Effective Film Speed with D76 Variants

Discussion in 'B&W: Film, Paper, Chemistry' started by sanking, Aug 1, 2009.

  1. sanking

    sanking Member

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    I am about to do some BTZS testing to compare film speed of Pyro-Uno with D76. In The Film Developing Cookbook there are several variants of the D76 formula. Does anyone know if all of these variants give the same film speed, if used freshly mixed?

    Sandy King
     
  2. Ian Grant

    Ian Grant Subscriber

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    No they vary, some by more than others, use straight D76/ID-11 as that's the Standard.

    Ian
     
  3. MikeSeb

    MikeSeb Member

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    Ian, have you found much difference between standard D76/ID-11 and D76H (more metol, no HQ)? I haven't seen much difference, myself.
     
  4. Tom Kershaw

    Tom Kershaw Subscriber

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    Michael,

    You use XTOL as standard if I recall correctly?

    Tom
     
  5. sanking

    sanking Member

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    I have tested those two versions and never found much difference in either energy or EFS.

    Today I mixed up the D76R variant described in the FDC, p 43, and was very surprised to find that it very much more energetic than both standard D76 and D76H.

    After seeing the results I looked at the formula and see that it used 20 grams of borax per liter, more than twice any of the other variants. Could this be a mistake? I ask because results are way off the wall from all other variants of D76 that I have tried.

    I see Bill Troop has been here today. Perhaps he will respond.

    I frankly don't understand why one would publish D-76 variants that are vastly different in terms of energy than the original formula.


    Sandy King
     
    Last edited by a moderator: Aug 1, 2009
  6. gainer

    gainer Subscriber

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    D-76R is replenisher for D-76. I remember from the good old days when Bob Schwalberg was playing with using D-76R straight as developer. It has the extra borax to deal with the reduction of pH due to production of HBr when film is developed.
     
  7. gainer

    gainer Subscriber

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    Sandy, I didn't realize you are such a young squirt.
     
  8. sanking

    sanking Member

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    Yes, all that makes sense. But D-76R is merely listed as a variant of D-76 in the FDC, not as a replenisher.


    Sandy
     
  9. Photo Engineer

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    Sandy;

    I checked and D-76R is the replenisher. It is not clearly identified in A&T as the replenisher, but is listed in other publications, notably the Kodak publications as the replenisher. It would have much higher activity due to the higher levels of Metol and HQ not to mention the alkali.

    So, the result you have is to be expected.

    PE
     
  10. sanking

    sanking Member

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    Hi Ron,

    You are right.

    Question for Bill Troop, why did you list this as a variant? I trusted your information, which in retrospect was a big mistake. Cost me a fair amount of time for no good reason except poor editing of that book.

    Look at page 43 of the Film Developing Cookbook. D76R is listed as one of the variants of D76, nothing in that chart about replenishment.

    Sandy King
     
  11. Ian Grant

    Ian Grant Subscriber

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    No I've not tried it Mike, but I've used D23/D25, and many the official Kodak variants, I preferred Adox Borax MQ which gave better acutance, tonality, film speed as well as finer grain. My own feeling is it shouldn't be listed as D76H as it wasn't a Kodak formula, but D76h was, Bill Troop states it's a hypothetical developer that Haist discussed with him which he knew would work.

    D76h also has 2.5g Metol with the usual amounts of Hydroquinone, Sulphite & Borax but has 15g of Boric acid added to the formula. There are other Kodak variants of D76 published by Kodak Research in the mid to late 1930's with no number designation.

    Ian
     
  12. Keith Tapscott.

    Keith Tapscott. Member

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    Ian, I have tried D-76d buffered-borax which uses 8 grams of borax and 8 grams of boric acid in each litre of stock. This has often been cited as the current commercial D-76 formula. I used to think that myself after reading the MSDS on Kodak`s site. I now strongly disagree, as I found that D-76d needs significantly longer development times with the films I tried
    (FP4 Plus and HP5 Plus).
    The Fomadon-P developer seems to be an M.Q. buffered-borax developer which you will find the times for on the massive development chart, which I assume is from Foma`s own technical-data. I wouldn`t bother making D-76d again.
    If you`re making a developer for one-shot use, make ORIGINAL D-76 (ID-11) and dilute it 1+1 for the working strength solution. For replenishment, then may be the Adox Borax MQ developer and replenisher is a better choice.
    You have experience with replenished developers where as I don`t.
    I may try the Adox formula one day.
    To me, once the hydroquinone is omitted and not replaced with a suitable alternative, it is no longer a developer of the D-76 type, but becomes a D-23 type with the addition of borax. I`m not saying that D-76H doesn`t work or doesn`t give good results as I`m sure it does, I just don`t consider it to be a D-76 type.
     
  13. Keith Tapscott.

    Keith Tapscott. Member

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    The formula I have for D-76H is just three constituents which are as follows.

    Metol = 2.5 grams
    Sodium sulphite, anhydrous = 100 grams
    Borax = 2 grams
    To make 1 litre of stock solution.

    This is why I don`t consider it to be a developer of the D-76 type.
     
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  15. Ian Grant

    Ian Grant Subscriber

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    D76h is a published Kodak formula, while D76H is one suggested to Bill Troop by Grant Haist, the H standing for Haist :D Very confusing. D103 is halfway between D23 & D76, and DK76b is D76 with no Hydroquinone and Metaborate as the buffer so Kodak had been playing ang publishing D76H type formulae.

    I think we said elsewhere that the actual formula for commercial D76 is likely to be somewhere between the published formula for D76 and D76d, it clearly has Boric acid in it but then looking at the MSDS:

    D76 MSDS
    Concentrate:
    85-90 Sodium sulfite
    4 Hydroquinone
    1-5 Sodium tetraborate, pentahydrate
    1-5 4-(methylamino)phenol sulfate
    < 1 Boric anhydride

    Working solution:
    85-90 Water
    5-10 Sodium sulfite
    1-5 Sodium tetraborate,
    < 1 Hydroquinone
    < 1 4-(methylamino)phenol sulfate
    ---------------------------------------

    Assuming Kodak's MSDS is right, most seem to be, we know that there's

    100 g Sulphite 10% in Solution
    5 g Hyroquinone 0.5% in soln
    2 g Metol 0.2% in soln
    10+ g Borax -- at least 1% in solution so 10 g or over

    So we know that's around 99% of the Dry weight, and that may have a small amount of a sequestering agent.

    That seems to indicate a maximum amount of about 1.3g Boric Anhydride (Boric acid)

    If the Borax has been increased to 10g then the Boric acid would be there to drop the pH back down

    Ian
     
  16. Keith Tapscott.

    Keith Tapscott. Member

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    That would make 118.3+ grams of dry components per litre of stock developer. I am still not convinced of the addition of boric-oxide in D-76 due to the description of borax by Grant Haist. Also, the dry weight of the components in the 1 litre packages of D-76 is stated as 110 grams. This is also mentioned in the MSDS that I have. I have found that the standard formula seems to match the commercial products for contrast with the recommended development times, but D-76d takes quite a bit longer.
    I am told that borax can form a whole myriad of boron-ions when it goes into solution, so this makes it difficult to analyse even for a chemist.

    KODAK D-76 MSDS.

    Weight % - Component - ( CAS Registry Number).
    Concentrate:
    85-90 Sodium Sulphite (007757-83-7)
    1-5 Hydroquinone (000123-31-9)
    1-5 Sodium Tetraborate (001330-43-4)
    1-5 Bis (4-hydroxy-N-methylanilinium) sulphate (000055-55-0)
    < 1 Boric Anhydride (001303-86-2)
    < 1 Pentasodium (carboxylatomethyl) iminobis (ethylenenitrilo) tetraacetate
    (000140-01-2)

    Weight of concentrate = approximately 110 grams/litre. (This it self rules out D-76d formula which is 123 grams per litre of stock, not to mention sequestering agents etc).

    From the book "Modern Photographic Processing" by Grant Haist, Volume 1:

    Borate Alkali's: "Borax,Na2B4O7.10H2O, is the common name for sodium tetraborate, an alkaline compound used in the preparation of low-contrast, fine-grain developers. Borax may be written (NaBO2)2.B2O3, which shows the boric anhydride that limits the alkalinity possible from borax.
    Borax acts as a buffer; that is, it maintains a reservoir of alkali but delivers only small quantities of hydroxyl ions at any one time. The alkalinity is maintained relatively unchanged until all of the borax has been neutralised."
    :confused:
     
  17. MikeSeb

    MikeSeb Member

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    For quite a while I did, Tom, and was well pleased with it.

    Lately I have been using more D76H which I mix myself of course. It's always fresh, it's quite simple, and I like the results with 400TMY better than anything else I've tried. I'm also using more TMAX dev and HC-110. I find I am shooting and developing a lot more color negative film these days than B&W, so my B&W developing sessions are fewer and farther between. These last two have very good shelf life.

    I think TMAX is an underrated developer. Its main drawback is its cost; it ain't cheap. But I like it for 100TMX and for 320TXP better than others I've tried.
     
  18. Photo Engineer

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    Sandy;

    I agree. That was an oversight.

    Like all authors, I am proofing my book and have found about 4 errors just on the first page. Grant Haist has shown me his "manuscript" of fixes if he should come out with a second edition of his two volumes. There are a lot of errata and changes he would make, and Bill has told me that he has a list of changes if the FDC has a second edition.

    This is just another to add to the list unfortunately.

    PE
     
  19. Ian Grant

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    Who knows Kodak could have countered a slight increase in activity by slight dilution to compensate.

    Ian
     
  20. sanking

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    Ron,

    Yes, we all make mistakes. Plus, I should not blame Bill for my own lack of attention. On looking at that D76R formula again it should be obvious that it would be much more energetic than the other versions of D76. But I had exposed some 4X5 comparison negatives with optimum lighting conditions yesterday morning and now will have to repeat the work.

    Sandy






     
  21. Keith Tapscott.

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    It would probably be better to buy either Kodak D-76, Ilford ID-11 or mix the standard D-76/ID-11 formula from scratch. I think it works better diluted 1+1 than at stock strength.
     
  22. sanking

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    Good advice. For a subsequent round of tests I just mixed the standard D76 and used it with the 1+1 dilution. That is what I should have done from the get go since I am going to use it fresh, and am not concerned with the keeping quality.


    Sandy King
     
  23. Keith Tapscott.

    Keith Tapscott. Member

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    Just one further note, due to complexes formed by hydroquinone and the sulphite, MQ developers usually work best when they have been left to sit for a day or two after mixing. If you use them within a week of mixing, then you shouldn`t have anything to worry about. :D
     
  24. wogster

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    Does anyone know why D76 is D76, was it the 76th developer that Kodak designed or bought, if so, what are the previous 75, and what was the last numbered developer, developed? Yeah that pun was intended :D
     
  25. Ian Grant

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    The number is irrelevant. It may just have been the 76th that Mees or someone wrote in a notebook.

    Many early Kodak developers were just generic clones of European developers or came from companies they bought like, Velox, Wratten Y Wainwright, Cadett & Neal and a whole host of others. D76 is itself probably a derivative of Wellington's MQ Borax developer, Kodak incrteased the Sulpite level substantially, but it was one of the newer Kodak designed developers at a point where Kodak began to seriously research film developers in the early 1930's.

    Ian
     
  26. Photo Engineer

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    Virtually 100% of the time, a product has one name internally at Kodak and another externally. They are not related, and the "inventor" has no input regarding the name chosen to sell the product under. All color developing agents, B&W developing agents, bleaches, blixes, fixes and etc are used within KP and KRL with other names on them until sold, then for a while dual names are on the bottles and finally the product name only will appear.

    Thus, my blix was first identified at Kodak as Blix 1066, then as Ektaprint 3 blix / 1066 and finally as Ektaprint 3 Bleach Fix. The ID is now RA-Bleach Fix. CD-3 is known internally as D-109AH, and CD-4 is D-99.

    Thus, there is little logic to it all except for the fact that developer numbers are increasing with time. So, we have HC-110.

    PE