ILFOCHROME HOME-BREWED BLEACH

Discussion in 'Color: Film, Paper, and Chemistry' started by brookse, Jan 21, 2010.

  1. brookse

    brookse Member

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    I’m a newbie on this site, but I’ve followed most of the threads on the dye bleach process for a while. As an organic chemist, I actually view the color darkroom as a laboratory, which can give me an artistic-emotional rush after each “experiment”. I think we are all aware of the convoluted, frustrating mess that Ilfochrome marketing has been over the last few years. We also know that the bleach step, and its precise chemistry has been shrouded in mystery for years. It is also obvious that it is this chemistry that provides all of the value-added for the process…and it is what you are actually paying for, big time. Currently, B&H is backordered on the P30 kits, while Freestyle can still drop-ship….with a $40 ship and hazmat fee added on top of the $100 for just two liters.

    So, I have now come up with a chemical synthesis of the active dye-bleach catalyst used in all modern formulae….Quinoxaline 7K (see all online MSDS’s for bleach components).

    I have also used e-bay extensively to buy “old” P30 kits, although exact ages cannot be determined. Without exception, part A of the bleach exhibits dramtatic decomposition wherein the solution turns dark greenish brown, while dark flock or tar separates. This problem is due to acid-induced decomposition of the active dye bleach catalyst. Additionally, the acid itself, in liquid formulation, is perhaps the main reason for the shipping restrictions. Chemically, you would have to be an idiot to formulate the kit in this manner, unless you desired planned obsolescence in time. To be fair, the larger volume (P3.20) and other roller transport formulations do not use this approach…. But, the acid used does indeed change to the cheaper sulfuric acid. So with the P30 kit formulation, only the little guy will have to worry about how long the item has been on the shelf.

    My approach is to use standard battery acid as the basis for a formulation. This is available locally, and over the counter and in convenient volumes at auto parts stores. In addition it is advisable in my mind to attempt to create more dilute bleach solutions which are safer and greener. However in this case, the process flow must be modified to include a bleach-fix step. Process time does not matter to me. My experimentation so far has been limited, and has been done only with outdated CLM.1K on the RC, non-deluxe, base.

    If you were able to gain access to the catalyst and the contrast control agent for Ilfochrome, you would also need to be able to answer, in the affirmative, the following questions:

    1) Can you mix a B&W low-contrast DIVIDED developer system as has often been described?
    2) Do you routinely use RA-4 blix (or Ferricyanide and non-hardening liquid fix conc.)?
    3) Can you locally purchase specific gravity 1.265 sulfuric acid for batteries?
    4) Can you easily go on e-bay to obtain a few additional, moderately-priced components?
    5) Do you have the ability to store used part-B of the divided developer to neutralize bleach?
    6) Have you got odds and ends around the house such as NaOH and non-natural vitamin C?

    I would like to gage the level of interest that other artist-craftsmen-teckies might have in attempting to formulate home-brewed Ilfochrome solutions. Respond to the post if you are desirous of pursuing such a project. I will respond back occasionally over the next few weeks, waiting to accumulate a list of candidates. Remember however that I can't give you anything on a silver platter....work and patience will still be required.
     
  2. tiberiustibz

    tiberiustibz Member

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    Sounds like an awesome way to waste time. I'm in! The ilfochrome process includes a standard B+w developer, a dye bleach, and a regular fix right? So I just need to make a dye bleach and mix/obtain a developer with similar characteristics... How much would variances in the dye bleach effect the image characteristics?
     
  3. Photo Engineer

    Photo Engineer Subscriber

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    Ilfochrome materials are much too expensive to play with for experimentation. You have to get it right quickly or you are into a lot of waste paper. The dye bleach process is just as prone to variations in balance and having crossover as any other color process, but has the additional burden of using a lot of acid.

    Well, that and the fact that KI is not all that nice at that pH either.

    I have lists of possible dye bleach formulas and catalysts here from our R&D on it at EK.

    PE
     
  4. hrst

    hrst Member

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    I'm very interested and like to experiment, but I have not much money to spend on paper. However, if there is some way we Apuggers can help, I'm in.
     
  5. Bob Carnie

    Bob Carnie Subscriber

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    So the idea is to bypass Ilford and make home brew ??
    How long before Ilford gets pissed and one raises the price of paper to compensate for loss of chemical sales?
    Who will one point fingers at if the home hobbyist can not mix right?:munch:
     
  6. ras351

    ras351 Member

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    At the moment I'm without a darkroom but give me six months and hopefully that will change. I have in the past used standard Beers B&W developer (+thiosulphate I think) and exposure adjustment as a way of tweaking contrast and it worked quite well. The fix was standard rapid fix. The bleach used was the P3 bleach which I used to be able to buy separately (albeit as three 2 litre bottles). The bleach step went to completion so wasn't significantly fussy about time so long as you gave it enough. I'm no longer sure about the availability of the separate bleach component plus it was hideously expensive here although the paper was still the main cost. If I'd have to buy the kits just to get the bleach (although I'd also use the fix) I'd certainly be interested in a home brew alternative. I have some old paper in the freezer but as mentioned I'll not be able to do anything for about six months by which time hopefully the new house will be finished and I'll have had a chance to put together the darkroom.
     
  7. hrst

    hrst Member

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    The prices of Ilfochrome materials are unbelievably high already. There is a small, loyal group of customers who buy the products to make gallery prints, but it's very possible that Ilfochrome is dying soon as it is quite unusable for normal printing due to its price.

    Probably any attempt to make it possible to use this fine process will increase their paper sales.

    Ummmmmmm...???? Maybe you can point your finger at yourself if you do something by yourself, for yourself?
     
  8. tiberiustibz

    tiberiustibz Member

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    I forgot to mention that I'm a poor schoolchild. I have hydroquinone, metol, sodium sulphite, borax, sodium metaborate, and probably one or two others im forgetting as well as enough C41 chemistry to open a small lab.
     
  9. brookse

    brookse Member

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    Well, I'm glad the dichotomy of whether such an undertaking would be good or bad for Ilford(Oji) has come out so soon. I find it hard to believe that a few lone experimenters could in any way alter the longevity of Ilfochrome in the marketplace. Forces larger than ourselves will determine that. But in the meantime, I just like to play...and as in any lottery, if you don't play, you can't win. The following is a link which describes a typical divided(part A with developing agents, and part B with activating alkali)developer:

    http://www.photography-forums.com/gainer-paper-developer-t92014p2.html

    Nicholas....You have almost everything you need already with the exception of a little potassium bromide!
    Try a google search for "divided developer" to find more.

    PE....I use only 15 ml. battery acid per liter, along with a little bisulfate. The P30 kit uses a total of 80 grams of organic and inorganic acids and more than twice the amount of silver ligand. I would love it you could dig out some your formulas! I know that you have been partial to phenazines on this site in the past. In my patent collection, the most commonly used phenazine is 2,3-diaminophenazine, which unfortunately is a suspected carcinogen. The quinoxalines are devoid of this problem.
     
  10. Photo Engineer

    Photo Engineer Subscriber

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    Both phenazines and quinoxalines are used in DB solutions. I have some patents here, but they are not in my usual repertoire. Kodak and Ilford have many patents on the subject. There are other classes of catalysts as well. In my research disclosure (Haist, King and Mowrey) you will see that no catalyst was used. Actually, one of the developing agents acted as an electron transport and did it as well or better than anything else. And, it was low in toxicity.

    PE
     
  11. Ray Rogers

    Ray Rogers Member

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    I have an old interest in the SDB process too...

    PE's lists would be very welcome... I do dream though, that someway around the use of such low a pH could be sought and found... That would be the best thing that could come out of a focus group from my POV... Yes, I know I am dreaming. But if anyone has ideas....
     
  12. Ray Rogers

    Ray Rogers Member

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    But still used very low pH... correct?
     
  13. Photo Engineer

    Photo Engineer Subscriber

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    AFAIK, the reaction to cleave Azo dyes into their constituent parts requires a strong acid on the order of pH 1.0 or thereabouts, or LOTS of heat and a milder pH of about 3 - 4. (200 C) See the RD. I forget the details offhand. It has been nearly 40 years.

    PE
     
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  15. John Meyer

    John Meyer Member

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    I remember Dye Chrome K2 chemistry used to make a kit that used a split bleach step. A C.C Phifer made it. Used it to control contrast..
    Called the number thats listed in Ctein's Post exposure book, but no answer.
    I still print Ilfochrome,have 100 sheets left. After that i will try something else
    ,its too much money if you can even get the chemistry.
    Wish some one thought about this ten years ago,for if i could get a steady supply of the stuff, its all i would print...
    Last week i printed my last sheet of pearl...

    John
     
  16. darragh

    darragh Member

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    Hi,

    I have a stack of out of date Ilfochrome classic and rapid paper and the chemistry is nearly impossible to get in Ireland, so I'd definitely be interested in some chemical experimentation.

    Darragh
     
  17. akaa

    akaa Subscriber

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    Count me in too. I bought an old darkroom setup with a RT Ilfochrome processor and haven't had a chance to try it out. I have some frozen paper and an old P3 1 liter kit to pitch in to the testing if needed.
     
  18. brookse

    brookse Member

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    OK Folks... Interest is now falling off! I would like first to deal with those who are in the US. Certainly Nicholas, and perhaps akaa. I will PM everyone shortly. One point however...In my hands, outdated ilfochrome is perfectly good for making formula changes, and assessing the resulting effects. However, in general, beyond 1-2 years post-date, the color values may get a bit muddy, with a greater propensity for the often mentioned cross-over condition where the lower densities go cyan, and the shadows go reddish. Before you begin, those of you with old paper should have some idea of how it performs currently using standard chemistry. Fresh ilfochrome is preferrable for any final result....yet, most of you have expressed your respective levels of poverty. Please give this some thought!
     
  19. schlger

    schlger Member

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    Ingredients of p3x bleach

    Potassium Iodide CAS 7681-11-0
    3 Mercapto-1 Propanesulfonic Acid sodium salt 17636-10-1
    2,3,6, Trimethylquinoxaline 17635-21-1
    Sodium Iodide 7681-82-5
    Sodium Bromide 7647-15-6
    Sulphuric Acid 7664-93-9
    Sulphonated Trialkylphosphine 86563-95-3
    Ethyldiglycol 111-90-0
    Sodium 3Nitrobenzenesulfonate 127-68-4

    pH<1
     
  20. brookse

    brookse Member

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    You are spot on schlger! Quinoxaline 7K is 2,3,6-trimethylquinoxaline...the active dye bleach catalyst. This is the molecule that I now synthesize (its effectively impossible to purchase this). Some items on this list are expressly required for the compounding format of the P3X concentrates, as well as the fact that the mixed solution will be used in roller transport mode with essentially open tanks.
     
  21. tiberiustibz

    tiberiustibz Member

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    If anyone has any paper expired ilfochrome paper for me to buy that would be awesome.
     
  22. Photo Engineer

    Photo Engineer Subscriber

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    Now all you need is the quantity of each ingredient you need to make the bleach.

    PE
     
  23. brookse

    brookse Member

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    PE...Thats where analytical chemistry comes in...e.g. I've been lyophilizing P30 kits which can be quite intructive as to total mass in parts A&B. A little pH manipulation...a little extraction...and of course argentometry and you're almost home.
     
  24. Photo Engineer

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    Since Sodium Iodide is not very stable, particularly in solution and KI is not stable for much longer, I would suggest you consider that they are present as Iodates to some extent.

    Also, I have read one report where the catalyst is present in the developer or even coated to give an even distribution when the dye bleach is kicked off. I believe it might be in the developer, but I doubt if it could be reliably coated unless there was a mild ballast of some sort. Of course, then again, many have gotten good results with Dektol, so the reports of it being in the developer may be just reportage or commentary for patent purposes, disclosing other routes to block patents.

    PE
     
  25. mmerry

    mmerry Member

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    Count me in. :smile:

    Thanks
    Matt
     
  26. Wayne

    Wayne Subscriber

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    I'm interested, hell I've been looking for a home bleach for years (but not doing much about it). But

    1) Processing time IS a concern to me, so what are we talking about?
    2) My darkroom has been disassembled so I probably wont be able to mess with it until whenever I get set up again. Dont know when that will be but hopefully this year...but do keep me posted, I'd definitely interested.


    Ilford should be thankful if this can be done, it will increase the paper sales and that's all we need them for. The day I have to make
    my own Ilfochrome paper is the day I give up.