Plea to APUG chemists and photographic engineers

Discussion in 'B&W: Film, Paper, Chemistry' started by Michael R 1974, Aug 11, 2011.

  1. Michael R 1974

    Michael R 1974 Subscriber

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    Can someone invent some kind of thing that will dye or tone or stain negatives yellow or green in proportion to silver density.

    I'm interested in the VC paper effects since the yellow or green Pyro-like stain acts like a graduated/variable low contrast filter. Maybe there's already something out there, but I don't know of anything.

    Please don't respond recommending Pyro. This would be for 35mm negatives and I don't like Pyro developers with small/medium format film.

    Thanks
     
  2. Gerald C Koch

    Gerald C Koch Member

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    In theory you could develop the film as C-41 film with the addition of a yellow coupler to the developer. For green you would add both a yellow and a blue coupler. This is essentially what was done with Kodachrome where the film itself contained no color couplers. Each of the three layers were developed separately. You could look at the developer formulations for this process to find which couplers and their concentrations. The process names were K-12 and K-14.
     
    Last edited by a moderator: Aug 11, 2011
  3. PhotoJim

    PhotoJim Member

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    Have you tried all pyro-based developers?

    PMK works well for me on 35mm.

    If you're not happy with 35mm results with pyrogallol or pyrocatechin, perhaps shooting 120 would let you get the results you want. I don't think it likely that a chemist will formulate a way to emulate pyrogallol staining when pyrogallol already does it.
     
  4. Michael R 1974

    Michael R 1974 Subscriber

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    PMK is a wonderful developer for sheet film but staining/tanning developers developers are too grainy for me in 35mm and even medium format. I'm not a medium format shooter anyway, just large format and 35mm. Sorry.
     
  5. Michael R 1974

    Michael R 1974 Subscriber

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    Interesting. I had started to think along these lines but only vaguely given the inadequate depth of my color chemistry knowledge.
     
  6. Mike Wilde

    Mike Wilde Member

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    The colour couplers are in C-41 film layers, but not in b&w film, afaik.
    C41 film couplers, when the oxidized development by-product can link to them produce a colour.

    I am not aware of how such a colour would be producted proportionately to the silver density in b&w film.
     
  7. erikg

    erikg Member

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    It sounds a little like the dye transfer method. Wasn't Technicolor done in a similar fashion? That is, bleach the silver and harden the gelatin, which would then be dyed and used as a printing matrix.
     
  8. holmburgers

    holmburgers Member

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    Michael, what you want to know about is dye-mordanting techniques. There are ways to do exactly what you want; stain an image in proportion to its silver desnity. You can even bleach out the silver leaving only a dye-image. A stain like malachite green should work admirably, and you can easily get this from a wide array of sources.

    It's different than dye transfer in that you won't be etching the film to make a relief matrix. I don't think this would work with commercially available b&w films. However, erikg is right in that a dichromate-bleach (like carbro) will harden the area surrounding the silver. In this way you could theoretically obtain a planographic matrix, which is not etched, but consists of tanned & untanned gelatin. The trick is, that the stain will go into the untanned areas, so that you be able to get what you're after. A relief matrix contains only tanned gelatin since you've etched/washed away all the untanned.

    This planographic matrix was used to make dye-imbibition prints (dye-transfer) in the old Pinatype Process. The dyes are different though, and you have to use positives instead of negatives. Technicolor used the relief technique, which is akin to Kodak's classic "Dye Transfer" process.

    If that sounds like what you're looking for, let me know and I'll try to dig up some resources.
     
  9. Michael R 1974

    Michael R 1974 Subscriber

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    I don't know I didn't even understand most of what you wrote :smile:
     
  10. holmburgers

    holmburgers Member

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    . . . . :sideways:


    Focus on the first paragraph. There are methods that allow you to "dye or tone or stain negatives yellow or green in proportion to silver density". This is called dye-mordanting, and it's fairly simple.
     
  11. jp498

    jp498 Member

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    I'm not a chemist. I was wondering if we could add instant coffee to xtol or another non-staining developer of choice to make it a caffenol-blend.

    I mixed up some coffee with developer the other day to try an 8x10 in. After I turned out the lights, I accidentally slipped the 8x10 sheet of film into the fixer instead of the prewash water. End of that opportunity.

    I'm not sure what 35mm film the OP is using, but I think 35mm tmy2 works great with PMK without being grainy.
     
  12. Gerald C Koch

    Gerald C Koch Member

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    No, with coffee what you would get would be an overall stain. What you want is a stain that is proportional to the amount of developed silver.
     
  13. Photo Engineer

    Photo Engineer Subscriber

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    Ok, here is what you want. Get Citrazinic acid, H-Acid or J-Acid. These are water soluble couplers that form greenish yellow dyes. Presoak your exposed B&W film in a solution of Epsom salts + Alkali + one of the above acids. This will cause them to stick to the film (mordant) in the gelatin. Then rinse briefly. Then run through the C41 process (no bleach or blix, just a fix) at room temp. If things go as expected you will get a black and green image.

    This should work. It works in parts and pieces, as I have done it before, but don't ask for specifics. If you want this, you must do the experiments yourself. Sorry.

    PE
     
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  15. Gerald C Koch

    Gerald C Koch Member

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    Thanks PE I knew you could say it better than I could.
     
  16. michaelbsc

    michaelbsc Member

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    Chris,

    How well is this likely to work with modern T grain and thin emulsion like Delta 400 or Tmax?

    It ssems like the lower silver content as well as the lack of emulsion to absorb stain both work against you.

    Do I understand this correctly? Or should I review the concepts again because I missed it?
     
  17. Photo Engineer

    Photo Engineer Subscriber

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    Unfortunately, mordanting does not work imagewise!

    PE
     
  18. michaelbsc

    michaelbsc Member

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    Pity. Sounded interesting.
     
  19. Photo Engineer

    Photo Engineer Subscriber

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    It could probably be made to do so by some hard work by a synthetic organic chemist and a team of engineers! :wink:

    PE
     
  20. desertrat

    desertrat Subscriber

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    There is a dye intensification process for negatives mentioned in Photographic Facts and Formulas, by E. J. Wall, 1924:

    Partially bleach the fixed and washed negatives in:

    Potassium Ferricyanide, 0.34 grams
    Ammonium Dichromate, 0.068 grams
    Glacial Acetic Acid, 8,5 ml
    Water, 1000 ml

    Then wash, and immerse in:

    Victoria Green (Malachite Green) 0.26 gram
    Safranin, 0.52 gram
    Glacial Acetic acid, 8.5 ml
    Water, 1000 ml

    Dye for 30 to 120 seconds and wash for 5 minutes.

    You can probably substitute Potassium dichromate from a chromium intensifier kit for the ammonium dichromate. You can probably also use indicator stop bath concentrate instead of glacial acetic acid and use twice (17 ml) as much. Dry malachite green and safranin stains can be bought from some biological or chemical supply houses. One that sells to individuals, but has a long lead time on delivery, is elementalscientific.net. I've bought from them, and always got what I ordered, but sometime it takes a couple of months. I think Artcraft will custom order things they don't stock on a quote. A solution of malachite green can be bought at some aquarium stores for treating certain skin infections of fish. The amount to use would have to be determined by trial and error. You might be able to get by with just the green dye without the safranin, which I think is red.

    The amount of time to 'partially bleach' the images would have to be determined by trial and error. I have no idea how well this would work with modern films, but it might be a fun experiment.
     
  21. holmburgers

    holmburgers Member

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    PE, I'm not so sure if that's correct. There are a number of dye-mordanting color processes from the past, like Uvachrome (go down the page).

    Ive's also used a similar process for his Kromskop images, and if I'm not mistaken (which could be a big if), J.S. Friedman's "Dye-Toning" technique works similarly.

    Here is what it says on page 340, 2nd ed. 1945, "...Mr. Miller decided that if the silver of the image is converted into silver iodide in the presence of high concentrations of potassium iodide, a completely transparent silver iodide-potassium iodide mordant is formed... When bleached in this solution, a completely invisible image composed of a complex potassium silver iodide, is formed, an image which absorbs dye..."

    This works for basic dyes, like malachite green, and would definitely be image-wise.
     
  22. Photo Engineer

    Photo Engineer Subscriber

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    Well, I'm not sure that the mordant worked imagewise or if the mordant was applied imagewise to an image formed by another method. You can always find something like this, but IMHO the description is not entirely clear. If you look at the classics, the mordant was "everywhere" and an image was applied to the mordant and stuck imagewise to a uniform layer of mordant.

    PE
     
  23. Michael R 1974

    Michael R 1974 Subscriber

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    Thanks everyone for the replies. I suspected it was complicated. I'm obviously in over my head on this one, but thought it was an interesting idea. I think for now though this will have to go on my list of "experiments to try maybe at some point".
     
  24. Ian Grant

    Ian Grant Subscriber

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    Michael, I've used the dye coupler route a lot in the past mainly for hand colouring images, but I've used it to intensify negatives as well.

    With negatoves it's rather like using XP1/XP2 film the only difference is you add the coupler to the colour developer rather than it being in the film and you can chose the colour or mix of colours.

    It has an adavantage in that a film can be passed through the cycle a few times, dev in a normal B&W developer & fix washn well then bleach in a rehalogenating bleach wasg dev in C41 ith the coupler(s), wash, then repeat the bleach/dev again. This technique was once very common with astro photography for colour films and called looping.

    So back to your initial question yes you can add a dye colour, proprtional to the exposure very easily.

    Ian
     
  25. Michael R 1974

    Michael R 1974 Subscriber

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    Interesting thanks for the input Ian. I think part of my nervousness with stuff like this has to do with the whole bleach-redevelop thing, which I've not explored in any detail, nor ever tried, other than with paper just to play around with some toners. But since I don't tone my prints in anything other than selenium, I never went any further, and on the film side I've never needed that kind of process, so I'd really have to do alot of reading on this subject before trying it.
     
  26. kevs

    kevs Member

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    Vanadium toning will turn your negs green. Sadly it isn't permanent.