ELECTRODEPOSITION The Materials Science of Coatings and Substrates Jack W. Dini Lawrence Livcrmorc National Laboratory Livemiore. Califorilia Reprint Edition NOYES PUBLICATIONS Westwood, New Jersey, U.S.A. Copyright 0 1993 by Jack W. Dini No part of this book may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording or by any informa- tion storage and retrieval system, without permission in writing from the Publisher. Library of Congress Catalog Card Number: 92-27804 ISBN: 0-8155-1320-8 Printed in the United States Published in the United States of America by Noyes Publications Fairview Avenue, Westwood, New Jersey 07675 IO 9 a 7 65 4 Library of Congress Cataloging-in-Publication Data Dini, J.W. Electrodeposition : the materials science of coatings and substrates /by Jack W. Dini. p. cm. Includes bibliographical references and index. ISBN 0-8155-1320-8 1. Electroplating. I. Title. TS670.D55 1992 671.7’32--dc20 92-27804 CIP MATERIALS SCIENCE AND PROCESS TECHNOLOGY SERIES Editors Rointan F. Bunshah, University of California, Los Angeles (Series Editor) Gary E. McGuire, Microelectronics Center of North Carolina (Series Editor) Stephen M. Rossnagel, IBM Thomas J. Watson Research Center (Consulting Editor) Electronic Materials and Process Technology DEPOSITION TECHNOLOGIES FOR FILMS AND COATINGS: by Rointan F. Bunshah et al CHEMICAL VAPOR DEPOSITION FOR MICROELECTRONICS: by Arthur Sherman SEMICONDUCTOR MATERIALS AND PROCESS TECHNOLOGY HANDBOOK: edited by Gary E. McGuire HYBRID MICROCIRCUIT'TECHNOLOGY HANDBOOK: by James J. Licari and Leonard R. Enlow HANDBOOK OF THIN FILM DEPOSITION PROCESSES AND TECHNIQUES: edited by Klaus K. Schuegraf IONIZED-CLUSTER BEAM DEPOSITION AND EPITAXY: by Toshinori Takagi DIFFUSION PHENOMENA IN THIN FILMS AND MICROELECTRONIC MATERIALS: edited by Devendra Gupta and Paul S. Ho HANDBOOK OF CONTAMINATION CONTROL IN MICROELECTRONICS: edited by Donald L. Tolliver HANDBOOK OF ION BEAM PROCESSING TECHNOLOGY: edited by Jerome J. Cuomo, Stephen M. Rossnagel, and Harold R. Kaufman CHARACTERIZATION OF SEMICONDUCTOR MATERIALS-Volume 1 : edited by Gary E. Mc Gu ir e HANDBOOK OF PLASMA PROCESSING TECHNOLOGY: edited by Stephen M. Rossnagel, Jerome J. Cuomo, and William D. Westwood HANDBOOK OF SEMICONDUCTOR SILICON TECHNOLOGY: edited by William C. OMara, Robert B. Herring, and Lee P. Hunt HANDBOOK OF POLYMER COATINGS FOR ELECTRONICS-Second Edition: by James J. Licari and Laura A. Hughes HANDBOOK OF SPUTTER DEPOSITION TECHNOLOGY: by Kiyotaka Wasa and Shigeru Hayakawa HANDBOOK OF VLSl MICROLITHOGRAPHY: edited by William B. Glendinning and John N. Helbert CHEMISTRY OF SUPERCONDUCTOR MATERIALS: edited by Terrell A. Vanderah CHEMICAL VAPOR DEPOSITION OF TUNGSTEN AND TUNGSTEN SILICIDES: by John E.J. Schmitz ELECTROCHEMISTRY OF SEMICONDUCTORS AND ELECTRONICS: edited by John McHardy and Frank Ludwig (continued) V vi Series HANDBOOK OF CHEMICAL VAPOR DEPOSITION: by Hugh 0. Pierson DIAMOND FILMS AND COATINGS: edited by Robert F. Davis ELECTRODEPOSITION: by Jack W. Dini Ceramic and Other Materials-Processing and Technology SOL-GEL TECHNOLOGY FOR THIN FILMS, FIBERS, PREFORMS, ELECTRONICS AND SPECIALTY SHAPES: edited by Lisa C. Klein FIBER REINFORCED CERAMIC COMPOSITES: by K.S. Mazdiyasni ADVANCED CERAMIC PROCESSING AND TECHNOLOGY-Volume 1: edited by Jon G.P. Binner FRICTION AND WEAR TRANSITIONS OF MATERIALS: by Peter J. Blau SHOCK WAVES FOR INDUSTRIAL APPLICATIONS: edited by Lawrence E. Murr SPECIAL MELTING AND PROCESSING TECHNOLOGIES: edited by G.K. Bhat CORROSION OF GLASS, CERAMICS AND CERAMIC SUPERCONDUCTORS: edited by David E. Clark and Bruce K. Zoitos HANDBOOK OF INDUSTRIAL REFRACTORIES TECHNOLOGY: by Stephen C. Carniglia and Gordon L. Barna CERAMIC FILMS AND COATINGS: edited by John B. Wachtman and Richard A. Haber Related Tides ADHESIVES TECHNOLOGY HANDBOOK: by Arthur H. Landrock HANDBOOK OF THERMOSET PLASTICS: edited by Sidney H. Goodman SURFACE PREPARATION TECHNIQUES FOR ADHESIVE BONDING: by Raymond F. Wegrnan FORMULATING PLASTICS AND ELASTOMERS BY COMPUTER: by Ralph D. Hermansen HANDBOOK OF ADHESIVE BONDED STRUCTURAL REPAIR: by Raymond F. Wegman and Thomas R. Tullos CARBON-CARBON MATERIALS AND COMPOSITES: edited by John D. Buckley and Dan D. Edie PREFACE INTRODUCTION This book grew out of a short course that I've taught with Mort Schwartz and then Dick Baker. When Rudy Johnson (my colleague for many years at Sandia) saw my notes he suggested that, they should be put in the form of a book. His suggestion was the prod that I needed to undertake this project. Knowledge of the relationships between microstructure and mechanical properties has always been one of the primary goals of metallurgy and materials science. This has led to the point that "tailored" properties of materials are now a reality. We are no longer limited to combinations of elements allowed by nature to form structures dictated by the small differences in the forces between atoms and the free energies in condensed matter that define equilibrium form. The fascinating field of electrodeposition allows one to "tailor" the surface properties of a bulk material or in the case of electroforming, the entire part. Deposits can be produced to meet a variety of demands of the designer. For this reason and for the possibilities that exist in terms of "new materials" for a variety of applications, a thorough understanding of materials science and principles is of utmost importance. This book is intended to provide some of that understanding. The sequence of chapters in the book takes the reader from the substrate to the outer surface of the coating. It starts with the substrate (Hydrogen Embrittlement), then proceeds to the substrate/coating interface (Adhesion, Diffusion), then the bulk of the coating (Structure, Properties, Addition Agents, Stress, Porosity) and finally to the environmental interface of the coating (Corrosion, Wear). Although the title ELECTRODEPOSITION: The Materials Science of Coatings and Substrates sounds specific to electrodeposition, this does not mean that other coating processes are not covered. Coating technologies such as physical vapor deposition, chemical vapor deposition, plasma spraying and ion implantation are occasionally discussed. Growth of films and their performance from a materials science viewpoint have a great deal of commonality regardless of the technique used to deposit the film. I am indebted to many individuals who have -provided help along the way. Ted Pavlish opened my eyes to the fascinatingfield of electroplal- vii viii Preface ing in 1950 and he and his brother Arnold nurtured me for 9 years at Cleveland Supply Company (now Pavco) during my high school and college years. Following this, a few years at Battelle Columbus Laboratories gave me the chance to work with people like Glenn Schaer, Bill Safranek, John Beach, Charlie Faust, and Hugh Miller, some of the forerunners in electroplating research and development at that time. At Sandia Livermore, Rudy Johnson and I were a team for over 15 years and even though we’ve been apart for the past 13 years, some people still mistake one of us for the other. It was always difficult to determine where Rudy’s effort stopped and mine began and vice versa. Also at Sandia, there were a number of highly talented, well educated young materials scientists and engineers who were quite helpful. Sandia’s practice of hiring top-of-theclass people from the leading schools in the country meant that you learned by just being around such talent. My thanks to all of these people and others who were so helpful during the years at Sandia. At LLNL, a key individual was Harold Wiesner who was always available for advice and suggestions. Others at LLNL who have been particularly helpful include Ron Reno, Fritz Rittmann, Den Fisher and Tom Beat. Special thanks are due to Mort Schwartz for his support in introducing me to and sharing short course assignments as well as results of his efforts with graduate students at UCLA. I also thank all of you have helped either through AESF or on mutual technical projects. Lastly, but not least, thanks to George Narita of Noyes Publications for his help and encouragement in seeing this book to fruition. Livermore, California J. W. Dini April, 1992 NOTICE To the best of the Publisher‘s knowledge the information contained in this book is accurate; however, the Publisher assumes no responsibility nor liability for errors or any consequences arising from the use of the information contained herein. Final determination of the suitability of any information, procedure, or product for use contemplated by any user, and the manner of that use, is the sole responsibility of the user. The book is intended for informational purposes only. Electrodeposition raw materials and processes could be potentially hazardous and due caution should always be exercised in the handling of materials and equipment. Expert advice should be obtained at all times when implementation is being considered. CONTENTS 1. INTRODUCTION .................................... 1 Comments on Electrodeposition ........................ 2 Factors Affecting Coatings ............................ 2 References ........................................ 9 2. HYDROGEN EMBRITTLEMENT ....................... 11 Mechanism ....................................... 20 Steels ........................................... 20 Prevention of Hydrogen Embrittlement ................. 22 Cd-Ti Plating ................................... 26 Mechanical Plating ...............................