Gold or Iridium in Pd printing
I had problems achieving smooth mid tones and highlights with a lot of papers I tried recently (Buxton excluded). Gold(III) chloride (HAuCl4) is used to change the color and contrast in Ziatype printing. Dick Arentz mentions in his book that gold chloride can be added to the sensitizer (development process) and "this may also reduce granularity".
I added 5 to 10% of 5% HAuCl4 of the Pd Volume to the sensitizer. This resulted in very smooth highlights and mid tones. There was a small color shift to cooler colors. Using NH4Pd I got very neutral tones and with LiPd a slightly less warm tone. I have to do more tests with different developers, contrast control and papers (e.g. still problems with Revere) but I would prefer to add some gold to the sensitizer than extensive pretreatment of the paper to get good full scale.
Irving Penn was also using Iridium together with Pt/Pd and it may have a similar effect as gold as toner. I found no references for what compound he used. Ir(III) chloride? I found no solubility data through my web search. Has anyone used any Iridium salts? What color shift one should expect.
I would expect the iridium would yield a colder tone to the prints, as all of Penn's work I've seen has been platinum-esque neutral to cold blacks.
Thanks for sharing this Jakobb.
Interesting though; IME, addition of gold chloride into the Ziatype (pop pd with Li2PdCl4) makes sensitizer more contrasty, giving relatively harsher tonal transitions - just the opposite of smooth. The color shift depends much on the moisture level in the paper during exposure, the lower is the RH the warmer will be the image, whereas the higher is the RH the colder will be the image. With Ziatype the smoothest results are obtained by using no additives or by adding small amounts of sodium tungstate only. (Which I don't like except for an occasional and very small addition that gives very mildly "yellow" highlights - only useful for a limited number of subjects IMHO...) Which paper was that? I haven't experienced this with Cot320, Weston and Masa papers myself...
Originally Posted by jakobb
I had the same experiences with the gold chloride addition to Ziatype (that is the reason I had some left in my drawer). In general I find a development process to give me a better tonal scale and abandoned any Pt/Pd print out process. For these tests I was using ammonium citrate as a developer.
I made more tests on some paper samples +/- the addition of HAuCl4 to the sensitizer(NH4Pd). There was only minor effects on Awagami Masa except slight reduction of printing speed and with Cot-320 a slight reduction of contrast. On Zerkall book and especially with Kozo I got much smoother mids and highlights. Herschel is already quite good without it but also got even smoother. The color change towards cooler and more neutral is at the concentration I was using it similar with all papers (most pronounced with Cot-320).
I print out gold, platinum, and palladium (as well as rhodium with gold) routinely. I stress the words "print out" as in brush the sensitizer onto dry paper, let it all dry nicely and print out the image. With gold alone, at 10% solution strength, I generally use Arches Aquarelle hot pressed paper, which is gelatin sized and yields exquisite, grainless chrysotypes with a full tonal range -- with the correct sensitizer. That would be ammonium ferric ferrous oxalate (AFFO), which is the standard 40% solution of ammonium ferric oxalate to each 10 ml of which one adds 6 to 8 drops of 1% ascorbic acid (vitamin C) solution for pure gold. Prints are gray on Aquarelle with some purple staining from the gelatin retaining moisture, but the image quality is so high a little purple is acceptable (and can be mitigated somewhat with a bath in weak muriatic or nitric acid (as in ~2%).
For gold-palladium prints, with the gold above 1/3 of the total solution same thing except I use Arches Platine. The palladium serves to extend the tonal range a stop or two and the print out is usually gray scale. Gelatin sizing is not necessary. Prints are not cooler; they are gray scale. For prints mostly gold, I used 10% gold and 10% lithium palladium chloride or potassium palladium chloride or sodium palladium chloride.
For pure palladium or for prints that are palladium with just a small percentage gold, I use the standard saturated 15% palladium solution to print out with lithium ferric ferrous oxalate (LFFO) for its higher contrast than AFFO. LFFO is lithium ferric oxalate prepared according to Richard Sullivan's formula and to each 10 ml of which I add 8 drops of 2% ascorbic acid solution. For contrasty negatives with pure palladium or with palladium and a few drops of gold, no further contrast boost is needed. For softer negatives, I add a drop or more of 26% ferric oxalate (no C added to it) to kick up the contrast without inducing grain.
I can also mix palladium, platinum and gold, though for any combination that is more gold and platinum than palladium, either AFFO or SFFO (sodium ferric ferrous oxalate) must be used as LFFO induces grain with gold and platinum alike. For prints that are more than about 60% platinum, a volume of 99.9% glycerine equal to the volume of platinum is necessary to prevent graining with the platinum. I use all metals in 10% solutions, until I reach about 66% of palladium or platinum, in which case I switch to the standard solution strengths for the dominant metal. 1/3 Pd, 1/3 Pt and 1/3 Au would be a 10% solution of each. As with pure palladium, ferric oxalate serves to boost contrast, if needed. I haven't printed much with palladium and the other metals because I respect Richard Sullivan quite deeply and feel it's his turf, as it were. But the look of gold with palladium when using AFFO, SFFO, or LFFO and 10% Au with 10% OR 15% Pd is quite different from the Ziatype results.
I put a lot of effort into gold and platinum -- mostly because when I showed Ed Buffaloe a print, he remarked that it sounded like an expensive process. I riddled out how to print out platinum dry (search for my channel on youtube for a video explaining the formula) AFTER I mastered gold and platinum (on Arches Platine). With mostly gold and up to about 40% platinum, prints are cool, slate gray. The tone can be shifted slightly with any of a weak solution of nitric acid, hydrochloric acid or very very weak bleach (as in about .15% solution of bleach). I never tried citric, tartaric, lactic or phosphoric acid because I found all of those simply pushed pure gold toward lavender or dark purple (the 1st two toward lavender, the last two toward purple). With platinum accounting for more than 40% of the solution, I switch to 20% platinum and the Fannintype formula (dry print out pure platinum). The result is not the atmospheric effect of violet, red, and blue in roiling clouds, but a continuous tone gray scale print in which the two metals interact synergistically, exhibiting the strong Dmax of gold with the nuanced tonal delicacy of platinum. I have literally had to yank prints out of people's hands as they gazed on the images (when I had other things to do).
If you have specific questions about dry print out gold, platinum, or palladium -- all of them alone and in any combination -- you may want to view my videos on youtube. You can also view an array of images on my Pinterest and Flickr pages. And feel free to contact me -- email@example.com.
Richard Eugene Puckett
Last edited by Richard Puckett; 07-26-2014 at 12:39 AM. Click to view previous post history.
Reason: Usual typos...
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Originally Posted by jakobb
I don't know what's your subjective definition of "better tonal scale", but I yet have to see a develop-out pd print that has a better tonal scale than a print-out pd print - in my subjective terms. I greatly appreciate the open shadows and very very long tonal scale of print-out pd prints; IME, the longer the exposure scale is, the better (= wider & smoother) is the tonal scale. My usual exposure scale with print-out pd is log 2.9-3.0, and that's about 2 stops larger than the usual I experience with the develop-out variant...
Im a newbie to the process ...but can someone tell me what the diff is between develop out and print out?
With develop-out pt/pd, you need a developer (potassium oxalate, sodium citrate, ammonium citrate etc.) to complete the reaction and to get a full image whereas with print-out pt/pd you don't need any developer, the image is fully formed during exposure. You just clear and wash the print. Develop-out pt/pd works with negatives with less density range, and the tonality is different due non-existent or very little self-masking that occurs during exposure. Print-out pt/pd nees negatives with much greater density range and there's heavy self-masking. Since there isn't any development phase, print-out pt/pd is simpler than develop-out pt/pd.
Hope this helps,
Two notes: for the OP, a palladium print with iridium, and a pure iridium print. And notes re dry print out, which is somewhat different with double ferric ferrous oxalates (ammonium, sodium, lithium, etc., ferric ferrous oxalate) from obsolete print out processes that use simple double ferric oxalates (such as, ammonium ferric oxalate, lithium fo, sodium fo and so forth).
A (Mostly) Iridium Print
This print is a 4x5 contact that 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 7 drops of 1% 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 baryta.
A 90% Palladium / 10% Iridium Print
The formula was 3 drops of ammonium ferric ferrous oxalate (7 drops 1% C to 10ml 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.
In his estimation of printing out with the noble metals, the good Loris Medici (whom I feel I practically know personally, having read so many of his genial and helpful posts in various photography forums) refers to variations on Pizzighelli's 1892 formula for printing out platinum. That venerable gentleman used ammonium ferric oxalate (AFO) and humidication (generally after exposure) to print out an image in platinum. The process was not particularly reliable, but had the advantage of allowing one to fall back on developing out a recalcitrant image that simply would not print out. Various persons picked up Pizzighelli's largely forgotten process. One attempted to control hydration of the paper before coating with AFO and platinum or palladium (and early in this century gold). Another simply based the process on palladium, which is a much more genial metal and prints out rather easily in the presence of AFO and high humidity. He substituted lithium chloride for potassium chloride, taking advantage of the highly hygroscopic nature of the lithium salt. That process was considerably more successful and is today widely used as the Ziatype.
However, almost exactly 3 years ago, I was struggling with printing chrysotypes. While so called "new" or S chrysotypes look reasonable scanned and posted on the internet at half or so original size, I did not find the face to print results I got acceptable. So, after a few weeks of cogitation about the chemical reactions that must occur in order to convert ferric iron to ferrous iron and simultaneously to reduce gold chloride to elemental gold, and with the divine intervention of a dream, I determined that the correct way to print out gold would be to convert some of the ferric iron in the ammonium ferric oxalate sensitizer to ferrous iron. My goal was to push the volume of ferrous iron to the critical mass appropriate for gold. The idea was to initiate the the reduction of gold chloride to elemental gold earlier in the exposure process. This would result in fine or invisible grain and also extend the tonal rendition of the image-forming gold, while eliminating the need for humidification of paper (with its concomitant problems -- grain, poor Dmax, unreliability, unpredictable gray scale). It worked far beyond my expectations. Printed on gelatin-sized paper, such as Arches Aquarelle, the Texas Chrysotype (which I dubbed my new ammonium ferric-ferrous oxalate formula in a rare patriotic mood) yields virtually grainless images that can render tones, from a negative, spanning 12 or more stops.
Kary with martini glass, 4x5, Chrysotype on Arches Aquarelle.
I later refined the formula further for printing out palladium, and prints that combine palladium and platinum provided the print was at least 50% palladium. To do so, I prepared lithium ferric oxalate (LFO) per Richard Sullivan's formula. To 10 ml of that LFO I added 8 drops of 2% ascorbic acid to create lithium ferric ferrous oxalate appropriate for full, dry print out with palladium and palladium-platinum. Dmax is quite strong and print out requires no consideration of humidifying one's paper, and the tonal range is as wide and rich as developed out palladium. Recommended paper is baryta-sized Bergger Cot 320, although Arches Aquarelle (with pure palladium or with palladium-gold but not with platinum), Revere Platinum and Arches Platine also work well. Very dense, contrasty negatives print out perfectly, generally with no need to tweak contrast or to boost of Dmax: they compare quite well with developed out prints. Softer negatives, such as those exposed and developed for printing on silver gelatin paper, need the contrast tweaked. Do so with any of the usual chemicals -- dichromates, sodium platinum, etc -- or with iridium at 5% to 10% strength. I generally use a few drops of straight 26% ferric oxalate (no C added) and rely on a slightly stronger first acid bath than citric acid -- a very weak solution of muriatic acid -- to get the extra iron out in such a case.
Gold Platinum Print Out (The Karytype)
Until AFFO (ammonium ferric ferrous oxalate) gold at any volume in the presence of platinum (or is it vice versa -- Loris Medici, do you know?) you could only get "interesting" atmospheric effects from that combination of metals: typically, blues, reds, violets in swirling clouds and so froth. With AFFO, you can mix the two together up to about 1/3 10% platinum and 2/3 10% gold and obtain grainless, slate colored pictorial images with a range about as wide as pure platinum and with Dmax as strong as or stronger than pure platinum. The two metals combine and form a pure pictorial image without the atmospheric effects. I have not yet tried mixing a little iridium in with the gold-platinum -- TBD what happens. The sensitizer is AFFO, 8 drops 1% C (ascorbic acid). The image prints out dry on baryta-sized Bergger cot 320 as well as Arches Platine. I have not tested it on Aquarelle, but I doubt results would be satisfactory.
Dry Print Out Platinum
Now, this is more like Loris' description of print out processes using the old 19th century ammonium ferric oxalate formula. I spent 3 months getting platinum to print out on dry paper, with no need for palladium as is the case with the Ware-Malde approach. Bottom line: I found I had to look back at Pizzighelli and his use of glycerin. Many writers assume he added glycerin to his formula to size the paper on the fly. I don't think so. I am convinced he added glycerin and dropped the potassium oxalate, in order to reduce the graininess of his print out process. I found I had to add 99% glycerin at a 1:1 ratio with platinum in order to avoid grainy platinum prints. I found ammonium ferric ferrous oxalate too soft for platinum, and that lithium ferric ferrous oxalate induces grain. So I compromised with sodium ferric ferrous oxalate prepared by adding 8 drops of 2% C to 10 ml of sodium ferric oxalate (prepared as per Richard Sullivan's formula). In order to obtain strong Dmax, I increased the number of drops of 20% platinum (either potassium platinum chloride or ammonium platinum chloride, whichever is easier to obtain) by 50%. In other words, for an 8x10 that would normally require 12 drops of 20% platinum, I recommend 18 drops. Because of the graining induced by the usual contrast boosting chemicals, I recommend either 26% ferric oxalate to boost contrast with platinum or the same technique (I am certain) used by the master printer Irving Penn -- a little iridium.
A Final Note on Dry Print Out
I have more recently begun experimenting with enhanced UV response with the double ferric ferrous oxalates. My goal is to obtain a solution sufficiently sensitive to permit enlarging negatives onto hand coated paper. I doubt I will succeed; however, I can print out a contact in about 15 seconds on a sunny hot Texas day. I have no knowledge of the equations to convert 15 second print out in bright, UV-rich Texas sunshine to the time required to print out a negative projected through a pre-1935 (uncoated) lens. I am hoping it is at least sufficient to revive the old 19th century practice of mirroring sunlight down a shaft to an indoor enlarger to print negatives on early enlarging paper. TBD.
Last edited by Richard Puckett; 08-09-2014 at 12:51 PM. Click to view previous post history.
Reason: Added note on rapid dry print out; typos
BTW, I failed to make the distinction in my longer post on the topic between the two types of print out: wet and dry. Most print out today is done with damp paper -- you actually have to humidify the paper before and sometimes after coating in order to get an image to print out. If the humidified paper dries out, no print out. There has even been an attempt to quantify the humidification of the paper, by specifying that the printer should construct a paper humidification chamber, maintain 78% relative humidity therein, and humidify paper for at least 72 hours before printing. The more common ziatype process, invented by the venerable Richard Sullivan (of Bostick & Sullivan, purveyors of all things alt process) just requires humidifying paper for an hour or so immediately before coating. Learning how to humidify the paper and keep it sufficiently humidified to obtain print out is part of the craft and learning curve.
Dry print out is a process whereby you mix up the sensitizer, brush it onto a sheet of dry paper with no concern for the RH, dry it down again, and print. I actually invented this exactly 3 years ago. You simply prepare a solution of 1% or 2% ascorbic acid (vitamin C powder) -- or 1 solution of each strength, since it has a good shelf life -- and then add the appropriate number of drops to 10 ml of one of ammonium ferric oxalate, sodium ferric oxalate, or lithium ferric oxalate. Shake the bottle vigorously and you have a ferric ferrous oxalate solution -- the C converts some but not all of the ferric iron to ferrous iron. This lets you print out images on dry paper. The difference among the 3 is basically the ammonium version has the lowest contrast, the sodium slightly higher, and the lithium version is very contrasty. Ammonium ferric ferrous oxalate is my choice for printing gold, sodium ferric ferrous oxalate for platinum, and lithium ferric ferrous oxalate for palladium. If you're really interested, I put up videos for all three of these processes on youtube.