Alternative Photographic Processes: Platinomicon

Preface to the Platinomicon ............................................................................................. 7
Preface to an Interim Report to the National Gallery of Art .............................. 8
1. Evolution of the Platinotype Process ...................................................................... 9
1.1 Discoveries of platinum and palladium ............................................... 9
1.2 Noble metals in photography............................................................ 10
1.3 Sir John Herschel's siderotypes ......................................................... 11
1.4 Charles Burnett's experiments .......................................................... 12
1.5 Platinum toning of silver images....................................................... 13
1.6 William Willis's invention................................................................... 14
1.7 Willis's Platinotype Company of London............................................ 24
1.8 Perfection of Platinotype................................................................... 29
1.9 Sepia Platinotype with mercuric salts ................................................ 33
1.10 Willis & Clements Company in the USA ............................................ 35
1.11 Platinotypes by enlargement............................................................ 40
1.12 Notable early users.......................................................................... 41
1.13 Book illustrations and artworks ....................................................... 44
1.14 Platinotype Company papers and fabrics ......................................... 48
1.15 Willis's "Japine" papers..................................................................... 57
1.16 Researches of Pizzighelli and Hübl .................................................. 59
1.17 Other commercial platinum papers.................................................. 61
1.18 "Faux platinum" silver papers .......................................................... 62
2. Transition from Platinum to Palladium................................................................64
2.1 Sources of platinum.......................................................................... 64
2.2 Platinum catalysis............................................................................. 64
2.3 Price history of platinum................................................................... 65
2.4 Alternatives to Platinotype: Nicol’s kallitype...................................... 66
2.5 Willis's "Satista" and "Satoid" papers.................................................. 68
2.6 Platinotype embargoed in Britain ...................................................... 69
2.7 Palladium supplements platinum ...................................................... 73
2.8 Palladiotype launched by Willis ......................................................... 74
2.9 Processing of Platinotype and Palladiotype ....................................... 75
2.10 Later history of the Platinotype Company......................................... 76
2.11 Rôle of Paul Anderson in the USA..................................................... 77
3. Early 20th Century Platinotype and Palladiotype .............................................80
3.1 Platinotypes by Alfred Stieglitz ......................................................... 80
3.2 The issue of "sloppiness".................................................................. 81
3.3 Glycerine development of Platinotypes ............................................. 82
3.4 Multiple coating of platinum papers ................................................. 82
3.5 Platinotype replaced by Palladiotype ................................................. 83
3.6 Elemental composition of Stieglitz prints .......................................... 85
3.7 Tonal reversal or "solarization"......................................................... 86
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3.8 Steichen’s treatment of Stieglitz's Palladiotypes................................ 87
3.9 Problems of conserving Palladiotypes ............................................... 88
3.10 Paul Strand’s platinum prints........................................................... 88
3.11 Composites with cyanotype and gum printing ................................. 89
3.12 Platinum printers contemporary with Stieglitz.................................. 91
4. Later 20th Century Platinum-Palladium Printing.............................................96
4.1 Irving Penn’s initiative ...................................................................... 96
4.2 Platinum-palladium revival in the USA ............................................ 100
4.3 Platinum-palladium processes in the UK......................................... 102
4.4 Impact of digital imaging................................................................ 103
4.5 Digital chemitype or chemical piezotype......................................... 104
4.6 Describing platinum and palladium prints ...................................... 106
4.7 Identifying platinum prints ............................................................. 108
4.8 Deposition of metals on palladium images ..................................... 109
5. Analysis of Platinum Papers and Prints............................................................110
5.1 Willis's formulae ............................................................................. 110
5.2 Sources of paper rawstock.............................................................. 111
5.3 Pizzighelli's formulations................................................................ 115
5.4 Sizing agents in Willis's papers ....................................................... 116
5.5 X-ray spectrometry ........................................................................ 117
5.6 Infrared and Raman spectroscopy................................................... 123
5.7 Analysis and simulation of "Japine" paper ....................................... 126
5.8 Analysis and simulation of "Satista" paper ...................................... 127
5.9 Identification of toned platinotypes ................................................ 129
5.10 Electron microscopy ...................................................................... 129
6. Traditional Platinotype and Palladiotype.........................................................132
6.1 Expression of solution concentrations ............................................ 132
6.2 Ferric oxalate ................................................................................. 133
6.3 Potassium tetrachloroplatinate ....................................................... 135
6.4 Health warning: platinum allergy .................................................... 135
6.5 Agents for increasing contrast........................................................ 136
6.6 Sodium tetrachloropalladate........................................................... 137
6.7 Salts of mercury(II) and lead(II)........................................................ 138
6.8 Choice of papers ............................................................................ 139
6.9 Silica and aluminosilicates in papers............................................... 141
6.10 Coating procedure......................................................................... 141
6.11 Drying and humidity control.......................................................... 142
6.12 Test target images......................................................................... 142
6.13 Ultraviolet light source .................................................................. 144
6.14 Exposure determination ................................................................ 145
6.15 Platinotype processing................................................................... 145
6.16 Palladiotype processing ................................................................. 146
6.17 Processing variations..................................................................... 146
6.18 Partial reversal of tonality .............................................................. 147
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7. Modern Printout Platino-Palladiotype...............................................................150
7.1 Working environment ..................................................................... 150
7.2 Sensitizer chemicals ....................................................................... 151
7.3 Processing chemicals...................................................................... 152
7.4 Apparatus for preparing sensitizer ................................................. 153
7.5 Equipment for printing ................................................................... 153
7.6 Iron solution preparation................................................................ 154
7.7 Platinum solution preparation......................................................... 154
7.8 Palladium solution preparation ....................................................... 155
7.9 Processing solutions....................................................................... 156
7.10 Suitable modern papers.................................................................. 157
7.11 Sensitizer composition and image colour....................................... 158
7.12 Sensitizer characteristics ............................................................... 158
7.13 Choice of print contrast................................................................. 159
7.14 Mixing the sensitizer solutions ...................................................... 159
7.15 Use of surfactant........................................................................... 159
7.16 Coating by glass rod...................................................................... 160
7.17 Drying and storage........................................................................ 161
7.18 Humidifying .................................................................................. 161
7.19 Ultraviolet light sources................................................................. 162
7.20 Exposure and printing frames........................................................ 164
7.21 Negative masking.......................................................................... 165
7.22 Wet processing procedure ............................................................. 166
7.23 Finishing, permanence and stability............................................... 166
7.24 Workflow for platino-palladiotype ................................................. 167
7.25 Printing in 100% Platinum.............................................................. 168
8. Cellulose Chemistry and Suitable Papers ........................................................169
8.1 Molecular structure and morphology of cellulose............................ 169
8.2 Water content of cellulose .............................................................. 171
8.3 Physical chemistry of photosensitised cellulose .............................. 173
8.4 Development versus print-out processes........................................ 175
8.5 Criteria for siderotype papers ......................................................... 177
8.6 Conflicting standards of archival papers ......................................... 180
8.7 Handmade paper for siderotypes.................................................... 181
8.8 Furnishings of flax versus cotton.................................................... 182
8.9 Handling of “vellums”..................................................................... 184
8.10 Machine-made papers for siderotypes........................................... 186
8.11 Japanese handmade papers: “washi”.............................................. 187
9. Deterioration and Post-Treatment of Platinum Prints ..............................189
9.1 Staining of Platinotypes by sulphides.............................................. 189
9.2 Slow development of iron stains ..................................................... 190
9.3 Packham's catechu toner ................................................................ 190
9.4 Early treatments for iron stains....................................................... 192
9.5 Artificial generation of iron stains................................................... 193
9.6 Conservation treatments for iron stains.......................................... 194
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9.7 Acidity catalysed by platinum ......................................................... 196
9.8 Offset imaging: “autoplatinography”.............................................. 197
9.9 Age deterioration of Platinotype paper............................................ 202
9.10 Diagnosis of fogged images .......................................................... 204
9.11 Black spots in platinum-palladium prints....................................... 206
9.12 Fading of Platinotypes and kelainotypes ........................................ 207
9.13 Methods for toning Platinotypes .................................................... 208
10. Relevant Aqueous Chemistry of Iron(III) .......................................................210
10.1 Summary for non-chemists .......................................................... 210
10.2 Hydrolytic reactions and colour .................................................... 211
10.3 Hydrolysis and precipitation ......................................................... 212
10.4 Free radicals................................................................................. 212
10.5 Coordination by oxalate ............................................................... 213
10.6 Solubility of potassium ferrioxalate .............................................. 215
10.7 Photochemical effects on iron(III) speciation ................................. 216
10.8 Staining of cellulose by iron(III)..................................................... 217
10.9 Chelation of iron .......................................................................... 220
10.10 Chemistry of clearing siderotypes................................................ 221
11. Chemistry of Platinum and Palladium Printing ..........................................224
11.1 Photochemistry of iron(III) oxalates............................................... 224
11.2 Ferric oxalate versus ammonium ferric oxalate............................. 225
11.3 Siderotype by reduction of noble metals ....................................... 227
11.4 Printing in palladium and platinum compared............................... 230
11.5 Effects of gelatin sizing on platinum printout ............................... 233
11.6 Characteristic curves by densitometry .......................................... 234
11.7 Aquation of platinum(II) and palladium(II) ..................................... 237
11.8 The iron(II)-platinum(II) redox reaction......................................... 237
11.9 Effects of mercury(II), lead(II) and silver(I) ..................................... 238
11.10 Mercury in platinotypes and palladiotypes ................................... 240
11.11 The 'inhibited edge' effect ........................................................... 243
11.12 Effects of gold(III) ........................................................................ 245
11.13 Choice of cation .......................................................................... 245
11.14 Optical properties of metal nanoparticles .................................... 247
11.15 Factors influencing image colour ................................................. 248
11.16 Control of humidity ..................................................................... 252
12. Quantitative Aspects of Siderotype Photochemistry ...............................256
12.1 Spectral emissivity of light sources ............................................... 256
12.2 Wavelength dependence of quantum yield.................................... 257
12.3 Absorbance of the photoactive species ......................................... 258
12.4 Absorption of UV by glass ............................................................ 260
12.5 Wavelength dependence of photochemical yield ........................... 262
12.6 Theory of exposure times............................................................. 263
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APPENDIX I Introduction to Relevant Photochemistry ....................................266
I.1 Oxidation and reduction exemplified by iron ................................... 266
I.2 Iron-based imaging systems ........................................................... 266
I.3 Classical platinum and palladium printing ....................................... 267
I.4 Modern platinum-palladium printing............................................... 268
I.5 Other siderotype processes ............................................................. 269
I.6 Chelating ligands for clearing prints ................................................ 269
I.7 Summary of photochemical principles ............................................. 270
I.8 Grotthuss-Draper law...................................................................... 270
I.9 Stark-Einstein law............................................................................ 271
I.10 Planck law ...................................................................................... 271
I.11 Bunsen-Roscoe law ........................................................................ 272
I.12 Beer-Lambert law ........................................................................... 272
APPENDIX II Technical Objectives of the NGA Project 2010-2015 ...........273
APPENDIX III Chronology of Platinotype & Palladiotype ................................274
APPENDIX IV Preparation of Digital Negatives ...................................................279
IV.1 Summary and purpose.................................................................... 279
IV.2 Calibration of equipment and materials .......................................... 279
IV.3 Fine-tuning negative opacities ....................................................... 281
IV.4 Tonal correction curves by the 'gamma' control .............................. 281
IV.5 Workflow for digital negatives in Photoshop CS .............................. 283
IV.6 Short version of the workflow ......................................................... 289
APPENDIX V Alphabetical List of Relevant Chemicals.....................................290
APPENDIX VI Chemical Preparations .......................................................................300
VI.1 Ammonium ferric oxalate ............................................................... 300
VI.2 Ferric oxalate ................................................................................. 300
APPENDIX VII Specifications of William Willis's British Patents..................302
VII.1 No 2011, June 5th, 1873................................................................. 302
VII.2 No 2800, July 12th, 1878 ................................................................ 304
VII.3 No 1117, March 15th, 1880 ............................................................ 306
VII.4 No 1681, February 2nd, 1887.......................................................... 309
VII.5 No 16,003, November 21st, 1887 ................................................... 312
VII.6 No 20,022, September 4th, 1913 .................................................... 316
APPENDIX VIII Conversion of Obsolete Units of Measurement...................321
VIII.1 Weight.......................................................................................... 321
VIII.2 Volume......................................................................................... 322
VIII.3 Area ............................................................................................. 322
APPENDIX IX Glossary....................................................................................................323
Notes and References ....................................................................................................339
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