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

alecrmyers · May 15, 2025

In a remarkable bit of serendipity I found a very useful video on YouTube yesterday (serendipitous because I was merely browsing and not looking for anything on this subject and the video was posted only 4 days ago). The channel is produced by someone who has rescued and repaired a scanning electron microscope and in this video he produces gold nanoparticles as a calibration target for his imaging.

Aside from the fact that we could have saved him a great deal of time trouble and money by directing him to Bostick and Sullivan to buy a $12 bottle of gold chloride solution rather than having to make his own from a gold ingot - he researches ways to create nanoparticles (of gold) at different sizes, by using different temperatures. He also introduces two reducing agents - citrate, and bisulphate, both of which should be accessible. He doesn't consider other capping agents like PVP.

This video is very interesting not just for these features but because he explains the nanoparticle formation, and then images the nanoparticles on his shiny new (to him) SEM.

This morning I ran some tests with palladium at different temperatures (2°C and 50°C) and didn't detect any clearly noticeable difference to image quality tone or density but I have to wait and see how things look when the paper is fully set (+24 hours or more) to be certain. However for anyone who is working with gold you might get different results. Either way the video is very educational. Nanoparticle formation from about 15 minutes in.

richyd · May 15, 2025

Cool stuff, great video, so well explained. I'm amazed at what people get up to in hobby labs. A SEM, crikey I used one many, many years ago when studying chemistry and materials science at university. In fact that is where I first learned to develop prints of the negs taken with the attached camera.

I came across a reference of using sodium citrate and the Turkevich method in one of the search links for capping agents so that might be worth a try, it sounds too easy with a readily available compound. He was trying to produce all sizes of particle where I guess we are looking for one size but not sure whether larger or smaller would make a better image.

alecrmyers · May 15, 2025

richyd said:
I guess we are looking for one size but not sure whether larger or smaller would make a better image.

Gee... I wonder who could answer that?

thinkbrown · May 16, 2025

I recently acquired a copy of The Theory of the Photographic Process by T. H. James and had the chapter on diffusion transfer and monobaths scanned. It didn't appear to be readily available on the internet so I hope it's helpful

alecrmyers · May 16, 2025

Very interesting, yes. Thank you.The flavour starts a little bit "consider the spherical cow" at first, but there are some more practical discussions that follow.

thinkbrown · May 16, 2025

Yeah, it pretty rapidly exceeded my understanding of chemistry. Didn't quite appreciate that I was buying what amounts to an organic chemistry textbook when I ordered it.

alecrmyers · May 16, 2025

It's certainly not a recipe book.

Looking at figure 16.4, you might think that silver sulphide would be an even better bet than palladium. And looking at the discussion of binding agents on 476 left column you might imagine that poly(vinyl alcohol) would be a good bet for a binder; so I just spent an hour making up various paper recipes with silver sulphide and various ways to use PVA. Alas they only generated very faint images. That could also be a developer incompatibility, though.

Another interesting point: the whole of Polaroid's coaterless chemistry is covered in but a single phrase, beginning "cyclic imides...", at the top left of p.475. This was obviously a new area when this book was published (and indeed most of the references are from the mid 1960's and earlier.

On the other hand I found the discussion of the mechanism for 1P5MT as a toner in section 5 helpful, and the comments there about image tone. So I am very grateful to have been able to read it.

thinkbrown · May 16, 2025

Happy it was of some interest. I've also recently acquired a copy of Haist's Modern Photographic Processing which includes a chapter on diffusion transfer in volume 2. That one is available as a PDF in various locations on the internet so I haven't gone to the trouble of having it scanned

alecrmyers · May 16, 2025

thinkbrown said:
Happy it was of some interest. I've also recently acquired a copy of Haist's Modern Photographic Processing which includes a chapter on diffusion transfer in volume 2. That one is available as a PDF in various locations on the internet so I haven't gone to the trouble of having it scanned

I haven't read it; is it helpful?

thinkbrown · May 16, 2025

It's substantially newer material and does cover dye transfer color prints as well as discussion of integral film. It's certainly more approachable material and contains a collection of formulas from patents in various countries.

alecrmyers · May 16, 2025

If you care to PM me a link to where I can read it, that would be helpful. I've had a copy in my eBay basket for a while, but not pushed the button on the purchase.

alecrmyers · May 16, 2025

Thank you for the private link. A quick scan of the relevant section (vol 2. pp372-393) suggests it's a fair attempt to mention the highlights of a lot of the period patents. Whistle-stop tour is actually the description that comes to mind. And really really high-level. For instance, something I've spent many many hours on, and is actually the basis of the entire coaterless receiver paper construction whizzes past with this bare comment: "... nuclei may be coated ... in the upper alkali-permeable surface formed by the hydrolysis of an alkali-impermeable polymer such as cellulose diacetate." And that's all. Don't blink, or you'll miss it.

I don't think I'd buy the book just for this chapter, but it's probably a good index or 'way in' to the patent literature if anyone wants to dive into it. Here is just the relevant section:

alecrmyers · May 16, 2025

From the back of a drawer I dug out my old ColorMunki photo thingumy that I used to use to calibrate prints and my screen, and using the ArgyllCMS open source software I was able to measure Dmax for a range of recent prints - and they all came out between 1.6 and 1.75, which is excellent for this medium, very much up there with the best examples in the patent literature.

It was also able to produce a spectral response curve. It's pretty flat for the palladium silica papers, but no so for the red/brown one of the CA/palladium coating. Here is what it shows for a mid-tone area (wavelength along the bottom):

That's for the top left background area in this image:

It's not a stunning insight that a brown image reflects more in the longer wavelengths but it's nice to be able to measure the effect.

thinkbrown · May 17, 2025

Only tangentially related to the thread, but I just learned PBS has a new documentary about Edwin Land and Polaroid that's being released on May 19th: https://www.pbs.org/wgbh/americanexperience/films/mr-polaroid/

Yezishu · May 18, 2025

alecrmyers said:
In a remarkable bit of serendipity I found a very useful video on YouTube yesterday (serendipitous because I was merely browsing and not looking for anything on this subject and the video was posted only 4 days ago). The channel is produced by someone who has rescued and repaired a scanning electron microscope and in this video he produces gold nanoparticles as a calibration target for his imaging.

Aside from the fact that we could have saved him a great deal of time trouble and money by directing him to Bostick and Sullivan to buy a $12 bottle of gold chloride solution rather than having to make his own from a gold ingot - he researches ways to create nanoparticles (of gold) at different sizes, by using different temperatures. He also introduces two reducing agents - citrate, and bisulphate, both of which should be accessible. He doesn't consider other capping agents like PVP.

Thank you so much for all your testing and sharing! The homemade Polaroid is truly beyond imagination.

If I may, I'd like to share a small note. Having published some papers on metal nanoparticles, I can say that the synthesis of gold, silver, platinum, or palladium nanoparticles is relatively simple. The main challenge often lies in discovering unknown methods. However, replicating reported methods typically just need some kitchen equipment. Many people here are doing similar things when they develop B/W films or use gold toning solutions. Essentially, they can control the formation of silver and gold nanoparticles.

To quickly acquire relevant knowledge, I suggest searching for the desired topic on Google Scholar. For example, searching for "Size Control of Palladium Nanoparticles" can lead you to research papers such as "Chen, Hongjun, et al. 'Synthesis of palladium nanoparticles and their applications for surface-enhanced Raman scattering and electrocatalysis.' The Journal of Physical Chemistry C 114.50 (2010): 21976-21981." or "Wang, Ying, et al. 'Size-controlled synthesis of palladium nanoparticles.' Journal of Dispersion Science and Technology 29.6 (2008): 891-894." These papers contain more methods and results that researchers have tried, as well as analyses of factors influencing the growth process. Reading them or following their methods is often simpler than mixing own C41 developer and make it work.

For example, if you need palladium nanoparticles with diameters between 25 and 100 nm, a paper says:" 100 ml of solution containing 0.01 g HAuCl4·3H2O was brought to reflux and 3 ml 1% sodium citrate solution was added while stirring. The boiling solution was then kept for another 40 min and left to cool to room temperature. The resulting gold sol contains 12 nm particles according to TEM.
The preparation of Pd nanoparticles was as follows. Six solutions (A–F) containing 10 ml 1.0 mM H2PdCl4 and a varied amount of 12 nm gold seeds (4, 3, 2, 1, 0.5 or 0.1 ml of solution), respectively, were prepared. Next, an excess amount of ascorbic acid (100 mM, 1.2 ml) was added to the above solutions while stirring. The red color of the gold sol changed to a dark brown color of palladium colloids, suggesting the formation of palladium nanoparticles. Throughout the experiment was kept at room temperature. ", From Lu, Lehui, et al. "Improved size control of large palladium nanoparticles by a seeding growth method." Journal of Materials Chemistry 12.2 (2002): 156-158.

alecrmyers · May 22, 2025

I have been experimenting with a different "processor" - a laminating machine like this:

By adjusting the feed speed and roller pressure I was able to get a Dmax and Dmin of 2.16 and 0.06 over a dynamic range of 9 stops (logΔE of 2.7) which is really excellent. Ilford Multigrade RC is Dmax 2.15, so we're matching that. I will try to plot some exposure/density curves.

alecrmyers · May 24, 2025

This is a HD curve from a test exposure. Are there any densitometry experts who are willing to opine on it?

Qebs · May 27, 2025

Has any one read any literature on the expected print longevity of diffusion transfer reversal images?

Raghu Kuvempunagar · May 28, 2025

Qebs said:
Has any one read any literature on the expected print longevity of diffusion transfer reversal images?

Haist, Modern Photographic Process, Vol. 2, Chapter The Diffusion Transfer Process, page #387-388.

Qebs · May 28, 2025

Thanks Raghu.
I might have missed it but how long did these prints last before starting to fade in comparison perhaps to a silver gelatin black and white print?

Raghu Kuvempunagar · May 28, 2025

Qebs said:
how long did these prints last before starting to fade in comparison perhaps to a silver gelatin black and white print?

Given all the factors that can contribute to the deterioration of the print without the protective overcoat (as discussed in Haist), we can expect their life to be shorter than an incompletely fixed silver gelatin print.

Qebs · May 28, 2025

Thanks again Raghu!
I've searched Google and would like to ask how years or decades would the pront last with out the protective coating. I just couldnt find a definite number for an under fixed silver gelatin print.

Thanks!

Oh and I like your flickr photos! Your series broad leaf vegetation is ver contemplative

alecrmyers · May 28, 2025

Raghu Kuvempunagar said:
Given all the factors that can contribute to the deterioration of the print without the protective overcoat (as discussed in Haist), we can expect their life to be shorter than an incompletely fixed silver gelatin print.

I think it would be unwise to generalize so widely - there are a lot of different formulations of receiver and developer possible, and I'd be very surprised if a single sentence summary about their longevity was usefully applicable to all of them.

richyd · Jun 6, 2025

I've got my darkroom light proofed again; have sodium borohydrate; new Agfa HDR-C x-ray film, all courtesy of a cousin visiting from Europe, but I seem to be going backwards.

Using the gold chloride, when I mixed with the sodium borohydride the solution immediately turned a deep, purplish black but also immediately started to agglomerate particles and became clearer. I coated a few sheets and tested with some old Ektascan x-ray film which worked before and got a weak, brown image.

I made another mix using Iron Out as before. The reaction appears to take longer and although the solution turns dark or rather grey, it does get darker over time so I coated about 30 mins later. This produced similar results as before with the Ektascan film and the supplied HR-U film but with the new Agfa film only a very weak image. I think the conclusion is that this Agfa, single sided film may not be suitable, rather like the ortho film I tried. The remaining coating solution started to gel in the beaker shortly after.

I have found a source of palladium chloride I may be able to obtain from the US and can obtain PEG, though that comes in a variety of molecular weights, so can potentially get closer to the published formula for the receiver part. PVP I could get but would cost a lot as it would come from India.

The Agfa single sided mammoray film I got to replace the last of the Ektascan film I used for other alternative contact printing processes. I have sourced some generic, green X-ray film and could try that. However, before going down that route, I now have enough ingredients to try and make a developer. If i can get that working to get similar results I have had with my remaining film and coating with gold chloride know I am on the right track, otherwise it will all be pointless. UK is a frustrating, terrible place to get stuff for things like this. Health issues may curtail my progress though as well.

alecrmyers · Jun 6, 2025

Sodium borohydride (vice borohydrate) I hope.

Try this source of PVP:

Polyvinyl Pyrrolidone - PVP K-90

Buy Polyvinyl Pyrrolidone PVP K-90 at the Best Price in the UK. Shop Polyvinyl Pyrrolidone PVP K-90 in Bulk Quantity at low prices directly from the largest Manufacturer and Supplier in the United Kingdom. Check Polyvinyl Pyrrolidone PVP K-90 price, Specifications, Certifications, Fast shipping...

www.vedaoils.co.uk

I haven't found any accessble gold salts to try, yet.

Here's a UK supplier of palladium salts (not cheap, but already in solution - 50ml of 17% will last you for ever)

Laboldtech Sodium Tetrachloropalladate sol. 17%, 50ml

This is the replenishment sensitiser- Solution A that is part of the Platinum/Palladium Kit that we sell from Laboldtech.

firstcall-photographic.co.uk

>I seem to be going backwards.

Yep. 9 days out of 10 involve backwards progress. Occasionally - forward progress.

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

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