Below I publish the revised and improved formula for the Chrystoype Supreme, which is a rebranding of the Texas Chrysotype to reflect an improvment in image quality so significant as to compete with platinum. Even more so than dry print out palladium, this is the most popular of my processes, at least based on the volume of email inquiries I receive about nuances involved in printing negatives of varying characteristics. The link to the formula for the palladium process (The Alamotype) can be found on the main page.
THREE FUNDAMENTAL SOLUTIONS
In August of 2011 I invented the Texas Chrysotype out of necessity. I did not want "blushing" chrysotypes -- prints made from a mixture of gold and palladium -- I wanted pure gold photographic prints. The only viable option for a high quality chrysotype was to reproduce Robert Hunt's formula from the 1850s. Hunt included that chrysotype in his Manual of Photography. He described (on pages 54 et seq. in the 4th Edition of that book) printing out a faint image on paper coated with ammonium ferric citrate. He then developed out that faint image with a wash of gold solution which he described as having the color of sherry. With gold running at about $45 a gram, the price of developing out was too high for my budget. I moved on
The next option was the so-called "New Chrysotype" or the obscurely named "Chrysotype S". Whatever its name, the process produces grainy and contrasty prints with a D-Range of only 5 or 6 stops. Poor (absent) D-Min and no zone 7. On examination I concluded that despite all the splashing of waters that had accompanied the announcement of the New Chrysotype S, the process was, in my analysis, nothing more than Richard Sullivan's gold ziatype with the gold solution roughly tripled in strength and a bogus "ligand" added). I moved on.
I knew that I could obtain reasonable prints that were arguably gold -- Richard Sullivan described printing a chrystoype with a maximum of 80% gold and the remainder palladium. The resultant images unfortunately are pink (the obsolete Chrysotype S process yields red or purple-red images). Any pink chrysotype print is invariably formed from an admixture of gold and palladium. Both Sullivan's gold-palladium ziatype and the "New" chrysotype process only work with heavy hydration of paper; the moisture causes the gold to precipitate at such an angle that it refracts light as pink. [Interestingly, some unscrupulous practitioners of the obsolete "New" chrysotype, persons who charge the gullible for workshops and sell books on the process, have made a great honking and crowing with "New" chrystoypes that "blush" with a pink hue, just like Sullivan's gold-palladium prints.]
After discarding the "New" chrysotype for what I perceived to be a failed derivative formula, I resolved to invent a genuinely new way to print in gold. One that would actually work. After all, Sullivan had been looking for a palladium print out process; gold was an afterthought. Knowing as I did that on exposure to UV light, a chemical reaction occurs in which the oxalate converts the ferric iron to ferrous iron, I grasped that if I were to "prep" ammonium ferric oxalate, I could convert some but not all of the iron to its ferrous state and thereby push it to a critical mass in which the noble metal salt -- gold chloride, palladium chloride, rhodium chloride and any of the others -- would begin to reduce to its elemental (and image-forming) state immediately on exposure to UV light. I decided that the chemical process was not a simultaneous transformation of the chemicals involved, but a step-by-step process: first the oxalic acid in in the ammonium ferric oxalate converted ferric iron to ferrous iron, which then fell into the paper fibers. Then when the ferrous iron reached critical mass, the metal salt -- gold chloride, in this case -- was reduced by the chemical release of the chlorine in the presence of that ferrous iron, and the gold would drop into the fibers of the paper. Intuiting how the chemical reactions actually occur, I was able to solve the longstanding problem of printing a continuous tone, grainless, gray scale photographic image in pure gold with a full and normal tonal range (D-Range) -- the Chrysotype Perfected.
I was correct in my surmision. That Chrysotype Supreme images print out with no hydration and no concern for relative humidity was a bonus. I presented the process to the Austin Alternative Photography Group on January 22, 2012, after my submission to the US Patent office was confirmed. In March 2012, View Camera magazine published my article on the long-awaited chrysotype process that delivers exquisite images without the addition of palladium -- draperies that are not pink and blushing, but that are pure gold and glow. In October of 2013 I presented the Texas Chrysotype in person at the APIS in Santa Fe, New Mexico. Then in July of 2014, I printed the largest gold print, an image of the Alamo: 40 inches by 53 inches. The sheer size made it impossible to print out on hydrated paper. The image is red because I wanted it to have a vivid presence on display; to make a chrysotype print out red with no hydration, I applied twice as much magic iron (ammonium ferric ferrous oxalate) as would have been normal. I had experimented with exactly that approach on a whole plate (6.5"x8.5") contact print from the original negative. The extra moisture and double volume of ferrous iron combined to drop the gold at just the right angle to refract light as red. Schiller wrote, Wahrheit ist Feuer und Wahrheit reden heißt leuchten und brennen. My prints burn with the golden truth of their purity and do not blush pink with the shame of deception.
The first fundamental solution is 10 ml of 40% ammonium ferric oxalate. That is achieved by dissolving 4 grams of ammonium ferric oxalate (AFO) crystals in 8 ml of warm (~85F) distilled water. The AFO dissolves easily and quickly. The reason for preparing only 10 ml at a time is that once the solution is transformed into what American wastewater treatment engineers perhaps whimsically call "magic iron", the shelf life plummets to a matter of only a few weeks. Weighing out 4 grams of ammonium ferric oxalate and dissolving them in a 8 ml of distilled water takes less than 5 minutes. The solution should be poured into a brown glass or opaque plastic bottle, capped tightly, and labeled "AFFO" (for Ammonium Ferric Ferrous Oxalate), with the date prepared below.
The second fundamental solution is 1% vitamin C. One needs very little of this solution and its shelf life is several months, so 10 ml is a good volume to prepare. Pour 10 ml of distilled water into a brown glass bottle or opaque plastic bottle. Weigh out 0.1 g of vitamin C (or of sodium ascorbate, which is time-release C with extra sodium added, which has no effect on the AFO). Pour the C into the water in the bottle. Cap the bottle and shake it vigorously for about 60 seconds. Label this bottle 1% C and date it.
The third fundamental solution is sodium sulfite (sodium sulphite). Prepare a 5% solution by dissolving 50 grams in 800 ml of hot water (~125F). Top the solution off to 1000 ml. Store the well-labeled bottle, decorated with a skull and cross bones, in a cold location (not your refrigerator!).
The fourth fundamental solution is a 1% acid bath, such as muriatic acid (~31.5% strength diluted to 1% -- 30 ml in 945 ml of water should suffice). Be aware that the citric acid and other weak acids recommended by people more anxious to sell books than results are not useful for removing the ferrous iron from heavy paper stock, such as 320 gsm Bergger Cot or 310 gsm Arches Platine. Save citric acid for prints on lightweight papers such as Clearprint vellum.
The fifth fundamental solution is 5% sodium carbonate (sold in the US as Arm & Hammer Washing soda). It serves to raise the pH of the paper fibers from lingering acid.
The sixth fundamental solution is Tetrasodium EDTA (T-EDTA), a chelating agent that attaches to iron particles like a chemical magnet and helps loosen them from the fibers of the print. When a sheet of paper so treated is subsequently washed in running water, ferrious iron is efficiently removed. Measure out 950 ml of water. Weigh out 100 g of T-EDTA. Dissolve the T-EDTA in the water. This is the last bath before the final, long water rinse.
The seventh fundamental solution is 26% ferric oxalate, the same light-sensitive compound used for develop out platinum and palladium printing. In this formula, however, the ferric oxalate (with no vitamin C added!) is additive to the gold-magic iron sensitizer, immediately before coating the paper. The ferric oxalate boosts the contrast in the final Chrysotype Supreme without introducing grain. The orange stain of the surfeit of iron is readily removed during the clearing steps. (If by some quirk the iron stain should persist an overnight bath in a working solution of Rit Dye Remover will eliminate the yellow cast. The active ingredient is Sodium hydrosulfite , also known as sodium dithionite.).
This is the most envied photographic printing formula since the Willis' Platinotype in 1873. Many have tried to obtain this holy grail of fine art printing, all failed. The quality of the Chrysotype Supreme surpasses even Hunt's chrysotypes of 170 years ago, and even the dubious Australian and other "chrysotypes" prepared with palladium. It is pure gold, it is gray scale, it is grainless, and it can hang comfortably on a wall not next to but between prints in palladium and platinum. Here are the simple ingredients:
I heartily recommend purchasing all chemicals from Artcraft Chemicals in Altamont, NY. You can purchase tetrachloroauric chloride (gold chloride) by the gram and mix it at any strength solution you choose, though I recommend 10% as the minimum strength. I have found that 15% is about the strongest dilution to use without wasting gold. The website is www.artcraftchemicals.com.
10% Gold Chloride
40% Ammonium Ferric Ferrous Oxalate (AFFO)
This step is crucial and must be performed carefully and correctly. It is this step that prompts me to advise APUG forum members to seek help from their parent or adult guardian.
26% Ferric Oxalate
Dissolving ferric oxalate seems to be as much a matter of luck as science.
5% Sodium Sulfite
Weak Acid Bath (2nd bath)
The removal of the ferrous iron from the paper is crucial; if ferrous iron is left in the paper with the gold, the iron will in time oxidize and the print will turn dark and eventually completely black. A mildly acidic bath enhances the break down and rinse out of ferrous iron.
Add to 1000 ml of tap water 3 tablespoons of white vinegar or citric acid, if using a lightweight paper. For heavy papers, use the 1% muriatic acid as described above.
Paper for the Texas Chysotype
Papers change from batch to batch by the same manufacturer. A paper purchased two years ago and that yielded superb prints may yield mushy prints in a newer batch. If a recommended paper yields soft or mushy results, size that paper in a 3% solution of arrowroot starch. Prepare arrowroot starch:
Papers found to work well with the Texas Chrysotype without sizing with starch are:
Arches Platine Hot Press White Rag Cotton
Bergger Cot 320 Rag Cotton
Clearprint 1000H 16 pound Rag Cotton Vellum (Puckers when solution applied, so presoak in distilled water and iron (with a thoroughly clean iron on medium heat) after it dries
Printing the Texas Chrysotype
Remember, for this and all of my processes, the paper must not be humidified. The paper must be dry. It is not necessary but can be useful to maintain controlled RH for the paper by storing it in a large container filled with a dessicant, such as silica gel cat litter. This is not one of the various obsolete processes that require hydration of paper!
For an 8 x 10 inch print:
Spot a print as you would a traditional black and white silver gelatin print.