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.
Originally Posted by Richard Puckett
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.
Oops, should've been ammonium iron(III) oxalate...
Originally Posted by Loris Medici
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?
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:
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.
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 ...
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.
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.
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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...
Originally Posted by Richard Puckett
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???
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/UC88...JIs_Ud7GHgYLeg). So are videos on direct print out palladium and of direct print out of platinum using the double ferric ferrous oxalates.
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.
Last edited by Richard Puckett; 08-15-2014 at 02:11 PM. Click to view previous post history.
Reason: removed unnecessarily rude comments
"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...
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...-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:
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.
Last edited by Loris Medici; 08-16-2014 at 07:56 AM. Click to view previous post history.
Reason: fixed a couple of typos