Aging Developer

Discussion in 'B&W: Film, Paper, Chemistry' started by David A. Goldfarb, Jul 13, 2004.

  1. David A. Goldfarb

    David A. Goldfarb Moderator Staff Member Moderator

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    Against what most of us start out learning as good darkroom procedure--for consistent results use fresh chemistry--every once in a while I see references to aging chemistry.

    Gordon Hutchings, for instance, in _The Book of Pyro_ writes that the A (pyro) solution in PMK benefits from age, and that he keeps a large jug of solution A in a constant stage of aging, and he back-blends some of the vintage pyro with each new batch of pyro.

    Users of Harvey's 777 developer seem to have a very firm belief that the first batch of film is never as good as subsequent batches, kind of like the first crepe.

    I think this is also said of some color chemistry in commercial processing, that the replenished chemistry provides better results than the original batch.

    On the other hand, D-76 and ID-11 are known to give contrastier results with age, and most common developers just go bad as they oxidize.

    Any theories, hypotheses, or views on what can be going on here? Anyone out there (intentionally) aging their chemistry, or have a good sense for why some kinds of chemistry might benefit from age?
     
  2. Jorge Oliveira

    Jorge Oliveira Member

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    AFAIK the main differences between aged and new devs is the bromide content (as a by product of the dev process). This may not apply to Pyro.
    Since I'm a single shot user, I cannot comment on how significant are these differences.

    Jorge O
     
  3. jnanian

    jnanian Advertiser Advertiser

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    hi dave

    you can add dk 50 to your list :smile:
    when i was doing all the lab-work &C for a portrait photographer in providence,
    she would use dk 50 for "X" sheets of film ( always doing replenishment ) ... when it was time to mix new chemistry, i would be instructed "never to clean the sides of the tank" and to " leave about 1/3 of the tank" to mellow out the developer. when i asked her what the deal was, she said that if she didn't mix spent and new developer together, the contrast would be too much.
     
  4. glbeas

    glbeas Member

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    HC110 acts the same way. In my days of doing darkroom work for the local newspaper we used it with replenishment, and a fresh mix alway gave grainy harsher looking negs than a well aged batch did. Month old replenished dilution B is a very nice fine grain developer, not mushy like Microdol-X.
     
  5. David A. Goldfarb

    David A. Goldfarb Moderator Staff Member Moderator

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    There would definitely be a bromide increase in developers used in tanks and replenished like 777, DK-50 and HC-110. One wonders then, why not add more KBr as a restrainer up front? I suppose from the manufacturer's point of view, this would decrease the life of the developer, but if you know you like it that way, it wouldn't be unreasonable so as not to have harsh results on the first batch, and then you could just keep replenishing.

    Pyro is a one-shot developer, so bromide isn't the issue. It's something to do with the alchemy of aging.
     
  6. Tom Hoskinson

    Tom Hoskinson Member

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    Depends on the developer and the associated breakdown and oxidation products.

    With ID-11 and D-76 you can chemically buffer the developer so that the "as-mixed" activity is the same as the "aged" activity. You can also buffer DK-50 and HC-110 (Pat Gainer will likely be heard from on these subjects).

    For the most part, I use 1 shot developers mixed from stock concentrates for maximum repeatability and predictability. Notable Exceptions are Ansco 130, Agfa 8 and Diafine.
     
  7. juan

    juan Subscriber

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    You can also add Pyro Triethanolamine to the list. Mix and use the working solution and top off with fresh developer.
    juan
     
  8. chrisg

    chrisg Member

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    I can offer a single data point for D76. I use D76 as a one shot. Last week I used the last of some three month old stock. I developed an HP5 test sheet (exposed thru a step tablet) in 1+3 at 68.0 F for 9 min. The HP5 test sheet yielded CI = 0.35. I got CI = 0.33 under the same conditions with fresh stock two days later. I don't have an extensive data set, but the CI with the new stock looks consistent with the last test sheets I developed with fresh stock. CI changes 0.020 per minute the way I process and I don't usually miss a target CI by more than 0.01, so I'm inclined to believe the observed difference was due to the developer not in how I was processing the sheets (hand agitated Jobo tank).

    Chris
     
  9. mobtown_4x5

    mobtown_4x5 Member

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    I was leafing through a book recently by a prominent portrait photog- the name escapes me...did lots of close up shots of craggy rock stars like Keith Richards, Iggy Pop, etc., very warm tone-
    anyway the thing that struck me was the constant references to mixing his new print developer with "old brown" which I took to be old developer- anyone heard of this practice or know what the point of it would be for prints?
     
  10. gainer

    gainer Subscriber

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    I'm so old I thought everyone knew this practice, though most probably no longer use it due to the proliferation of one-shot developers and the tendency to seek the characteristics of diluted developer. Hardly anyone uses reuses diluted stock, though replenished HC110 certainly would be such.
     
  11. Julia819

    Julia819 Member

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    Hmm...I have some semi-old D-76 in my darkroom. Diluted 1-1 and maybe a tad more developing time, what kind of results might I expect?
    I never really liked HC-110. I hated the grain I was getting even with finer grain films (such as Delta) and thought maybe it was due to something I was doing wrong in developing. Does anyone here use "aged" HC-110? I might try that as well, just for comparison.

    Julia
     
  12. Scott McFadden

    Scott McFadden Member

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    I was told about this idea when I bought extra darkroom stuff.
    Basically the same as a pre flash for paper.
    Used primarly to bring out the highlights a bit better.
    of course this is definatly a bit over simplifyed but good enough for me.
     
  13. PJC

    PJC Member

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    Just a few observations...

    Using Xtol, I found that freshly mixed (2-8 hours) produced very contrasty negs as compared with same film/exposures developed 24-48 hours later.

    Using Rollo Pyro I did not notice any difference between freshly mixed or month(s) old stock solutions, but when I added used solutions to fresh I just noticed increased staining so only used it one shot.

    PyrocatHD also no difference between freshly mixed or month(s) old stock solutions.

    Given my observations with Xtol, I tend to always allow all freshly mixed stock solutions to "rest" 24 hours before using them. As far as adding used solutions back to fresh, particularly with pyro developers, I do not see any benefit to doing this as it just seems to increase general stain.

    Regards, Pete
     
  14. m. dowdall

    m. dowdall Member

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    I've been using Ansco 130 for about a year now. Mixed up a two litre bottle that I use over and over again. As the volume goes down, I just top up with fresh dev. mixed 1:1. It gives a nice warn tone to my prints now, when it was fresh the tone was a little bit cooler. Only once after heavy use did I toss any. The paper began fogging. So one litre was saved and the rest made up with 1:1. It's still going strong.
     
  15. Les McLean

    Les McLean Subscriber

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    One of the many methods I use to reduce contrast in the print is to use old print developer as a two bath with a fresh print dev. It also warms up the print particularly with a warm tone paper.
     
  16. m. dowdall

    m. dowdall Member

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    "One of the many methods I use to reduce contrast in the print is to use old print developer as a two bath with a fresh print dev. It also warms up the print particularly with a warm tone paper."

    I didn't know it could effect the contrast. I was doing paper tests with a step tablet yesterday with the old dev. Today I'll try some with fresh dev. to see what difference there is.
     
  17. modafoto

    modafoto Subscriber

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    The gooooooo ol' Hot Rod

    As always I'm preaching The Hot Rod!

    Rodinal will give you:

    - One shot convenience and always fresh developer hitting the film.
    - Will work after many years even though it has gone black.
    - Gives you nice sharpness and BEAUTIFUL grain structure

    Viva Rodinal
     
  18. sanking

    sanking Member

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    The role of bromide in developer systems that are replenished is fairly well documented in the literature and I have frequently seen recommendations to add a little of the old developer to new stock solutions when they are mixed from scratch.

    And the reason why old D-76 and ID-11 is also understood. Fresh D76 has a pH of around 8.5 but in storag the pH will increse to well over 9, activating the hydroquinone in the formula which at lower pH is largely inactive. This gives higher contrast. Many modern versions of these developers are buffered to prevent the increae in pH, however, and some versions even recommend the total elimination of hydroquinone.

    However, I am not aware of any mechanism that would explain why PMK benefits from age. Does Gordon Hutchings say what these benefits are? In my own experience in working with fresh solutions of both PMK and Pyrocate-HD I have noticed no benefits to aged solutions. However, I would recommend that if you mix your own stock solutins with these developers best practice would be to wait until the next day to use them since it may take that long for all of the chemicals to go into solution completely.

    Sandy King
     
  19. David A. Goldfarb

    David A. Goldfarb Moderator Staff Member Moderator

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    I'm aware of the bromide issues with other developers, but knowing that this isn't the issue with PMK, I find it a little mystifying, too, which is why I asked. I hunted down the citation from _The Book of Pyro_ (1992, Third printing, p. 71), and he writes under the heading "Adding Stain":

    So presumably he believes that aged stock gives stronger stain, but I'm not sure whether he means image or background stain, and if background stain, that's subject to all the usual questions as to why one wants it. Elsewhere (p. 14) he also mentions that the color of the "A" solution reaches an equilibrium point after about two weeks, which may also be relevant.
     
  20. john_s

    john_s Subscriber

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    I have used PMK for several years, and have found that freshly mixed, it produced only a very subtle stain (in HP5+ which is regarded as "staining well"). The colour of the Part_A seems to be correlated with the degree of staining. When part_A stabilizes to bright yellow, it has settled down, and can remain constant for at least a couple of years. I top up my Part_A with some fresh from time to time.

    I know that my experience is different to that of others. Some find stain constant from the start. Maybe pyrogallol quality varies?

    Although I do not have a measuring device to ascertain how much background stain I have, I know that it's not much. My image stain, however, i believe is somewhat subtle compared to the descriptions of others who claim bright green etc. Mine are a sort of olive/ sepia. Quite obvious alongside a pyrocat-HD neg, which is browner and appears less coloured.

    As a matter of interest, having been confident that PMK would almost never go off, I mixed up some fresh and put a small amount of it in a bottle (Schott lab bottle with good quality plastic screw cap) with a lot of air. I was surprised some months later to see that it had turned almost black. I was alarmed, and threw it out, but I'm going to do it again to see if the black developer works.