Pyro-TEA developer

Discussion in 'B&W: Film, Paper, Chemistry' started by ongarine, Aug 2, 2004.

  1. ongarine

    ongarine Member

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    Being curious about Pyro-TEA dveloper, could someone share his experience about it?
     
  2. juan

    juan Subscriber

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    Jay,
    Do you use P-TEA one shot or can you reuse it for a while?
    juan
     
  3. gainer

    gainer Subscriber

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    The Pyro-TEA is a concentrated stock solution of long storage life. Dilute it 1+50 or so with water to get the working solution. Jay can and probably will tell you more about practical use than I can, even though it was my idea.
     
  4. noseoil

    noseoil Member

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    Jay, I'm curious about your findings on the activity level of the Pyro-Tea formulation. I've been using ABC for large format with azo and have found it to be a bit too active with the slow film I'm using. Sulfite to sulfate, low film speeds and a general P.I.T.A. compared to PMK come to mind. With the dilution you have been using, how does it compare to a more common developer (one you normally use and can compare from your data) with respect to times. It sounds like a decent developer and I have more pyrogallol I can use to give it a try. Thanks, tim
     
  5. Alex Hawley

    Alex Hawley Member

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    I'm coming in late here with a dumb question: What is TEA?
     
  6. Tom Hoskinson

    Tom Hoskinson Member

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    Triethanolamine.
     
  7. sanking

    sanking Member

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    I would estimate that you could get about 4 sheets of 8X10 film from a liter of a developer that contained one gram of pyrogallol, but only if you developed all of the sheets at the same time, or at least split the liter into two parts and develop the films two and two.

    The literature and my own practical experience indicates that when pyrogallol is the only reducer in a developer effective film speed is low and the grain is very large. I would be almost certain, without ever having tried it, that the effective film speed of Pyro-TEA is significantly lower than that of developers like PMK, Pyrocat-HD, WD2D and Rollo Pyro. How much slower will depend on film but 1/4 to 1/2 stop less is not unusual for ABC and I would suspect the same for Pyro-TEA.

    I would also expect that the Pyro-TEA would produce a lot of stain. Could someone who is using it comment on this. ABC with no sulfite is a very different developer than ABC with a little sulfite added.

    Sandy
     
  8. ongarine

    ongarine Member

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    May I know the formula of the Pyro-TEA developer? And some developing times for the films that Pyro-TEA users have experimented? Could be good to have a basis to start the thoughts.
     
  9. fingel

    fingel Member

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    This just proves my ignorance in chemistry, I was going to ask if he uses Lipton or some other brand and how many tea bags/leaves per liter do you use. :smile:
     
  10. Tom Hoskinson

    Tom Hoskinson Member

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    P-TEA Stock solution (Gainer)

    TEA ------------------------ 100 ml
    Pyrogallol ----------------- 7 grams

    Dilute 1 + 50 (with water) for use

    I haven't done enough testing with P-TEA to recommend times and temperatures. Hopefully, either Jay or Pat Gainer will respond.

    A developing time guess for TMY is 10 min at 70 F with 10 sconds of agitation per minute.

    A 0.1% sodium sulfite solution can be used (instead of water) to prepare the developer if you want a non-staining result.
     
  11. Alex Hawley

    Alex Hawley Member

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    Me too Scott. With all the exotic brews running around, I had to ask to make sure.
     
  12. Tom Hoskinson

    Tom Hoskinson Member

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    You really don't want to drink this "TEA."

    Triethanolamine is an organic with a pH in the 9 to 10 range. It is quite toxic when ingested. When it is used as the Pyro solvent (without water), it acts as a Pyro preservative. When water is added, it acts as an organic alkali.
     
  13. ongarine

    ongarine Member

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    Thank for the formula and comments. May be Pat Gainer the formula creator or others users of Pyro-TEA have something to add before I start my test?
     
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  15. gainer

    gainer Subscriber

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    Nope. Go at it and report.
     
  16. ongarine

    ongarine Member

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    My chemical store is on holidays, no TEA until 20 August, so I have time to last questions:
    a) the TEA need a special temperature or it will work at ambient degrees (around 24/25 C degrees her in summer)?
    b) I guess that also pirocatechin will have the same caratteristics if disolves in TEA, any idea how many grams? 100 grams could be good in your opinion?
    Thanks
     
  17. Tom Hoskinson

    Tom Hoskinson Member

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    In the March/April 2004 edition of Photo Techniques, Pat Gainer published his
    CAT-P-TEA formulation:

    Triethanolamine------100 ml
    Phenidone------------0.2 grams
    Pyrocatechol---------10 grams

    Heat the triethanolamine to dissolve the phenidone and pyrocatechol.

    For use, dilute 1 part CAT-P-TEA with 50 parts of water
     
  18. Tom Hoskinson

    Tom Hoskinson Member

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    In my experience the TEA developers will work from 20 degrees C (and probably lower) through 25 degrees C (and probably higher).

    You can use the Ilford Microphen time/temperature charts to estimate the effects of temperature on developing time.
     
  19. gainer

    gainer Subscriber

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    I must add that this Cat-P-TEA is the essence of and inspired by Sandy King's Pyrocat HD.

    A source of pretty cheap TEA and propylene glycol is www.chemistrystore.com.
     
  20. sanking

    sanking Member

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    Just curious what might result if you added a little phenidone to the Pyro-TEA formula. Pyrogallol is superadditve with metol and I would assume that it would also be superadditive with phenidone? If so the addition of phenidone should produce a big boost in developer energy.

    Sandy
     
  21. sanking

    sanking Member

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    I am sure you could substitute hydroquinone for catechol because several popular developers are based on this combination. However, you can not make an equal parts substittution of hydroquinon for catechol in the case of Pyrocat-HD without dramatically changing the working qualitiy of the develper. I am saying this based on experience because I have actually tried it.

    I am going to assume that the substitution of pyrocatechin with hydroquinone in equal parts in the Cat-P-TEA formula would not work as well but I don't know that for a fact since I never actually tested it.

    Sandy
     
    Last edited by a moderator: Aug 7, 2004
  22. ongarine

    ongarine Member

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    Thank you all for your kindness.
    Pat your indication for chemical products store is really appreciated, but I live in Verona - Italy.
    If someone would be so gently to send me via email the Pat Gainer's developers formulas they will be really appreciate. Photo Techniques is not well distributed here. Thanks
     
  23. sanking

    sanking Member

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    Just one more comment.

    I think that a really interesting direction for development of either Cat-P-TEA or Pyrocat-HD would be to add a little ascorbic acid to the mix. I experimented with this briefly about 5-6 years ago with Pyrocat-HD and found that the ascorbic acid is very superadditive, maybe I should say super/superadditive, with pyrocatechin and phenidone. Unfortunatley I have lost my notes from the experiments but as best I recall the addition of ascorbic acid in approximately the same amount as phenidone in the Pyrocat-HD formula made the developer much, much more energetic than with just the pyrocatechin and phenidone. The addition of ascorbic acid also reduced the stain slightly, which made me abandon the tests at the time. However, I think there is a lot of potential with the combination of pyrocatechin/phenidone/ascorbic acid for a super elegant developer, fine grain from the stain, very high definition because of the low quantitiy of reducer, but also very, very energetic.

    And oh yes, B+f was also very low with the combination.

    My feeling is that anyone interested could pursue the experiments with either Cat-P-TEA or with Pyrocat-HD, with the stock solution in either water or glycol.


    Sandy
     
    Last edited by a moderator: Aug 7, 2004
  24. gainer

    gainer Subscriber

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    A bunch of things to talk about.
    Yes, phenidone and pyrogallol are superadditive, and like catechol and hydroquinone it needs a pinch of sulfite to achieve that synergism. It would take more sulfite to prevent formation of stain than to activate the synergism (this is a shorter word than "superadditivity"), so it should be safe to try. I estimate the hydroquinone and catechol need a little more than equal weight of sulfite in the working solution to get full synergism.

    I found a strange thing when I added ascorbate to HC110. It is a PQ developer and from my experiments adding more Q had no appreciable effect on activity. It responded vigorously however to addition of ascorbate. The PA combination needs no sulfite to activate it, but I was surprised that the P had not been "used up" by the Q. When you use catechol as a non-staining developer, it behaves pretty much like hydroquinone, so adding ascorbate or erythorbate to Pyrocat HD would probably give a boost in activity, but I wouldn't guarantee that the stain will be likewise boosted. You might have to cut developing time to keep the silver image under control, but I have a feeling the stain would still be only proportional to that part of the silver image formed by the cat.

    Yes, hydroquinone will produce a stain when substituted for catechol in the Pyrocat HD formula, but it is a different color, which you may or may not like. It does make a good bleach-and-redevelop intensifier. All you need for the redeveloper is some hydroquinone and carbonate in water. Development is to completion, so H&D curve is of no consequence in that application. The dye image provides the intensification.
     
  25. gainer

    gainer Subscriber

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    I will dig up my manuscript and excerpt the pertinent parts for you. It won't take too long.
     
  26. gainer

    gainer Subscriber

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    Developers in organic solvents.

    Safer glycols
    I found an auto supply store that had the safe propylene glycol antifreeze. It worked as well as the ethylene. Another benign solvent that works is glycerol (glycerine at the drug store), but it is very viscous, even more so than HC110 syrup.
    Technical grade propylene glycol is readily available. It works, so I am sure that the additives in the antifreeze that make it green had no appreciable good or bad effect.
    There are other activator solutions that you might use with A1:

    1. Try 100 grams of sulfite and 2 grams of borax per liter as the "B" solution. Add 20 ml of the "A1" solution per liter just before use. This is a kind of extended life split-stock developer of the type of Paul Lewis' Mytol.

    2. Use 5 grams of borax + 5 grams of sodium carbonate + 20 ml of "A1" per liter of working solution (no sulfite). Development time will be about 8 minutes at 70o F. One teaspoon each of borax and carbonate will be accurate enough due to the buffering action of the combination.
    Other uses for propylene glycol.
    Use propylene glycol in place of water to make the "A" solution of Pyrocat-HD. Leave out bisulfite and bromide. Heat to hasten dissolving and to drive off water. Let's call it "A2". Use the standard Pyrocat-HD "B" solution.
    See http://unblinkingeye.com/Articles/PC-HD/pc-hd.html for the standard formula and developing times for Pyrocat HD.
    Alternatively, use hydroquinone in place of catechol in A2. I'll bet you didn't know that hydroquinone can be a staining developer. Hydroquinone is 1,4-dihydroxybenzene. Pyrocatechol is 1,2-dihydroxybenzene. According to theory, any developer with two or more active hydroxyl groups will be an active tanning and staining developer.
    Dilute 1:1:50. Add "B" to working solution just before developing. Don't be put off by the immediate change in color. Develop 7 or 8 minutes at 70o F.
    If you keep phenidone in alcohol solution, use propylene glycol instead of the alcohol. Rumors that there is no way to keep phenidone in solution are greatly exaggerated. Heat the glycol or you will have to wait a week or so for the phenidone to dissolve.
    Dire and not-so-dire warnings.
    If you repeat my experiments but do not have a microwave oven, put the glycol in a Pyrex pitcher, set that in a baking dish in an ordinary oven. Set the oven at 250o F.. A candy thermometer is a good investment. Check the temperature of the liquid now and then, but not with your finger. If you see steam rising from the glycol it is most likely water vapor.
    Propylene glycol (1,2-propanediol) and glycerine (1,2,3-propanetriol) are non-toxic to the extent that they can be used in foods, medicines and cosmetics. Propylene glycol is poisonous to cats but not to dogs. I don't think cats will ingest it willingly. Ethylene glycol is bad stuff for everyone. Dogs and little children love it because it is sweet, but it kills them. If you use it, do so with caution. HC110 contains it and diethylene glycol as well, and many of us use HC110 without a lot of worry. Maybe we don't worry enough. If you are careful, you will not have to worry.
    Single solution developers
    It is possible to prepare single solution developers with excellent storage life by using an organic base as solvent and activator. The organic bases become alkaline in the presence of water. Triethanolamine (TEA for short) is an example, and it is readily obtainable without hazmat shipping charges. One problem you may have is that it freezes at about 70o F. If your darkroom is colder than that you will have the strange experience of having to thaw out iced TEA before you can pour it. The freezing point will be lowered somewhat after you dissolve the solids in it. Here are some useful formulas.
    P-C-TEA
    Call it whatever you want. It is a phenidone-ascorbic acid developer with TEA as activator and solvent. I can't find the grain in properly exposed HP5+ or 400TMY at less than 20 power enlargement.
    You may scale up the formula to any desired amount.
    100 ml of TEA
    9 grams l-ascorbic acid powder (Vitamin C Powder)
    0.25 grams phenidone (1/8 tsp will be close enough.)
    Heat the TEA to 250o F before adding the other ingredients. It won't boil, but some steam may be given off if there is any water in the solvent mixture. Steam will be evolved when the powdered ingredients are added, which I presume to be from water produced in a reaction between the ascorbic acid and part of the TEA.
    Dilute 1+50 to develop 400TMax in 9.5 minutes at 70o F.
    CAT-P-TEA
    The name does not refer to its appearance or its bouquet. I heard it in a British sit-com and just couldn't resist using it. This developer contains catechol and phenidone. It is a staining developer.
    100 ml TEA
    0.2 gram phenidone
    10 grams catechol
    You may use a like amount of hydroquinone in place of the catechol if you like to save money. Call that Q-P-TEA.
    Heat as before. Dilute 1+50 for use. The negatives will be lower in contrast to the eye than to the printing paper, and lower in contrast to VC than to graded paper.
    If you use a 1% sodium sulfite solution (10 gram/liter) to dilute the stock you will have a fine-grain non-staining developer. You can experiment with different proportions of stock, sulfite solution and water.
    P-TEA
    This name also does not refer to its appearance but to the fact that pyrogallol is the sole developing agent. This and D-23 are the simplest single solution developers I know of. It is the only single stock concentrate that I know of with only two ingredients.
    Many fear pyrogallol. That is a healthy fear, but with reasonable care there is no need to inhale or handle the pyro while mixing or using this developer.
    100 ml TEA
    7 grams pyrogallol
    Dilute 1 + 50 for use.
    Again, the negatives will be stained. This developer will produce a strong dye image on 400TMY film. It will prove to you that Pyrogallol alone is not intrinsically a coarse-grain developer.