This dissertation has been 64—7070 microfilmed exactly as received WINCHELL, Jr., Robert Eugene, 1931- X-RAY STUDY AND SYNTHESIS OF SOME COPPER-LEAD OXYCHLORIDES. The Ohio State University, Ph.D., 1963 M ineralogy University Microfilms, Inc., Ann Arbor, Michigan X-RAY STUDY AND SYNTHESIS OF SOME COPPER-LEAD OXYCHLORIDES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosopher in the Graduate School of the Ohio State University Robert Eugene W inchell, J r ., B. S ., M. S. The Ohio State University 1963 Approved ty Id viser Department of Mineralogy ACKNOWLEDGMENTS The author wishes to acknowledge the assistance, cooperation and encouragement of a great number of people without whom this thesis could not have been completed. The specimens used in the study of these rare oxychlorides were obtained from a number of sources. Dr. C. S. Hurlbut, Jr. supplied samples of a l l the sp ecies from the c o lle c tio n s o f Harvard U n iversity. Dr. Paul E. Desautels provided additional samples of all the minerals except pseudoboleite from the collections of the United States National Museum. Dr. Raymond Hocart, of the University of Paris, supplied several overgrowths of cumengeite on boleite, which had been given to him by G. Friedel, Dr. S. Grolier, of the St. Etienne School of Mines, St. Etienne, France, provided material that had been available to G. Friedel during his study (Friedel, 1906) of boleite, pseudoboleite, and cumengeite. Dr. S. Caillere provided specimens of boleite, cumengeite and pseudoboleite from the collections of the Paris Museum of Natural History. Dr. P. G. Embrey furnished type percylite from the material described by Brooke (1850) and d ia b o leite and ch loroxip h ite from the Mendip H ills. The specimens furnished by Dr. Embrey were supplied from the collections of the British Museum of History. Mr. Karl Schwartzwalder made available to the author certain facilities of the AC Spark Plug Division of the General Motors Corporation. The author is also indebted to Dr. William Shulhof of i i the AC Spark Plug Division for his cooperation during the use of these facilities. Thanks are also due Dr. Charles Sclar and Dr. George Cocks of Battelle Memorial Institute who made certain equipment available for use in this study. Dr. Reynolds M. Denning of the University of Michigan was also kind enough to provide the use of equipment in the Department of Geology and Mineralogy. Financial assistance which made it possible for the author to devote full time to the research involved in the thesis was provided through the William J. McCaughey Fellowship and the author wishes to thank the contributors to this fellowship for their assistance. The author wishes also to thank the faculty in the Department of Mineralogy for their direct and indirect assistance and encouragement in the course of this study. Most particularly he wishes to thank Dr. Henry £. Wenden, his adviser, for assistance and encouragement during this investigation. Lastly, the author wishes to thank his wife Grace for her encouragement and perserverance, since this dissertation could never have been completed without them. iii CONTENTS Page ACKNOWLEDGMENTS i i LIST OF TABLES v i LIST OF ILLUSTRATIONS v i i i INTRODUCTION 1 I . HISTORICAL SURVEY 2 I I . SCOPE OF THE INVESTIGATION 19 I I I . EXPERIMENTAL METHODS 21 Specimens X-ray Analysis Heating Stage C rystallographic Measurements Specific Gravity Measurements Synthesis MLcrochemical Tests IV. CUMENGEITE...................................................................................... 29 H isto r ic a l Summary Results of Present Study V. PSEUDOBOLEITE................................................................................ 77 H isto r ic a l Summary Results of Present Study VI. BOLEITE ............................................................................................. llJi H isto r ic a l Summary Results of Present Study V II. THE BOLEITE PROBLEM..................................................................... 166 iv CONTENTS (Continued) Page V III. FERCYLITE.............................................................................................. 173 H isto r ic a l Summary Results of Present Study IX. EPITAXY IN THE BOLEITE G R O U P ............................................... 185 X. DIABCLEITE........................................................................................ 192 H isto r ic a l Summary Results of Present Study XI. C HLOROXIP HI T E ................................................................................. 20U H isto r ic a l Summary Results of Present Study X II. SYNTHESIS.............................................................................................. 209 Introduction Experimental Procedure R esults X III. SUMMARY AND CONCLUSIONS............................................................. 222 BIBLIOGRAPHY AND REFERENCES ......................................... 229 AUTOBIOGRAPHY................................. 233 v LIST OF TABLES Table Page 1. Minerals of the boleite group .............................................. 8 2 . The b o le ite g r o u p .................................................................. ........ 11 3. Angle table for cumengeite .................................................... 3U U. Indices of refraction for cumengeite (Hadding, 1919) • 36 5. X-ray powder data for cumengeite ....................................... hi 6. Comparison of x-ray parameters according to the setting of Friedel (1906) ................................................................. 53 7. Crystallographic data for cum engeite ......................... Sh 8. Presence criteria for cumengeite ....................................... 55 9. Specific gravity values for cumengeite ...................................... 68 10. Chemical analyses for cumengeite ................................................ 69 11. X-ray data for cum engeite .................................................... 73 12. X-ray powder data for pseudoboleite ................................ 91 13. Crystallographic data for pseudoboleite ..... 103 lU. Presence criteria for pseudoboleite . 10U 15. Cleavage observed in boleite try Hadding (1919) . • 126 16. Thermal cycle for b o le ite .............................................................. l 5 l 17. X-ray powder data for b o leite ...................................................... 1$6 18. X-ray and microchemical examination of percylite speci­ mens .................................................................................................... 183 19. Comparison of parameters for members of the boleite group determined in this stu d y ....................................... 189 v i LIST OF TABLES (Continued) Table Page 20. X-ray powder data fo r d i a b o l e i t e .............................. 19U 21. Comparison of cell dimensions for diaboleite . 198 22. Forrailas and reagents used in synthesis experiments . 211 23. Summary of diffusion experiments ........................................ 215 2J4. Summary of evaporation exp erim ents ....................... 216 25. Summary of pyrex tube experiments .............................. 217 26. Summary of pot bomb experim ents .............................. 220 v i i IIST OF ILLUSTRATIONS Figure Page 1. Morphology of natural cumengeite (Hadding, 1919) . , U2 2. Morphology of natural cumengeite U2 3. Powder diffraction pattern of natural cumengeite (Sainte- Etienne 2750) ................................................................................ U5 U. Powder d iffr a c tio n pattern of natural cumengeite (USNM 9U6U0) ............................................................................................. , 16 5. Powder diffraction pattern of natural cumengeite from an overgrowth of cumengeite on boleite (Hocart specimen) ...................................................................................... 16 6. Powder diffraction pattern of natural cumengeite from an overgrowth of cumengeite on boleite (OSU collections) ..................................................... .... U5 7. Diagramatic representation of the space group FTnmm . 57 8. Diagramatic representation of the twinned space group FU/m 2/m 2/m developed from ty twinning across (110) or rotation of 90° about 001 ....................................... 57 9. Diagramatic representation of the space group FU/m 2/m 2/m........................................................................................ 61 10. Diagramatic representation of the twinned space group FU/m 2/m 2/m developed from P^/m 2/ m 2/m an n-glide in (001) ......................................................................... 61 11. Disordered form of AuCu^ (after Cullity, 1956) . * 65 12. Ordered form of AuCu^ (after Cullity, 1956) . 65 13 • Morphology of sy n th etic cumengeite ....... 71 lii. Morphology of synthetic cumengeite 71 15. Powder diffraction pattern of natural cumengeite from an overgrowth of cumengeite on boleite (Hocart s p e c i m e n ) .................................................................. 7U v i i i LIST OF ILLUSTRATIONS (Continued) Figure Page 16. Powder diffraction pattern of aynthetic cumengeite obtained try alow diffusion at 25>°C. from stoichio­ metric proportions for pseudoboleite ...... 7k 17 . Powder d iffr a c tio n pattern o f sy n th etic cumengeite obtained in a sealed glass tube at 170°C. from stoichiometric proportions for cumengeite • . 7U 18. Powder diffraction pattern of synthetic cumengeite obtained in a