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Information to Users INFORMATION TO USERS This reproduction was made from a copy of a manuscript sent to us for publication and microfilming. While the most advanced technology has been used to pho­ tograph and reproduce this manuscript, the quality of the reproduction is heavily dependent upon the quédlty of the material submitted. Pages in any manuscript may have indistinct print. In all cases the best available copy has been filmed. The following explanation of techniques is provided to help clarify notations which may appear on this reproduction. 1. Manuscripts may not always be complete. When it is not possible to obtain missing pages, a note appears to indicate this. 2. When copyrighted materials are removed from the manuscript, a note ap­ pears to indicate this. 3. Oversize materials (maps, drawings, and charts) are photographed by sec­ tioning the original, beginning at the upper left hemd comer and continu­ ing from left to right in equal sections with small overlaps. Each oversize page is also filmed as one exposure and is available, for an additional charge, as a standard 35mm slide or in black and white paper format. * 4. Most photographs reproduce acceptably on positive microfilm or micro­ fiche but lack clarity on xerographic copies made from the microfilm. For an additional charge, all photographs are available in black and white stcmdard 35mm slide format.* *For more information about black and white slides or enlarged paper reproductions, please contact the Dissertations Customer Services Department. IVBcrofilnis lateniai^oiial 8612390 Lee, Jong-Kwon STRESS CORROSION CRACKING AND PITTING OF SENSITIZED TYPE 304 STAINLESS STEEL IN CHLORIDE SOLUTIONS CONTAINING SULFUR SPECIES AT TEMPERATURES FROM 50 TO 200 DEGREES C The Ohio State University Ph.D. 1986 University Microfilms I nternstionel 300 N. zeeb Road, Ann Arbor, Ml 48106 PLEASE NOTE: In all cases this material has been filmed in the best possible way from the available copy. Problems encountered with this document have been identified here with a check mark V 1. Glossy photographs or pages. 2. Colored illustrations, paper or print. 3. Photographs with dark background ,/^ 4. lilustrations are poor copy ______ 5. Pages with black marks, not original copy _ 6. Print shows through as there is text on both sides of p ag e. 7. indistinct, broken or smali print on several pages 8. Print exceeds margin requirements _____ 9. Tightiy bound copy with print lost in spine _______ 10. Computer printout pages with indistinct print. 11. Page(s) ___________ lacking when material received, and not available from school or author. 12. Page(s) ___________ seem to be missing in numbering only as text follows. 13. Two pages numbered . Text follows. 14. Curling and wrinkled pages ______ 15. Dissertation contains pages with print at a slant, filmed as received _________ 16. Other____________________________________________________________________ University Microfiims International STRESS CORROSION CRACKING AND PITTING OF SENSITIZED TYPE 304 STAINLESS STEEL IN CHLORIDE SOLUTIONS CONTAINING SULFUR SPECIES AT TEMPERATURES FROM 50 TO 200°C DISSERTATION Presented 1n Partial Fulfillment of the Requirments for the Degree Doctor of Philosophy in the Graduate School of the Ohio State University By Jong-Kwon, Lee, B.S, M.S. ***** The Ohio State University 1986 Reading Committee: Prof. Susan Smialowska Approved By Prof. John P. Hirth Prof. Bryan E. Wilde Adviser Department of Metallurgical Engineering To my parents To my wife 11 ACKNOWLEDGEMENTS I wish to express my deep appreciation to professor S. Smialowska for her advice and encouragement during the course of this study. I would like to thank Professor 0. P. Hirth and B. E. Wilde who served as members of reading committee for this dissertation. I am also Indebted to Dr. G. Cragnolino for sincere discussion and guidance. My special appreciation must be given to V. Jaganathan for correcting my English. I also wish to acknowledge the encourgement from colleagues; M. Y. Lee, C. 0. Park, H. Betrabet, J. R. Park and S. H. Shim. I wish to thank the following workers for their assltance; R. B. Farrar, C. Macdonald, L. Otenberger, D. Murfleld, T. Biggert and S. Euans. Financial support from the Electric Power Research Institute Is also gratefully appreciated. Also, I would like to thank Korea In stitu te of Machinery and Metals and Korea Science and Engineering Foundation for their encouragement and support. Finally, I'd like to express my appreciation to my parents, my wife, my brother and sisters. ill VITA June 1, 1955 .................. Born - Daegu, Korea 1977 ........... .......................... B.S., MetalTurglca Engineering, Seoul National University, Seoul, Korea 1979 .......................... M.S. m aterials Science Korea Advanced In stitu te of Science, Seoul, Korea 1979 - 1982 ................... Research Scientist, Korea Institute of Machinery and Metals, Changwon, Korea 1982 - 1985 ................... Gradute Research Associate, Department of Metallurgical Engineering, The Ohio State University, Columbus, Ohio FIELD OF STUDY Major Field: Metallurgical Engineering Studies in Corrosion: Professors S. Smialowska, D. D. Macdonald, R. A. Rapp and F. H. Beck Studies in Physical Metallurgy: Professors G. W. Powell, G. Meyrick, P. G. Shewmon and J, P. Hirth Studies in Chemical Metallurgy: Professors G. St. Pierre and W. Johnson Studies in Mechanical Metallurgy: Professors R. G. Hoagland and R. Wagoner Studies in Electron Microscope: W. Clark iv TABLE OF CONTENTS DEDICATION ........................................................................................................ il ACKNOWLEDGEMENT ............................................................................................... H i VITA .................................................................................................................... iv TABLE OF CONTENTS ........................................................................................... v LIST OF TABLES ................................................................................................. ix LIST OF FIGURES ............................................................................................... xi CHAPTER I. INTRODUCTION ............................................................................................. 1 II. LITERATURE SURVEY .................................................................................... 3 2.1 Introduction ................................................................................... 3 2.2 Stress Corrosion Cracking of Sensitized Type 304 Stainless Steel .............................................................................. 3 2.2.1 Stress Corrosion Cracking in Chloride Solution . 3 2.2.1.1 Effect of Chloride Ion Concentration .. 4 2.2.1.2 Critical Potential ...................................... 7 2.2.1.3 Effect of pH ................................................ 15 2.2.2 Effect of Dissolved Oxygen Content in Water on the Stress Corrosion Cracking Susceptibility ... 18 2.2.3 Effect of Sulfur Species on the Stress Corrosion Cracking Susceptibility ............................................ 29 2.2.3.1 Solution ........................................................ 29 2.2.3.2 Effect of Potential ................................... 44 2.2.3.3 Effect of pH ................................................ 49 V 2.3 Pitting Corrosion ..................................................................... 53 2.3.1 Chloride Environment ................................................... 53 2.3.1.1 Chloride Concentration ............................. 53 2.3.1.2 Temperature ................................................... 58 2.3.1.3 pH .................................................................... 62 2.3.1.4 Effect of Anion Addition ......................... 65 2.3.2 Solution Containing Sulfur Species ....................... 69 2.4 Chemistry of Sulfur Species .................................................. 76 2.4.1 Potential-pH Diagram ................................................... 76 2.4.2 Oxidation of Sulfide ................................................... 83 I II . EXPERIMENTAL PROCEDURE ...................................................................... 97 3.1 Materials ..................................................................................... 97 3.2 Solutions ..................................................................................... 99 3.3 Equipment ..................................................................................... 99 3.3.1 Slow Strain Rate Test ................................................. 99 3.3.2 Electrochemical Measurement ..................................... 107 3.4 Experimental Procedure ............................................................ I ll 3.4.1 Specimen Preparation ................................................... I l l 3.4.2 Solution Preparation ................................................... I ll 3.4.3 Slow Strain Rate Test with Measurement of Corrosion Potential ..................................................... 113 3.4.4 Measurements of Polarization Curves ...................... 115 3.4.5 Potentiostatic P itting Potential Measurement . 116 IV. RESULT..................................................................................................... 118 Vi 4.1 Slow Strain Rate Tests ........................................................... 118 4.1.1 Slow Strain Rate Tests In Air ......................... 127 4.1.2 Slow Strain Rate Tests In Air-Saturated
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