The definitive word (I hope) on color stabilzers!

Discussion in 'Color: Film, Paper, and Chemistry' started by Photo Engineer, Apr 13, 2012.

  1. Photo Engineer

    Photo Engineer Subscriber

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    I have gotten quite a few queries regarding color stabilizers and have therefore undertaken a project investigating them and trying to clarify them in one post.

    Here goes.....

    Cyan and Magenta couplers react with their respective dyes causing brown stains and loss of dye. This makes a print, slide or negative turn red or green with a brownish border or light areas that brown up. In addition, color materials have all of the silver removed during processing, and since silver is a biostat killing microorganisms, color materials can be "eaten by bugs".

    Traditionally, formaldehyde was used to combat both problems. Formalin (Formaldehyde gas in solutions) was the answer. E6, E4, C41 and C22 processes for film used this and Ektaprint C and Ektaprint 3 used it as well.

    Formalin reacted with the left over coupler and also the gelatin to form substances that resisted both coupler induced degradation and the bug attacks. But, it was found to be harmful to humans doing the processing (and perhaps afterwards). Now, formalin is used in the sizing of new clothing and in the finish of new furniture, but that did not matter to those who safeguard our health by force! So, Kodak undertook a project to eliminate the formalin from all stabilizers (Film and paper)

    In the 60s, a paper stabilizer was citric acid at pH 4.5 with benzoic acid and sorbitol + formalin. A film stabilizer was formalin + Photo Flo 200 or the equivalent. When E6 and C41 rolled around, they kept the same stabilizer but paper eliminated the stabilizer by incorporating some of the stabilizing agents into the paper itself. So, C22 stab = C41 stab = E6 stab = E4 stab at about 1970. Remember this!!!!

    Along the way, the "people who control us all" decided that formalin must go. Well, a coupler R&D program is expensive but a process R&D project is not so expensive, so the product with the most "weight" in sales got the biggest R&D share. That was C-41. A new family of couplers was introduced around 2000 and this family of couplers no longer needed Formalin. It was exclusive to C41. E6 OTOH, used the old couplers and embedded formalin in a bleach pre-bath that imbibed in a harmless version of formalin which was activated during processing.

    So, we now have 4 stabilzers/final rinses.

    Stabilzers C41 = E6 (pre about 2000) which contain formalin.

    Final rinses (C41) which is a biocide and the functional equivalent of Photo Flo 200 only and E6 which requires a formalin precursor and a biocide and also both an anionic (I think) and non-ionic surfactant (that good old Photo Flo 200 again). The current E6 final rinse has a new ingredient which looks like an anionic surfactant. That is all I can say at this time.

    Older E6 and C41 Stabilizers can be used for all films but the modern versions cannot be used with early films (pre ~2000) or must be used with a pre-bleach such as used in E6 to release formalin during bleaching. The E6 bleach is designed to do so.

    Anyhow, the oldest expiration date that I can find on Stabilizer III for C41 is about 2003 so that kind of dates this solution. After that, a final rinse was used for C41.

    At the present time an RA4 final rinse is also made. It is intended for processes with low or no wash and IMHO is courting disaster.

    What does this mean? ALL C41 films made before about 2000 and all E6 films need formalin in sole form or another. Leave it out and your negatives and slides will turn green or red and may show a brown stain. If your process for these films does not contain formalin you will have problems in months, days or years. I cannot predict the failure rate. E6 processes without formalin or a pre-bleach bath will cause eventual problems whatever the date the films were made.

    This applies (apparently) to both Fuji and Kodak products.

    This does not address motion picture films and I would ask that this subject no be brought up in subsequent posts. Thanks.

    How to make a formalin stabilzer? Easy!

    Mix up Photo Flo 200 as directed on the bottle. To one liter of this add 3 - 10 ml of 37% Formalin solution. That is it. The reason for the spread is that I have found several formulas with values like that. I use 10 ml to be on the safe side.

    Oh, and this type of fade is dependent on density and therefore is non-linear. It cannot be corrected by filtration or in Photo Shop scans. Sorry.

    PE
     
    Last edited by a moderator: Apr 13, 2012
  2. kb3lms

    kb3lms Subscriber

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    Thank-you, PE. Very-informative!
     
  3. mts

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    Thanks for a concise explanation, but one question remains...being on the lazy side I have long used C41 stabilizer (with formalin) for both E6, C41 and B&W, the latter in place of mixing separate Photo-Flo. I reason that B&W contains inherent biocide (silver), but a rinse in formalin containing stabilizer doesn't hurt. That lets me keep one liter of universal stabilizer that I generally replace about once a year, or whenever it seems to fail the sniff test--not smelling of formalin. I do re-use the bath with a few cc being lost lost in each processing.
     
  4. Athiril

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    Stabiliser III is still for sale here iirc. Also Tetenal E-6/C-41 stabiliser is on the shelves here which is basically the same thing. C-41 usage is about 1+50 for Stabiliser III, the concentrate contains ~116 mLs/litre of formalin (100%) I think.
     
    Last edited by a moderator: Apr 14, 2012
  5. Photo Engineer

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    Formalin can only be made at a maximum of 37%, as that is the limit of solubility of the gas in water and 20 C.

    PE
     
  6. Athiril

    Athiril Subscriber

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    100% formalin (37% formaldehyde), not 100% formaldehyde.
     
  7. Photo Engineer

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    You are correct Dan.

    PE
     
  8. Simonh82

    Simonh82 Member

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    Thanks PE, this is very useful. I hope Formalin is not too dangerous, as I always discover that my gloves have developed a hole after prolonged Ilford wash method agitation, by retrieving a reel from the jug of stabilizer and feeling it sloshing around inside my glove.
     
  9. hrst

    hrst Member

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    Formalin is used everywhere... It's not a good thing, but the concentration in the diluted stabilizer is low. Don't wash your hands in the stabilizer (at least very often), but if you have a hole in your protective gloves every now and then, it is absolutely no problem. (Of course, wash your hands immediately every time this happens with any chemical.)
     
  10. wogster

    wogster Member

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    If your concerned, then double glove.... What some folks do, is they wear two pairs of gloves, when they see a hole in the outer pair, they toss those, the inner pair become the outer pair and they put on new inner ones.
     
  11. EdSawyer

    EdSawyer Member

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    Thanks

    Thanks for sharing all the great details on stabilizers and such, PE! Most appreciated.
     
  12. cinejerk

    cinejerk Member

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    formalin source

    Took me a while to find a source for formalin. Searching through ebay proved fruitless !!

    I'm not affiliated with this guy just found his prices reasonable.

    Talk to Tom at: lsalow@peakpeak.com
     
  13. Photo Engineer

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    I might note here that the Formulary will often special order chemicals, and also has some chemicals on-hand that are not in the catalog. Talk to Sherry or Bud.

    PE
     
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  15. Bertil

    Bertil Subscriber

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    I have a bottle of Kodak Photo-Flo (polyethoxyethanol and ethylene-glycol), is it the same stuff as Kodak Photo-Flo 200 ? My bottle doesn't add 200 on the label.
    /Bertil
     
  16. Photo Engineer

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    That is not Photo Flo 200. That is probably Photo Flo 600, as Photo Flo 200 has Propylene Glycol, not Ethylene Glycol. It would most likely work, but the concentrations would have to be adjusted properly. If you have instructions for the bottle you have, make 1 L and add 3 - 10 ml /l of 37% Formalin.

    PE
     
  17. DREW WILEY

    DREW WILEY Member

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    This is interesting, Ron. But to back up to your comment on RA4 so-called stabilizer - I have never used it and in fact wash my prints about triple the recommended time & volume, so feel comfortable
    I've done a good job. But what is the premise behind the stabilizer, or is there any other than a
    shortcut in cumulative dry to dry processing time? I've never even look up the ingredients for this
    stuff.
     
  18. Photo Engineer

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    There are 3 color paper stabilzers. They are designed to maintain pH, present an oxygen barrier against fading, and to prevent growth of micro-organisms in the coating. One of them supposedly allows for reduced wash rate and / or time.

    The original type 2 stabilizer would increase image stability by over 2X. It is no longer available and IDK how it would perform with current papers.

    Disadvantages include increased tackiness to prints.

    But then I said most of this in my OP.

    PE
     
  19. Roger Cole

    Roger Cole Member

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    I did find sources for 10% formalin on eBay, though, one in a reasonable size in the UK and this lifetime supply in the US:

    http://www.ebay.com/itm/LOT-OF-4-GA...186?pt=LH_DefaultDomain_0&hash=item33667a0a6a

    Couldn't this just be used at 3.7x the concentration? Or are there other ingredients that would be hostile to film?
     
  20. Photo Engineer

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    Roger, that formalin is just fine. Just adjust the amount.

    PE
     
  21. Roger Cole

    Roger Cole Member

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    Thanks. I noticed in the photos it has an expiration date listed of 8/27/2012. Does this stuff really go bad?
     
  22. Photo Engineer

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    Roger, it forms several types of polymers as well as a trimer. These do revert to formaldehyde on proper treatment.

    PE
     
  23. hrst

    hrst Member

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    I think formalin solution is usually stabilized with methanol, which increases its shelf life. At least mine is. Is it available without methanol stabilization? If it is, make sure you get the stabilized version, because the methanol doesn't cause any problems.
     
  24. BrendanCarlson

    BrendanCarlson Member

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    So I can use a 37% dilution of 10% formalin?
     
  25. Photo Engineer

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    Think about it Brendan. I'll give a quiz on this on Monday. :wink:

    PE
     
  26. ulysses

    ulysses Subscriber

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    Fishy formalin

    I just got a pint of formalin from petsolutions.com (via Amazon) for not a lot of money. No detailed information as to what else (if anything) might be in the bottle, but it does say the active ingredient is "37% formaldehyde." It's a clear liquid and smells like formaldehyde. As a long-time aquarist I know that formalin has been used for many years to treat parasitic infestations. I'll see how good a stabilizer it makes. A pint should last me a while...

    Ulysses