UNIVERSIDADE DE ÉVORA ARCHMAT (ERASMUS MUNDUS MASTER IN ARCHaeological MATerials Science) Mestrado em Arqueologia e Ambiente Morphological and chemical characterization of tintypes and ambrotypes Leonor Costa 34314 Supervisors: Professor Teresa Ferreira, Universidade de Évora Professor Catarina Miguel, Universidade de Évora Évora, September 2016 A Tese não inclui as críticas e sugestões do Júri i Acknowledgements I want to acknowledge my supervisors, Professor Teresa Ferreira and Doutora Catarina Miguel, for their much prised advice, guidance and support. I am very thankful to Margarida Nunes for her precious help, patience and availability to clarify (a lot) of things I struggled with. Also, Sónia Costa for the technical photography and Milene Trindade for handling the conservation issues. I also want to thank my friends and fellow Archmatians, Milan Marković for his kindness and wholehearted friendship; Whitney Jacobs, Diego Badillo and Dauren Adilbekov for their friendships and wide-ranging conversations, sometimes, though rarely, even about our projects; and everyone else for sticking together and having fun wherever we went. Finally, and most vitally, I want to thank my parents. For so many things they wouldn’t fit. ii Table of Contents Acknowledgements ........................................................................................................................ i Table of Contents ........................................................................................................................... ii List of figures .................................................................................................................................. ii List of tables ................................................................................................................................... v Abstract .......................................................................................................................................... ii Chapter I: Introduction 1.1. Introduction to the subject ................................................................................................... 1 1.2. The basic elements of photography ....................................................................................... 1 1.3. Historical context ................................................................................................................... 3 1.4. The wet collodion process ...................................................................................................... 4 1.4.1. The Ambrotype ................................................................................................................ 8 1.4.2. The Tintype .................................................................................................................... 11 1.4.3. Retouched photographs ................................................................................................ 15 1.4.4. Finishing varnishes ........................................................................................................ 17 1.5. Degradation of photographic objects .................................................................................. 18 1.5.1. General degradation ..................................................................................................... 18 1.5.2. Degradation of the image forming particles ................................................................ 18 1.5.3. Degradation of the collodion ........................................................................................ 19 1.5.4. Degradation of the support ........................................................................................... 20 1.6. Review of the analytical techniques used in the characterization of photographic items .. 22 1.6.1. Working principles of the analytical techniques used in this work ............................... 23 1.6.1.1. Technical photography ........................................................................................... 23 1.6.1.2. Optical Microscopy (OM) ....................................................................................... 24 1.6.1.3. Scanning Electron Microscopy coupled with Energy Dispersive Spectroscopy (SEM-EDS) .................................................................................................................................... 25 1.6.1.4. Micro-Fourier Transform Infrared Spectroscopy (µ-FT-IR) .................................... 26 ii 1.6.1.5. Micro-Raman Spectroscopy (µ-Raman) ................................................................. 27 1.6.1.6. Micro X-ray Diffraction (µ-XRD) ............................................................................. 28 Chapter II: Materials and Methods 2.1. Sample selection .................................................................................................................. 32 2.2. Methodology ........................................................................................................................ 35 2.2.1. Technical photography .................................................................................................. 36 2.2.2. Optical Microscopy (OM) .............................................................................................. 36 2.2.3. Scanning Electron Microscopy coupled with Energy Dispersive Spectroscopy (SEM- EDS) ............................................................................................................................................. 37 2.2.4. Micro-Fourier Transform Infrared Spectroscopy (µ-FT-IR) ........................................... 37 2.2.5. Micro-Raman Spectroscopy (µ-Raman) ........................................................................ 38 2.2.5. Micro X-ray Diffraction (µ-XRD) .................................................................................... 38 Chapter III: Results and Discussion 3.1. Morphological and chemical characterization ..................................................................... 40 3.1.1. Technical photography .................................................................................................. 40 Ambrotypes ......................................................................................................................... 40 Tintypes ............................................................................................................................... 43 3.1.2. Optical Microscopy (OM) .............................................................................................. 45 Ambrotypes ......................................................................................................................... 45 Tintypes ............................................................................................................................... 51 3.1.3. Scanning Electron Microscopy coupled with Energy Dispersive Spectroscopy (SEM- EDS) ............................................................................................................................................. 56 Ambrotypes ......................................................................................................................... 56 Tintypes ............................................................................................................................... 66 3.1.4. Micro-Fourier Transform Infrared Spectroscopy (µ-FT-IR) ........................................... 73 Ambrotypes ......................................................................................................................... 73 Tintypes ............................................................................................................................... 74 iii 3.1.5. Micro-Raman Spectroscopy (µ-Raman) ........................................................................ 75 Ambrotypes ......................................................................................................................... 75 Tintypes ............................................................................................................................... 77 3.1.6. Micro X-ray Diffraction (µ-XRD) .................................................................................... 79 Ambrotypes ......................................................................................................................... 79 Tintypes ............................................................................................................................... 81 Brass mats ........................................................................................................................... 83 Chapter IV: Conclusions .............................................................................................................. 85 References .................................................................................................................................. 87 Appendices ................................................................................................................................. 93 iv List of figures Figure 1: steps in the formation of a silver halide image. ............................................................. 2 Figure 2: Niépce's first photograph. Source: hrc.utexas.edu ......................................................... 3 Figure 3: iodized collodion being poured onto the plate (top) and the excess being poured back into the bottle (bottom). Source: americanhistory.si.edu .............................................................