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

[MattKing]

I'm so sorry for my mistake. But thank you for your response.

No problem - you are new here .
This thread raises all sorts of fascinating possibilities. If as a result, you wish to discuss other issues, feel free to start a new thread.

 

[alecrmyers]

Having made up some pods with developer it's easier to work in total blackout without getting sticky fingers, so I took the opportunity to run a sheet of Ilford HP5 (right) and compare it to HR-U (left).

It looks like the HR-U is about a stop slower, and of higher contrast. It also transfers more silver. So anyone who wants to use this with Ilford film is going to have to adjust the developer recipe.

Is there anyone from Harman reading who would like to sub me a couple of dozen boxes of HP5 4x5 to work on doing this?

 

[alecrmyers]

I doubt anyone is still reading this ridiculously long thread, but if you are, this might excite you (if you're of an excitable nature).

I put together an assembly of film, pod, receiver paper and sponge using some double sided and masking tape, so that when stretched out, the film overlaid the pod and receiver, and was long enough to insert into a film carrier through the dark slide slot.

The film had to be about 8.5 inches x 3.75 inches - narrower than 4 inches because it had to slip between the film rails. It's a bit hard to explain but the regular film slot ends at the dark slide end.

I also used a hand perforater ($12 on Amazon - where would this project be without Amazon) so the ends of the receiver paper where the pod and sponge were attached with tape could be easily removed.

This is what the assembly looks like when stretched out (clearly this is a dummy because this film is fogged by the daylight - it has to be assembled under safelight):

Here it is folded over. You can see how the film lines up over the receiver paper, with the end of the pod sandwiched inbetween the two.

Inserted into the carrier:

And with the dark slide:

Once the dark slide is in place, the assembly is daylight proof.

This is what a (different) assembly looks like when in the camera. The paper and pod is a bit awkward hanging down, but it could be rolled up. EDIT: Almost. this one is actually inserted into the camera facing the wrong way which explains why the image was black. Oops. For the next one, I inserted the film carrier correctly so it worked.)

Once exposed, it's taken to a darkroom; the film/paper assembly is pulled out of the film holder, flipped over so the film is overlaid on the paper (very easy since they are hinged by a piece of tape) and then placed in the developing folder and run through the machine. This is really very easy because everything falls into place already lined up.

This is after processing:

And here is the result:

And after the perforated sections are removed:

That's kind of fun, isn't it? The scratches are because the darkslide slot is really too narrow for both dark slide and film, so the film scrapes. But I guess that's fixable.

Also happy to report 100% success with the pods - no spreading failures so far. You can even hear each of the two chambers 'pop' as they burst, while they roll through the pressure rollers.

 

[Truzi]

Your most recent post reminds of Polaroid roll-film. We have my great grandmothers The 800, which takes (took) Type-40 film.

 

[richyd]

Appreciate your efforts with the pods, it will make the processing part easier and less messy in the darkroom. I only envisaged using a pod in the darkroom to setup the fim and receiver sandwich. In the past for Polaroid sheets I have changed defunct pods with good ones making a sort of jig to line everything up in the dark.

I finally sourced some silica and as I had a bottle of Iron Out I made a small batch of paper using the gold chloride I have. I'm not sure I got the quantities right as I got mixed up weighing liguids as I had the amounts in my head but as my gold chloride is 1% solution it might work ok. Next time I'll dilute the gold chloride to 0.1%. I have to wait to re-blackout my darkroom area though to test this paper.

On mixing I found that adding the Iron out to the stirring base solution didn't dissolve well producing white lumps so I made a second batch this time adding the Iron out to a few mls of distilled water with a drop of gold chloride. It turned black, good, and then added that to the silica mixture. About after half an hour I noted some black precipitate in the solution.

You mentioned paper recipe 249 and developer 152. Can you post the details of these?

Re HP5. It's quite a low contrast film anyway, maybe try Foma?

 

[Peter Schrager]

Please ditto on the formulas !!
Paper #249
Developer #152
Ive been doing emulsions for POP paper for 4 years. Im a little behind here but have gathered some of the ingredients ...
Yes the thread is long but its uber incredible
Thanx to all!!

 

[alecrmyers]

Appreciate your efforts with the pods, it will make the processing part easier and less messy in the darkroom. I only envisaged using a pod in the darkroom to setup the fim and receiver sandwich. In the past for Polaroid sheets I have changed defunct pods with good ones making a sort of jig to line everything up in the dark.

I finally sourced some silica and as I had a bottle of Iron Out I made a small batch of paper using the gold chloride I have. I'm not sure I got the quantities right as I got mixed up weighing liguids as I had the amounts in my head but as my gold chloride is 1% solution it might work ok. Next time I'll dilute the gold chloride to 0.1%. I have to wait to re-blackout my darkroom area though to test this paper.

As I'm sure you know, a 0.1% aqueous solution is (adequately close to) 10mg solids to 10ml of water. It's challenging to measure out anything smaller than 10mg to any degree of accuracy. And when you're running a series of experiments the relevant precious metal chlorides get pricey to use quantities larger than that each time. Doubly so when the lifetime of the made-up coating mixture is only an hour - see my point later about PVP.

That said, it may be helpful to know that 1 'drop' from a typical dropper bottle with a pointy dropper weighs about 50mg and although its not very precise it is quite repeatable, drop to drop. So the equivalent of 500mg of 0.1% solution is close to 1 drop of a 1% solution.

On mixing I found that adding the Iron out to the stirring base solution didn't dissolve well producing white lumps so I made a second batch this time adding the Iron out to a few mls of distilled water with a drop of gold chloride. It turned black, good, and then added that to the silica mixture. About after half an hour I noted some black precipitate in the solution.

You don't say, but you may find that the black precipitate settles out to the bottom. It may even take on a brown colour - that of metalic gold. That would be what I was referring to when I said that without PVP I wouldn't expect the mixture to keep well. The PVP is a well-known capping agent that stabilizes nanoparticles; without it your nanometre gold balls will likely aggregate together to larger and larger particles and drop out of suspension. That is certainly what happens with palladium, silver, zinc, and the other metals I have used. Once that starts to happen the solution is useless for your purpose. Unfortunately your government doesn't trust you to own the acids you'd need to turn the gold back into solution so (unless anyone can think of an alternative) you'll just have to discard it. However - PVP isn't the only stabilizer that exists - maybe you could research something else that is more available?

Does Google in the UK give an AI overview? This might get you going:

Google Search

(My first thought would be to try PEG - it's available in quantities billlions of times more than you'd need at pharmacies, as a laxative.)

You mentioned paper recipe 249 and developer 152. Can you post the details of these?

I think there's enough information in this thread already to get people a head start on the process; I'm hoping that other experimenters will find and share their own solutions to some of the issues that crop up.

Re HP5. It's quite a low contrast film anyway, maybe try Foma?

Noted.

Which silica source did you use? Looking forward to hearing about the results.

 

[Donald Qualls]

This is starting to approach the level of a Polaroid 500 or 550 single-sheet holder and the New55 material. I've still got a 500 in one of my boxes; if I could assemble the film packets, I'd use it again.

 

[alecrmyers]

I just spaffed 25 Canadian Pesos on a Polaroid 800 camera somewhere local. When I pick it up I'll play around with trying to get a film to develop in it. However - the original Polaroid process and what I have going have different reaction kinetics - rolling the thing through a slow contact roller system vs. pulling it quickly through a roller system that leaves a still thin but thicker film of developer between the sheet and film for a longer period. There would probably be some significant differences in the developer formulation between the two. And there are other differences like the stripping layer.

I don't mind playing around with the Polaroid camera for fun, but being free from the shackles of having to work with a cohort of existing cameras has enabled a lot faster progress towards what I want to achieve.

 

[alecrmyers]

The 800 camera was a bust, but I'll maybe get a 95 model on eBay to play with.

 

[alecrmyers]

In the mean time I improvised a way to put a sheet of 83 paper and HR-U film through the processing rollers of a Polaroid 545 back ($2.50 on eBay). I used a blob of developer, no need for a pod for this test. For verisimilitude I cut some of the rails material from a deconstructed 803 unit and glued them to the paper so the developer thickness would match. (There are much easier ways of providing rails, but I wanted as exactly as possible to match the Polaroid way, initially.)

 

[BardM]

You mentioned paper recipe 249 and developer 152. Can you post the details of these?

Yeah, I have the same problem. This thread has many steps, and I am lost between the versions of the receive paper and the developer totally.

 

[Raghu Kuvempunagar]

Yeah, I have the same problem. This thread has many steps, and I am lost between the versions of the receive paper and the developer totally.

This is an evolving thread with continuous improvements being made to various aspects of the solution. However, with the help of @alecrmyers, @moderators should conisder updating OP with links to key posts that provide the necessary information for beginners to get started with the process without having to wade through 10+ pages.

 

[alecrmyers]

The last recipes I published were in this post and the one following.

 

[alecrmyers]

Yesterday and today I have been working on how to get a full 4x5 frame printed, how much developer is needed for full coverage and minimizing artefacts from where the developer is placed and how the edges of the frame overlap the various elements. Also looking at how even areas of Dmax are. This was a reasonable result in trying to get the whole film sheet printed. An unexposed sheet of film is a pretty tough test.

 

[richyd]

Which silica source did you use? Looking forward to hearing about the results.

I ended up getting a bottle from Creativeglassshop. No indication of concentration of content.

Ok, I made a print from that paper I coated where the particles partly precipitated out. Grainy, splotchy and dark, not unexpected. Batch 1-1

So, I created another batch this time adding a drop of PEG. I didn't pre mix the gold chloride with Iron out as I had learned to do before but went ahead anyway and there was no indication of the gold reduction. It produced a very feint image. After an hour or two the remaining solution jellified so the PEG failed.

One of the articles in that search for capping agents came up with PEG, EDTA, PVP and PVA. I have some EDTA (plain not the salt variations). The article listed those reducing agents in the order of particle size created from large to small, PEG > PVA. That may be of interest.

I then created another batch this time pre-mixing 2 drops of 1% gold chloride solution in about 3 mls of distilled water then added a pinch (corner edge of a spatula) of EDTA and the added a similar amount of Iron Out whilst stirring. The solution darkened showing the reaction working. This was then added to the silica solution plus a drop of tween with stirring.

Hours later now the mixture still looks good, no precipitation and still liquid.

I coated a few sheets of Yugo paper and another make I don't have the details of. I only made two film exposures, not knowing how the paper would turn out but in fact messed up my holder labelling so trashed one. The Yugo paper is nice and comes in several weights. The 154grm is good
,
The print came out pretty well, smooth but light overall, weak blacks. Image Batch 3-1.The film was a few years old single sided x-ray, some more exposure would probably help. I am getting some more x-ray film via personal delivery from Europe at the end of the month, I also have some Ilford Ortho and might try with some Foma 200 if I can rig up a jig to place the film in the dark with the receiver sheet.

If you think there is anything to help on the mixing side I'd be happy to hear. I'll try coating with the 4u bar too and try to measure out the EDTA and Iron Out next time, this was a bit quick and dirty. Spelling PVP with two 'rr's and one 'l' I found a source of PVP, UK manufacturer but the minimum order is 1Kg. But the EDTA seems to do the trick. That search also came up another compound for capping, Sodium Acetate, which I also have. It says it has reducing properties too.

 

[alecrmyers]

Fabulous. I hope you're thrilled with the first-effort images - I would be. I'm pleased they're neutral toned, too.

I have found there are (at least) two ways the coating mixture can age out. The silica can gel, or the metal can aggregate. The capping agent will help with the second but not the first, I think. I haven't got a good handle on what makes the silica gel - sometimes a coating lasts in the bottle for a month, sometimes it's gelled after a weekend. A change in pH can do it, but silica suspensions are available in both acid and basic media, so it's not a simple thing.

Nanoparticle aggregation :you can spot this because the brown colour of the mixture turns to grey, then eventually clear with a precipitate at the bottom. That outcome is delayed or prevented by the PVP, or otherwise.

I don't have a good source of gold salts, but I may have to find one to compare with the palladium.

Dozens of experiments don't reveal to me much of a consistent difference between mixing the metal chloride into the silica and adding the powdered reducing agent, or working the reduction separately and adding the result to the silica.

Is this the silica?

Colloidal Sillica Hardener - 1ltr

www.creativeglassshop.co.uk

What is your developer?

 

[richyd]

Yes I was really chuffed, especially as I was using different materials though most of the hard work was yours to get to this stage.

Yes, that is the silica suspension from creativeglassshop.co.uk

Regards the silica gelling. If it is due to pH change then maybe the EDTA has helped here in this case. I'll monitor it over time.

Gold Chloride solution is readily available from Bostick & Sullivan, Photographers Formulary and other alternative photography suppliers but don't know where in Canada. At first appearance I would say that the overall tone is slightly warmer than the palladium ones I made but can't really tell until I get a good film exposure.

I found that adding powdered compounds to silica solution would tend to clump and not dissolve, at least for a while so I was wondering if it was dissolving. Maybe is it the due to the particular brand of colloidal silica.

The developer is yours, 143 I believe. I found it works very well but there is no way I would be able to mix that in the UK. Uracil is impossible, though maybe something like potassium or sodium thiocyanate would substitute. Likewise DEHA and AEEA.

 

[richyd]

ERRATA:

I just looked at the mangled label of the old bottle of what I thought was PEG and it is in fact Polypropylene glycol which is why it didn't work so ignore any comment to do with that in above post #241

Also in another post I said I had noted some fading in prints and said they were paper formula 212 when in fact they were formula 83.

 

[alecrmyers]

Non-gelling forms of silica suspension are available as a polishing medium. The MSDS shows that they contain about 20% PEG. My suspicion is that wouldn't work for a nucleation layer as it needs to gel as it dries. I have managed without any gel prevention mechanism so far, so I don't know how important that is. I imagine that PPG would be much the same though, there not being much chemical difference.

I'd really like to find a more attainable developer - but, as I have written, among the challenges seem to be the stain. All readily accessible developing agents have coloured oxidation products. If one is not fussed about rinsing the print (and the hardened silica layers are very tough, once the paper is few days dry after coating) this may not be as much of a problem.

In 2004 Donald Qualls published a monobath developer (R3) which uses Ilford rapid developer and Kodak HC-110 (hydroquinone and dimezone S) and ammonia, which itself was used as a launching off point for the now defunct New55 project, most likely by mixing the R3 at some concentration with CMC as a thickener - I'm sure he would know more.

 

[Donald Qualls]

New55 went their own way and I know nothing about their process other than that it was loosely based on my realization that it was possible to make a developer work fast enough to use rapid fixer for a monobath. There was also a commercially sold monobath that was more closely based on my formula as well, but it's out of production now. I had nothing to do with the development of either product, other than to more or less reintroduce the idea of a practical monobath for modern films.

 

[richyd]

Non-gelling forms of silica suspension are available as a polishing medium. The MSDS shows that they contain about 20% PEG. My suspicion is that wouldn't work for a nucleation layer as it needs to gel as it dries.

Ah, the first silica suspensions I looked were polishing mediums. My last batch of receiver coating suspension was still good after one day but the day after that it had gelled.

I coated some more paper a day later, made another print using the old x-ray film and it is similar to the previous one lacking dMax and is light overall. I gave it another 1/2 stop exposure.

I tried one with Ilford Ortho plus rated at usual speed of 80. The negative came out quite dense and the print was very, very light, with hardly any transfer. I also noted that the shadow areas on the negative had a slight silvery appearance. One thing I have noticed is that the developer adds speed to emulsions by about 1 1/2 stops judging from previous tests so I ought to expose this film less.

With the Ortho film what could cause the faint print image? I noted a tester earlier on in the thread got a similar result using Agfa Aviphot 200 film. Could the denser negative (too much exposure) be one thing switching the balance between negative development and solvent-silver-halide production? The other thing that came to mind is maybe more developer is required as the emulsion layer is relatively thicker, I think, than the x-ray film so maybe absorbs more developer and not enough of the solvent-silver-halide has transferred to the receiver? Or maybe it just needs a different developer.

I then tried another sheet of Ilford Ortho, this time exposing at 200. I used a slightly thicker bead of developer and let the sandwich sit for over a minute after processing. This time more image appeared on the print but lacks dMax and is overall light but at least a full image is there. It is close to the ones done with the x-ray film.

I am getting some borohydride at the end of the month so will try with that, it might make all the difference. I noticed that my mix was not as dark as the one in the video you made. Was also thinking in that last batch I used too much Iron Out which as it has so much other stuff it may affect the print density.

 

[alecrmyers]

Ah, the first silica suspensions I looked were polishing mediums.

Yes - it was your link to the polishing materials company that informed me that silica sol was used as an abrasive for polishing. So - refractory coatings, polishing, and now once again photographic materials.

With the Ortho film what could cause the faint print image?

Any one of dozens of things, really.

None of those images look hugely overexposed - may a bit, to taste, but the frame lines are your Dmax, and there's a fair amount of shadow detail approaching that density. It's just the transfer that is weak.

It's pretty clear that different film emulsions are going to benefit from differently constituted chemistry not to get good development but to get good image transfer. My one test with HP5 gave a very pale print. But at $3-4 per sheet it's 20x (not a typo) more expensive than HR-U. So I don't see myself working up a developer for it - or any other traditional film, unless (as I said) Harman or anyone else wants to send a dozen boxes.

It's also possible that some emulsions will never be great for this process. There's a throwaway comment online from someone at the dead New55 project that no T-grain emulsions are suitable. It's not sourced or evidenced so I'd prefer to treat it as another target to be knocked down, but it's at least plausibly true. Not saying that Ilford Ortho is such, but very little is understood about the microphysics here.

Two variables at your own control are the concentration of metal salt in the silica, and the plating thickness. I note that because of the relative molecular masses, a weight percentage of gold chloride is about half the molarity of palladium chloride - maybe double the gold in your next trial for a fairer comparison with the palladium paper?

Also: most of my testing is done by making contact exposures under a transmission step wedge that I made with some layers of neutral density lighting filter, and a spotlight connected to a timer that allows me to control the exposure duration accurately and repeatably. It's much faster than loading film into a camera and the repeatability is essential when it comes to judging one developer, paper or procedure against another. You might be able to set something like that up. If you have a darkroom enlarger setup that would be perfect, of course.

 

[richyd]

Two variables at your own control are the concentration of metal salt in the silica, and the plating thickness. I note that because of the relative molecular masses, a weight percentage of gold chloride is about half the molarity of palladium chloride - maybe double the gold in your next trial for a fairer comparison with the palladium paper?

Yes, I thought about that. In the first solution I made where I mixed up the quantities a bit I ended up using a more of the gold chloride and although the solution precipitated out quite quickly I still got a print from the first paper coated, albeit spotty, but the density looked OK. I was sure I used more in this last batch but will increase again next time.

I was questioning myself in the above post about exposure, negative density and image transfer, then this morning I scanned through part of that Polaroid patent paper you posted and the interesting take away is this. They say that to get a good print you need to underexpose the negative in relation to its normal rating sometimes many times less. It also talks of a Diffusion Transfer Exposure Index. The difference between the two exposures I made with Ortho film seems to show this with the one rated at 200 transferring more and producing a better print. Doubling the exposure again might produce a decent result. I obtained a part used 4x5 box of Ortho film for a not a lot and have a box of 8x10, quite expired, so if I can a good result it would be a way of using that but won't spend a lot of time on it. Maybe less exposure with HP5 may come out better.

 

[alecrmyers]

I scanned through part of that Polaroid patent paper you posted and the interesting take away is this. They say that to get a good print you need to underexpose the negative in relation to its normal rating sometimes many times less. It also talks of a Diffusion Transfer Exposure Index.

I think - I might be wrong - Land invented the "Diffusion Transfer Exposure Index" to capture the idea that with the right chemical cocktail in the developer you didn't need to see a well developed negative to get a good positive; you could expose on the toe of the emulsion. I don't think it caught on as an industry term. Doing so is more or less exclusionary with trying to get a useable negative from the process, so it depends what your goals are.

He also invented or discovered a phenomenon that he called "Solubilization by incipient development" that appears in several patents (here's a puff piece from ACS archives on the subject: https://pubs.acs.org/doi/10.1021/cen-v046n027.p015). It may or may not be in play in the Polaroid 612 product with the 20000 ASA rating. I'm not sure how relevant it is to what you and i have been trying to do though. It's outside the scope of this thread but it also sounds like it's possible with the right chemicals to get a decent positive (reversal) image in the original emulsion if it's sufficiently (several stops) underexposed relative to what would normally be used to get a standard negative.

On the subject of the 612 - you'll see the MSDS lists propylthiouracil. I've bought some, but I still have no idea what it's good for. More work needed!

IN my experiments what I found was that for all the developer mixtures I've tried, for HR-U there was a correct EI, that gave both a decent negative and positive. Deliberately underexposing gave me nothing but the expected dark print. Please try with other emulsions!