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  1. #1
    Ian Grant's Avatar
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    Modern Rodinal Substitutes

    The formula for Rodinal R09 has never been officially published by Agfa. In the "Agfa" Book of Photographic Formulae, published by the Berlin Aniline Company in 1910, the company tells us:

    As "AgfA"-Rodinal contains only traces of carbonic alkalies, the use of distilled water for dilution is not necessary. In connection with the use of "Agfa"-Rodinal the following remarks should be carefully noted:

    In addition to neutral sulphite and water "Agfa"-Rodinal contains only an alkaline salt of Paramidophenol, but no excess of caustic alkali.

    PDF Rodinal 1910

    However it's possible to make formulae that's close to the current versions.

    Original Rodinal contained p-Aminophenol (once called Paramidophenol by Agfa) and this was formed by precipitation of the free base from p-Aminophenol hydrochloride using sulphite and carbonate (hence Agfa's comment "contains only traces of carbonic alkalies".


    The formula for Rodinal has changed and evolved presumably as high grade p-Aminophenol free base became commercially available, allowing Rodinal to be completely free of carbonates.

    J. Desalme published a " Concentrated Paraminophenol Developer of the Rodinal Type" in 1913, this was later included in L.P. Clerc's book "Photographic Theory and Practice".

    Sodium Carbonate & Sodium Sulphite are added to a solution of p-Aminophenol Hydrochloride which precipitates the free base, which is filtered and collected.

    The paste of p-Aminophenol free base is then added to a solution of Sodium Metabisulphite and Sodium Hydroxide added until all the free base is dissolved, finally a small amount of Metabisulphite is added until the first crystals of p-Aminophenol free base begin to form again.

    This mirrors Agfa's own description of early Rodinal, and accounts for the traces of carbonates, and the "no excess of caustic alkali". (J. Desalme was a photographic chemist specialising in aminophenols and other developing agents particularly for colour processing).

    Now we reach a point of contention "Free base" or "Hydrochloride", genuine Rodinal has always been made using the Free base of p-Aminophenol . (50g of p-Aminophenol is equivalent to 66.2 g p-Aminol hydrochloride). There is no evidence to suggest that Rodinal of any form has ever contained p-Aminophenol Hydrochloride.

    The MSDS sheets for both Rodinal and Calbe R09 show clearly that both developers contain p-Aminophenol free base (CAS 123-30-8) and not p-Aminophenol hydrochloride (CAS 51-78-5).

    Making a Rodinal substitute with p-Aminophenol Hydrochoride will leave free chlorides in the solution, and neutralise more Hydroxide, the amount of developing agent would need to be increased along by a factor of 1.33 and also more KOH added.

    Data on early Rodinal is hard to find but in a thread on Photo.Net "Edward Zimmermann" wrote:

    The formulas for Rodinal, resp. R09 (1964 to present), have never been published. The patent is for Paramidophenol developers and there are many recipes making the rounds since the late 1800s. One of the most famous is attributed to Eder. From my copy of Spörl and Neumann, "Fotografisches Rezeptbuch" 1943 edition, p.50):

    N16:

    • Paramidophenol 50g
    • Kaliummetabisulfit [Potasium Metabisulfite] 150g
    • Wasser 625ccm (ml)

    Then a solution of

    • Ätznatron [Sodium Hydroxide] 215g
    • Water 500ccm (ml)

    is slowly added untill the cloudyness breaks. According to the book it says this is typically around 350ml.
    Then the solution is diluted with water to make 1 liter.

    My note: 350ml of the Sodium Hydroxide solution contains 150.5 gms Sodium Hydroxide.

    The same formula was published in the British Journal Photographic Almanac (1910 & earlier) as:

    Paramidophenol.
    ONE-SOLUTION

    Potassium metabisulphite 300g
    Distilled water 1 litre
    Paramidophenol 100g

    Dissolve in the above order and add gradually:
    Caustic soda or potash to dissolve the precipitate first formed.

    For use, dilute 1 part. with 10-20 parts of water.

    No final volume of solution is given but it's likely to be 2 litres if you want the equivalent of early Rodinal.

    It's important to note that these sources clearly indicate the use of the free base, as they go on to also include p-Aminophenol Hydrochloride film developers. These are in the 1910 "Agfa" Book of Photographic Formulas, the 1910 BJP Almanac and Ed Zimmermann's book all from quite different sources & countries.

    However other versions of this formula appear in various books from the early 1900's onwards, but using p-Aminophenol Hydrochloride, because of the difference in Molecular Weight and the effects of the additional Hydrochloride they won't be quite the same. Dr M. Andresen, of Agfa, who discovered & patented p-Amaninopheol and designed Rodinal published it himself in the "AGFA Photo-Handbook" he did not claim it was similar to Rodinal, listing it as - Formula 21: Concentrated single solution. (As above proportions but using p-Aminophenol Hydrochloride).

    L.P.Clerc and others indicate that Potassium Metabisulphite was the preferred source for the Sulphite in Rodinal, Potassium salts are used in preference to Sodium because of their greater solubility in water which becomes far more important in concentrated developer solutions. Metabisulphite and Hydroxide form Sulphite in solution.

    At some point before or during WWII Agfa began using Potassium Sulphite and also adding Potassium Bromide and an anti-foggant to Rodinal. It's entirely possible that Agfa modified Rodinal so that it was more suitable for roll & particularly 35mm films which became cfommon in the 1930's.

    Some have made the assumption that this formula might be "Classic Rodinal" but if we compare it to a modern MSDS's it's only close s to Calbe's R09 MSDS for the p-Aminophnol.

    P-Aminophenol 50g - 5%
    Potassium Metabisulphite 150g - 15%
    Sodium Hydroxide - very approx 150g - 15%
    Water to 1 litre

    Calbe R09 MSDS

    P-Amininophenol 5%
    Potassium Sulphite 30%
    Potassium Hydroxide 4%

    However Potassium Metabisulphite is quite acidic in solution and will neutralize a considerable proportion of the Hydroxide. Replacing it with Potassium Sulphite cut's the amount of Hydroxide needed very substantially. Potassium Metabisulphite 5% solution has a pH of 3.8 - 4.6, while a similar Potassium Sulphite solution has a pH of 9 - 10

    Only one parameter seems to stay constant from early published alternatives through to Orwo/Calbe R09 - the fact that Rodinal is a 5% solution of p-Aminophenol free base in a sulphite solution, with no excess of alkali. It's reported that the Calbe product usually has a few crystals of the free base in the bottom of the bottle, which indicates no excess of Hydroxide.

    The British RAF report into the "Agfa Film Factory - Wolfen" reported by G.C. Brock, London : H.M.S.O. gives a formula for Rodinal as:

    Dissolve 34 kg of para-aminophenol in 340 litres of water. Add 558 kg of a 30% solution of potassium sulphite at 55C followed by 50 kg of a 34% potassium hydroxide solution, then 5.52 kg of potassium bromide in a little water. Add 42 g P.1347 (an Agfa-specific anti-foggant). Filter and allow to stand for 14 days.

    Knowing the Specific Gravities etc this seems to be around:

    p-Aminophenol 34kg
    Potassium Sulphite 128.08kg
    Potassium Hydroxide 12.57 kg
    Potassium Bromide 3.75 kg

    We aren't given a final volume, but if we relate this to the 5% p-Aminophenol of the Calbe MSDS this works out as:

    p-Aminophenol 5%
    Potassium Sulphite 19%
    Potassium Hydroxide 1.85%
    Potassium Bromide 0.77%

    But the Calbe/Orwo version of R09 is the pre-WWII formula and it's MSDS is

    p-Aminophenol 5%
    Potassium Sulphite 30%
    Potassium Hydroxide 4%
    Potassium Bromide - not included (below 1%)

    Unfortunately we can't really completely trust the RAF report, none of the Allied F.I.A.T. reports about Agfa products is entirely accurate, after all some Agfa employees were former members of the National Socialist Party (Nazi's). There is insufficient Potassium Hydroxide to react with the p-Aminophenol free base, and it is possible the resulting solution was then adjusted until the free base had just fully dissolved.

    Patrick "Gadget" Gainer has published "EZ Rodinal" which in terms of its ratio of p-Aminophenol to Potassium Hydroxide is probably close to Calbe R09 as there will be no excess of Hydroxide, the weights in brackets have been scaled to give a concentration of 5% p-Aminophenol.

    EZ Rodinal

    To 400 ml water, add:
    Sodium sulfite (anhyd) 85 g (106.3)
    p-Aminophenol base 40 g (50 g)
    Stir well. Add
    Sodium hydroxide 13.8 g or Potassium hydroxide 19.2 g (24g)
    Add water to make 500 ml. (1 litre)

    If EZ Rodinal; is adjusted a little further by adding 300 g of Potassium Sulphite in place of the Sodium Sulphite, some Potassium Bromide added plus some Benzotriazole and Potassium Hydroxide added slowly until the free base just dissolves

    EZ Rodinal New (Calbe R09 substitute)

    To 800 ml water, add:
    p-Aminophenol base 50 g
    Potassium sulphite (anhyd) 300 g
    Potassium hydroxide 24 g
    Potassium Bromide 0.8 g
    Benzotriazole 1% 10 ml
    Water to make 1 litre)

    This would be a lot close to the pre War formula and Calbe RO9, although this is itself now being made in a more concentrated form so that the dilutions & dev times are more comparable to Agfa /A&O Rodinal (post 1964)

    Patrick's second Rodinal substitute formulae is close to the Bayer/Agfa/A&O MSDS data-sheets for modern Rodinal:

    p-Aminophenol 4.1% (A&O)
    Potassium Sulphite 30-40%
    Potassium Hydroxide 2.7% (A&0)
    Potassium Bromide 1-5%
    Anti-foggant - not specified
    pH 14

    Gainer Rodinal Substitute

    To about 750 ml of water at room temperature, add
    p-Aminophenol 38 g
    Sodium sulfite (anh) 160 grams
    Sodium hydroxide 23 grams
    Water to 1 liter.

    This is on the right track, you need to use the free base and an excess of Hydroxide unlike the older R09 formula which has nearly 20% more p-Aminophenol and also requires using at a higher concentration to get equivalent results.

    In a post about Patrick's version a comment was made about the pH at 1:50 being roughly 11.6, Agfa Rodinal has a stock concentrate pH of 14 and a dilute pH of 11.55 so if this is the case Patrick's formula is about right, except too little Sulphite and there's no Bromide or anti-foggant.

    Agfa's modern Rodinal 1964 onwards uses an excess of Hydroxide and as a consequence is more active despite the lower level of p-Aminophenol than the previous formulae. Calbe R09 concentrate has a pH of 11.8.

    This is what I would use as a starting point for a good modern substitute:

    Rodinal Substitute

    p-Aminophenol.(free base) ................... 41 g
    Potassium sulphite (anh) ..................... 348 g
    Potassium Hydroxide ........................... 27 g
    Potassium Bromide ............................. 10 g
    Benzotriazole 1% ............................... 10 ml
    EDTA Na4 (optional) ........................... 6 g
    Water to make .................................. 1 litre.

    If necessary adjust to pH 14

    Some notes:
    The balance of the Bromide & Benzotriazole may need adjusting upwards..
    The mixed developer should be left a couple of weeks before use.

    Contrary to what has been written in some books Rodinal has always used the free base of p-Aminophenol although in the early days this was prepared from the Hydrochloride first.

    Ian

  2. #61
    Ian Grant's Avatar
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    One thing we can be sure of is that the Andresen formula used in the FDC isn't true Rodinal, of any vintage, there's no way Agfa would have published the formula.

    Add to that the fact that Agfa themselves say Rodinal (1910) "contains only traces of carbonic alkalies," which can only have come from the preparation of the free base.

    At present I'm working on building a database archive, with refeences to original sources, I've had some help from other APUG members, Tom Hoskinson was going to help cross check etc before he had his stroke, as was Gerald Koch, (who's also disapperaed). The aim is to place it on a site like APUG, but allow others tto share the data. I'd guess I have something like 1200 developers, some fixers and toners. A huge number of developers are very similar, some no longer possible as the dev agent's not made, some are extremely interesting and worth looking at. When I find the right collaborator I'll share & pass over data.

    I should add I get constant help & support from other APUG members who send me books, or scans etc of data, and in return I pass information etc back.

    But we do need the Formula section here on APUG kicking into a decnt shape

    Ian

  3. #62
    Photo Engineer's Avatar
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    Which brings me bact to a few topics.

    1. There is no magic bullet but there are more developers than can be rationally accounted for let alone easily counted and it is not at all feasible to even test them well to prove any claim about them.

    2. Many of the developing agents are gone missing and the developers cannot be reproduced.

    3. Many were designed with old films and emulsions in mind and cannot be used today. Anyone using an ammonia or iron based developer?

    4. There is quite a gap between old developers and new developers which have not been explored fully. We talk our heads off about old style developers and I have yet to see you or anyone fully describe a modern developer, except perhaps for my description about how HC110 is made (synthesized would be a better word).

    5. Stop baths and fixers have been gloriously ignored. There are quite a few advanced formulas never even discussed let alone used. Super Fix is an example that has never been fully discussed. I don't suggest use of it, but rather that it embodies quite a bit of advanced chemistry.

    Just some thoughts on all of this recent activity. Mainly, who is going to "prove" efficacy of any old formula and who is going to point out which is most correct?

    PE

  4. #63
    Ian Grant's Avatar
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    Quote Originally Posted by Photo Engineer View Post

    Just some thoughts on all of this recent activity. Mainly, who is going to "prove" efficacy of any old formula and who is going to point out which is most correct?

    PE
    Consensus, and an acknowledgement that when two or three versions exist of a formula, they are noted.

    On that point Edward Lowe has D72 in his 1939 book with the rounded off weights, while you & I have the more accurate version in 1940's etc Kodak publications.

    We have to take what a company publishes itself as Gospel. But there's a huge differance between a rounded off formula and an error, which of course can & does happen, typsetters made more before comuters

    Ian

  5. #64
    Photo Engineer's Avatar
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    Yes, before comuters!. Just an ordinary misteak. Right? It is the person at the keyboard in all cases Ian.



    PE

  6. #65
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    Most human languages have enough redundancy that we can spot typos and misspellings. The spell checkers in our comytwrs are not as good as one of us well eduvatrd persoms.
    Gadget Gainer

  7. #66
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    Patrick;

    It is obvious that you have not struggled with Japanese homonyms where one word can have mutiple meanings or Chinese tonality being expressed in writing. Then there is Russian spelling which is Byzantine to say the least. (IMHO)

    In Chinese, 3 words are used to make a poem of about 5 lines that has a different meaning in each line.

    Smelling is everything!

    PE

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    Patrick, Ian;

    In an earlier post, someone commented that the Metol version of Rodinal that Patrick had brought up some time back does not appear to have long shelf life.

    This has been bothering me for 2 reasons. Metol is a very close relative to pAP. It should keep better as it is a less powerful reducing agent IIRC or less strong base in any event. Also, its properties with Sulfite are quite different than HQ and more like pAP. So, if it keeps poorly something else is going on here that might give clues to Rodinal.

    Any thoughts?

    PE

  9. #68
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    Kodak's own EAA developer

    This is a very clean working developer, never sold, but used internally for testing photographic emulsions. It is a pure surface developer and does not have any solvent effects on buried image.

    Elon-------------2.5 g
    Ascorbic Acid---10.0 g
    Kodalk----------35.0 g
    KBr--------------0.4 g
    Water to 1 liter

    pH 9.8

    Note the use of decimals.

    PE

  10. #69
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    Quote Originally Posted by Photo Engineer View Post
    Patrick, Ian;

    In an earlier post, someone commented that the Metol version of Rodinal that Patrick had brought up some time back does not appear to have long shelf life.

    This has been bothering me for 2 reasons. Metol is a very close relative to pAP. It should keep better as it is a less powerful reducing agent IIRC or less strong base in any event. Also, its properties with Sulfite are quite different than HQ and more like pAP. So, if it keeps poorly something else is going on here that might give clues to Rodinal.

    Any thoughts?

    PE
    Coincidentally, just a few hours ago I did a Metol version again, but somewhat differently. This time I did not bother to try to separate out the Metol base from the sulfate. I used KOH instead of NaOH. I haven't got my good K sulfite, so used Na. I put 41.5 grams of metol in about 750 ml water. I added 100 grams of Na2SO3 and added KOH until everything dissolved. The sulfate resulting from the neutralizing of thr H2SO4 is still in there. The solution is an amber color which is hardly seen in the measuring syringe. It appears that diluted 1+50 it is about a 10 minute developer for EDU 400 Ultra. Needless to say I have no idea how long it will last as stock, but the color of what I have is much different from what I had then. When I get a negative that I'm willing to show as a picture, I'll post it.
    Gadget Gainer

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    Nothing in this thread accounts for the statement, on Rodinal packages, going back several decades, that hydroxide is only 3%.

    A 1998 MSDS confirms this; in its entirety it gives

    potassium hydroxide, 3%
    potassium sulfite, 30-40%
    potassium bromide, 1-5%
    p-Aminophenol, 1-5%

    and the pH is 14 (!!!) - - which is massively higher than other figures, published by Agfa, that we have all seen.

    It is obvious from this disclosure that many ingredients off the list are present, because it is unlikely you could make up any combination of this formula and have a stable liquid capable of developing film in a reasonable time at 1:100 dilution. The secret is pretty obvious, even without the hints Agfa published in the literature of the 1950s and 1960s.

    As I have said before, Agfa agreed to allow Bob Schwalberg to publish all manufactured formulas for Rodinal since its inception except the then-current one, which was as radically different from its predecessors as they were from theirs. This was one of Bob's last projects, in the latter mid-1990s, and was frustrated only by his sudden death. The main points were: 1. there have been many formulas, 2. no published formula has ever been accurate, 3. there are many surprises.

    Well, it's only ten years later. Who's up to tracking down the surviving Agfa b/w honchos and getting them to agree to re-open this? Not me - - my conversational German isn't up to it.

    My theory throughout life has been: if you want a good answer, go to the world's expert. Why is it that I remain the only person around willing to do this? But I can't do the Agfa people - - there's too much of a language barrier.

    By the way, I noticed that nobody has taken up the most interesting educational remark made here, which was by Ron and the relationship between potassium bromide and edge effects.



 

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