Self-Made HypoClear any good?

Discussion in 'B&W: Film, Paper, Chemistry' started by RalphLambrecht, Nov 26, 2006.

  1. RalphLambrecht

    RalphLambrecht Subscriber

    Messages:
    8,213
    Joined:
    Sep 19, 2003
    Location:
    Florida
    Shooter:
    Multi Format
    I started to make my own HCA, mixing 20g of sodium sulfite to 1 liter (2%) as a working solution. I noticed that when I poured the solution into the tray that the last 10% or so were not as clear as the rest (the solution is a week old), but it seemed to mix OK.

    After fixing, I power-washed for 5 minutes and then used the HCA for 10 minutes, followed by a 30 minute wash. Then, I wiped the prints off (squeegee) and hung them to dry. I noticed later that the wiped-off liquid turned white. Apparently, some of the HCA is still in the print after a 30 minute wash!

    Questions:

    1. Does the residual HCA harm the print?
    2. What is the best way to deal with this?
     
  2. Ole

    Ole Moderator Staff Member Moderator

    Messages:
    9,281
    Joined:
    Sep 9, 2002
    Location:
    Bergen, Norw
    Shooter:
    Large Format
    3: A 2% solution of sodium sulfite should be perfectly clear, and not show any sign of sediment.

    Since yours did, there's something else in it. My first guess is that it's been mixed with "hard" water, so that you've got calcium sulfite (and sulfate) coming out of solution.

    If the wash water is also "hard", you'll have a little calcium absorbed in the emulsion which reacts with the sodium sulfite again, leading to even more white stuff! So it's not the HCA which is still in the prints, it's a trace of calcium sulfite/sulfate.

    After washing, give the prints a few minutes in deionised water. Use deionised water for mixing "HCA", or filter the solution before use.
     
  3. RalphLambrecht

    RalphLambrecht Subscriber

    Messages:
    8,213
    Joined:
    Sep 19, 2003
    Location:
    Florida
    Shooter:
    Multi Format
    Ole

    Many thanks, that makes a lot of sense, because the prints brown-toned perfectly (sodium sulfite is a toner stop bath). I filtered the solution right after your post, and will use deionized water in the future. Any idea why this never happend with Kodak's or Ilford's WashAid? ... and, do you think it might harm the archival properties of the print?
     
  4. David Brown

    David Brown Subscriber

    Messages:
    3,597
    Joined:
    Feb 16, 2004
    Location:
    DFW, Texas
    Shooter:
    Multi Format
    I could be wrong, but I have read somewhere that Kodak included in some of their formulas chemicals to deal with the impurities in domestic water. Somebody else will have to confirm this (or refute it).
     
  5. Ole

    Ole Moderator Staff Member Moderator

    Messages:
    9,281
    Joined:
    Sep 9, 2002
    Location:
    Bergen, Norw
    Shooter:
    Large Format
    The commercial mixes all contain a sequestering agent (Calgon, EDTA or similar) for precisely this reason.

    I wouldn't expect a hint of gypsum to have any serious effects on the longevity, no. After all there's already a layer of barium sulfate in there (baryta)!
     
  6. Peter De Smidt

    Peter De Smidt Member

    Messages:
    1,064
    Joined:
    Oct 20, 2004
    Location:
    Fond du Lac,
    Shooter:
    Multi Format
    I think Ole is right. I had some serious print staining/cloudy solution problems when I moved my darkroom. It turned out that the water was simply too hard for the sequestering agents to do their job properly. Changing to a better water source eliminated the problems.
     
  7. Ian Grant

    Ian Grant Subscriber

    Messages:
    18,040
    Joined:
    Aug 2, 2004
    Location:
    West Midland
    Shooter:
    Multi Format
    Both Ilford and Agfa gave details for making your own HCA.

    Agfa recommend using Carbonate in their literature for fibre based paper processing, the Ilford bit is in Mason's Photographic Processing Chemistry, (he was head chemist a few years ago) where he recommends using Sodium Sulphite.

    The chemicals have no effect on the image at all, they help to make the residual traces of silver complexes formed during fixing more soluble, and so easier to remove.

    Most of the research was carried out during WW2 when it was discovered that salt (sea) water used to wash prints on board navy ships accelerated the washing process.

    The chemicals used in HCA / wash aids are very soluble in water so wash out extremely quickly.

    Ian

     
  8. RalphLambrecht

    RalphLambrecht Subscriber

    Messages:
    8,213
    Joined:
    Sep 19, 2003
    Location:
    Florida
    Shooter:
    Multi Format
    Thanks Ian

    This is not the reason for the thread, but the actual research is much older than WW2. The WW2 story is a nice myth; the facts, you stated on the other hand, are true.
     
  9. dancqu

    dancqu Member

    Messages:
    3,676
    Joined:
    Sep 7, 2002
    Location:
    Willamette V
    Shooter:
    Medium Format
    A bit of chemistry trivia. Brown toners are sulfide
    toners. Polysulfides are used. Sulfur will dissolve in
    sodium sulfide making a Polysulfide. Sulfur dissolves
    also in sodium sulfite making Thiosulfate. So, a stop
    of sulfite works because it ties up available sulfur.

    It MAY be easy to make brown toner. I've some
    sulfide solution ready. Wonder if P. Formulary carries
    sulfur. Should be interesting and maybe rewarding
    to experiment. Dan
     
  10. RalphLambrecht

    RalphLambrecht Subscriber

    Messages:
    8,213
    Joined:
    Sep 19, 2003
    Location:
    Florida
    Shooter:
    Multi Format
    Dan

    Does that mean I'm creating fixer when trying to stop the toning?
     
  11. dancqu

    dancqu Member

    Messages:
    3,676
    Joined:
    Sep 7, 2002
    Location:
    Willamette V
    Shooter:
    Medium Format
    That's my understanding. Not very much though.
    Those brown toners are used very dilute. Likely the
    sulfur is an easy catch for the sulfite. The sulfur
    oxidizes the sulfite to a thio - sulfate. Dan
     
  12. rjas

    rjas Member

    Messages:
    227
    Joined:
    Jan 4, 2006
    Shooter:
    Medium Format
    How long can I be saving HCA? I use the powdered kodak HCA packets and just use a tablespoon per liter and have been dumping after every session no matter how many prints I run through because I was told that it oxidized in a matter of hours. Am I wrong in dumping it or can I use it for a couple days? I'm switching to the Ilford Permawash liquid because its all I can get here soon but I still have one last packet of Kodak HCA.
     
  13. gainer

    gainer Subscriber

    Messages:
    3,725
    Joined:
    Sep 20, 2002
    You should be able to get sulfur at a druggist, or a farm supply store.

    What happened to the theory that HCA is worse than residual hypo? Maybe that was only for the formulae that contained peroxide.
     
  14. Sponsored Ad
  15. Tom Hoskinson

    Tom Hoskinson Member

    Messages:
    3,879
    Joined:
    Mar 7, 2004
    Location:
    Southern Cal
    Shooter:
    Multi Format
    That theory wasn't about HCA (Kodak's Hypo Clearing Agent), Pat - it was about HE-1 (Kodak's Hypo Eliminator - which does contain Hydrogen Peroxide).
     
  16. Ian Grant

    Ian Grant Subscriber

    Messages:
    18,040
    Joined:
    Aug 2, 2004
    Location:
    West Midland
    Shooter:
    Multi Format
    Back to your original post I'm very surprised that you had any chemicals left in the paper, in 45 years of printing I've never seen what you are describing.

    As I said the chemicals used in wash aids / HCA are extremely soluble in water and wash out very easily.

    Only two things spring to mind, first the prints aren't being washed properly, maybe they are sticking together, or you have exceptionally hard water. I'm more inclined to go for the latter explanation.

    Oh I put a date on the washing in sea-water, perhaps I shouldn't have assumed WW2 :smile:

    Ian


     
  17. dancqu

    dancqu Member

    Messages:
    3,676
    Joined:
    Sep 7, 2002
    Location:
    Willamette V
    Shooter:
    Medium Format
    It is that uncertainty with the usual sulfite based
    HCAs on the market that has me ready to switch to
    Agfa's recommended sodium carbonate based HCA.

    A study quoted in a post to rec.photo. darkroom
    recently told that sodium sulfite was, IIRC the exact
    words, "as good as any other". That is, not any better
    than some others. I suspect Agfa's recommended
    sodium carbonate is as good as sulfite and it
    does not oxidize. Agfa's instructions may
    still be on the WWW. Dan
     
  18. RalphLambrecht

    RalphLambrecht Subscriber

    Messages:
    8,213
    Joined:
    Sep 19, 2003
    Location:
    Florida
    Shooter:
    Multi Format
    Ian

    It turned out to be the hard water. Thanks.
     
  19. john_s

    john_s Subscriber

    Messages:
    1,103
    Joined:
    Nov 19, 2002
    Location:
    Melbourne, A
    Shooter:
    Medium Format
    However there are many posts on rec.photo.darkroom stating that sulphite is better than carbonate. I agree that carbonate is tempting since it is cheaper and used at a lower concentration and lasts longer in solution. It would be better than nothing.

    The Agfa pdfs might not be all findable on the web. I have some of them. FWIW, this text is cut from the most recent pdf on fibre paper:

    <start quote>
    Soda intermediate bath

    A soda bath (1 % sodium carbonate solution) should be included
    for fibre-base paper, between fixer and final wash (time: 3
    minutes). This ensures that the fixer is washed off the paper
    surface faster and more thoroughly.
    This not only cuts down the final washing time by about 30 %,
    and in particular it increases the prints' durability.
    If a hardener-fixer is used, the soda intermediate bath is not
    recommended.
    <end quote>

    In the unlikely event that hardening fixer is used, the carbonate is not recommended because its alkalinity would negate the hardening which is pH dependent. I wonder if the alkalinity would leave the paper emulsion softer which might make it vulnerable to some toning processes.
     
  20. Wolfgang Moersch

    Wolfgang Moersch Member

    Messages:
    569
    Joined:
    Jan 20, 2005
    Location:
    Cologne Germ
    Shooter:
    Med. Format RF
    Ralph

    If you prefer a low pH level HCA try this

    EDTA4Na 12g or DTPA pentasodium salt (solution) 25ml
    Sodium sulfite 200g
    Sodium bisulfite 6g
    Sodium citrate 4g

    to make 1000ml stock solution
    dilute 1+9 for working solution

    Wolfgang Moersch
    www.moersch-photochemie.de
     
  21. RalphLambrecht

    RalphLambrecht Subscriber

    Messages:
    8,213
    Joined:
    Sep 19, 2003
    Location:
    Florida
    Shooter:
    Multi Format


    I didn't realize that much sodium sulfite would disolve in water. Couldn't you make this more me? I'm just on the other side of town.
     
  22. Robert Hall

    Robert Hall Subscriber

    Messages:
    2,047
    Joined:
    Aug 18, 2004
    Location:
    Lehi, Utah
    Shooter:
    ULarge Format
    I have heard that the working solution is only good for a few hours. If that is the case, how long would the stock solution last?
     
  23. Wolfgang Moersch

    Wolfgang Moersch Member

    Messages:
    569
    Joined:
    Jan 20, 2005
    Location:
    Cologne Germ
    Shooter:
    Med. Format RF
    Ja klar, komm vorbei. Ist alles vorhanden.
    Heiss gelöst geht das schon. Man kann aber auch mit einem Liter Wasser starten, das macht den Kohl nicht fett.
     
  24. RalphLambrecht

    RalphLambrecht Subscriber

    Messages:
    8,213
    Joined:
    Sep 19, 2003
    Location:
    Florida
    Shooter:
    Multi Format
    Robert

    I think your Weston quote has a spelling error. True?
     
  25. Robert Hall

    Robert Hall Subscriber

    Messages:
    2,047
    Joined:
    Aug 18, 2004
    Location:
    Lehi, Utah
    Shooter:
    ULarge Format
    Sie haben Rechts, danke mein Herr.
     
  26. RalphLambrecht

    RalphLambrecht Subscriber

    Messages:
    8,213
    Joined:
    Sep 19, 2003
    Location:
    Florida
    Shooter:
    Multi Format
    I guess Edward was right, it's hard work to be perfect (I'm still working on it). This gave me a chance to look at your work. Very impressive!!!