Lith developer formulation question

Discussion in 'B&W: Film, Paper, Chemistry' started by Mark Fisher, May 9, 2013.

  1. Mark Fisher

    Mark Fisher Subscriber

    Messages:
    1,692
    Joined:
    Dec 13, 2003
    Location:
    Chicago
    Shooter:
    Medium Format
    I've been trying to develop a decent lith developer with mixed success. I've figured out the right balance between hydroquinone, sod. sulfite, and KBr for me. I'm using saturated Pot. carbonate as the alkali. I'm basically not happy with the developer life both on the shelf and in the tray. With help, I figured out I want the Part A to have a pH of 4.....what is the best acid to achieve that? Regarding the tray life, is there anything other than sodium sulfite that would serve as an anti-oxidant? Thought about ascorbic acid, but it seems that adding a developing agent would be a bad idea.
    Anyway any insight from the chemists out there would be greatly appreciated.
     
  2. MaximusM3

    MaximusM3 Member

    Messages:
    762
    Joined:
    Jul 11, 2010
    Location:
    NY
    Shooter:
    35mm RF
    Mark, have you ever tried what is known as Ilford ID13/Ansco 70 formula? Just curious, as I wanted to try mixing my own as well and some people have had success.
     
  3. Ian Grant

    Ian Grant Subscriber

    Messages:
    19,262
    Joined:
    Aug 2, 2004
    Location:
    West Midland
    Shooter:
    Multi Format
    ID13 isn't really a lith developer it's just a high contrast developer, Kodak 85b is a lith developer though and works well.

    You might ask what the difference is - Lith developers have a property called "Infectious development".

    Ian
     
  4. Marco Buonocore

    Marco Buonocore Member

    Messages:
    409
    Joined:
    Mar 18, 2005
    Location:
    Toronto
    Shooter:
    Medium Format
    Hi Mark,

    It's amazing how simple a lith developer can be. My problem with the more simple formula (hydroquinone, sodium sulfite, potassium bromide & alkali) was that they had no tray life. Sometimes 5 8x10 prints was all I would be able to pull from a litre or two. Considering the first one was usually ordinary, that wasn't so great. If you seperate the alkali (like in ID-13), you get a pretty stable developer in terms of shelf life.

    Boric acid is used in lith developer formula. It might be a good choice to achieve the ph you're after. It also has benefit of acting as a ph buffer in small amounts; or so a chemist told me. There's mention of it in this thread:

    http://www.apug.org/forums/forum37/114235-boric-acid-substitute.html

    I'm no chemist, for the record!

    Insofar as ID-13 (and the other similar formula), it works. I usually found diluting it in the ballpark of 1:1:9 was ok for lith printing. If you use a stronger concentration, the sodium sulfite levels are too high and you won't get infectious developer. Colour wise, and dmax wise, it's nothing special. You can definitely lith print with it, but when you compare it to a commerical product like LD20 or Moersch... well... it's rubbish.

    Good luck!
     
  5. MaximusM3

    MaximusM3 Member

    Messages:
    762
    Joined:
    Jul 11, 2010
    Location:
    NY
    Shooter:
    35mm RF
    Thanks, Ian, yes, I am aware of that. Some people have had success with certain papers (notably Slavich, which is hard to tame in most commercially available developers).
     
  6. OP
    OP
    Mark Fisher

    Mark Fisher Subscriber

    Messages:
    1,692
    Joined:
    Dec 13, 2003
    Location:
    Chicago
    Shooter:
    Medium Format
    I talked with a chemist friend of mine and he recommended acetic acid to pull down the Part A pH. I had tried sulfuric with poor results since sulfuric is also a nice oxidizer (didn't know that). I tried boric acid figuring that I'd get some buffering out of it too, but I added quite a bit and the pH didn't move much. I'm not that sure I really need a buffering agent anyway. I'm sure I can get good enough shelf life. Tray life is really the challenge. I know it is possible because the Rollei and Moersch have much better tray life. The same chemist friend suggested either more hydroquinone or maybe trying ascorbic acid. Ascorbic acid is a weak developing agent, but it may be OK in small amounts. Worth an experiment or two.

    Regarding Ansco 70, it looks like the main difference between it and what I am doing is that it uses potassium metabisulfite rather than sodium sulfite. Is potassium metabisulfite a better anti-oxidant? The other differences are more KBr and a different alkali.

    I'm a good mechanical engineer, an OK photographer and a lousy chemist!
     
    Last edited by a moderator: May 9, 2013
  7. Marco Buonocore

    Marco Buonocore Member

    Messages:
    409
    Joined:
    Mar 18, 2005
    Location:
    Toronto
    Shooter:
    Medium Format
    Hello Mark,

    I'm following up on this old post as I've been lith printing again this week.

    Did you ever get anywhere using either Boric Acid as a buffering agent, or Ascorbic Acid as a developing agent / anti oxidant?

    I - like you have mentioned in the first post - have tweaked a formula of hydroquinone, sodium sulfite and potassium bromide using potassium carbonate as the alkali. I have a big stack of Forte Polygrade, and I knew that with a bit of work I could dial something in. The results are terrific, but of course it's being used 1-shot. I do four 8x10s in 2 litres all at once, and then dump it. I stagger the prints by 2 or 3 minutes, and it takes about ten minutes until I snatch it. I suspect the developer is dead by around 20 minutes.

    The plus side is, the developer is tailored to my paper: infectious development takes place, colour is great and development time are where I like them. I prefer these results to LD20, which is my standard lith developer. Down side is the tray life.

    I wonder, for the chemists out there, how much Ascorbic Acid would be needed to compliment the 1.5g of hydroquinone I'm using in 1000ml of developer? I'm guessing less than a gram. Would such a small amount make any difference in preserving the developer in the tray? Am I on the right track with that? Sodium sulfite levels have to be quite low, or the dmax really suffers. It's around 2g of sulfite per 1000ml developer.

    Any insight would be great! Thanks!
     
  8. RauschenOderKorn

    RauschenOderKorn Member

    Messages:
    300
    Joined:
    Apr 14, 2016
    Location:
    Bavaria, Germany
    Shooter:
    Medium Format
    Just out of curiosity, where did you get this information from?
    How long are you exposing in comparison to a traditional print?
     
  9. Marco Buonocore

    Marco Buonocore Member

    Messages:
    409
    Joined:
    Mar 18, 2005
    Location:
    Toronto
    Shooter:
    Medium Format
    I've seen the information in several places. Here's a post from Tim Rudman on the subject:

    https://www.freelists.org/post/pure-silver/ParaformaldehydeAcetone-in-lith-developers,5

    It also must be in his first book on the subject, the Master Photographer's Lith Printing Course. I don't have the book in front of me now, it's down in the darkroom.

    Here's some information from Ryuji Suzuki:

    https://books.google.ca/books?id=cF...r&q=ryuji+lith#v=snippet&q=ryuji lith&f=false

    In Grant Haist's book Modern Photographic Processing, Chapter 11 covers lith developers, and the information of sulfite levels is mentioned on page 491. He states that "...quantities of sodium sulfite above 2g/litre destroy the lith effect." There is an accompanying table that states this as well.

    In practice, it is quite easy to prove as well. If you make a simple lith developer with only hydroquinone, potassium bromide, an alkali and sodium sulfite as the components, you can see at what point the sulfite levels prohibit infectious development.

    From what I understand, formaldehyde proved to be a good solution to this problem, as it bonded to the sodium sulfite preventing it from inhibiting infectious development. It still retained the anti-oxidant qualities, however, allowing the developer to have a good tray life. I think a chemist would do a better job of explaining that than I could! Most commercial lith developers use formaldehyde, with the Moersch products being the exception.

    Hope that helps!
     
  10. RauschenOderKorn

    RauschenOderKorn Member

    Messages:
    300
    Joined:
    Apr 14, 2016
    Location:
    Bavaria, Germany
    Shooter:
    Medium Format
    Thanks. Sulphite levels need to be low, no doubt. But I would assume that "low" in this context in relative to the HQ level and depending to a certain extent on bromide level and exposure times, too.

    I was just curious where the max. 2g/litre are originating. Grant Haist is an excellent source (unfortunately I have not been able to buy a copy), but Tim Rudman quotes a lith developer recipe (The World of Lith Printing, page 150 second paragraph) "My single-solution lith developer recipe" by Kate Mokac containing 60g sodiumsulfite / liter to be diluted 1:5, i.e. 12 grams / liter of working solution.

    Actually I have already tried it, and I can get excellent results with way higher levels than 2 grams / litre of working solution.
     
  11. Marco Buonocore

    Marco Buonocore Member

    Messages:
    409
    Joined:
    Mar 18, 2005
    Location:
    Toronto
    Shooter:
    Medium Format
    Something I learned when trying different formula for lith developers was that one of the more important factors was the paper being used in combination with the developer. I would "tailor" a developer to suit the characteristics of a certain batch of paper. Some papers wanted more restrainer, or more hydroquinone, etc... I found it a more graceful solution to simply changing dilution. Sulfite levels varied, but I don't remember anything sitting above 3.0g/L. Certainly, I was doing very rudimentary tests. 12g/L does seem awfully high. In fact, with many of the developers listed in Rudman's books (or other online sources), I would work out "ideal" dilution starting points to keep the sulfite levels down around 2.0g/L.

    If you get excellent results, that's great! That's all I particularly care about - whether or not I got good infectious development, and that the prints looked good.
     
  12. Marco Buonocore

    Marco Buonocore Member

    Messages:
    409
    Joined:
    Mar 18, 2005
    Location:
    Toronto
    Shooter:
    Medium Format
  13. RauschenOderKorn

    RauschenOderKorn Member

    Messages:
    300
    Joined:
    Apr 14, 2016
    Location:
    Bavaria, Germany
    Shooter:
    Medium Format
    @ Marco: Many thanks for your input, I really appreciate it.

    These 2g/l seem to come all from the same original source, but I have not been able to locate / read the publication by Karl Frank.
    It would be good to properly analyse the assumptions and conditions under which this figure was originally published - and to what extent experimental testing and further research has been made.

    One of the assumptions stated relates to Lith Film researched and not to a Lith effect on conventional photographic paper. Furthermore, I´d guess that a main design criterion was reproducibility at industrial standard, i.e. put film and developer in a black box and after a pre-set period of time take a finished product out, no inspection, snatch point or something similar. Furthermore, I´d guess that short development times were a requirement, too, and maybe the developer was also designed as one-shot product anyway?

    Under the a.m. mentioned conditions (highly reactive, short development time to get to Dmax, one shot product, short tray live only), it makes sense to use a minimum sulphite HQ developer, i.e. nothing or almost nothing.

    I have found some older research showing the relationship between Dmax and Sulphite content, clearly stating that after a steep decline in Dmax while slowly increasing Sulphite concentration, after a certain point the Dmax actually increases again together with the Sulphite before the developer eventually dies at a very high sulphite concentration. I will try to scan the graph and share tonight or tomorrow.
     
  14. Sponsored Ad
  15. adelorenzo

    adelorenzo Subscriber

    Messages:
    1,034
    Joined:
    Mar 10, 2012
    Location:
    Whitehorse, Yukon
    Shooter:
    4x5 Format
    The Lith Printing Group on Facebook would be another good resource, it is quite active and a number of people are mixing their own developers.

    Here is one formula that was posted recently using 1g/L of Sodium Sulfite: Hq 1g/l SS 1g/l PB 1g/l SC 30g/l
     
  16. RauschenOderKorn

    RauschenOderKorn Member

    Messages:
    300
    Joined:
    Apr 14, 2016
    Location:
    Bavaria, Germany
    Shooter:
    Medium Format
    I had time to scan and upload the graph. Unfortunately, I only have a secondary source, too (from "Grundlagen der photographischen Prozesse mit Silberhalogeniden - Band 2 - Die photographische Emulsion und die Verarbeitung photographischer Schichten", page 895).

    HQ_Sulfite_Effects.jpg

    The Graph shows the Dmax measured (S like in "Schwärzung") depending on the modification of the sodium sulphite concentration in a HQ only developer with different development times (2 to 6 minutes).

    You can clearly see that the highest densities can be achieved with no sodium sulphite at all, but that there is an "optimum" at a concentration of about 1,25 Mol/l (approx. 157 grams / l) of sodium sulphate. Unfortunately, the secondary source does not specify the composition of the HQ developer or material (film/paper) used.

    Now I do not think that these results apply one-to-one to lith developers, but they are a strong indicator that the "more than 2 grams will kill the lith effect" is not universal either. Especially if HQ is used in significant excess (factor 2 or 3), there should be no interference.
     
  17. RauschenOderKorn

    RauschenOderKorn Member

    Messages:
    300
    Joined:
    Apr 14, 2016
    Location:
    Bavaria, Germany
    Shooter:
    Medium Format
    +1 but:

    I would add as a third factor the exposure time. I think there are 3 main factors: emulsion - exposure time - developer dilution
     
  18. RalphLambrecht

    RalphLambrecht Subscriber

    Messages:
    9,636
    Joined:
    Sep 19, 2003
    Location:
    K,Germany
    Shooter:
    Medium Format
    developer formulation is best left to the expertsand I'm not one of them.
     
  19. Gerald C Koch

    Gerald C Koch Member

    Messages:
    7,903
    Joined:
    Jul 12, 2010
    Location:
    Southern USA
    Shooter:
    Multi Format
    One of the oxidation products of hydroquinone (1,4 - dihydroxybenzene) is 1,2,4 - trihydroxybenzene which can cause fogging. Borates like boric acid form a complex with 1,2 - hydroxybenzenes and so prevent the fog from occurring. The addition of boric acid has nothing to do with buffering or changing the pH. BTW, the action of borates in MQ developers has been known for a long time and a small amount, 1 to 2 grams, was often added to them. When referencing catechol (1,2 - dihydroxybenzene) you will find the warning never to use borates as the alkali in developers with it. Doing so would very seriously diminish the developer activity.
     
  20. Gerald C Koch

    Gerald C Koch Member

    Messages:
    7,903
    Joined:
    Jul 12, 2010
    Location:
    Southern USA
    Shooter:
    Multi Format
    Ralph is right. Unless you have a good knowledge of chemistry and photochemistry in particular you really should not attempt to devise your own developer.
     
  21. OP
    OP
    Mark Fisher

    Mark Fisher Subscriber

    Messages:
    1,692
    Joined:
    Dec 13, 2003
    Location:
    Chicago
    Shooter:
    Medium Format
    I wish there were people with better photochemistry knowledge than I have, but in the little niche we occupy, there isn't much interest so I'm willing to give it a shot. I may not succeed, but that's OK. There are enough existing formulas out there and the issues seem pretty obvious. There is a Kodak patent I ran across that seems to suggest a few potential options. Give me another 5 years and maybe I'll manage to test these!
     
  22. Oxleyroad

    Oxleyroad Subscriber

    Messages:
    1,079
    Joined:
    Jun 26, 2007
    Location:
    Formally Oz, now MI USA
    Shooter:
    Multi Format
    Mark I'll be waiting and watching here for you to document your discoveries.
     
  23. Gerald C Koch

    Gerald C Koch Member

    Messages:
    7,903
    Joined:
    Jul 12, 2010
    Location:
    Southern USA
    Shooter:
    Multi Format
    Did a quick search for lith developers and found many recipes. Why is it necessary to develop your own?
     
  24. OP
    OP
    Mark Fisher

    Mark Fisher Subscriber

    Messages:
    1,692
    Joined:
    Dec 13, 2003
    Location:
    Chicago
    Shooter:
    Medium Format
    There are a couple of reasons. First, I want one that is formaldehyde free with decent tray life to as much as possible mimic the old Rollei/Maco/Labor Partner developer. I don't like the Moersch developer as much as the Rollei, but it is the best available today for my taste. The problem is the price in the States. Wolfgang/B&H sells only part A if you'd like which helps quite a bit, but I still feel like I can get something closer to my taste. Also, there are indeed a lot of formulas, but the formaldhyde free versions I've tried have lousy tray life. I've done a bit more research on other developers and developer patents and have a few ideas of methods to minimize oxidation. I'm an engineer with a lot of chemistry exposure so my progress will probably be more about iteration than inspiration!
     
  25. Rudeofus

    Rudeofus Subscriber

    Messages:
    3,138
    Joined:
    Aug 13, 2009
    Shooter:
    Medium Format
    If I interpret the literature available to me correctly, then the addition product of Formaldehyde with Sulfur Dioxide is much more stable than Acetone plus Sulfur Dioxide. If the 2 g/l free sulfite level is generally accepted as the limit for lith developer property, you can add a lot more sulfite, if you use Formaldehyde instead of Acetone. If you want to improve working solution life of your dev, you'd have to find either something which binds Sulfur Dioxide as tightly as Formaldehyde, or you have to find a different preservative for Hydroquinone.

    Given Formaldehyde's unpleasant smell I assume that both venues have been researched in the past, with nothing much to show. I guess it will be generally difficult to long term stabilize lith developers, since their working principle is that a slightly oxidized dev agent goes ballistic.

    PS: there are several patents for stabilizing sulfite against aerial oxidation, and most follow the "must sequester trace heavy metals" path. You could try and experiment with TEA and Salicylic Acid, sort of following Ryuji Suzuki's path to stabilizing Ascorbate. If you can get your hands on DTPA, you might gain even more, see Xtol.
     
  26. RauschenOderKorn

    RauschenOderKorn Member

    Messages:
    300
    Joined:
    Apr 14, 2016
    Location:
    Bavaria, Germany
    Shooter:
    Medium Format
    Give them a try, you will find out they either need formaldehyde or they suck as tray developers for paper. They were intended to be used highly concentrated for lith film, and most are quite unsuitable/unstable in the tray at high dilution.