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

[alecrmyers]

I put up a small website about this process with a couple of recipes and comments:

Diffusion Transfer Printing – DIY instant photography

Anyone is welcome to send the link to their colleagues or friends.

 

[koraks]

@alecrmyers excellent; I've just done two things:
1: Made this thread a sticky post so it always remains on top of this forum.
2: Added the link to the site above to post #1 so it's immediately visible to new visitors.
Thanks for your commitment to this project!

 

[analogwisdom]

Back in the lab (cellar)!

This batch of receiver uses PdCl₂ (palladium [II] chloride) reduced with KBH₄ (potassium borohydride) as the nucleation layer. The detail is excellent - if you zoom in you can see the texture of the doll's shirt.

 

[alecrmyers]

The Dmax and tone both look excellent.

As far as detail goes - this process is effectively a contact print from a large format negative. The detail should be absurdly fine (and I have some prints where it is). If the detail isn’t eye-popping then there’s something to investigate.

 

[Qebs]

I have not, I've been on a short hiatus from experimenting and testing during March. I'm going to get back to it soon and I will let you know, though.

How on earth are you coating such giant receiver sheets? I'd imagine a mayer rod and granite slab big enough to coat 32 inches are massively expensive.

Thanks so much! My only attempt with xray film was massively over exposed at 320 iso estimation. But it doesn't look like I need to use the 1P5MT (for now).
But did you ever make a solution or find a way to measure how much you were using?

Sorry not been on the forums, as experimentation was on hold due to the laminator machine we modified jammed or something and the gear box broke. We now switched from a DC to AC stepper motor. Enough torque and slow enough speeds.

Concerning the receiver sheets, I had a custom spiral bar applicator made. I can send you the companies details if you're interested.
For the flat surface, all I could figure out so far was a giant sheet of aluminum. It hasn't been treated to be super flat, but granite would be too expensive and heavy. Though, aluminium will corrode with some of the chemicals we all use, it's good enough for now.


------


Does anyone know why when I did a test with xray film and plastic paper, the xray film's surface seemed to stick to the plastic paper, leaving areas and specs of black.
I did use a stripping layer of 2% or 5% Gum Arabic on the receiver sheet.

Thanks

 

[analogwisdom]

But did you ever make a solution or find a way to measure how much you were using?

I have not. I'm getting good enough results without it that I haven't messed around with it very much. You could test yourself and let us know!

I'm more curious about different additives and ratios in the developer currently, that's where I'm going to start playing around a bit more.

I just really, really hate mixing and then waiting on the cellulose. I'm considering buying some kind of mixer like you can see around the 1:40 mark in NileRed's video from his Polaroid factory visit. Being able to mix in an inert atmosphere would be nice, I could start experimenting with hydroquinone developers again. It's hard for me to mix those without creating a bunch of oxidation.

 

[MCB18]

I have not. I'm getting good enough results without it that I haven't messed around with it very much. You could test yourself and let us know!

I'm more curious about different additives and ratios in the developer currently, that's where I'm going to start playing around a bit more.

I just really, really hate mixing and then waiting on the cellulose. I'm considering buying some kind of mixer like you can see around the 1:40 mark in NileRed's video from his Polaroid factory visit. Being able to mix in an inert atmosphere would be nice, I could start experimenting with hydroquinone developers again. It's hard for me to mix those without creating a bunch of oxidation.

That looks expensive lol

 

[thinkbrown]

That looks expensive lol

Not if you can find one that says VEVOR on the side

 

[analogwisdom]

Honestly they're not super expensive. I'm sure if I watched eBay long enough, I could find a good deal. They're called vacuum mixers - WhipMix and Renfert are two brands.

Sadly I don't think Vevor makes one. Shame.

 

[analogwisdom]

Fun little experiment today. Made some "duochrome" film (like the stuff modern Polaroid makes) with some waterproof paper that comes in different colors.

It was an absolute nightmare to coat onto this stuff compared to the usual (Highh Image) paper, so I doubt I'll do much more of this.

 

[alecrmyers]

I have not. I'm getting good enough results without it that I haven't messed around with it very much. You could test yourself and let us know!

I'm more curious about different additives and ratios in the developer currently, that's where I'm going to start playing around a bit more.

I just really, really hate mixing and then waiting on the cellulose. I'm considering buying some kind of mixer like you can see around the 1:40 mark in NileRed's video from his Polaroid factory visit. Being able to mix in an inert atmosphere would be nice, I could start experimenting with hydroquinone developers again. It's hard for me to mix those without creating a bunch of oxidation.

Mixing in an inert atmosphere is very straightforward. You just need a round flask with two necks, a couple of vacuum adapters and a cylinder of nitrogen or argon at your choice. Do the mixing on a stirplate and flush the cavity above the ingredients through with your choice of inert gas before and during the mixing. You can turn the flow right down once you've flushed the air out. There is no need for any heavy equipment.

There is very little to be gained though, and a much more practical alternative is simply to cover the mixing vessel with plastic wrap. There is very little oxygen in the air space in a small beaker; if there are oxygen-reacting items in the mix they will quickly exhaust what there is. The plastic wrap will prevent more oxygen diffusing in. If you're really determined, use an argon cylinder to dribble argon into the beaker before covering it. It's significantly heavier than air and will displace it all.

I have done all of the above at various times. My overall experience is that it achieves nothing very useful and is a lot of work. YMMV.

If you have really sensitive contents you'll want to deaerate the water you use to mix of course. (Good luck with that! - it's extremely hard to do.)

What you cannot do however is mix in any significant kind of vacuum; by the time you have reduced the partial pressure of oxygen enough to make a real difference to the chemistry the ambient pressure in your vessel will be low enough for the water in it to boil.

 

[analogwisdom]

thank you for once again already trying something so I don't have to... lol

I got "name brand" hydroxyethyl cellulose - Natrosol 250HHBR, the same stuff Polaroid used (and still uses). It is a hell of a lot easier to mix than the cheap stuff from Amazon. I don't know if it'll make any other difference.

 

[alecrmyers]

HEC and CMC: I mix them up in buk a litre at a time in a Kitchenaid blender. The shelf life is long.

You should try anaerobic mixing; I'm the last person to want anyone not to try anything - but there are easy ways to give it a go without expensive purchases, to see if it does anything for you.

Just for data: 50ml of air contains 0.4 millimoles of oxygen. 2g of DEHA (as an example developer) is 22 millimoles. Google tells me the stoichiometric ratio for the oxidation of DEHA with oxygen is 4:9, so the oxygen in a 50ml beaker will wipe out less than 1% of the DEHA. If it were oxygen-sensitive.

 

[alecrmyers]

double post

 

[Qebs]

Hey everyone,
I'm back at it again.

2nd motor is in the laminator after the first one's gear box "blew up" due to a hang up in the chain. This time I'm using an AC stepper motor. Thanks to my friend Tony, a mechanical engineer, everything is installed and working smoothly.

Tonight I tried using the Fuji Xray paper, CMC/NaOH/Uracil/DEHA/AEEA/Metol developer, and the Silica/PalladiumChloride receiver.

It looks like I made a mistake during mixing, or during application, or I fogged the xray negative.

But the point of this post is to figure out, why is the xray negative disintegrating and sticking to the receiver sheet. Is one of the chemicals dissolving the negative material?

Has anyone else had an issue with this?
It's quite a distraction for the eye and while I'll probably figure out what my other issues are, this one has me stumped and is concerning.

Thanks so much!
Be well

 

[analogwisdom]

It looks like I made a mistake during mixing, or during application, or I fogged the xray negative.

Your negative looks developed, which to me says it is a problem with the receiver.

What exactly is the brand of paper you're coating onto?

 

[analogwisdom]

I've been experimenting with multiple cyclic imides as silver solvents. If you're interested, in a batch of developer, instead of 2g uracil try:

1.1g uracil
600mg 6-methyluracil
300mg 5-methyluracil (thymine)

Nucleotide bases: no longer just the building blocks of life!

 

[analogwisdom]

Today I experimented with TBHQ-based developers again. I seem to have (re?)-discovered a way to allow most of the residual developer to stick to and peel away with the negative, allowing the print to be dry and have minimal staining. I believe the streaks are from incomplete mixing of the developer.


Here's the formula:

Developer Type 18

• 33g base (10% NaOH + 2.5% HEC)
• 3g sodium thiosulfate pentahydrate
• 1.05g sodium sulfite
• 600mg TBHQ
• 100mg Metol
• 120mg 6-mercaptopurine

Any cellulose polymer you already have should work, no need to run out and get HEC. The 6-mercaptopurine may be hard to get ahold of, and it's fairly expensive. It's typically used as a medicine to treat certain types of leukemia.

 

[alecrmyers]

Ooh. Fabulous. That would be a step forward. Is the mercaptopurine responsible do you think? Does it work with DEHA?

 

[analogwisdom]

Ooh. Fabulous. That would be a step forward. Is the mercaptopurine responsible do you think? Does it work with DEHA?

US3345166, US3642473, US3765892 (Fuji)

It's not the mercaptopurine. US3642473 deals with this additive, I'm going to work with that some more in the future, after Polacon NYC. I noticed a very slight increase in speed with the amount I added here, further testing needed.

The Fuji patent explains the mechanism here... "first, a film which can be easily stripped off is formed by the mutual action of the cellulose derivative and the oxidized product of said alkylhydroquinone. Therefore, the surface of the positive image is smooth and clean. This action is especially remarkable when t-butylhydroquinone is used."

I think this partly solves some of the mystery why Polaroid used TBHQ instead of other hydroquinones!

 

[OrientPoint]

What is the role of mercaptopurine in your latest developer?

 

[analogwisdom]

What is the role of mercaptopurine in your latest developer?

I am poor at translating what I have read/learned into something that isn't just word vomit, so I'll just link the relevant patent...

https://patentimages.storage.googleapis.com/4b/e9/f8/cbf240a8fddd48/US3642473.pdf

here's a table from the patent. Compound "B" is 6-mercaptopurine.

\

The idea of the purine compounds was to give better images across a wide variety of temperatures. I am more interested in the increase in "Diffusion transfer exposure index" (read: effective ISO/ASA) they give.


More testing required! A majority of my nights the last several weeks have been spent wading through dozens and dozens of patents, cross-referencing various compounds and then seeing which of the most commonly mentioned compounds are actually attainable. I have a short list, none have been mentioned prior in this thread. It'll take me some time, but I'm enjoying the work.

 

[analogwisdom]

Great results tonight using Agfa CP-GU M (Ortho x-ray) as the negative. Exposure index was around 800.

 

[analogwisdom]

Last night I unintentionally made some sepia images. I find it very pleasing. I would love to have it as an option, so I will work on finding out if I can replicate it consistently.

 

[analogwisdom]

The diffusion transfer print...

...the fixed negative from that DTR print (Agfa CP-GU M) on a light table (phone pic)...

...and a quick and dirty inversion of that phone pic. Pretty neat!