Gold or Iridium in Pd printing

Discussion in 'Alternative Processes' started by jakobb, Mar 14, 2013.

  1. jakobb

    jakobb Member

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    I had problems achieving smooth mid tones and highlights with a lot of papers I tried recently (Buxton excluded). Gold(III) chloride (HAuCl[SUB]4[/SUB]) 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% HAuCl[SUB]4[/SUB] 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 NH[SUB]4[/SUB]Pd 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.
     
  2. TheFlyingCamera

    TheFlyingCamera Membership Council

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    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.
     
  3. Loris Medici

    Loris Medici Member

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    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...

    Regards,
    Loris.


     
  4. jakobb

    jakobb Member

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    Hi Loris,
    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 HAuCl[SUB]4[/SUB] to the sensitizer(NH[SUB]4[/SUB]Pd). 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).
     
  5. Richard Puckett

    Richard Puckett Member

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    Gold+Palladium

    Jakobb,

    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 -- richardepuckett@texaschrysotype.com.

    Regards
    Richard Eugene Puckett
     
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  6. Loris Medici

    Loris Medici Member

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    Hi again,

    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...

    Regards,
    Loris.
     
  7. bibowj

    bibowj Member

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    Im a newbie to the process ...but can someone tell me what the diff is between develop out and print out?
     
  8. Loris Medici

    Loris Medici Member

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    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,
    Loris.
     
  9. Richard Puckett

    Richard Puckett Member

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    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.

    55Ir45Pd.jpg

    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.

    irPd.jpg

    PRINT OUT

    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.
    karyAu45.jpg

    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.
     
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  10. Richard Puckett

    Richard Puckett Member

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    bibowj,

    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.
     
  11. Loris Medici

    Loris Medici Member

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    Richard, thank you for your very long posts full of information. This variant definitely caught my attention; will try with Li2PdCl4 and ammonium iron(III) citrate soon - I have plenty of vitamin C (L ascorbic acid)... Dry print out sounds really interesting, could be easier to control. Thanks much, will return with the results and comments ASAP.

    OTOH, I would like to add that "wet printing" (as you name it - there's nothing wet actually...) isn't that much complicated, you absolutely don't need any humidification chamber or pre/post-humidification with the usual pop pd processes - at least so with Ziatype. Works well enough w/o these practices. My usual practice is coat the paper and wait 30 minutes and then expose - I still manage to get neutral or very slightly warm prints - and it's simple as it can be; no extra steps (pre or post humidification ect.) or concerns... If the air is too dry (under 40-50%) then I put 1-2 drops of glycerine per ml of coating solution and that solves the problem of getting warm prints - when you need neutral ones. I think you make it sound a little more complex than what it actually is...

    But then, ability to print with bone-dry paper is attractive in a context where you absolutely need identical prints (in terms of tint/hue) when printing an edition.

    Thanks again, I'll try this soon.

    Regards,
    Loris.
     
  12. Loris Medici

    Loris Medici Member

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    Oops, should've been ammonium iron(III) oxalate...
     
  13. Loris Medici

    Loris Medici Member

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    BTW, I don't understand why you opt to convert some of the Fe(III) into Fe(II)? We need Fe(III) to complete the redox reaction. To my knowing Fe(II) is useless in making photographs?
     
  14. Richard Puckett

    Richard Puckett Member

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    Hey, Loris,

    Yes, you need mostly Fe3 to initiate the reduction of the metal salt to its elemental state, but it is Fe2 that attaches to the elemental metal and falls with it into the paper to form the image. In effect, the ammonium ferric oxalate (or lithium or sodium, or even guanidine) is "seeded" with ferrous iron. This accelerates the image-forming drop out. I realize the idea is counter-intuitive to anyone who understands how the double ferric oxalates work, but it does work. Go to youtube, search for Richard Eugene Puckett and/or chrysotype or palladium, etc., and watch one of the videos. Quality is rather poor but results are quite evident.

    If you wish to try the formula, let me specify for you:

    Gold
    Prepare a 10% solution of gold chloride (from tetrachloroauric acid).
    Prepare 10 ml of 40% ammonium ferric oxalate (AFO).
    Prepare as small a volume of 1% ascorbic acid (ascorbate, vitamin C) solution as possible.
    Count 7 drops of the 1% C into the 10 ml of AFO and shake the (capped) bottle vigorously for about 15 seconds. You have AFFO.
    For a 4x5, count 3 drops of AFFO into a shot glass. Then count 3 drops of 10% gold into the glass and swirl to mix the two.
    Coat a sheet of 1 of these papers, with a just damp brush:

    Arches Aquarelle (best quality -- widest tonal range, finest grain, smoothest tones)
    Bergger Cot 320 -- baryta-sized paper (very close to the results with Arches Aquarelle)
    Arches Platine -- easy print out but visibly less smooth than the previous two, slightly narrower rendition (about 1 stop of latitude less)
    Canson Colorline Bright White -- cellulose paper, cheap but prints out gold comparably to Platine
    Clearprint 1000H precut rag cotton vellum. Beautiful, strong, rich print out. I bought a roll and had trouble getting it to print out for reasons unknown. I ended up using a .15% bleach solution to make the images clean and grayish.
    Revere Platinum sized with gelatin

    Allow the coated paper to dry. I recommend 15 minutes, but it's however long it takes the paper to dry down well. If you establish a standard technique for preparing the brush (i.e, always a full water immersion followed by 3 hard shakes outside, or 2 firm wipes with the same kind of paper towel, etc.), you can get consistent, repeatable results.

    Print out in sunlight or a UV box. I usually clear in a first bath of water, but weak citric acid, weak muriatic acid, etc., suffice. Lately my preference has been about .5% nitric. Lactic, tartaric, and I believe phosphoric acids will yield a purplish cast. Nitric gives the most neutral cast. Cool water also works to neutralize the AFFO, after which you can use any acid without altering the tone of the print. After the initial stop/clearing, the usual wash in water, then in tetrasodium EDTA, then water, the more t-edta and a long final bath suffice.

    Palladium
    I urge you to buy some lithium carbonate, oxalic acid and ferric oxalate and make lithium ferric oxalate for palladium. You need little or no contrast tweaking with lithium ferric ferrous oxalate because of its inherently contrasty nature. It only serves for palladium, as it induces terrible grain with gold or platinum.
    With 10 ml of either ammonium ferric oxalate (as described above) or of lithium ferric oxalate (prepared as per Richard Sullivan's formula on his "Everything you want to know about ferric oxalate" page on the bostick-sullivan website), add 8 drops of 2% ascorbic acid (twice the strength as for gold, and a little more volume).
    Prepare a 15% solution of either potassium palladium chloride or lithium palladium chloride, or just sodium palladium chloride (Byron Brauchli did just that because he only had plain palladium chloride and was worried whether it would work-- I told him to just add plain, non-iodized table salt to dissolve it, and it worked fine).
    For a test 4x5, count 3 drops of lithium ferric ferrous oxalate and 3 of the palladium chloride into a shot glass, and mix.
    If using ammonium ferric ferrous oxalate (prepared with the same 8 drops of 2% C), you should add at least 1 drop and probably 2 drops of 26% ferric oxalate (with no C added to it!). Alternatively, use dichromates or sodium platinum if you prefer those. I don't know whether potassium chlorate works with palladium; I don't think it does. But unless you're printing with a really contrasty negative, you'll need to boost contrast for ammonium ferric ferrous oxalate with palladium. (If you have any iridium(III) chloride hydrate -- and who doesn't? -- try adding 1 drop of 5% iridium to the ammonium ferric ferrous oxalate solution, as well.)
    Dry the coated paper as for gold, striving for a technique you can repeat for every print. Palladium will print out on most anything -- my favorite is baryta-sized Bergger Cot 320: gorgeous. Aquarelle is also nice, with Platine and Revere Platinum perfectly good, though visibly less 3 dimensional and rich than the Bergger Cot.
    My preferred bath is .5% muriatic acid (hydrochloric), but citric acid is also fine. Same clearing as for gold.

    Perhaps I do exaggerate the difficulty of humidification -- I'll tell you in all honesty I believe I misunderstood many posters to be saying Arches Platine was the paper for printing gold (and palladium). You can appreciate how challenging it can be to humidify that heavy stock for even a ziatype. After many months of dogged effort, I had several nice palladium prints -- though the best were those I obtained by steaming the paper with an inexpensive clothes steamer before and immediately after printing. And the chrysotypes, even those obtained simliarly with steaming, were not to my liking. Had I originally tried printing gold on Canson colorline and palladium on 140 gsm Revere Platinum, I probably would have gotten better results and never would have resolved to make those metals print out on bone dry paper. Regardless, for me printing requires no more preparation then cutting a piece off a long roll of Arches Aquarelle, or pulling a sheet of Bergger Cot 320 from its package, coating, drying and exposing. I would have no patience with 15 minutes of leaving a sheet of paper on a shelf in the bathroom while the shower runs. Not necessary, not predictable, not reliable, and it stifles my impulse when I decide I need to try == right way == mixing ruthenium with gold, or rhodium with palladium. Oddly, though I am a "gotta see the results ASAP" type with printing, I do not own a digital camera. There's something comforting about listening to Mahler or Debussy in the dark, amid the stench of developer and fixer ...

    Regards

    PS: As I found tonight, while typing this reply, ruthenium does not play well with gold. I believe it needs the stronger 8 drops of 2% C solution -- more ferrous iron present at the onset of exposure -- to print out. By the way, I've never seen any printed out palladium with iridium, rhodium, or ruthenium, or gold with rhodium -- I wonder whether it is even possible without the presence of the ferrous iron.
     
  15. Richard Puckett

    Richard Puckett Member

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    Oh, afterthought. I was distracted by a gold-ruthenium print I was making, which is now soaking in a tray upstairs. Also, grainless, gray scale chrysotyes rendering 12+ stops are only obtainable with ammonium ferric ferrous oxalate (7 drops 1% C), on Arches Aquarelle (gelatin sized) or Bergger Cot 320 baryta-sized. That is a tremendous difference from humidified print out of ~17% gold with plain ammonium ferric oxalate. Further, a 10% gold solution costs little or even no more than printing 15% palladium ($45 gram Au vs $30 gram Pd, but you use 50% more Pd). It's truly a viable alternative to palladium for subjects suited to gold's unique personality (see the 4x5 I posted, earlier, of Kary with a martini glass, which is a Texas Chrysotype.
     
  16. Loris Medici

    Loris Medici Member

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    I don't agree on the assumption of the presence of Fe(II) will "accelerate" the reaction; it will simply fog the paper, or - much more likely - will cause precipitation of noble metal *immediately* - I mean as soon you mix the sensitizer with the metal solution! I'd rather prefer that the metal precipitates "by the action of light", otherwise, that would be simply wasting precious resources...

    After a second thought, I'm not convinced at all - won't pursue trying this. I think you're confusing iron printing with silver printing... (I've came into that conclusion-feeling by the fact that you're writing about "seeding" and because you refer to COT 320 as a "baryta sized" paper - which in fact is a gelatin sized paper with zero baryta content.) Maybe it's time to revisit the basics of iron printing???

    Thanks nevertheless...
     
  17. Richard Puckett

    Richard Puckett Member

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    Well, Loris, I presented my processes, not your misassumptions, publicly at the October 2013 APIS in Santa Fe, New Mexico -- a symposium of which you may have heard? -- and the reality, which decries your flawed expectations about the behavior of the noble metals in the presence of ferrous iron, was recorded by a gentleman named Eric Jervaise -- of whom you may have heard? -- and is on youtube (https://www.youtube.com/channel/UC881Zn4d5JIs_Ud7GHgYLeg). So are videos on direct print out palladium and of direct print out of platinum using the double ferric ferrous oxalates. [video=youtube;MqGvy1ULXYc]https://www.youtube.com/watch?v=MqGvy1ULXYc[/video]

    As to your rude assertion -- I am not remotely confusing iron and silver. When I write baryta-size Bergger Cot 320, Loris, I mean Bergger Cot 320 paper, sized with baryta and no silver, purchased from Bostick and Sullivan. I went to bostick-sullivan.com, I selected bergger cot 320, 8x10, 25 sheets and the paper delivered was bergger cot sized with baryta. It is not silver gelatin paper, Loris, it is bergger cot 320 sized with baryta, presumably for ink jet printing. However, it prints palladium (sensitized with ammonium ferric FERROUS oxalate) with no fogging and no wasted resources beautifully.

    I do not need to revisit the basicis of iron printing, having invented the only chrysotype process that yield grainless, gray-scale, wide-toned gold images (see the March/April 2012 issue of View Camera -- a magazine of which you may have heard? -- for my Texas Chrysotype article), the only process for printing rhodium (with ferric-ferrous oxalate), the only process for partially printing out gold with with ammonium ferric ferrous oxalate and developing it out fully with silver nitrate, the only process for the same with ruthenium, and having printed the only photographic images ever with ruthenium and palladium, ruthenium and gold, and rhodium and palladium.
     
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  18. Loris Medici

    Loris Medici Member

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    [U]http://www.bergger.com/us/special.html[/U]

    "COT 320: ...Originally designed as the fiber base for Bergger's highly acclaimed Silver Supreme enlarging paper, this uncoated version has a sumptuous quality and excellent sizing which making hand coating easy and consistent..." (emphasis mine)

    I don't intend to plunge into futile arguments with someone who doesn't know their materials and chemistry. (I happen to know a little something about the latter...)

    Sorry if I sounded rude, but I have great antipathy against disinformation - couldn't help myself. Nothing personal and no offense intended...
     
  19. Richard Puckett

    Richard Puckett Member

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    Loris, you did not "sound" rude, you were rude and you continue to be appallingly rude. I realized, however, on checking my notes, I did misspeak (or what you call in your gentlemanly discussion "disinformation") -- I used not unsensitized baryta-sized Bergger Cot 320 paper but unsensitized gelatin-sized Bergger Cot 320 paper. To avoid another onslaught of insult from you, I add this from http://www.linhofstudio.com/products/Bergger-Fibre-Based-Papers:

    'NB Cot 320 is a non sensitised luxurious 100% cotton rag paper base without withening agent.Weight: 320 g/m2
    For all Alternative Processes Prints. Very Similar to Prestige Fine Art but with only a thin coating of gelatin."

    As for the other issues, regarding all you know so much about, here are articles online at unblinkingeye.com and alternativephotography.com. Please feel free to reply, not with insults, but with links to your articles on major alt process websites, in magazines, and presentations at alt process symposia explaining how completely dry print out with gold, platinum, and palladium is not possible and that my authoritatively proven and authenticated claims to do so constitute "disinformation". I'll have to share your revelations to the many people who have emailed me explaining they prefer 7 drops of 1%C added to ammonium ferric oxalate for printing out gold, or sodium ferric ferrous oxalate over lithium ferric ferrous oxalate for printing out palladium, and so forth:

    http://www.alternativephotography.com/wp/processes/chrysotypes/texas-chrysotype-formula
    http://unblinkingeye.com/Articles/DPPP/dppp.html
    http://www.alternativephotography.com/wp/processes/miscellaneous/electrumtype-kary-prints
    http://unblinkingeye.com/Articles/TxChryso/txchryso.html
     
  20. Loris Medici

    Loris Medici Member

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    OK, people. I did a test print with 8 drops of 2% L-ascorbic acid (Vitamin C) added to 1.04M (~ 45%) ammonium iron(III) oxalate.

    As soon as I added vitamin C into AFO a brown precipitate formed - probably rust, something (we) Pt/Pd printers avoid as hell! This precipitate then dissolved to tint the beautiful bright emerald green color to a darker browner shade...

    Then I added an equal amount of 0.52M (~ 13.6%) Li2PdCl4 into it and coated a piece of COT 320 paper - using a puddle pusher. See the attached results.

    As you can see very clearly the paper is full of precipitated Pd speckles, extremely concentrated in the upper part - where you pull the puddle pusher out of the coating area and soak the excess. (I could already see the vast amt. of precipitated Pd inside the bead that forms in front of the puddle pusher...)

    It wasn't surprising at all to notice these speckles in the coating solution; since there's already Fe(II) in the sensitizer which will instantly precipitate elemental Pd upon contact. This is something we absolutely don't want because:

    1. You get flawed prints with speckles - obviously...
    2. Your actual strength of Pd is weakened because some is lost to the *unnecessary* Fe(II) in the coating solution - this Pd simply can't be used for the image; it will either stain the paper or washed down the drain w/o any useful purpose. No good fate for some expensive material we pay $$$...
    3. We want metal to be precipitated by action of light in accordance to the negative we put over the paper, not by including mumbo jumbo additives into the (othervise healthy) coating solutions.

    Now, no self-respecting Pt/Pd printer would actually pursue with this paper; they would simply rip the paper off and look for the source of "contamination" in their materials / workplace instead... In this case we know the contaminant; it's the vitamin C in the sensitizer, plus the uneducated / wrong assertions / claims by Mr. Puckett - eventually.

    I printed the paper anyway, it's drying now. I'll print another test with the standard formula (= no vitamin C addition) and compare them side by side later today or tomorrow - whatch here.


    BTW, Mr. Puckett, having been published doesn't mean your assertions and claims are practically and scientifically correct... If in doubt, always go for science. I beg that you read some chemistry books before playing with your (and other people's) expensive materials.
     

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  21. Richard Puckett

    Richard Puckett Member

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    I'll have to email Byron Brauchli, who last spring guided his students through printing palladium mixed with AFFO(8:2%C), prepared by adding 8 drops of 2% ascorbic acid to 10 ml of 40% ammonium ferric oxalate, and this past summer through printing gold with AFFO(7:1%C), that the prints they made in his workshop were imaginary, hallucinations.

    I'll have to email the attendees at the 2013 APIS in Santa Fe that the prints I made before their eyes were hallucinations.

    I'll have to contact the members of the AAPG here in Austin to point out to them that the prints they made during my proof of process demonstration, with freshly prepared ammonium ferric oxalate and ascorbic acid mixed on the spot, don't really exist ... all because a self-righteous forum troll who pretends to vast knowledge and experience is incapable of preparing a simple solution of ammonium ferric oxalate and ascorbic acid. Or perhaps the person in question forgot to add the sodium chloride to the palladium? In any case, I won't watch that person's foredefeated attempts at printing, and will not return to APUG, because I innocently shared information with the OP only subsequently to be trolled. I mistakenly anticipated gentlemanly behavior in the forums.

    For those who are interested, I will within a few months be publishing on alternativephotography.com an article on sizing satin (polyester) for printing palladium (the sensitizer will be either ammonium ferric oxalate or lithium ferric oxalate to which 8 drops of 2% ascorbic have been added.) I chose polyester satin over silk and cotton because it does not yellow or stain and will last rather longer than either of the other two. I will also be publishing an article on developing out ruthenium with silver nitrate. And, I will be summing up either in print or on alternativephotography (or similar venue) my results from printing ruthenium, rhodium, iridium, and copper with gold, platinum and palladium (all using either AFFO[7:1% C], AFFO[8:2% C] or Lithium Ferric Ferrous Oxalate with 8 drops of 2% C, and with the mixtures of noble metals developed in traditional solutions). The most interesting result, to me, that I observed was ruthenium mixed with palladium: print out ranged from 15 seconds to 90 seconds, depending on how many drops of 2% ascorbic acid I added to 10 ml of 40% ammonium ferric oxalate (more drops resulted in faster print out, fewer in slower print out). This would be a boon to printers who live in extreme northern or southern latitudes as well as to those who live in cloudy zones (and all who choose not to print in a UV box). I don't think it of any use to one who lives in a cloud.

    I chose not to test the remaining two noble metals: mercury and osmium. I regard those two as simply too toxic to risk my physical well-being to obtain known results, with mercury, and what would likely be bluish images with strong Dmax, from osmium -- more or less a redux of adding iridium to palladium.
     
  22. Loris Medici

    Loris Medici Member

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    Ok. As I promised, you'll find the scan of the pop pd test prints together, attached to the end of the message. (I scanned them together in order to eliminate exposure & settings differences that may happen between two separate scans...) I'll let people decide which one's is better technically - a picture is worth a thousands words. The test print with the ascorbic acid "contaminant" is on the right (marked with a C letter) and the test print made with the standard formula is on the left.

    Both prints were made on the same paper (COT 320 cut in half) using exactly the same workflow. 26C, 50% RH, air dried for 30 minutes, exposed for 16:00 minutes under a bank of BL tubes.

    Hope this helps.

    Regards to all,
    Loris.
     

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