Selenium Toning - Overall Stain Due to Fix Acidity

Discussion in 'B&W: Film, Paper, Chemistry' started by Bill Burk, Jan 25, 2014.

  1. Bill Burk

    Bill Burk Subscriber

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    In a recent thread I discussed my procedure for printing and toning and it's a simple procedure.

    I mentioned that "when I rush" or "when I use old chemicals" I occasionally get stains. But most of the time I have no problem.

    Last night, I learned the procedure that leads to stains: When I leave out the wash between Fixer and Toner.

    I can fit four trays in my sink, I wash prints by putting a small table under the holding tray and attaching a Kodak Tank and Tray Siphon to it.

    ---
    This process leads to stain-free prints...
    ---
    Print session:
    1. Develop in Dektol 1:2 for 3 minutes.
    2. Stop in Kodak Indicator Stop Bath 4cc in 32 ounces water for 30 seconds.
    3. Fix in Kodak Rapid Fixer 1:7 (4 ounces + 28 ounces water) for 6 minutes each print fixed individually with continuous attention.
    4. Holding tray of water during print session.
    ---
    After print session:
    Empty and rinse trays 1-3, raise tray 4 and attach siphon to running water.
    5. Wash prints 2 hours.
    6. Allow prints to soak overnight.
    7. Turn the wash water back on in the morning.
    ---
    Toning session:
    8. Kodak Rapid Selenium Toner 1:32
    9. Wash prints 2 hours.

    ---
    ---
    ---
    This process leads to an unpleasant brown cream colored stain over the entire print...
    ---
    Print session:
    1. Develop in Dektol 1:2 for 3 minutes.
    2. Stop in Kodak Indicator Stop Bath 4cc in 32 ounces water for 30 seconds.
    3. Fix in Kodak Rapid Fixer 1:7 (4 ounces + 28 ounces water) for 6 minutes each print fixed individually with continuous attention.
    4. Holding tray of water during print session.
    ---
    After print session:
    Empty and rinse trays 1-3, raise tray 4 and attach siphon to running water.
    But do not wash prints fully, instead proceed quickly to Toning session because you want to be able to dry the prints in the morning...
    ---
    Toning session:
    5. Kodak Rapid Selenium Toner 1:32
    6. Toss prints in the trash.
    ---

    Now California is in a drought, so I am inclined to "do my part" and modify my working procedure with the addition of Hypo Clearing Agent. I think I would have been better off if I had used that... But my standard procedure relied upon the complete wash between fix and toning.
     
  2. Chrismat

    Chrismat Subscriber

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    Nice post, this is good information.

    This is obviously for fiber prints, correct? When I had a darkroom (may have another one later this year) I mostly printed on Ilford RC paper and I used selenium toner at about 1:50.

    Chris
     
  3. Bill Burk

    Bill Burk Subscriber

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    Thanks Chris,

    Yes, Fiber Based, Ilford Galerie.
     
  4. Tom1956

    Tom1956 Inactive

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    I believe I have read somewhere I cannot recall, but it was a reputable source... If you selenium tone after washing, it must be a thorough archival-style washing. If you tone after fixing, then go straight from fixer to toner with no rinse whatsoever. Otherwise, staining. Wish I could remember where I saw that, but I do remember it was some book of trustworthy repute.
    Side note. Seems almost a pity and a shame to go through an archival wash, just to contaminate the print and have to do it all over again.
     
  5. Bill Burk

    Bill Burk Subscriber

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    I think you have to change something significant (e.g., Use an Alkaline Fix, Plain Hypo for second bath, add Plain Hypo or Hypo Clearing Agent in the toner)... Before you can follow the advice to go "direct to toner from fix" without staining.
     
  6. Ronald Moravec

    Ronald Moravec Member

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    Quick rinse in water after fix and tone. Learned this from Fred Picker I believe decades ago.

    The laborious first method also does work , but since you are getting stains, it is telling you the wash is not removing ALL the fix. First you need several rinses after fix, hypo clear, then wash. Soaking in a tray in insufficient. The best method without a print washer is with two trays, fill first with water and interleave prints while second tray is filling. Transfer prints to second one at a time, interleave two cycles while first tray is being refilled. Repeat through 8 trays of fresh water and it will take around 30 minutes. I have prints 50 years old that are fine.

    Since you are getting stains, your method will show as stained prints at some point. I urge you to change method.
     
  7. michael_r

    michael_r Subscriber

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    Bill, I suggest reviewing Ilford's washing/toning instructions as well as Kodak's (see link below):

    http://www.kodak.com/global/en/professional/support/techPubs/g23/g23.pdf

    I have a couple of questions about your processes which may or may not be related:

    1) While I don't use Kodak Rapid Fixer specifically, are you sure about the 6 minute fixing time? That seems awfully long for a rapid fix, which could make it much harder to wash effectively (I'm also assuming you don't add any hardener).

    2) In your second procedure, do the prints simply go directly from fixer to a standing water tray? If there isn't at least a thorough rinsing first, it seems the fixer would continue working (perhaps unevenly since there is no agitation) and remain in the paper while it is in the soaking tray, since it would be quite slow to diffuse out in a tray of standing water.

    3) In your first method in which the paper receives a full 2hr wash, why would you leave it soak overnight? Why not let it dry and then re-wet the next day? While such greatly extended wet times may or may not impact brighteners and paper stability (tests would need to be done), surely it cannot help.

    4) It would seem when one is rushed it might be best to include a hypo clearing agent in the process.

    Thoughts?
     
    Last edited by a moderator: Jan 25, 2014
  8. Bill Burk

    Bill Burk Subscriber

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    The stain appeared immediately when placed in Toner.
     
  9. Bill Burk

    Bill Burk Subscriber

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    I could easily shorten the fixing time. Last night I used "paper strength" and have seen instructions for shorter times which use "film strength". I figured paper strength would need longer time. I don't add the hardener, those little bottles are accumulating...

    I leave it to soak overnight because it's late and all I do is turn off the faucet and go to bed.
     
    Last edited by a moderator: Jan 25, 2014
  10. michael_r

    michael_r Subscriber

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    Oops I edited my post and added some more questions while you were responding....see above. Sorry about that but I thought of some other things after I posted.

    I'd check Kodak's instructions for those fixing times. For example, assuming Kodak Rapid Fixer is similar to Ilford Rapid Fixer at the working dilution, Ilford recommends 1 minute.
     
  11. Tom1956

    Tom1956 Inactive

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    How about 2-bath and then straight to toner? Second bath with Hypo and sulfite only.
     
  12. clayne

    clayne Member

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    Bill, I'm certain you do not need to fully wash between fixer and toner. I have never had any significant staining going from fix (2 bath) to holding tray to KRST (1+10 or 1+20). Usually this would be with Emaks K-888, but also MCC110, Galerie, and MGIV. Selenium toner is 30% Ammonium Thiosulphate; it already has fixer in it.

    Selenium toner is also used as a fix strength test (search threads, numerous ones with PE chiming in) where Se toner will stain if there is still undeveloped silver left - because the toner is effectively "developing" that silver. Now I do recognize that there's another range of staining possible with pH levels that some people have run into, but this hasn't happened to me.

    dev -> stop -> fix1 (2-3 min) -> hold (1-2 hours), fix2 (2 min) -> hold (5 minutes until I'm done with fix2 of all held prints) -> toner ->wash.

    The fix baths I use are Arista odorless fixer, 1:4 ratio. I think Kodak Rapid Fix 1:7 is too weak!

    Here's the MSDS for Arista Premium odorless fixer:

    Ammonium Thiosulphate: 45-50%
    Sodium Bisulfite: 5-8%

    Here's the MSDS for Kodak rapid fixer with hardener:

    Ammonium Thiosulphate: 40-45%
    Sodium Acetate: 5-10%
    Boric Acid: 1-5%
    Ammonium Sulphite: 1-5%
    Acetic Acid: 1-5%
    Sodium Bisulfite: 0.1-1%

    Here's the MSDS for KRST:

    Water: 55-60%
    Ammonium Thiosulphate: 25-30%
    Sodium sulphite: 10-15%
    Selenious Acid, disodium salt: 1-5%

    You'll notice additional hardener ingredients in the Kodak rapid fixer that may be contributing to pH differences vs the Arista fixer. I still wouldn't use the Kodak fix at 1:7 though, prefer 1:4.
     
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  13. GeorgK

    GeorgK Member

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    It is very difficult to wash a FB print properly after over-long fixation. Once the fixer gets "stuck" deep within the paper fibres, it is almost impossible to get rid of it. With 2-bath fixation and a good basic (or neutral) modern rapid fixer, 1+1 minutes (with constant agitation) is already plenty and on the safe side. Such prints are easily washed in 15 minutes.
    Unfortunately, "longer fix = better fix" is a very persistent darkroom myth. And washing prints overnight is - sorry - ridiculous.

    G.
     
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  15. Bill Burk

    Bill Burk Subscriber

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    To the question about going straight from fixer to standing tray... yes, although it's fresh water, and some agitation, generally the prints are allowed to sit there until I switch to wash configuration. I occasionally pour another quart of water in the tray.
     
  16. Bill Burk

    Bill Burk Subscriber

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    clayne, What fixer do you use? It might be a difference that matters.
     
  17. clayne

    clayne Member

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    Bill, updated my previous post with the details. I use Arista Premium odorless fixer at 1:4 ratio for both baths.
     
  18. Bill Burk

    Bill Burk Subscriber

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    Overnight soaking is a physical convenience. It allows me to sleep. I don't believe it harms the prints, though if I modify my routine such that I tone in the same darkroom session, I won't have to leave the prints wet overnight.
     
  19. clayne

    clayne Member

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    Yeah soaking overnight in a holding bath is unlikely to do anything bad to prints. I usually try to get toning out of the way because it's fast and part of the batch finishing up process, but I know what you mean when you're feeling tired and just want to go to sleep.

    Myself I'm not a big believer in that fiber somehow absorbs inescapable amounts of fixer the longer you fix it. Seems like it would violate basic diffusion theory to me in that if one fixes longer, than wash longer - but I don't think if one fixes lets say 5 minutes a print the print is going to fall apart in 50 years. There's plenty of empirical evidence showing that isn't true.
     
  20. Bill Burk

    Bill Burk Subscriber

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    Thanks clayne for the update. There's enough difference between the brands to make a possible difference in the outcome.

    I think my best bet to go forward is to add Hypo Clearing Agent into process steps similar to yours, just before toning.
     
  21. clayne

    clayne Member

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    Try a fixer without hardener components first. Remember too that hypoclear is basically sodium sulphite, of which KRST already consists of (in addition to ammonium thiosulphate). You can do it without the additional step of HCA and anything that is less steps == less water == less hassle. The only time I use HCA is with brown toner, and that's to put the brakes on the toning.
     
  22. Bill Burk

    Bill Burk Subscriber

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    That is how I wash my film. So I know you are right.

    I trust the process I had been using with the Tank and Tray Siphon washes. I do interleave sheets and ensure complete water replacement.

    But the shortcut where I tried to go to toner after only a brief holding period in water... that variation on my process I am cutting out forever.

    I don't care if others do it, I'm not going to try that anymore. (It is not a valid process with the chemicals that I currently use).
     
  23. Bill Burk

    Bill Burk Subscriber

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    For reprints from last night's session, I went back to my tried and true method. No stains.
    ---
    Print session:
    1. Develop in Dektol 1:2 for 3 minutes.
    2. Stop in Kodak Indicator Stop Bath 4cc in 32 ounces water for 30 seconds.
    3. Fix in fresh mixed Kodak Rapid Fixer 1:7 (4 ounces + 28 ounces water) for 5 minutes each print fixed individually with continuous attention.
    4. Holding tray of water during print session.
    ---
    After print session:
    Empty and rinse trays 1-3, raise tray 4 and attach siphon to running water.
    5. Wash prints 2 hours, leaf through prints occasionally, empty tray twice during the wash.
    6. Kodak Rapid Selenium Toner 1:20 (it was always 1:20, earlier post 1:32 was a typo).
    7. Wash prints 2 hours, leaf through prints occasionally, empty tray twice during the wash.
    ---
     
  24. Bill Burk

    Bill Burk Subscriber

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    Here's a fun question and thought from the lesson...

    Is the stained print good? Suppose one day I want the look of cream-base paper. I know how to achieve it.

    When you consider that I made two 11x14 prints in this session, what value would two-bath fixing offer me?

    If I was in the darkroom every day making many prints, then I'd be able to recycle bath 2 as bath 1. But the literature says discard after a week... So both baths 1 and 2 would be fresh if I were to adopt two-bath fixing. If I were to go with 1:3 instead of 1:7, and two baths instead of one, I'd have to use 16 ounces of concentrate per session to get the film strength, two bath, fixing... Sounds like a bad deal to me.
     
  25. clayne

    clayne Member

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    You do *not* discard after a week. You discard based on usage. Whatever literature told you to discard either bath after a week is just plain wrong - especially based at the frequency you're printing at.

    2 baths is cheap insurance and little work beyond 1 bath.
     
  26. Bill Burk

    Bill Burk Subscriber

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    Well, now that I've gotten to the bottom of the staining problem, I can start to look at bringing other changes to the process...

    I had been using fixer as one-shot for printing because of the staining, thinking that re-using old fixer was causing it.

    I also just dumped a partial bottle of Dektol last night because it was so dark I was afraid it would cause stains. I wish I'd kept it so I could prove to myself that dark Dektol is nothing to fear.