Diffusion Transfer Printing ("Polaroid" peel-apart) recipes

alecrmyers said:

Short answer: (only) time will tell.

The prints I made last year (gelatin based coating) haven’t faded at all. The silica ones I haven’t had around long enough to know.

The latest developers I’ve been using avoid sulphur-containing (thiosulphate) silver solvent, which the literature records as a concern, so that’s a plus. Leaving a bunch of “fixer” unwashed in your print seems like a bad idea.

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That's good to hear. You'd definitely know by now. Polaroid prints that required coating would start fading or turning brown in a matter of weeks or even days if left uncoated.

This is a representative print of the best of the latest work I've been doing. More widely, I have been using different combinations of palladium chloride and silver nitrate with a variety of reducing agents (borohydride, dithionite, UV radiation, ascorbic acid) and matrix materials (silica, gelatin, chitosan). I would say in summary it's very easy to produce dense images with a strong brown sepia tone, with yellow and sometimes red highlights. It has proven very difficult to find a formulation that gives a dense, neutral tone print. According to the literature, it's all about the size and distribution of the nanoparticles. I have again added poly(vinylpyrrolidone) as it is know as a nanoparticle stabilizer.

If anyone is following along, the developer is recipe 143 (detailed previously) and the paper is a new recipe (reference 212) which is prepared as follows:

10g silica solution
under continuous stirring:
add 1 drop 10% PVP
trace of sodium borohydride (I'll have to determine the exact quantity later and report, but it's too small to measure directly with my regular scale)
Stir well
add five drops of 0.1% PdCl2/HCl solution (again while stirring)

Coat onto 8x11.5 waterproof paper with a 4 micron coating bar, using about 0.5ml - 1ml per sheet. Allow to dry flat then cut into 4.

I realize that "five drops" is an inadquate specification for others to reproduce exactly, so at some point I will try to measure the equivalent mass.

I have been using this with Fuji x-ray film type HR-U. This film gives results 5-7 stops faster than the Ilford multigrade paper. The print below was at f/4.7, nominal shutter speed set between 1/50 and 1/100 seconds. This compares with manual timing of 4 seconds for the Ilford paper. I repeat that the shutter is old and may run slow - I have not measured its actual exposure time.

Procedure

When ready to print a (5x4) negative, the paper has a narrow bead of developer applied at one edge, and the film is superimposed exposed-side-down over it. Then they are fed together through an office laminator (on the 'cold' setting) inside an improvised developing pouch (two sheets of the same waterproof paper will do, taped together at the short edge). A short strip of Kleenex placed in trail to the positive/negative sandwich will absorb excess developer and help to stop it leaking out all over the rollers. The machine takes about 60 seconds to roll through the complete 8.5x11 assembly; the negative and positive are separated a further 60 seconds after the pouch clears the machine.

Comments

When coating the paper, a 4 micron coating bar gives a good glossy finish. A 1 micron coating bar works too, and dries faster, but is not as dense, and the finish is more matte.

No rails are used to spread the developer; the considerable pressure from the laminator machine spreads the developer very evenly, and the thickness of the emulsion and coatings on the paper and film seem to absorb a quantity of developer and solvent sufficient to complete the relevant reactions while they are in contact. When the negative and positive are separated, the positive comes away touch-dry instantly. The prints are robust and rub-resistant.

The quantity of developer needed for a 5x4 sheet is less than 250mg. A 25g batch of developer is good for about 100 prints, therefore. This process is very economical with the materials.

Aside from an instant print, this process produces an instant negative too - it is well developed and looks like it will print nicely. The negative needs a fixer bath, not least to remove the undeveloped silver halide from the reverse, since x-ray film is emulsion coated both sides. Then wash it in water, as you would expect. The emulsion is very fragile while wet and scratches easily, but only the one side with the image needs to be protected.

The print and negative are very grainy. I don't yet know if this is a feature of the film, or the developer. Probably both.

There is a yellow (and sometimes purple/pink) cast to the highlights, which appears after the print fully dries. The silica appears to be stained to a creamy yellow colour by the high level of hydroxide in the developer, leading to the yellow cast, and I think the pink is the trace of metol oxidizing. You can see a pink band on this print - and the fact that it is a band suggests it can be got rid of.

Some other silica-based formulations I have been using show a tendency to lose efficacy some number of hours or days after the paper is prepared. That is - paper a few days old gives a much weaker image. I will be checking over the next few days if that's the case here.

I will now work on some different developers and see if a less grainy print can be achieved, with a more neutral tone. Good luck to anyone who tries this.

Looking back I don't think I did detail developer 143, so here it is (very similar to 140):

25g base (2.5% CMC and 10% w/w NaOH)
2.5g uracil
1.0g diethylhydroxylamine (DEHA)
0.5g aminoethylethanolamine (AEEA)
0.1g metol

The metol ( 4-methylamino)phenol sulphate ) appears to be superadditive with the DEHA. The silver solvent is uracil, aka pyrimidine-2,4(1H,3H)-dione.

Have you considered the Harvard Polaroid Archive to get data from?


Series IIIA and IIIB might be promising?

Not sure if there'd be anything in there that would be helpful that isn't already detailed in patents, but Harvard will provide free scans of things you request as long as you don't share the scans directly and it's for research purposes.

It's on my bucket list to arrange a trip to see the archive. If anyone asks me which historical figure I want to invite to dinner, my answer is now Meroë Morse.

alecrmyers said:

It's quite a strange feeling that I'm probably the only person on the planet actively experimenting with this process at the present time. Obviously it was a focus of commercial activity fifty years ago but other than the late Bob Crowley I don't know of anyone who has pursued this in an amateur capacity but in a serious manner since then. If anyone has, please do step forward.

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Hi!

You’re not the only one. I’m not on here though, I’m really only on Reddit.

I started experimenting with this at about the same time as you. I got good results after about a week of experimentation, in February 2024.

I guess the difference between our goals is that I have a requirement to only source components from photography supply stores and grocery stores.

I haven’t worked much to improve anything since March last year since I at the moment get the kind of results I want. I’m not after getting flawless pictures since that kind of defeats the purpose of this in my opinion.

Welcome aboard @ianbakke!
You piqued my interest with the requirement of using only readily available (to consumers) components. Could you elaborate a little more on your process?

ianbakke said:

Hi!

You’re not the only one. I’m not on here though, I’m really only on Reddit.

I started experimenting with this at about the same time as you. I got good results after about a week of experimentation, in February 2024.

I guess the difference between our goals is that I have a requirement to only source components from photography supply stores and grocery stores.

I haven’t worked much to improve anything since March last year since I at the moment get the kind of results I want. I’m not after getting flawless pictures since that kind of defeats the purpose of this in my opinion.

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Great pictures!

On the subject of product availability: materials available from photographic suppliers is my goal too, but I take a long term view. If this process works well with, for example, aminoethylethanolamine, and people want to use it, then I have no doubt Photographer’s Formulary will be happy to stock it and sell it, just like they do with a raft of other “sophisticated” chemicals at present. But we have to create the demand first.

Could you please describe your materials and process? I’m fascinated to hear an independent evolution of this.

@alecrmyers generously sent me a pack of paper and developer paste. Weather, work and other matters have conspired to keep me from doing much with it for the past couple of months, but I did manage to get out and take a couple of outdoor exposures. I used Ilford Multigrade IV Pearl paper as the negative, cut down to 4x5. Camera was a modified Polaroid 110a. The sample below is on "Type 83" paper and was shot at f4.5 and 1/15th sec in full day light, handheld. It's shrubbery at the front of a building, although you'd be hard pressed to tell. I believe my poor result is down to exposure, subject matter (very little contrast) and my not pressing hard enough when processing. For my next round of exposures I've set up a static, indoor test subject and proper lighting. Hopefully I'll have much better results to show in the coming week. I know the material is capable of it.

I have a good amount of old Polaroid 8x10 type 803 (ISO 800) material, inherited from a studio. It all expired in 2008 and is hit or miss today, with only about 50% of the sheets in a given box still viable (better than 0% I guess). Out of curiously I exposed an 803 negative and ran it through the Polaroid 8x10 processor on a now-dry positive sheet with a bead of @alecrmyers developer paste run across the top. The results were pretty encouraging! (See below). Tone is obviously not neutral as it is with original Polaroid developer but I find it pleasing, and it's quite sharp. I took this in a basement at night with limited light using a simple box camera I've rigged up with a Schneider 90mm Super Angulon XL lens. Exposure was 2 seconds @ f11. The lens doesn't cover 8x10, although it's fairly close. The fall off towards the edges is due to the lens and limited light.

I need to save the developer I have for more tests with @alecrmyers paper, so I probably won't do any more 803 tests for now, but I've love to try again one day. This developer formulation seems like a good way to revive old material.

OrientPoint, Thanks for sharing!
May I ask which formula you used?

OrientPoint's post neatly highlights two of the technical challenges I am working to overcome. Achieving adequate image density, and achieving a neutral tone.

The papers that he used were prepared in December; I've noticed that the silica coating appears to have a fairly short shelf life under certain circumstances, giving very pale images. It may be a function of drying out, or something similar. So I wouldn't be shocked if what I sent him has "expired" by now; looking at material longevity hasn't been my focus so far. That's understandable: I want to try new ideas for paper coatings as soon as possible, and putting experiments on the shelf for three months to see how they last would slow down the progress. But I'll get there.

On the question of image tone: I have come across some new information that might lead to blue/black toned images with this non-staining developer much more easily vs red/yellow, and I'm waiting on some materials ordered yesterday to find out if they help. They may be able to help provide a Polaroid 80X developer paste that gives decent b/w prints. The. non-staining developer is important because it removes the need to wash the print.

I have made some progress on reducing image stain and graininess; here's a test from today, using the laminating machine. The print came out dry and clear, with very smooth tones and no observable grain. This approach is appealing because it scales up more or less indefinitely, and both the paper I'm using and the x-ray film are available in 11x17 format.

Wow, that's a great print! I want mine to look like that.

I hadn't realized that the paper had such a short shelf life. If I had known I would've got onto using it immediately. I'm expecting to do another run of tests this weekend and we'll see if my results are consistently poor.

@alecrmyers With regards to use of film, I have some Fuji "green" X-ray film. Would it be worth trying that with the papers and developer I have? I usually shoot it at ISO 50 with good results.

OrientPoint said:

Wow, that's a great print! I want mine to look like that.

I hadn't realized that the paper had such a short shelf life. If I had known I would've got onto using it immediately. I'm expecting to do another run of tests this weekend and we'll see if my results are consistently poor.

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I don’t think I knew it had a short shelf life either - that’s why this is interesting. And in fact it may not, the weak image density may be for another reason. But it’s a possibility. I have confidence in the developer though having a shelf life in the at least weeks to months range.

Regarding x-ray film. Do please try. But I did not get good results with it with those papers.

Your ISO for the paper is interesting: I have been using it at about 800. So if you get plain white results, try shorter exposures.

alecrmyers said:

Your ISO for the paper is interesting: I have been using it at about 800. So if you get plain white results, try shorter exposures.

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Which paper are you referring to? With the Ilford paper I was shooting at ~ISO 3. For the Polaroid 803, I shot at ISO 800 - box speed for that type.

Sorry - Fuji green x-ray film. I am shooting it at about ISO800. Albeit with an old shutter which may be running slow.

Really? For pictorial use I've only ever used it at 50 or 100. I'm using a lens with a reasonably accurate shutter. I'll have to try it at 800 and see what I get.

One of the (possible) uses for this process is as a quick process to develop a negative, regardless of the quality of the positive print. I get a well developed and fixed negative from the x-ray film within 10 seconds of of contact with the developer, using the pressure roller system. The X-ray film does need a fixer bath to remove the halide from the reverse side and to remove the residual developer but it’s a fast process nevertheless.

You might find it interesting to find the appropriate film speed using the developer you have from this perspective. You simply need to find a laminator machine to try it. If you do I emphasize the minimal quantity of developer to use; the excess will spread itself all over the inside of your machine, so include a sponge inside the sandwich. The 30ml tube will easily process 100 4x5 prints that way.

A natural question to ask is whether the coated paper is required at all, if this is to be used purely as a negative development process. Feel free to try it both ways.

An interesting variation I toyed with this week was to include the active element from the paper coating in the developer instead. Then I was able to achieve a positive print on out-of-the-box uncoated paper, and the process turns into on where the “active product” is simply a tube of develop-print gel and nothing more.

I'm see if I can use the Polaroid 8x10 processor I have as the laminator. Its relatively easy to clean, unlike the laminators I've seen. Otherwise it's easy enough to find a cheap laminator.

Was there any draw back to using uncoated paper? Polaroid always used coated receivers. I assumed there was some magic absorption property inherent in the material. That's belief rather than science though.

You can try the Polaroid processor. My limited understanding is that it uses finely engineered expensive stainless steel rollers set with a precise gap that is adjusted to provide consistent results with the thickness of the peel-apart package which includes rails, the whole system engineered to leave a very steady layer of developer of a thickness equal to exacly 2.0 (or whatever) thousands of an inch between the receiver and the negative. The laminator uses dirt-cheap spring-loaded rubber rollers that provide a very large and mostly steady pressure, without rails, doing it's best to leave exactly zero gap between the receiver and negative (which is why so little developer is needed.) The thickness of the developer paste left between the negative and the receiver in this case is determined by how much of the liquid developer is absorbed directly into the layers - the gelatin emulsion on the film and whatever coats the paper - on those two elements in the very short time before they pass between the rollers and the excess is squeegeed ahead. The thinness of the layer of developer left between the two is why the print comes out almost completely dry right away.

That's a very long way of saying that the Polaroid process may work better than, as well as, or not as well as a laminator. Or not at all. The laminator is also cheap at $50, vs several hundred for the Polaroid machine.

The image that I got with uncoated paper (for the avoidance of doubt, this is the same waterproof photocopier paper that I just didn't coat with anything, not the same as "uncoated" art paper or any other such meaning) was somewhat low contrast and didn't have a great tone. But it was just a look-see. I didn't put any effort into it. The idea of including the nucleation particles in the developer is mentioned in passing in most of the patents (all patents do a sort of hand-wavy land grab of vague ideas related to their subject so put anyone off later saying the idea was originally theirs) but I don't believe anyone made a commercial product out of it.

Polaroid receiver paper - at least of their later products, probably not the early stuff - has several layers, including at least, a stop layer, a timing layer, an image layer and a stripping layer. Each one was introduced to solve or improve one or more particular technical challenges. I don't think the customer was ever going to be satisfied with what could be produced without some sort of coating on the paper, so wrapping as much as possible into the developer would not have simplified either use or production in any significant way. That's my inexpert opinion. For an amateur who wants a cool darkroom idea to try, the calculus is different though.

To add: there were more developed - no pun intended - patents with examples given where water or another simple solvent was washed over the exposed negative before it was rolled against some special paper whose coating contained the developer, doing it the other way around, if you see what I mean. That was the basis for various commercial office document wet duplication systems that were on the market, prior to the invention of dry xerography. I think there's a whole chapter on them in Neblette.

alecrmyers said:

That's a very long way of saying that the Polaroid process may work better than, as well as, or not as well as a laminator. Or not at all. The laminator is also cheap at $50, vs several hundred for the Polaroid machine.

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Laminators are cheaper, unless you already have a Polaroid machine, which I do. I'll give it both a whirl and report what happens. It's exploration for the benefit of all mankind.

alecrmyers said:

The image that I got with uncoated paper (for the avoidance of doubt, this is the same waterproof photocopier paper that I just didn't coat with anything, not the same as "uncoated" art paper or any other such meaning) was somewhat low contrast and didn't have a great tone. But it was just a look-see. I didn't put any effort into it. The idea of including the nucleation particles in the developer is mentioned in passing in most of the patents (all patents do a sort of hand-wavy land grab of vague ideas related to their subject so put anyone off later saying the idea was originally theirs) but I don't believe anyone made a commercial product out of it.

Polaroid receiver paper - at least of their later products, probably not the early stuff - has several layers, including at least, a stop layer, a timing layer, an image layer and a stripping layer. Each one was introduced to solve or improve one or more particular technical challenges. I don't think the customer was ever going to be satisfied with what could be produced without some sort of coating on the paper, so wrapping as much as possible into the developer would not have simplified either use or production in any significant way. That's my inexpert opinion. For an amateur who wants a cool darkroom idea to try, the calculus is different though.

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Makes sense. Does this mean that the everything-in-the-developer approach is a dead end? Is it something you might pursue further?

alecrmyers said:

To add: there were more developed - no pun intended - patents with examples given where water or another simple solvent was washed over the exposed negative before it was rolled against some special paper whose coating contained the developer, doing it the other way around, if you see what I mean. That was the basis for various commercial office document wet duplication systems that were on the market, prior to the invention of dry xerography. I think there's a whole chapter on them in Neblette.

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Ah yeah. I remember those wet duplication systems. My father had one, which was fascinating to watch (and sniff). The technological connection between those and diffusion transfer/Polaroid never occurred to me until now though. Fascinating!

OrientPoint said:

Makes sense. Does this mean that the everything-in-the-developer approach is a dead end? Is it something you might pursue further?

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Not at all dead end - I think it's a cute idea. Overall I'm looking for an simple process that gives deep blacks, clear highlights, a good image tone, and can be produced by an unskilled amateur easily from ingredients that are adequately available (or could become so.) I don't have an ideological preference for which chemical goes where.

Since you asked, I tried the develop/print paste again - through the laminator, and this is what the results look like - test plate, and continuous tone photo. The tone is ok, the density isn't great. It could probably be improved with work.

Now that I look at it, it looks like the exposure could be shortened too.

Have you evolved the developer anymore? I have been burying myself in Polaroid patents and journal articles again, and also more thoroughly read this thread again. I saw the post where you referenced a previous post containing info from a Polaroid MSDS - I scoured the Internet Archive and found more Polaroid MSDS. In case you haven't come across them, here are the ingredients in the developer fluid listed for each one:


P/N Film (55/665/etc.):

Coaterless films (53/663/54/664/72/672,etc.):


612 (a 20,000 speed film made for a few decades. Interestingly, the developer used is detailed in US3326683 [Google Patent Link], which from a quick skim discusses using the developer to increase the "Diffusion Transfer Exposure Index" of underexposed negatives):

Films requiring print coating (107/52/57/etc.):


Polaroid 600 B&W (OG Polaroid's short-lived integral B&W. Notice the TiO2 ):



It'd probably be safe to assume these are the (disclosed) chemicals used in the pods in their final forms, since these MSDS were published just 4 years before Polaroid's demise. Hopefully this is useful to you!

Yes, I’ve been doing a lot of work on developers; about 20-30 hours a week at this point.

That data is very helpful; I see a lot of the “usual suspects” in there, but it’s good to have confirmation.
out of interest I’m very curious (and have been for a while) about SNP22E and SNP22K!

It’s also worth noting that the MSDS doesn’t have to list items that are present in harmless quantities. There’s stuff in those developers not listed, which may be very significant.