Pink/Magenta Stain (not blue, which is a different issue)

Discussion in 'B&W: Film, Paper, Chemistry' started by Photo Engineer, Nov 23, 2010.

  1. Photo Engineer

    Photo Engineer Subscriber

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    Having been reading a lot of Kodak data sheets recently during the debates over washing, fixing, stops and the like, I ran across something that kind of put some things into perspective for me.

    See here on page 9 for a comment by Kodak: http://www.kodak.com/global/en/professional/support/techPubs/f4016/f4016.pdf

    New films use a combination of layered dyes and dyes complexed with Osmium compounds (2 electron sensitization). These dyes can leave a pink or magenta stain in some films. Since dyes have a positive charge, acid fixers are more prone to this. Since high Iodide and strong dyes inhibit fixation, longer fix times and longer wash times are needed, especially if you season or re-use your fixer and especially if it is acid or neutral.

    Kodak is aware of this change, but it is necessary for us to be aware of the fact that a magenta tint may be due to underfixing and/or underwashing. This is probably a warning flag for all of us.

    PE
     
  2. Christopher Walrath

    Christopher Walrath Member

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    In personal experience alone, I concur with your remarks, Ron. Using Kodak films and chems, I have, a few times, withdrawn the film from the tank only to see the pink hue. Upon further fixing and the re-rinsing the film clears, every time.

    Now, just waht is the purpose of these dyes? And I presume this is a recent development in film production, meaning, the stepped up dyes? At least, that's how it sounded.
     
  3. Gerald C Koch

    Gerald C Koch Member

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    Soto voce, after all the fuss about cadmium and lead in papers does the EPA know about the osmium in films? Osmium compounds are highly toxic and exposure to oxidizing chemicals can release osmium tetroxide. Osmium tetroxide is a violent poison and just a whiff can kill you. Repeated or prolonged exposure to even very low levels of osmium compounds can be dangerous. Of course we don't know the actual amount of osmium in the film or the wash water.
     
    Last edited by a moderator: Nov 23, 2010
  4. OP
    OP
    Photo Engineer

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    Chris;

    These methods impart higher speed to finer grained emulsions. This also improves sharpness by reducing turbidity.

    Jerry;

    Cadmium was used at about 5 - 15 grams per mole of Silver but Osmium is used at about 6 x 10^-6 moles per mole of Silver. Does that put it into perspectiive? It uses about 6 orders of magnitude less metal.

    PE
     
  5. Gerald C Koch

    Gerald C Koch Member

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    PE thanks for the additional information.
     
  6. Sirius Glass

    Sirius Glass Subscriber

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    To drive film users crazy! Ba-wah-ha-ha!

    [Damn, I forgot Halloween has already past! My Bad. :sad:]
     
  7. Christopher Walrath

    Christopher Walrath Member

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    What a Turkey.
     
  8. Gerald C Koch

    Gerald C Koch Member

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    If some of the dyes incorporate an osmium atom this could also explain why they are hard to remove. Ossmium atoms are large and this would hinder the movement of the dye through the emulsion.
     
  9. Christopher Walrath

    Christopher Walrath Member

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    So, as a rule of thumb, should fixation duration be lengthened with Kodak films? Others?
     
  10. mts

    mts Subscriber

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    A good justification for processing LF in white trays, for the fixer at any rate. The pink stain is quite noticeable against the white tray bottom. I fix until it disappears completely which is generally 2-3 times longer than my rapid fix takes for older emulsions, Efke for example.
     
  11. Sirius Glass

    Sirius Glass Subscriber

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    I double the time [10 minutes rather than 5] for TMAX films.

    So Chris, just gobble this information up. :laugh:

    Steve
     
  12. OP
    OP
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    If there is a pink stain, Kodak suggests the use of longer fix and wash times. See the URL above.

    PE
     
  13. MaximusM3

    MaximusM3 Member

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    Ron,

    This is all interesting but I find even more amusing that I, for example, always fix Tri-X for 5 minutes with fresh Ilford Rapid Fixer and wash always the same way, with distilled water with the Ilford method, but...the pink stain is sometimes there and sometimes it is not. At times, it keeps coming out with every water fill/dump and sometimes it doesn't, yet the film comes out clear. What are the variables here? Does Kodak put these in the same amounts to the same films, in various emulsion batches?

    Thanks!

    Max
     
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  15. Christopher Walrath

    Christopher Walrath Member

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    Good question, Max, as my results are intermittent as well. Well, until a year ago. I have not used current Kodak emulsions in the interim.
     
  16. msa

    msa Member

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    Lately I've been processing a couple of dozen of old bulk loaded rolls of T-Max that my GF shot several years ago.

    Ran into this on the first couple, then started using a 12 minute fix time, and 2 15 minute rinse cycles (plus 2 minutes in the hypo clear, of course.) It was a little unexpected, since nearly all of my Kodak B&W experience has been on Plus-X and Tri-X.

    It's worth noting that these new emulsions are also pretty hard on fixer. I've been trying to replace 1L of fixer after each 7-8 rolls. Something to keep in mind, especially with these longer fix times.

    In the future, guess I'll stick with Plus-X and Tri-X. :D (I have a lot of Tri-X still in the fridge from just before the emulsion change.)
     
  17. mabman

    mabman Member

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    This might be one of the lesser (or at least less-mentioned) advantages of (semi-)stand development. I normally use Rodinal 1+200 for 2 hrs with a variety of 35mm and 120 films, and so far I've seen the pink/green/blue/magenta stain wash out when I dump the developer every time. No further stain in the stop, fix, or final wash.
     
  18. Ronald Moravec

    Ronald Moravec Member

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    TMax 100 needs frest Rapid fix or TF4 fresh, then wash and it will clear. If the fix is insufficient, no amount of washing will clear it.

    I use 5 min in TF4, Ilford wash sequence, then 3 soaks of 60 sec @. Perfectly clear every time.
     
  19. OP
    OP
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    Kodak suggests HCA in the presence of stubborn stain. In my experience, alkali seems to help and so high pH developers and alkaline fixes seem to do a better job.

    One of the variables may be water supply or variations in them rather. Some people do report good results one day and bad results the next. It may also be due to the number of rolls or square footage processed. As you have noted, these new films are hard on fixers. The high iodide and high levels of dye exhaust fixer faster in my experience. The wash times seem longer.

    Using the test solutions will help get you a baseline for your workflow.

    PE
     
  20. Jerevan

    Jerevan Member

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    Just a question - would the 2 electron sensitization/dye layers be possible to use when making "older" films (as Tri-X/Plus-X)? I.e. should I worry about the fixing when using other films than the T-grain ones?
     
  21. msa

    msa Member

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    PE,

    It's interesting that you mention water.

    I live in the southwest, and have some pretty hard water here, which I believe to be contributing. The fixer was fresh (made that day) for those two rolls, and I think I have the pink tone all worked out now with some washing and fixing time changes. I do use HCA.

    Thanks!
     
  22. OP
    OP
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    I'm not sure what products use these techniques. It would suffice to say that if you get a pink stain, the film probably uses the technique(s) in question.

    PE
     
  23. msa

    msa Member

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    I've seen a pink wash and slight pink cast (cleared while washing) with the new Tri-X. It's not nearly as bad as T-Max, or as hard on fixer, but it is there if you look.

    I also just dug through my fridge and found a roll of new Tri-X (Exp 4/2008.) I laid it next to some of my old stock Tri-X. If you compare an old and new roll, looking at the emulsion side of the leader, you can see a very slight pink cast to the new Tri-X.

    Not sure about Plus-X. Maybe I'll test a new roll when I pick up my slides today.

    Edited to add:

    Forgot to mention this, but the cast is so slight and washes out so quickly with Tri-X that I haven't been adjusting fix times, but I usually use 6 minutes rather than 5 anyway. With T-Max, it's 10-11ish, maybe 12 depending on the age of the fixer.
     
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  24. pentaxuser

    pentaxuser Subscriber

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    Interestingly a U.K. based author called Harry Fearn, of "Better in Black and White" fame wrote about this as far back as 2000. TMax 100 and 400 were his favourite and thus his stock films. He fixed for as long as he developed which was between 10 and 11.5 mins for 400 and 100respectively.

    It would seem that there is something different about these Kodak films. I have never seen this phenomenon with Ilford or Fuji films.

    It would seem this is the price you pay for the benefits of using these films. It would appear to be a true price in that the films exhaust fixer quicker than comparable( or not comparable if you think Kodak Tmax films to be better)films or is the jury still out on the quicker fixer exhaustion aspect?

    pentaxuser
     
  25. Ian Grant

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    As a long term Tmax user from ut's release until 2 or 3 years ago I'd agree partially with Harry Fearn, but I always fixed until the pink colour started to disappear.

    Having switched back to Ilford films it's actually a relief how much easier their films are when it come to fixing, particularly fixer economy etc.

    Ian
     
  26. Greg Davis

    Greg Davis Member

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    While I was performing the washing tests, I used T-Max 400 and noted that the pink stain was gone when following the instructions, but could be stubborn if washed without HCA and even worse if a hardening fixer was used without a followup of HCA. A non-hardening fixer used in conjunction with HCA cleared the film completely every time. I used Kodak Rapid Fixer for 5 minutes in a manual tank at 75°F (24°).
     
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