SPECTROSCOPIC STUDIES OF COPPER-BASED PIGMENTS by Marcie B. Wiggins A dissertation submitted to the Faculty of the University of Delaware in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry & Biochemistry Spring 2019 © 2019 Marcie B. Wiggins All Rights Reserved SPECTROSCOPIC STUDIES OF COPPER-BASED PIGMENTS by Marcie B. Wiggins Approved: __________________________________________________________ Brian Bahnson, Ph.D. Chair of the Department of Chemistry and Biochemisty Approved: __________________________________________________________ John Pelesko, Ph.D. Interim Dean of the College of Arts and Sciences Approved: __________________________________________________________ Douglas J. Doren, Ph.D. Interim Vice Provost for Graduate & Professional Education I certify that I have read this dissertation and that in my opinion it meets the academic and professional standard required by the University as a dissertation for the degree of Doctor of Philosophy. Signed: __________________________________________________________ Karl S. Booksh, Ph.D. Professor in charge of dissertation I certify that I have read this dissertation and that in my opinion it meets the academic and professional standard required by the University as a dissertation for the degree of Doctor of Philosophy. Signed: __________________________________________________________ Jocelyn Alcántara-García, Ph.D. Professor in charge of dissertation I certify that I have read this dissertation and that in my opinion it meets the academic and professional standard required by the University as a dissertation for the degree of Doctor of Philosophy. Signed: __________________________________________________________ Steven D. Brown, Ph.D. Member of dissertation committee I certify that I have read this dissertation and that in my opinion it meets the academic and professional standard required by the University as a dissertation for the degree of Doctor of Philosophy. Signed: __________________________________________________________ Cecil Dybowski, Ph.D. Member of dissertation committee I certify that I have read this dissertation and that in my opinion it meets the academic and professional standard required by the University as a dissertation for the degree of Doctor of Philosophy. Signed: __________________________________________________________ Robert Opila, Ph.D. Member of dissertation committee ACKNOWLEDGMENTS I have had many great teachers and advisors who have guided me and encouraged me on the way. Mr. Cowder, my high school chemistry teacher, made the material in the classroom and in the laboratory finally connect. Dr. Eric Breitung, my undergraduate research advisor, gave me my first true research experience and taught how to take ownership of my projects. Dr. Meredith Gill, my undergraduate art history advisor, supported my dual interest in art history and chemistry and helped me to combine them. I would like to thank my graduate co-advisors, Dr. Jocelyn Alcántara- García and Dr. Karl Booksh. Dr. Alcántara-García continues to push me so I can improve in every phase of research as an excellent advisor and friend. Dr. Booksh has allowed me to pursue and advance my interests, and he has never shied away from a new project or challenge. I would also like to thank my committee members for their guidance and feedback during my studies. I want to thank the UD’s Office for Graduate and Professional Education and the UD’s Department of Chemistry and Biochemistry for financial support of my research. Thanks needs to be given wholeheartedly to all of the Booksh research group (past and present), including its honorary members Zachary Voras and Chris Goodwin. Dr. Josh Ottaway, Dr. Zachary Voras, Dr. Anna Murphy, and Chris Goodwin have been terrific mentors and friends during the process, even if most conversations stray to cover any topic under the sun (and beyond!). I want to thank the faculty and staff in the UD’s Department of Art Conservation and Winterthur Museum, Garden and Library for their support. I especially thank Winterthur’s iv Scientific Research and Analysis Laboratory staff for the opportunities they gave me and the knowledge they shared. Catherine Matsen, Dr. Rosie Grayburn, and Dr. Judy Rudolph gave endless help and were great role models. Portions of this work would not be possible without the contributions of my undergraduate students, Lizzy van Winkle and Emma Heath, who have also made me a better teacher. My friends and family have provided never-ending reassurance, comfort, and motivation during this period. I give special thanks to my parents, Mike and Margie Wiggins, for continuing to support me despite the fact I am “always going to be in school,” and I hope to continue to make them proud. There are no words to thank Stephen Christian enough for always supporting and encouraging me during every high and low, whether it is in the form of keeping me on schedule or taking a holiday. However, his most important task, by far, was distracting the cat, Boe, long enough for me to write this dissertation. Boe has provided an endless supply of smiles (and some tears…) for entertainment and distraction alike, but, honestly, he was quite jealous and angry over the amount of attention I paid this thesis instead of him. v TABLE OF CONTENTS LIST OF TABLES ......................................................................................................... x LIST OF FIGURES ....................................................................................................... xi ABSTRACT ................................................................................................................. xv Chapter 1 INTRODUCTION .............................................................................................. 1 1.1 Motivation ................................................................................................. 1 1.2 Overview of Dissertation ........................................................................... 3 1.3 Importance ................................................................................................. 6 REFERENCES ............................................................................................................... 8 2 REVIEW OF COPPER SALTS IN CULTURAL HERITAGE ....................... 12 2.1 Introduction ............................................................................................. 12 2.2 Use in Cultural Heritage .......................................................................... 12 2.2.1 Paintings ...................................................................................... 13 2.2.2 Paper ............................................................................................ 14 2.3 Preparation and Characterization ............................................................ 14 2.3.1 Verdigris (Copper Acetates) ........................................................ 14 2.3.2 Basic Copper Chlorides ............................................................... 16 2.3.3 Characterization Methods ............................................................ 17 2.4 Alteration and Treatment Studies ............................................................ 18 2.4.1 In Paintings .................................................................................. 19 2.4.2 On Paper ...................................................................................... 20 2.5 Conclusion ............................................................................................... 22 REFERENCES ............................................................................................................. 24 vi 3 EXPERIMENTAL OVERVIEW ..................................................................... 35 3.1 Introduction ............................................................................................. 35 3.2 Instrumentation ........................................................................................ 35 3.2.1 X-ray Fluorescence ...................................................................... 35 3.2.2 Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy ................................................................................ 36 3.2.3 X-ray Diffraction ......................................................................... 37 3.2.4 X-ray Photoelectron Spectroscopy .............................................. 40 3.2.5 Time of Flight-Secondary Ion Mass Spectrometry ..................... 42 3.2.6 Fourier-Transform Infrared Spectroscopy ................................... 45 3.2.6.1 Transmittance FTIR ...................................................... 45 3.2.6.2 Attenuated Total Reflectance FTIR .............................. 46 3.2.7 Raman Spectroscopy ................................................................... 46 3.2.7.1 Multivariate Curve Resolution-Alternating Least Squares ......................................................................... 49 REFERENCES ............................................................................................................. 51 4 CHARACTERIZATION OF GREEN PAINTS IN MING & QIAN DYNASTIES LIN’XI PAVILION ................................................................... 53 4.1 Introductory Remarks .............................................................................. 53 4.2 Introduction ............................................................................................. 53 4.3 Materials .................................................................................................