Fine grain developer from Paracetamol/Tylenol

Discussion in 'B&W: Film, Paper, Chemistry' started by Alan Johnson, May 28, 2013.

  1. Alan Johnson

    Alan Johnson Subscriber

    Messages:
    1,472
    Joined:
    Nov 16, 2004
    Ingredients p-aminophnenol/sulfite are a curiosity from history.

    First I made some clear PaRodinal:
    http://photo.net/black-and-white-photo-film-processing-forum/00UxmB

    20ml 10% hydrochloric acid was added to 50ml clear PaRodinal,giving a precipitate (p-aminophenol) which was allowed to settle 24hrs,the clear liquid decanted and the precipitate filtered off,being left overnight for the liquid to soak through the filter paper.
    48g sodium sulfite was dissolved in 600ml water(=80g/L sulfite).The filter paper and contents were soaked in this solution,the precipitate soon dissolved at room temperature.

    HP5+ was developed 20m 20C in this solution,I call it PRS-1 (PaRodinal Solvent),see attachment (a 0.1 in square section of negative),this is from EI=320.
    For comparison I don't have HP5 in Xtol so give Tri-X in Xtol at EI=400.

    Evidently p-aminophenol/sulfite works but more work woul be needed to see if it is possible to make a developer giving as fine grain as metol/sulfite.
    Thanks for comment.
     

    Attached Files:

  2. Ian Grant

    Ian Grant Subscriber

    Messages:
    17,897
    Joined:
    Aug 2, 2004
    Location:
    West Midland
    Shooter:
    Multi Format
    Original Rodinal is p-Aminophenol in sulphite with no free Hydroxide, so similar but with a much higher level of sulphite.

    The sulphite in Rodinal is generated by adding Potassium Hydroxide to Potassium Metabisulphite the difference beteween Calbe/Orwo R-09 and agfa (post 1963) Rodinal is the first has no free hydroxide, the second uses less developng agent at a higher pH wit an excess of Hydroxide.

    Mees did similar in his early days at Wratten & Wainwright when he worked on p-aminophenol around 1908 :D

    Ian
     
  3. Gerald C Koch

    Gerald C Koch Member

    Messages:
    5,925
    Joined:
    Jul 12, 2010
    Location:
    Southern USA
    Shooter:
    Multi Format
    The following quote is by Bill Pierce and appeared as Rodinal Re-jiggered in Popular Photography (Sept 1966).

    "When diluted 1:100 with 7.5% sodium sulfite solution, Rodinal may be used as a deep tank developer. Replenish with 1 ml of Rodinal for each roll of film. The replenished solution keeps for one month. Decrease development times by 20% from those used for Rodinal diluted with water. Used in this manner, Rodinal-sulfite becomes a medium fine-grain developer producing prints with very clean highlights."
     
  4. dorff

    dorff Member

    Messages:
    459
    Joined:
    May 31, 2011
    Location:
    South Africa
    Shooter:
    Multi Format
    Yes, this is interesting. I think the issue in practical use is whether the developer lasts long enough, and whether the developing times are too long for some to be practical. But that p-aminophenol can be made to act in different ways depending on the formula (just like metol or phenidone) is good to know. I have read somewhere that using Rodinal at much colder temperatures (16 C) also gives finer grain, and the converse is of course also true. It is also super-additive with ascorbate etc. That out of all the possibilities we have only Rodinal as a widely-used developer, is then strange given how many metol and phenidone formulas there are. I can only guess that it has to do with cost and/or a lack of longevity. Do we have any indication how long the original Rodinal (not the replenished) lasted? My understanding is that it was used as a stock solution, not single shot concentrate that had to be diluted. With those sulphite levels, the sulphite would be the major contributor to cost, not the developing agent. Which might explain why it wasn't pursued commercially.
     
  5. Ian Grant

    Ian Grant Subscriber

    Messages:
    17,897
    Joined:
    Aug 2, 2004
    Location:
    West Midland
    Shooter:
    Multi Format
    There's no evidence that using Rodinal at different temperatures has any effect on the grain size in a negative. However the hydroxide in Rodinal can have a softening effect on the surface of the emulsion causing micro reticulation, this only occurs when temperature variations are excessive during processing and is more likely to happen at higher temperatures. The results is prints with more apparent graininess.

    Rodinal has always been diluted, I posted the pre-WWI instructions here on APUg, and by 1907 other companies wre making similar p-Aminophenol concentratrated developers, like Ilfor Certinal, I'm not sure when Kodak introduced Kodinol but it was before WWII (it was never made or sold in the US).

    Ian
     
    Last edited by a moderator: May 29, 2013
  6. Alan Johnson

    Alan Johnson Subscriber

    Messages:
    1,472
    Joined:
    Nov 16, 2004
    Ian,
    Just out of interest,I know there was a formula for Rodinal that got "liberated" in 1945.Do you know if yet earlier versions of Rodinal were the same or was it different at first?Was there ever a version comprising only p-aminophenol and sulfite?
    Jerry,
    I would guess the formula you quote must be slow acting as Rodinal 1:100 at its natural high pH takes about 20min to develop a film.Perhaps that is why that formula you quote is not well known.
    Dorff,
    IDK why p-aminophenol was abandoned in favor of Metol.It was about 120 years ago, the information may be lost.
    A good idea of yours to try to speed up development with ascorbate.I could try using the p-aminophenol made from 50ml PaRodinal (=3g original paracetamol/tylenol) to replace the phenidone in Pattons E-76.
     
  7. Ian Grant

    Ian Grant Subscriber

    Messages:
    17,897
    Joined:
    Aug 2, 2004
    Location:
    West Midland
    Shooter:
    Multi Format
    Alan, Agfa stated over 100 years ago that Rodinal was an alkali salt of p-Aminophenol in neutral sulphite and water with no excess of caustic alkali (hydroxide). Calbe's R-09 still meets that criteria but in the 1930's an anti oxidant was added it was also a mild wetting agent.

    Agfa may have increased the level of Sulphite with the uptake of 35mm in Europe to help produce finer ghrain but they always foremd the sulphite by adding Hydroxide to Metabisulphite. Fine grain developers became more important in terms of research in the mid to late 1920's.

    Metol was probably cheaper to produce and developers could be sold in powder form, that may not be possible with p-Aminophenol which was also Patented by Agfa.

    It was recommended by Agfa themselves to dilute Rodinal with Sulphite solution 5-10% (cryst, half that for anhyd) to greatly extend the keeping properties, and again first publishe over 100 years ago.

    Ian
     
  8. Gerald C Koch

    Gerald C Koch Member

    Messages:
    5,925
    Joined:
    Jul 12, 2010
    Location:
    Southern USA
    Shooter:
    Multi Format
    Rodinals formulation has undoubtedly changed since its first introduction. So there have probably been variations before the 1945 formula.

    Remember that the developing times are 20% shorter with added sulfite so that 20 min becomes 16 min. With the high salt concentration there is no reason that higher developing temperatures cannot be used. Or for that matter a higher concentration say 1+49. There are lots of variations possible. Both Rodinal and sodium sulfite are cheap enough to use in a one-shot developer. I used this method years ago and it worked very well. Finer grain and beautiful prints.
     
  9. Michael R 1974

    Michael R 1974 Subscriber

    Messages:
    6,437
    Joined:
    Feb 2, 2010
    Location:
    Montreal, Canada
    Shooter:
    Multi Format
    A study by M. H. Dickerson presented in Haist's book showed the threshold alkalinity for p-Aminophenol to be 9.35 (compared with 7.25 for Metol, for example), which would be fairly incompatible with fine grain development. Perhaps the general trend toward fine grain developers helps explain why p-Aminophenol was not ultimately more widely used as a developing agent.

    Ian could probably comment on a note in Anchell/Troop (FDC) regarding later versions of "Agfa Rodinal" (or at least Agfa Rodinal as it existed at the time that book was written). Among other things they say it contained a restrainer and speculate this must mean p-Aminophenol was no longer the sole developing agent in the formula (presumably based on the low fog characteristic of p-Aminophenol on its own.
     
  10. Ian Grant

    Ian Grant Subscriber

    Messages:
    17,897
    Joined:
    Aug 2, 2004
    Location:
    West Midland
    Shooter:
    Multi Format
    Michael, in a 1930's Agfa Patent they were using a wetting agent sodium dibutyl-napthalene-a(alpha)sulphonate in a p-Aminophenol developer to overcome uneven development. This also has anti-oxidant properties.

    It's known that Sodium benzenesulfonate was used by Orwo & Foma in R-09 from Soviet and Polish publications. Kodak, Fuji and Ilford all have Patents relating to Sodium benzenesulfonate or it's derivatives, citing them as anti-oxidants and wetting agents. These componds aren't developing agents.

    There's an issue of what is or isn't a developing agent, a compound might have an ability to develop a very weak image (in an alkali solution), or it might provide an additive effect to a developing agent. Sodium benzenesulfonate or it's derivatives have been used alongside colour developing agents to increase solubility and promote more efficient development.

    Ian
     
  11. eclarke

    eclarke Member

    Messages:
    1,972
    Joined:
    Jun 11, 2004
    Location:
    New Berlin,
    Shooter:
    ULarge Format
    I am obsessive about making all my chems. Ian steered me on to a homebrew bersion of Rodinal which I call Ianol. I have made two versions with different pH. The lower hydroxide version is the one I use and it's excellent at 1+50, jobo agitation @68 deg. The higher pH version is extremely close to Rodinal. I've used two gallns of the stuff so far...at 1+50!!


    I have made the quantity as follows because I can get the potassium sulphite in a 1 liter bottle and make a complete batch..

    Ianol:
    Higher pH
    p-Aminophenol.(free base) ................... 53 g-----58g new recipe
    Potassium sulphite 45% sol...................... 1L
    Potassium Hydroxide ........................... 54 g------59g new recipe
    Potassium Bromide ............................. 13 g
    Benzotriazole 1% ............................... 13 ml
    Water to make .................................. 1.3 L

    Stock pH 13.2
     
  12. Alan Johnson

    Alan Johnson Subscriber

    Messages:
    1,472
    Joined:
    Nov 16, 2004
  13. Alan Johnson

    Alan Johnson Subscriber

    Messages:
    1,472
    Joined:
    Nov 16, 2004
    In another experiment I looked at making a developer from Paracetamol/Tylenol without using any sulfite.
    Note, Sodium Hydroxide is hazardous, caustic:
    http://www.ccohs.ca/oshanswers/chemicals/chem_profiles/sodium_hydroxide.html

    Solution A:
    I dissolved 20g sodium hydroxide in 250ml water, added 15g (contents of 30 capsules) Paracetamol whilst hot,with stirring.
    After filtering through cotton wool the solution was left in a 250ml sealed bottle for 72 hrs.The paracetamol hydrolyses to p-aminophenolate which is a developing agent.

    LS-1b Developer:
    Solution A above...............................50ml
    Ascorbic Acid....................................20g
    Sodium Carbonate photo grade anh.....6.7g
    Water to ..........................................1L
    pH~9

    HP5+ was developed in LS-1b 10m 20C, EI~250, see attachment showing 0.1 in square section of negative.
    It's a mid-acutance rather than fine grain developer.

    Later I may try washing soda crystals instead of sodium carbonate anh, the developer could then be made from Paracetamol,Caustic Soda pellets, Ascorbic Acid (Vitamin C from the health food shop) and washing soda crystals.
     

    Attached Files:

  14. Sponsored Ad
  15. Alan Johnson

    Alan Johnson Subscriber

    Messages:
    1,472
    Joined:
    Nov 16, 2004
    Slow progress on this one.
    After 46 days the pH of LS-1b has fallen from the initial 9 to 6.5 and it no longer works.It is falling towards the pH of sodium ascorbate and the only explanation I can think of is that free sodium ions that initially supported pH 9 may be complexed in some way and taken out of service by ascorbate.
    I may try less hydroxide to make solution A, needing less ascorbic acid,and possibly adding sodium bicarbonate to give some buffering, as ascorbate/carbonate did not work.
    It was in a nearly full bottle and the pH drop seems too much for the small amount of oxidation to have been the cause.
     
  16. Trask

    Trask Subscriber

    Messages:
    1,343
    Joined:
    Oct 23, 2005
    Shooter:
    35mm RF
    Alan - what just looking at the three photos you've posted, the first looks by far the best in terms of grain, the second starts to look mottled/clumped, and the third just above is looking like some form of reticulation. What do you think?
     
  17. Alan Johnson

    Alan Johnson Subscriber

    Messages:
    1,472
    Joined:
    Nov 16, 2004
    What you say may be true and the grain comparisons would need to be done again using the same film and scanning procedure for all.
    But first I would like to produce a developer that has a stable pH using paracetamol, sodium hydroxide, sodium carbonate, sodium bicarbonate and ascorbic acid only as these can all be obtained from local shops.
    I don't count sodium bisulfite used in wine-making as a local shops chemical so sulfite is not allowed.
    I'm looking at Ryuji Suzuki's DS-2 using p-aminophenol made from paracetamol in place of metol and without the sulfite, although this would not be fine grain:

    http://web.archive.org/web/20091005...s/Film_Developer_Recommendations#Introduction
     
  18. Alan Johnson

    Alan Johnson Subscriber

    Messages:
    1,472
    Joined:
    Nov 16, 2004
    Another chemical mud pie noted:
    A moderately buffered solution was made to try to avoid the pH drop problem.

    Solution A (this is to hydrolyse Paracetamol/Tylenol to the developing agent sodium aminophenolate.)10% more sodium hydroxide than theoretically needed was used.
    Content of 16 Paracetamol capsules....................8g
    Sodium Hydroxide...........................................4.64g
    Water to.......................................................100 ml
    Leave in a full sealed bottle for 1 week at room temperature for the hydrolysis to complete.

    LS-1b1
    Ascorbic acid....................................................10g
    Solution A above...............................................50ml
    Sodium Bicarbonate...........................................10g
    Sodium Carbonate Decahydrate...........................10g
    Water to............................................................1L
    Develop for 1.5x Xtol 1+3 times.It worked at first.

    However this buffer did not stop the pH drop problem, initial pH of 9.0 fell to 8.8 after 7 days,7.8@14 days, 7.7 @23 days.
    I am now trying a more strongly buffered solution, 50g/L Sodium Carbonate anh equivalent.

    Note sodium hydroxide is caustic, hazardous:
    http://www.ccohs.ca/oshanswers/chemicals/chem_profiles/sodium_hydroxide.html
     
  19. Relayer

    Relayer Member

    Messages:
    236
    Joined:
    Jun 14, 2009
    Location:
    Odessa, UA
    Shooter:
    35mm
    Some time ago I was research some pH-stability issues in ascorbate devs. 1st replace ascorbic acid to sodium ascorbate or ascorbic acid with valid amount of sodium carbonate for produce sodium ascorbate. 2nd - make your buffer solution. For pH=9 try ~10g/l of Borax, or borax+sodium carbonate
     
  20. eclarke

    eclarke Member

    Messages:
    1,972
    Joined:
    Jun 11, 2004
    Location:
    New Berlin,
    Shooter:
    ULarge Format
    I have used gallons of this and it's excellent..

    ave made the quantity as follows because I can get the potassium sulphite in a 1 liter bottle and make a complete batch..

    Ianol:
    Higher pH
    p-Aminophenol.(free base) ................... 53 g-----58g new recipe
    Potassium sulphite 45% sol...................... 1L
    Potassium Hydroxide ........................... 54 g------59g new recipe
    Potassium Bromide ............................. 13 g
    Benzotriazole 1% ............................... 13 ml
    Water to make .................................. 1.3 L

    Stock pH 13.2
     
  21. Alan Johnson

    Alan Johnson Subscriber

    Messages:
    1,472
    Joined:
    Nov 16, 2004
    Hi Relayer,
    The unique feature of my developer, if I ever manage to produce a stable form,is intended to be that all the ingredients should be available from small town local shops, not internet.
    Viz:tongue:aracetamol/Tylenol (aka acetaminophen), Sodium hydroxide (aka caustic soda or lye), Ascorbic acid (aka vitamin C), Washing Soda (aka sodium carbonate mono- or deca-hydrate) and Baking Soda (aka sodium bicarbonate).
    My health food store carries ascorbic acid but not sodium ascorbate. I cannot buy borax in local shops any more, there is some kind of EU ban. So I cannot use the chems you suggest.
     
  22. Athiril

    Athiril Subscriber

    Messages:
    2,930
    Joined:
    Feb 6, 2009
    Location:
    Melbourne, V
    Shooter:
    Medium Format
    Try this:

    20mL/L of PaRodinal (or 2.5 paracetamol tablets 500mg, if tablets you'll need to let hydrolysis occur).
    100g/L of Sodium Sulphite
    30g/L of Sodium Chloride
     
  23. A-Shooter

    A-Shooter Member

    Messages:
    7
    Joined:
    Feb 15, 2012
    Shooter:
    Multi Format
    Why the salt? (Sodium chloride)
    Salt has no positive function in a developer. You may get dichroic fog from it and it isn't washed out of the film by the stop bath and by this is transfered to the fixer where it reduces the action of the fixer. If you need something to tame fog, use KBr.
     
  24. Athiril

    Athiril Subscriber

    Messages:
    2,930
    Joined:
    Feb 6, 2009
    Location:
    Melbourne, V
    Shooter:
    Medium Format
    Sodium Chloride gives finer appearing grain, the recipe above is essentially a DIY Perceptol with Rodinal. The solvent action, combined with giving up a stop of film speed gives extra fine grain.
     
  25. A-Shooter

    A-Shooter Member

    Messages:
    7
    Joined:
    Feb 15, 2012
    Shooter:
    Multi Format
    No, Sodium Chloride, AKA common salt does NOT give finer grain.
    Giving up a stop of film speed DOES give finer grain. Try the recipe without the salt and you will get the same results without the problems that salt in the developer introduces. There are some reasons why Kodak doesn't use salt in their developers. :smile:
     
  26. Alan Johnson

    Alan Johnson Subscriber

    Messages:
    1,472
    Joined:
    Nov 16, 2004
    If you search for Microdol-X msds it will be found that this Kodak developer did contain sodium chloride.Sodium Chloride is usually mentioned on APUG as a mild grain solvent.
    Any evidence this is not right please give details.