Zdanuk, and Pat Gaskins served successively as moder­ators for the four sessions. The first session was opened with aninvited paper by E. A. Gulbransen and was followed by two contri­buted papers pertaining to oxidation. An invited paper was presentedin the second session by E. Robens on the genera] problem of themass defect produced by thermal gradients. In the third session,W. H. King presented an invited paper on applications of the crys­tal oscillator microbalance. Of the nineteen papers presented,seventeen are included in the proceedings and an eighteenth wasaccepted for publication after the conference because of its rele­vance to the other papers in the volume. Discussion questions andanswers that followed each presentation are incorporated at the endof each paper. The cooperation of the participants and authors,which made it possible to document this valuable material, is grate­fully acknowledged. The format of the volume, abbreviations, ref­erences, etc., conform to that of previous volumes as outlined bythe publisher, Plenum Press. In addition, the editor thanks all theauthors for their cooperation in using the definitions developed for

4Gram DA - ARO-D-31-124- G1l57 to Clarkson Coll ege of Technology with A. VI.Czanderna as Principal Investigator.

5 Announcements, J . Vac . Sci. Tech. 6 : 277. 1969.

6Chem . Eng. News, Feb. 24. 1969, p. 96; May 19, 1969, p. 46.7 Research /Development. May 1969. p. 46; June 1969, p. 40.

INTRODUCTION vii

microbalances 8 and the AVS standard symbols for vacuum sys­tems.i

It is a pleasure to thank all the people who contributed to thesuccess of the Eighth Conference. Two complete mailings of the"Call for Papers n were handled by Pat Gaskins and Colin Williamsand the staff of the Cahn Division of the Ventron Instruments Com­pany. The papers for the technical program were selected by S. P.Wolsky and A. W. Czanderna on the basis of abstracts submitted.Local arrangements for the meeting at the Colonial Statler Hiltonwere made by S. P. Wolsky, E. J. Zdanuk, and Mrs. M. Dor andi.The participants enjoyed hospitality provided by the Cahn, Rodder,Sartorius, and Worden Instrument Companies. Considerable typingand secretarial contributions were made by Mrs. A. Hollister fromthe planning stages to the publication of this volume. The painstak­ing task of copyediting the manuscripts and proofreading the galleysfell on Mrs. A. Czanderna and her assistance is gratefully acknowl­edged. Finally, it is my pleasure to thank Dr. H. M. Davis of theARO-Durham, Dr . E . E . Anderson, Chairman of Physics at Clark­son College of Technology, and Dr. S. P, Wolsky, Director of Re­search at P, R. Mallory and Son, Inc., whose administrative deci-s ions and / or expertise led to direct financial support that made itpossible to hold the E'ighth Conference on Vacuum MicrobalanceTechniques.

Alvin W. CzandernaPotsdam, New YorkNovember 1969

8 Czanderna , op. cit. •p. 10-11. These definitions evolved from an. original se t suggestedby T. N. Rhodin and were an outgro wth of interaction by S. P. Wolsky. R. L. Schwoebel,E. 1. Zdanuk, and A. W. Czanderna. They are recommended for use by all workers inthe field .

9Graphic Symbols in Vacuu m Technology AVS Standard 7.1-1 966. J. Vac. Sci. Tech.4 : 139-142.1967.

Contents

Conference Participants . . . . . . . . • • . . . • . • . • . . . • xi

Interpretation of Vacuum Microbalance Data during theHigh-Temperature Oxidation of Materials (Invited) 1

E. A. Gulbransen

The Simultaneous Use of Mass Spectrometer and Micro­balance Techniques for the Carbon - OxygenSystem . .. . . . . . . . . . . . • . • . . . . . . . . . • . • 17

J . Graham Br own, John Dollimore , Clive M. Freedman,and Brian H. Harrison

A System for the Determination of Oxidation- ReductionKinetics in Nonstoichiometr ic Metal Oxides . . • • . 29

I. Bransky and N. M. Ta llan

An Automated Bakeable Quartz Fiber Vacuum Ultra-microbalance .. .. . ....... ....... •.••• 43

J. Rodder

Adsorption Studies with a Bakeable Quartz AutomaticRecording Ultramicrobalance ..•.... .••...• 55

Stanley E. Fink and Robert P. Merrill

The Effect of Thermal Gas Motion on MicrobalanceMeasur ements (Invited) ..•.........••...• 73

E. Robens

Gravimetric Adsorption Studies of Hydrogen on GranularMetal Surfaces Using a Vacuum Microbalance 97

D. A. Cadenhead and N. J. Wagner

Gravimetric Measurement of the Molecular Area ofSome Adsorbed Gases .•..•.....••...•••• 111

E. Robens, G. Sandstede , and G. Walter

ix

x

Vapor Adsorption Studies on Low-Energy SolidsJ. W. Whalen

CONTENTS

121

Momentum Artifacts in the Gravimetric Measurement of 131Fast Desorption .....•..•.......•.....•

Robert P. Merrill, Charles R. Arnold, andAndrew J. Robell

On the Development of Electromagnetic Balances inRecent Years .....•..•...•.....•••.. 0 • 141

Tho Gast

Pressure of Light Used as Restoring Force on a Micro-balance .••. 0 0 0 •• 0 0 0 • 0 • 0 • 0 • 0 0 • 0 • 0 0 0 0 0 147

Karl P. Zinnow and Jens Po Dybwad

Vacuum Microbalance Apparatus for Rapid Determinationof Low-Temperature Vaporization Rates . 0 • • • • • 155

J, Gordon Davy

Wireless Temperature Measurement of a Sample inVacuum. 0 0 0 • 0 0 0 0 • 0 0 0 0 0 • 0 0 • • • • • • • • • • • 173

G. Richard Blair

Applications of the Quartz Crystal Resonator (Invited) 183Wo H. King, Jr.

Thermal Degradation of Piperazine Copolyamides . . . . • 201Stephen D. Bruck and Ashok Thadani

A Thermal Analysis System for Radioactive Materials. . 215W. J. Kerrigan, J. S. Byrd, and P. Do Holloway

Thermal Degradation of an Anhydride-Cured EpoxyResin by Laser Heating 0 0 •••••• 0 • 0 • 0 0 0 0 0 • 229

A. So Vlastaras

Author Index

Subject Index

243

247

Conference Participants

Richard M. AlireLos Alamos Scientific

LaboratoryP. O. Box 1663Los Alamos, New Mexico 87544

Warren A. AndersonSylvania Ltg. Center100 Endicott StreetDanvers, Massachusetts 01923

Klaus BehrndtGranville-Phillips Co.5675 E. Arapahoe StreetBoulder, Colorado 80302

Joseph R. BiegenDepartment of PhysicsClarkson College of TechnologyPotsdam, New York 13676

G. Richard BlairHughes Aircraft CompanyElectron Dynamics DivisionTorrance, California 90509

1. BranskyWright-Patterson AFBARL(ARZ) Bldg. 450Ohio 45433

S. D. BruckNational Heart InstituteNational Institute of HealthBethesda, Maryland 20014

xi

D. A. CadenheadDepartment of ChemistrySUNY at BuffaloBuffalo, New York 14214

Peter G. ChamyGeneral Electric Company6901 Elmwood AvenueMaterials Laboratory - 10-779Philadelphia, Pennsylvania 19142

Edward G. Clarke, Jr.Department of PhysicsClarkson College of TechnologyPotsdam, New York 13676

A. W. CzandernaDepartment of PhysicsClarkson College of TechnologyPotsdam, New York 13676

J. DollimoreDept. of Pure and Applied

PhysicsUniversity of SalfordSalford 5, Lancashire,England

Jens Peter DybwadSpace Physics LaboratoryAir Force Cambridge Research

LaboratoriesBedford, Massachusetts 01730

Owen FietTRW Systems1 Space ParkRedondo Beach, California 90278

xii

Nelson C. GardnerChemical Engineering Science

Division618 Glennan BuildingCase Western Reserve Univer-

sityCleveland, Ohio 44106

Pat Gaskins, Consultant11811 Marble Arch DriveSanta Ana, California 92705

Theodor R. GastTechnische Universltat of BerlinKurfiirstendamm 195/1961 Berlin 15, Germany

Leonard J. GordonMIT Lincoln LaboratorySpace Communications D-013Lexington, Massachusetts 02173

George P. GraySystems Research Laboratories7001 Indian Ripple RoadDayton, Ohio 45440

Earl A. GulbransenWestinghouse Research

LaboratoriesPittsburgh, Pennsylvania 15235

M. HablanianNorton CompanyVacuum Equipment DivisionNewton, Massachusetts

Eugene A. HarlacherContinental Oil CompanyPonca City, Oklahoma 74601

M. H. HoustonMassachusetts lust. of

TechnologyCambridge, Massachusetts

CONFERENCE PARTICIPANTS

Donald W. KempAmerican Cyanamid1937 Main StreetStamford, Connecticut

W. J. KerriganSavannah River LaboratoryE. 1. du Pont de Nemours and

Co.Aiken, South Carolina 29801

W. H. King, Jr.Esso Research and Engineering

Co.P. O. Box 121Linden, New Jersey 07036

Morton LiebermanSandia CorporationSandia BaseAlbuquerque, New Mexico 87115

Thomas D. McGeeIowa State UniversityAmes, Iowa 50010

Robert P. MerrillDept. of Chemical EngineeringUniversity of CaliforniaBerkeley, California 94720

Donald E. MeyerTexas Instrumentsp. O. Box 5012 MS-913Dallas, Texas 75238

Edward B. MurphyMIT Lincoln LaboratoryBox 73Lexington, Massachusetts 02173

William NoakesVentron Instruments Ltd.27 Essex RoadDartford, Kent , England

CONFERE NCE PARTICI PA ~T S xii i

Ray D. WordenWorden Quartz Products6121 HillcroftHouston, Texas 77036

Colin J. WilliamsCahn Div, - Ventron Instruments

Co.7fiOO Jefferson StreetParamount, California 90723

James W. WhalenDepartment of ChemistryUniversity of Texas at El PasoEl Paso, Texas

Jerry WeilCahn Dlv, - Ventron Instruments

Co.7500 Jeffers on StreetParamount , California 90723

Nor man WagnerDepartment of ChemistrySUNY at BuffaloBuffalo, New York 14214

J. RedderRodder Instrument Company775 Sunshine Dr iveLos Altos , California

Walter TrippSystems Research Laboratory7001 Indian Ripple RoadDayton, Ohio 45440

Erich RobensBattelle-Institut e . V.6 Frankfurt /Main - 90Wiesbadener Strasse, Germany

Edward ZdanukA. S. Vlastaras r . R. Mall or y and Company ,General Electric Com pany Inc.6901 Elmwood Avenue N. W. Ind. ParkPhiladelphia, Penns ylvania 19142 Burlington,Massachusetts 01801

Peter H. PriceAC Electronics DivisionGeneral Motors CorporationWakefield, Massachusetts 01880

James S. RadawskiCalm Div. - Ventron Inst, Corp.7500 Jefferson StreetParamount, California 90723

Daniel A. RankinGeneral Oceanology27 Moulton StreetCambridge, Massachusetts02138

Karl P. ZinnowSpace Physics LaboratoryAir Force Cam br idge Research

LaboratoriesBedford, Massachusetts 01730