THE CHRYSOTYPE SUPREME

Texas Chrysotype Fannin Monument, Goliad Texas

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.).  
 

Chrysotype Supreme

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

  1. Dissolve 1 gram of tetrachlorauric acid in 9.5 ml of distilled water .
  2. Pour solution into a brown glass bottle, cap it and label it 10% Au. 

 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. 

  1. Draw off  from its bottle, in a  standard eye dropper, a volume of the 1% C solution you prepared above, under Three Fundamental Solutions. 
  2. Uncap the 10 ml bottle of 40% Ammonium Ferric Oxalate (AFO) you prepared as above, under Three Fundamental Solutions. 
  3. Count 3 drops of the 1% C solution into the 10 ml bottle of AFO. 
  4. Recap the AFO bottle.
  5. CRITICAL: Shake the AFO bottle vigorously for 20 seconds. 
  6. On the label, write 3:1% C after "AFO".

26% Ferric Oxalate

Dissolving ferric oxalate seems to be as much a matter of luck as science. 

  1. Measure out 9 ml of distilled water.
  2. Weigh out 2.6 g of ferric oxalate powder.
  3. Stir the powder into the water. It will not dissolve at room temperature; you will obtain a milky green liquid. 
  4. Place a microwave-safe container with the ferric oxalate in a microwave and heat it for 10 seconds on high. Alternatively, boil water in a pot and place the heat-safe container of the 10 ml of ferric oxalate in the water for about 15 minutes. Stir regularly to encourage the ferric oxalate to dissolve.
  5. After strong warming of the solution stir vigorously for several minutes.
  6. Place the container with the ferric oxalate in a dark place at room temperature. 
  7. When you check on the ferric oxalate after 60 minutes you should find a clear, dark green liquid. If you do not, repeat steps 4 through 6 above but with the liquid heated for only 5 seconds this time (but for the same 15 if you use the boiling water method).
  8. When the solution is finally a clear dark green, pour it into a brown bottle or opaque plastic bottle and label it "26% Ferric Oxalate".  

5% Sodium Sulfite

  1. Measure 1000 ml of tap water into a beaker (or other container). 
  2. Weight out 50 grams of sodium sulfite.
  3. Pour the sodium sulfite slowly into the water, with vigorous and constant stirring. If a mound forms at the bottom of the container, stop adding the sulfite and stir the solution to dissolve the mound.  
  4. Pour the completely dissolved sodium sulfite solution into a bottle or jar and cap it and label it 5% Sodium Sulfite. 
  5. Place the sulfite solution in a freezer about an hour before printing. It needs to be ice cold. If you find this too risky, pour the solution into a suitable tray and add sufficient ice to lower the temperature to below 35F -- the colder, the better.

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:

  1. In a large sauce pan, slowly dissolve 30 grams of starch in a very small volume of distilled water, just enough water to produce a smooth paste.  
  2. Set to the heat to LOW.
  3. Slowly pour in the remaining water (typically 1000 ml of size is sufficient for quite a good amount of paper) while stirring vigorously.
  4. Ideally, locate a spouse or child to volunteer to take over stirring at this point. The starch must be heated slowly and steadily with constant stirring. You MUST NOT heat the starch so high that it congeals. If it forms lumps, the starch is ruined and you must start over. 
  5. After upwards of 30 minutes of constant stirring on LOW heat, the starch should clarify and you will be able to see the stirring spoon clearly at the bottom of the pan.
  6. Remove the pan from the heat and allow the starch to cool to room temperature. Do NOT damage paper by immersing it in a tray of hot starch. Let the starch cool.
  7. Pour the starch into a tray sufficiently large for the volume. 
  8. Float a sheet of paper in the starch. Place the paper face down -- that is, the smoother side, the side to be coated, is to be face down in the starch. 
  9. Remove the paper from the starch after 1 minute.
  10. Hold the paper by one corner to drain off excess starch. 
  11. Rotate the paper and hold it by the opposite corner to drain the remaining excess. 
  12. Rotate the paper and a third corner and drain more starch. 
  13. Rotate the paper to the 4th corner and hang it from a clamp to dry. Dry indoors to avoid dust and insects from collecting on the paper.  A string hung lengthwise over a bath tub should serve well for drying sized paper. 
  14. Repeat the immersion, draining and drying 4 times. 
  15. Do not use the paper for at least 24 hours after it has dried from its 4th immersion. 

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
Arches Aquarelle
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:

  1. Dampen a fine 2" to 4" brush. I coat with a Richeson 9010 series brush. Other fine-bristle brushes are acceptable. 
  2. Count 12 drops of the AFO 3:1%C into a shot glass.
  3. Count 16 drops of the 10% gold chloride into a shot glass.
  4. Swirl the glass to mix the two thoroughly.
  5. If printing a low contrast 4x5 inch negative (such as would print well on Grade 3 silver gelatin paper), add 3 drops of 26% ferric oxalate; add 1 or 2 drops for a contrasty negative (such as would print well on grade 1 or 2 silver gelatin paper); add none or at most 1 drop for a high contrast negative. Note that the number of drops is proportional to the volume of sensitizer. An 8x10 inch print requires 4 times the volume of sensitizer as a 4x5 inch print; it also requires 4 times the number of drops of ferric oxalate. I recommend printing the Chrysotype Supreme with negatives exhibiting contrast between that observed in a negative suitable for printing on Grade 2 silver gelatin paper and one suitable for printing with platinum and/or palladium. 
  6. Swirl to mix if you add ferric oxalate.
  7. Pour about half of the solution in a zigzag across a dry sheet of paper and brush it out evenly with deft and confident sweeps of the brush. Get it spread as evenly as possible. 
  8. Pour the remaining solution onto the paper, with swift and confident brushstrokes, where needed to even out the coating. 
  9. Place the sensitized paper in a dark, dry place to dry.  
  10. When the paper is dry place it face up on the bottom of a contract print frame. 
  11. Place a 2 or 3 mil thick sheet of clear mylar on top of the paper.
  12. Place the negative emulsion side down on the mylar.
  13. Sandwich the paper, the mylar and the negative between the bottom of the frame and the glass of the frame. 
  14. Expose the whole to UV or sunlight. 
  15. When the overbrushed area (you did brush outside the negative area, didn't you?) turns dark gray, drop the back to examine your print's progress.
  16. When the print is slightly darker, about 1/3 stop, than you want the final to appear, remove it from the sunlight/UV.
  17. Pour the ice cold 5% sodium sulfite solution into a tray large enough to accommodate the print. 
  18. Immerse the print face down in the sulfite. 
  19. Flip the print face up, then down, at 30 second intervals for five mintues.
  20. Transfer the print to a tray of cool running water. Let the print wash for 2 minutes.
  21. Transfer the print to a tray of the acidified water. Wear rubber gloves at least for this step as the acid has its sting... Let the print soak face down for 2 minutes.
  22. Transfer the print to a tray of cool running water. Let the print wash for 2 minutes.
  23. Transfer the print to a tray of sodium carbonate. Let the print soak face down for 5 mintues.
  24. Transfer the print to a tray of cool running water. Let the print wash for 2 minutes.
  25. Transfer the print to a tray of the 10% T-EDTA. Wear rubber gloves at least for this step if not the others: T-EDTA has a bite if it finds a scratch or cut in the skin. Agitate the print by flipping it over every minute for about 10 minutes total.
  26. Transfer the print to a tray of cool running water. Wash a Clearprint vellum print for 30 minutes. Wash a print made on Bergger Cot or Arches Platine for 60 minutes.
  27. Carefully lay the washed print to dry on a frame or rack with a bed of fine screen -- plastic screen is good.    

Spot a print as you would a traditional black and white silver gelatin print.