Ruthenium's applications in alternative process printing are too rewarding to ignore. Whereas for the past 170 years ruthenium eluded all attempts to use it for printing or even toning, the deliberate introduction of ferrous iron into a solution of ammonium ferric oxalate has at least tamed the ruthenium beast somewhat. In a new article on alternativephotography.com (here, in a new window), I lay out the formula for developing out ruthenium with silver nitrate. Note that toning is only practicable for strong, contrasty images as gold and palladium reduce density and contrast in the final image. Forthcoming soon are formal notes on ruthenium's use with palladium, gold and platinum -- and possibly with rhodium.
After you dissolve 4 grams of ammonium ferric oxalate crystals in 8 ml of distilled water, top the solution off to 10 ml and pour it into a stoppered brown bottle. Add ascorbic acid solution (1% for gold or 2% for palladium and/or platinum) to the bottle of 10ml of 40% ammonium ferric oxalate (or of sodium or lithium ferric oxalate). As I describe repeatedly in my videos and online articles, remember that you have to shake the bottle vigorously -- for 15 to 30 seconds -- to disperse the ferrous iron subsequently created evenly throughout the solution. Otherwise, the ferrous iron will simply precipitate out of solution and fall to the bottom of the bottle: you likely won't get satisfactory results when you attempt to print with a solution of AFFO in that state.
I have found the best prices for iridium and ruthenium to be had at ArtCraft Chemicals iridum and ruthenium in 5 gram units and Pressure Chemical Company Iridium by the gram and Ruthenium in 10 gram units. Read on to understand why I mention this. Purchase iridium(III) chloride hydrate and ruthenium(III) chloride hydrate. Dissolve directly in distilled water at 20% or less working strength for iridium and 10% or less for ruthenium.
Iridium is a noble metal of the platinum family. The master printer and photographer Irving Penn frequently mixed iridium with platinum and with palladium for his prints. Based on my results with iridium, I suspect Penn's motivation was to nudge print color toward neutral gray scale and also to deepen the Dmax of his prints. Warning: read the MSDS on iridium and take proper precaution with this metal.
This contact print, on Revere Platinum 140 gsm paper, illustrates the value of iridium as an additive to palladium (or platinum, or gold). The formula was 3 drops of ammonium ferric ferrous oxalate (8 drops 2% C added to a bottle containing 10ml of 40% ammonium ferric oxlate), 2 drops of 26% ferric oxalate (no C added), 3 drops 15% lithium palladium (potassium palladium would work equally well), and 1 drop 5% iridium. The image printed out fully at normal speed (~5 minutes in my 6 13w UV bulb box). It looks like a platinum print with a contrast boost more than palladium. Notice the amazing black of the model's eyes -- that is faithful to the original print.
As this 4x5 contact print shows, iridium is a vigorous medium. It also exhibits slight grain, more so than platinum (at least than the virtually grainless platinum obtained with my Fannintype, in which I use glycerin to constrain the grain). This image was made by mixing 2 drops of 10% iridium with 1 drop of 15% palladium. The sensitizer was 3 drops of ammonium ferric ferrous oxalate, of course, prepared with 8 drops of 2% C. An additional 2 drops of 26% ferric oxalate (no C) boosted the contrast nicely. Clearing was citric acid, water, t-edta, water, t-edta and a final wash. Paper was Bergger Cot 320 sized with gelatin.
I have previously developed out iridium with silver nitrate. The image was strong and vigorous as this one. Because of the grain, however, I expect to keep my use of iridium with palladium, platinum, and gold down to about 25% maximum of total metal solution. Tip: Ruthenium will smooth over any roughness or grain induced by iridium.
Only possible with ammonium ferric ferrous oxalate, the "magic iron" of my dream almost three years ago made reality. This giant image is formed from elemental gold, deposited on the dry paper with the surfeit of ferrous iron in 36 ml of ammonium ferric ferrous oxalate mixed with 24 ml of 10% gold chloride.
The negative for this print was an inkjet transparency, prepared with tremendous dedication by Bobby Valentine of GicleePrint.net. Bobby tolerated my destruction of the first negative trying to wet mount it on a sheet of 3/8" acrylic, and my obsessive-compulsing over two further negatives before he riddled out what the hell it was I wanted in my negative.
The frame was a simple construction with a sheet of acrylic glass and 9 crossbars held on with gate clamps. Fifteen corks on 2" screws allowed me to adjust the pressure precisely on the back of the paper, keeping it from pulling away from the negative. Instead of wet mounting, I simply stretched paper and negative taut and taped each separately against the acrylic.
Clearing started in a 10' diagonal wading pool in my dim workroom and finished in my bathtub. I furiously drained and refilled the tub, mixing in at different points: bleach, nitric acid, dithionite, tetrasodium EDTA, and hydrochloric acid (it's one clean tub now!).
The subject is the most sacred building in the western hemisphere: The Alamo. (Photo Credit: Kary)
I have succeeded in working out a formula for printing photogprahic images in copper developed out with silver nitrate. This process offers the printer
The Kytheratype Article on Alternative Photography opens in a new window.
Prepare a 20% solution of copper chloride. Prepare a solution of ammonium ferric ferrous oxalate by adding 8 drops of 2% C to a bottle containing 10 ml of 40% ammonium ferric oxalate and shaking the bottle vigorously for up to 30 seconds. Prepare a 4% solution of silver nitrate (e.g., 4 grams dissolved in 100 ml warm distilled water). For an 8x10, count 8 drops of copper into a shot glass. Count 20 drops (roughly 1 ml) of AFFO(8:2%C) into the shot glass. Swirl to mix the two. The blue copper takes on a milky appearance. Brush (or puddle push) the solution onto a sheet of hot pressed paper. Arches Platine, Revere Platinum (140 or 300 gsm), Canson Colorline White all work well. After the paper dries completely in a dark place, expose the coated side, in contact with a negative, in a frame, to UV light. Test strips are helpful as there is no printout whatsoever: the exposed paper stays white, like silver gelatin paper. Place the exposed paper emulsion side up in a flat-bottomed tray. Mix 15ml of 4% silver nitrate with 15 ml of grocery store corn syrup. Pour this solution onto the paper just outside the image area. Rapidly but evenly brush the silver across the image area. Development is instantaneous. Clear exactly as below for ruthenium developed out in silver nitrate. The cleared image is gray scale, with just a touch of grain. It very much resembles a silver print. You will want to tone in one of palladium, platinum, or gold.
Ruthenium is a member of the platinum metals group. Although ruthenium is extraordinarily rare, the price is relatively low, lower than palladium. Although ruthenium will not print out fully on its own, not even with a double ferric ferrous oxalate, it has three big applications for photographing printing:
Prepare fresh ammonium ferric oxalate as for dry print out with palladium, as above with 8 drops 2% C added to the 10 ml 40% ammonium ferric oxalate IN THE BOTTLE. Shake the bottle for 30 seconds! You have 10ml AFFO(8:2%C). Label it. Alternatively (and preferred for the Serebrutype), mix up a fresh solution of lithium ferric oxalate (or buy some from Bostick & Sullivan). (For Mr. Sullivan's lithium ferric oxalate formula, go here to his B&S Article on All About Ferric Oxalate.) I mix my own from oxalic acid, ferric oxalate and lithium carbonate (which I bought at a local glass making/pottery place where middle-aged, middle-class women go to learn how to make pots). Pour 10 ml into a brown bottle and add 8 drops of 2% C, cap the bottle tightly, and shake vigorously. The lithium ferric ferrous oxalate is considerably contrastier than ammonium ferric ferrous oxalate and so you need to add less contrast booster.
Prepare a solution of ruthenium by dissolving 1 gram of ruthenium(III) chloride hydrate in 20 ml of warm water (~90 degrees Fahrenheit). Ruthenium will dissolve at 10% at 68 F, but it tends to drop out of solution. 5% is better. The solution is so thick, there's no visible difference between a 5% and a 10% solution. Note: Ruthenium is available from Artcraft and a few sellers on Ebay. See my default page for links to suppliers (just reload browser). General price is $20USD to $30USD per gram, typically with a 5 gram minimum purchase. I bought 5 grams for $145 including shipping. It mixes up to 100 ml.
To mix with palladium, for a 4x5 print, add 3 drops of the AFFO(8:2%C) or the preferred LFFO(8:2%C) to a shot glass. Count 3 drops 15% potassium palladium chloride OR lithium palladium chloride into the shot glass. Add 1 drop of 5% ruthenium to the palladium and AFFO/LFFO. You may find 1 drop of 2.5% ruthenium is preferable: you won't know until after you make your first print and let it dry down completely. (Depending on your negative's contrast, you may need to add anywhere from 1 to 3 drops of 26% ferric oxalate (NO ascorbic acid added!), or ammonium dichromate or Bostick and Sullivans Na2 contrast booster. Use whatever works for you -- on hand, cheapest, least dangerous, whatever. If you use lithium ferric ferrous oxalate you probably won't need to add any ferric oxalate (or other contrast booster). Swirl to mix thoroughly. Brush onto a sheet of Revere Platinum, 140 or 300 gsm, or onto Arches Platine, Canson Colorline, or other Pd-friendly paper. Do not be concerned if any precipitated ruthenium particles are present: they will break down during drying and subsequent exposure to UV. Place in dark to dry completely (~15 minutes).
Expose paper, by inspection, in frame in contact with negative.Print out is very fast with ruthenium, much faster than with gold, platinum, or palladium. I obtained a 15 second print out, in sunlight, with an older (~3 months) bottle of AFFO(8:2%C), and a 90 second print out with a fresh solution. When print out is slightly lighter (~1/3rd to 1/2 stop than desired) remove print from frame and immerse in 10% citric acid if colorline or Revere 140 gsm, in very weak (.5%) hydrochloric (muriatic) acid if Platine or 300 gsm Revere Platinum. Then wash in running H2O and continue clearing as for palladium. A print made using process as described:
The above print was slightly warm (a golden honey tint to it) and the contrast was much softer when still damp. Almost surreal smoothness. To preserve at least something of that, of course coat in gelatin while still damp and then harden with chrome alum.
The Texas Revolution in Gold, the Texas Chrysotype, is a new formula for printing photographic images in gold. It differs from other chrysotype processes in that:
For over 130 years it was mistakenly believed that ammonium ferric oxalate (or other double ferric oxalate) was the correct light sensitive compound to employ for printing pictorial images with palladium, platinum, and gold. Ammonium ferric oxalate lies at the heart of the process invented by Giuseppe Pizzighelli, back in the 1880s, for printing out platinum. However, Pizzighelli was wrong.
Double ferric oxalate compounds (ammonium, sodium, lithium, guanidine, etc.) can barely be used to print out any metal. Heavy hydration of paper is required, at a minimum, and consistent and reliable results are uncertain. Little wonder that many serious printers continue to develop out their platinum and palladium prints. Gold can hardly be printed at all with the double ferric oxalates, even with extraordinary paper hydration efforts. The images so printed are garish, gritty, grainy and altogether unsatisfactory for pictorial rendering.
The reader may benefit from understanding in a general sense what happens when ultraviolet light strikes a coating of ferric oxalate or any double ferric oxalate mixed with a noble metal salt. The UV light triggers a chemical reaction as a result of which the ferric iron is slowly reduced to ferrous iron. The more UV light that reaches the surface of the paper (passing through the thinner areas of a negative), the more ferric iron is converted to ferrous iron. Beyond a certain point, the ferrous iron can no longer stay in suspension and drops into the fibers of the paper. At the same time, the metal salt (gold, platinum, or palladium) is reduced to its elemental state. A molecule of ferrous iron attaches to an atom of elemental metal, no doubt the attraction of charged ions associated with the two, and together they fall into the paper fibers and form an image.
Understanding how the process works, I realized that the answer to proper print out with the noble metals lay in a fundamentally new formula, a new light-sensitive compound, one that dispensed with worrying about humidity and instead focused on getting the ferrous iron to its critical max quickly and efficiently. Given that the print process with ferric oxalate relies on the chemical conversion of iron from its ferric state to its ferrous state, I grasped I needed a formula in which I replaced ferric oxalate with a ferric-ferrous oxalate compound: ammonium ferric-ferrous oxalate (and sodium, and lithium ferric-ferrous oxalate). Ammonium ferric oxalate is just the starting point and the printer must mix up their own ammonium ferric-ferrous oxalate. Happily, the key ingredient is ascorbic acid, vitamin C.
Vitamin C reduces ammonium ferric oxalate to ammonium ferric ferrous oxalate. Add a whole lot of C to a small volume of ammonium ferric oxalate and you end up with pure ammonium ferrous oxalate (which is useless for printing). But add just the right amount of C and you can print out gold images with a range of 11 or more stops and no grain. Add a little more and you can combine gold and platinum and coax those two nobles to print out. Add even more and you can print out on dry paper pure palladium, palladium-platinum, palladium gold, and palladium-gold-platinum. No learning curve. No guess work. No waste. If you already know how to brush sensitizer onto paper, your first print will be perfect.
With ammonium ferric-ferrous oxalate, we all of us, photographers and artists, have the tool we need at last to print grainless, pictorial images in gold with a wide tonal range. And we have for the first time the ability to combine gold and platinum -- the Karytype -- to print out images that have the three-dimensional plasticity of silver gelatin prints but with much richer and delicate highlights, Dmax unattainable with palladium and platinum, and a palette of colors from neutral gray, to slate, to coral.
Forget about constructing a hydration chamber to prepare paper for printing with the noble metals. Forget about buying a hair dryer to dry just the emulsion while leaving your paper damp. Forget about heating up a steam kettle to salvage an image that doesn't print out. Forget about grainy, red gold prints with a tonal range so narrow you have to expose black and white film as if it were old Kodachrome 25 with its maximum 3:1 contrast ratio. The noble metals are unleashed, their full potential for art is realized with the double ferric-ferrous oxalates. Instead of wasting time and money learning an obsolete and often unrewarding craft, invest time and money in printing beautiful images.
Welcome to the twenty-first century revolution in printing with the noble metals. The revolution started on August 13, 2011, with my discovery that artificially aging ammonium ferric oxalate with ascorbic acid – vitamin C – allows the artist to print out, in gold, with no development and no humidification of the paper, an image that approaches platinum in technical quality. An image with no grain, with latitude that holds details in deep shadows and highlights, and with a three-dimensional richness on a par with any other process. This revolution spread over the ensuing months to dry print out with palladium, then birthed a new hybrid process – gold and platinum together – and finally platinum, palladium-platinum, and gold-palladium.
Not only is this a revolution in aesthetics and new ways to express one's vision, it is a practical revolution as well. Any of the noble metals can be printed alone, or in any combination, in a dry print out process. Quickly, inexpensively, and reliably. Repeating a print involves nothing more than observing the image appear on the paper and stopping exposure at the same moment as the previous one.
Sir John Herschel invented the Chrysotype process in 1842. Dissatisfied with the results of the images he produced, Herschel declared gold unsuitable for photographic printing. In the 170 or so years after Herschel's experiments, several attempts have been made to coax gold into forming a continuous tone image. All have excited the imagination, few have excited the eye. Despite announcements accompanied by great fanfare and met with wild enthusiasm, the Chrysotype remained a chimera, apparently never to be seen in all its glory. Now the Texas Chrysotype lifts away the veil of grain, garish colors, weak Dmax and blown highlights that have characterized gold prints since 1842.
In 1873 William Willis was awarded a patent for the first practical Platinotype process. With Willis' success, photographers enjoyed, just over thirty years after the birth of photography, an expressive print medium that not only was permanent but also exquisite. The popularity of palladium followed decades later, when photographers adopted that metal as a less expensive alternative to platinum. in 1913, Willis patented the Satista print, a hybrid process for silver and platinum. (Exactly 100 years later, the first new alternative printing process since then was announced: my Karytype, which is a hybrid process for gold and platinum.)
The 19th century processes faded when twentieth century photographers embraced the beauty, simplicity of process, and quality of silver gelatin prints. For nearly eighty years, silver gelatin dominated photographic printing. But even as the early silver prints were starting to show mirroring and to fade, a new technology replaced them almost overnight. Photographers abandoned their enlargers and their chemicals and rushed out to buy inkjet printers. Little did it matter that their images were garish, soulless caricatures of photographic images that faded in months – it was all too easy to be seduced by effortless printing at the push of a button.
Silver gelatin's fall from grace did not entirely announce the collapse of quality of photography. As digital cameras steadily improved in dynamic range and pixel counts, it became practicable to make inkjet negatives of sufficiently high quality to contact print in 8x10, 16x20, and larger. That convergence of technologies, perhaps nudged along by the zeitgeist of photography in the early twenty-first century, awakened a new interest in printing with platinum, palladium, and even gold. Old formulas from the nineteenth century were pored over for clues to simplifying – and improving – image-making with the noble metals. Of all the new processes that were handed photographers as the twentieth century closed and the twenty first began, the Ziatype offered practicality, quality, and relative simplicity. The tray of toxic chemicals required for developing out platinum and palladium was replaced with humidification of paper. Complex metal salts – lithium palladium, gold chloride and sodium platinum – never before brought together facilitate the print out and enhance the process. Photographers who would never have used an inkjet printer for anything more than an image constituted of pigment dots began making negatives from digital files and contact printing in the noble metals.
Gold serves the palladium in the Ziatype in the role of a sort of handmaiden of hues, particularly lavender. Efforts to eliminate the palladium and leave only the gold in the process proved gold could be printed out. Interest began to rise in the possibility of the Chrysotype. In the span of a few years, two new formulas were announced, nudging the metal a little closer toward image-forming viability. Finally, the correct formula, the Texas Chrysotype, was announced. Humidity is now of concern only to printers obsessed over their smooth complexion. The formula is so simple not even a PhD in chemistry could find enough jargon to obfuscate it. Vitamin C, ammonium ferric oxalate, and gold chloride are mixed together, brushed onto dry paper, and, once the sensitizer has dried, placed in contact with a negative – film or digital – and exposed to ultraviolet light. The image that subsequently prints out fully, with no development, is all the more stunning precisely because it is capable of exhibiting smooth tones across 11 or more stops, deep blacks, excellent detail in shadows and highlights, and no grain. With the Texas Chrysotype process, gold finally takes her place between her noble sisters, palladium and platinum.
The only manual for dry print out in gold, platinum and palladium is now available! The Old Made New presents the formulas for dry print out -- no development, no humidification -- of the following seven processes:
No exotic chemicals are required to prepare sensitizers -- vitamin C, ammonium ferric oxalate, ferric oxalate and the metal salts are all that is needed for gold and palladium; platinum also requires glycerine, which is available in every pharmacy or grocery store. All chemicals can be purchased from Bostick and Sullivan in Santa Fe, New Mexico, or Artcraft Chemicals in Altamont, New York. Both companies have online sites and both are operated by friendly and helpful folk. Papers are available in art stores, from dealers such as Freestyle Photo Sales, Digital Truth, and Bostick and Sullivan. Nothing you cannot easily obtain at reasonable cost is required for these processes. Neither do you need a degree in chemistry to prepare any of the solutions, much less to understand the content of the manual.
Start printing out palladium right away. If you already have palladium chloride (lithium or potassium) and ammonium ferric oxalate, all you need is ferric oxalate (to boost contrast) and powdered vitamin C. Use Arches Platine, Revere Platinum, Rives BFK, or Clearprint vellum. View
Ziatype+: Dry Print Out Palladium in a new window.
The Old Made New is available for $15.00 in hard copy, $4.99 in PDF. USA shipping for the hard copy is an additional $3.50. Shipping for the hard copy outside the USA is an additional $10.00.
|USA $18.50 Total||Outside USA $25 Total||PDF $4.99 Total|
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This print is pure gold. I scanned the 4x5 negative as a color image with no adjustments other than reducing saturation to minimize the strong blue cast my HP g4050 scanner gave it. It is otherwise not retouched and faithfully reproduces the original print. The Dmax is rather stronger in the original, the skin tones, particularly on the model's left cheek, are somewhat smoother, and the shadows on the right side of her face gentler. Even so, no other gold printing process is capable of this degree of smoothness, three-dimensional spatiality and extremely fine grain.
The first new photographic printing process in exactly 100 years. Experts, who have never succeeded in proper print out of gold or platinum, will assure you this combination is a chimera. The earth is round, the moon is not made of cheese, and you CAN print gold-platinum.
The image speaks for itself -- and the scan is quite faithful to the original 4x5 contact print (except for the hint of speckling, especially in the darkest areas: that is introduced by my HP G4050 scanner that desperately needs replacing). The image has a solidity, a sort of vigor to it that isn't normally found in platinum (or palladium), but is characteristic of gold prints in the Texas Chrysotype formula. Yet it also has the full tonal range of platinum -- observe how detail is held in the highlights, with the lightstruck keys and top of the flute not blown but holding their silvery tonality at the threshold. Every Karytype is like this.
This is one of only 3 prints in the world that are an admixture of platinum and gold. No development and no paper hydration. Make a Karytype up to 1/3 platinum and 2/3 gold with nothing more than platinum chloride (ammonium or potassium), gold chloride, ammonium ferric oxalate, and ascorbic acid. Make a Karytype with more than 1/3 platinum and up to 2/3 platinum (and the remainder gold) with the same chemicals plus 99% glycerine (which restrains grain) along with ferric oxalate to boost contrast as necessary. Use the much contrastier lithium ferric oxalate (2% vitamin C) instead of ammonium ferric oxalate to minimize or eliminate the need to boost contrast at all with most negatives. Brush on the chemicals and place the paper in a dark, dry place for about 10 minutes. When solution and paper are totally dry, print out the image by examination. For a sensuous, flesh-toned image, immerse the print in a first bath of 6% nitric acid. Alchemical magick!
I developed this process before I modified my original chrysotype formula (which now yields 11+ stops from base black to base white). My goal was to extend the tonal range of a gold print without using the Ziatype's palladium. As it turned out, gold and platinum interact synergistically, complementing each other's finest qualities while overcoming their faults. I've literally had to pull my Karytype prints away from people entranced by the amazing organic quality of the image tones. There's just something mystical about the look of a print that is 1/4 to 1/3 platinum and the rest gold and which was given a first clearing bath in nitric acid.
A quick demonstration of the Karytype (not Karyotype!) -- the first gold and platinum pictorial process ever. A Karytype exhibits the strong Dmax of gold and platinum's delicate highlights. The color of a Karytype can be neutral grayscale, slate, pink, or coral. In this video, I mix only 1 drop of 10% ammonium platinum chloride with 3 of 10% gold chloride. You can substitute platinum for up to 40% of the gold without changing the formula. More than that and the formula becomes much like the Fannintype, my dry print out platinum process, except you only use 10% platinum (instead of the 20% to 25% platinum for the Fannintype). The paper is Arches Platine. I have not tested the Karytype on other papers but am sure it would print out perfectly on (dry) vellum; it would likely print out on Revere Platinum and other commonly available hot press rag cotton papers.
A quick demonstration of Palladium AFFO -- the first dry print out palladium process. Forget the six month learning curve on printing Ziatypes! The learning curve for this is about 10 minutes; the time it takes you to mess up the first one and then do the second one right. In this video, I mix 15% lithium palladium chloride (or is it potassium palladium chloride? it doesn't matter which you use!) with AFFO created by adding 8 drops of 2% ascorbic acid solution to 10 ml of ammonium ferric oxalate. Normally, I would use lithium ferric oxalate for its greater contrast, but I ran out and had no lithium carbonate handy to mix some up fresh (I bought some after this video, from a glass blowing supply house). The paper is Arches Platine, but Revere Platinum (300 or 145 gsm) works fine with palladium, as do Fabriano Artistico, Stonehenge Rising, and Rives BFK.
Inventor of the Texas Chrysotype (the only continuous-tone gold process), the Fannintype (the only dry print-out, pure platinum process), the Karytype (the only gold-platinum printing process), and the Ziatype+ (dry print out palladium, palladium-platinum, palladium-gold, and palladium-gold-platinum).
Fine art photographer specializing in prints from large format film negatives.
Eyes half-lidded, nostrils flared,
areolae pale moons, the belly taut,
the golden mons tumescent: lacquered nails
caress the glistening flesh -- carnelian lips
apart to speak, between the nacre teeth,
like flame within a pearl,
the tongue revealed ...
A rushing wave about to break
you rise from sleep as foam
uplifted from the hissing surf
and swept across the sky