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Modern Rodinal Substitutes

Kodak found that early PPD developers were affected by the acid used to make the salt, and converted to either the Sulfate or the p-Tosyl salt which you see in use today. This is true to the present time in CD-6 and CD-3 for example. The chloride had varying adverse effects on early Cl/Br emulsions used in print films and papers. I don't know what all was affected, as the change was complete when I joined EK.

As for a standard sensitometric test, the pAP developers were not in use by the end of the war, and at Kodak they used an Elon + Ascorbic Acid developer called internally EAA. I do not remember the formula.

My military manuals from the 50s do not describe any developer such as the one above nor does any Kodak manual. They basically describe Metol + HQ developers with 50 g/l or so of Sodium Sulfate, and that is the reason I asked the question.

PE
 

In the days before NASA, NACA managers came up from the engineering ranks. That was the only way you could advance above GS-14. So, the better you were as an engineer, the more likely you were to become a manager, where you could no longer do what you loved doing. If anyone had asked me, I would have asked what they planned to do with the hot hydrofluoric acid exhaust besides kill people.

We tend to forget that NASA means National Aeronautics and Space Administration. Human factors apply to both, but my theories and experiments applied mostly to pilots of aircraft.
 


Kodak also did a lot of work on p-Aminophenol and it's derivatives in the 30's & 40's, there are various Patents etc, Sheppard was involved and must have moved from Wratten to Rochester with Mees.

Your comments about the PPD acid salts are matched by Kodak's use of p-Aminophenol Oxalate, and Edmund Lowe's Gradol the sulphate form and confirm what I'm thinking about the importance of the free base in Rodinal.

On the point of ascorbic, here's the second to last paragraph from Edmund Lowe's 1939 book on Developers:

As for developers, it is probable that the next few years will see the introduction of a series of developing agents that that can actually be eaten if desired. Some, chemically related to Vitamin C, are available now though at enormous cost. One call almost see the advertisement of the new Zero-Grane 999 (1960 A.D.) ----- "Try Zero-Grane 999. Non-poisonous. Enlargement to 999 diameters, miraculously discovered by George Gizzlewski after 84 years of painstaking research. If it won't develop your negative, take two teaspoonsful after each meal. It puts spring in your step and a light in your eye. $10 per 2 oz. bottle sufficient for 89 rolls of film."

It's Lowe's nice way of saying there's no magic bullets.

Ian
 
My military manuals from the 50s do not describe any developer such as the one above nor does any Kodak manual. They basically describe Metol + HQ developers with 50 g/l or so of Sodium Sulfate, and that is the reason I asked the question.

PE

The manual I have,TM 1-219, was written under the direction of the Chief of the Air Corps. There was no separate Air Force at the time, so the front cover only mentions the War Department. It is truly basic photography. I suspect that most of the formulas were designed to be capable of high contrast for aerial photography.
 
Here is Kodak's DK-15 Tropical Developer from 1941

Water-------------------750 cc
Elon---------------------5.7 g
Sodium Sulfite (anh)-----90 g
Kodalk------------------22.5 g
Potassium Bromide--------1.9 g
Sodium Sulfate----------45.0 g
Water to 1 L

Use up to 90 F but at temperatures up to 75 F the Sodium Sulfate may be omitted for some films.

This formula or derivatives of it were in use through the 50s for tropical processing of films. The USAF manuals for photography are 95- series, and the AFIT (Air Force Institute of Technology) also issues a set of books for the course in photo science. I have copies of both. They are rather hefty 8x10 size books and take up quite a bit of shelf space.

PE
 
Kodak also published D13 which is a Kodelon (p-Amininophenolol / Hydroquinone) Tropical developer:

D13 Tropical Developer

p-Aminophenol Hydrochloride 5,2 g
Sodium Sulphite (anh) 52.5 g
Sodium Carbonate (anh) 50 g
Hydroquinone 10.5
Sodium Sulphate 45 g (105 cryst)
Potassium Iodide 2.1 g
Water to 1 litre

Dev times 6-7 mins @ 29°C

(Both p-Aminophenol Hydrochloride and the Oxalate have been sold as Kodelon)

Ian
 
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And, I have found absolutely no reference in US publications of that approximate era to Kodelon, pAP or D-13. Your formula does include the Sulfate I see, even though the earlier formulas do not. I would have to say that the use of the Sulfate is necessary with most films or about 75 F just as with my formula.

I have found references here to similar developers with Sulfate by Tom Hoskinson and also a reference to Kodelon by Mees in his 1921 textbook on photography.

PE
 
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There are rather a lot of official Kodak formulae not in the Formulary etc, but Kodak published them none the less.

It's exactly the same with Ilford, Agfa & Agfa Ansco, etc none of their books contain all the officially published formulae

In the case of D13 my source differs from Tom Hoskinson's source (posted previously on APUG) because his says Kodelon, mine says p-Aminophenol Hydrochloride and had UK spelling, all UK formulae use Hydrochloride, US usually Oxalate.

Ian
 
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We cross posted

But there is this gap of knowledge where it's hard to find the original Kodak references etc.

Presumably Mees book is a continuation of what he began at Wratten with Sheppard, I'd guess the pair worked od Kodelon there.

Ian
 
And, the correct formulas for some of these is either lost or in peril of being lost.

That is why I believe that we should develop a new formulary with some sort of accuracy, to weed out and verify the best of the best. There are just too many dissenting "votes" on Rodinal type developers just to pick one, and high temperature developers to pick another.

PE
 
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
 
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
 
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
 
Yes, before comuters!. Just an ordinary misteak. Right? It is the person at the keyboard in all cases Ian.



PE
 
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.
 
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
 
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
 
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
 
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.
 
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.
 
Who is Dr Elie Scheour "of Agfa", (or rather who your readers assume is from Agfa, as he's not) ?

I quote "According to Bill Troop, Agfa's Elie Shneour provided the following mixing instructions for what is generally agreed to be, for all intents and purposes, Rodinal." and another "According to Elie Shneour of Agfa, the original Rodinal". I have to admit that I assumed he was probably from Agfa when I first read the FDC.

Agfa, Bayer & A&O have published far more accurate MSDS's than the one you quote.

Even the original Agfa Rodinal could be used at 1+100 it's in the 1910 Agfa books etc used for papers at that dilution, and the modern version while it contains approx 20% less p-Aminophenol will work well at 1+ 100 because of the higher pH. The increased Sulphite helps with the stability of the modern developer.

Edward Zimmermann is particularly authoritative about Rodinal, and knows his facts, and I tend to agre with all he's written on the subject.

Ian
 
Ian, where are you quoting from? You don't say. Certainly not from my book. Can I suggest you buy a copy and keep it in your overnight luggage? It would save a lot of trouble when you're 'quoting' from it. Alternatively, you could learn to use Google Books. Like I've said before, think before you post. I do! You're not, I must say, displaying the signs of a good researcher. By the way, have you -- or anyone you know -- done any spectrographic analysis of Rodinal? Shneour, a well-known biochemist, has, and has shared his results with me.

Regarding something Ed Zimmerman wrote about me and Rodinal on the Net in 2003

http://www.photo.net/bboard/q-and-a-fetch-msg?msg_id=006fc5

which is practically indistinguishable from this thread, but go ahead and read it to prove Nietzsche's doctrine of the Eternal Recurrence of the Same -- and while away some more time not taking good photos, I asked Dr Schneour to comment, and he did as follows:

'I have read the exchanges about "Rodinal". These consist mainly of flailings about its formula (actually a whole bunch of them) which in the last analysis mean nothing in today's world. There are at least two outstanding issues regarding "Rodinal". One of them is the variations in the actual early formula which were made almost continuously and thus it is today difficult to discern which of these variants was the actual "original" formula. The other issue is that one of the remarkable properties of "Rodinal" was its long life before dilution for use. The caveat to this long life was (and is) that its developing properties change importantly but subtly as a function of time and storage conditions, to say nothing about the quality of the water used in the dilution for use. The formula I have settled on and which is listed in the now classic Anchell & Troop "The Film Deevloping Cookbook" is stored at about 15 degrees Celsius after compounding and is "marinated" for six months before first use. When compared to an old version (about 1936) it is undistinguishable for my uses. The conclusion must be that the arguments about "Rodinal" and its successor(s) will remain controversial because there are so many versions and so many usage and storage variations as to make any emotional discussion about that developer unproductive and a total waste of time. Instead, if you work with monochrome photography, make or buy the stuff, work out your best combination of variables and be productive rather than engage in idle chatter signifying nothing.'

I've seen it all before. I actually like Ed Zimmerman, who is very intelligent if irascible, but he and Ian both belong to that class of pestiferous readers who submerge themselves in the exquisite frustration of not having written a book that someone else has written. They then spend a substantial part of their lives making that author's life as miserable as possible, instead of letting him get on with his work, much less getting on with their own. I have noticed before that the impulse to create one's own work is not really compatible with the impulse to criticize other people's work. That's probably one reason why Ian hasn't written a book about photochem.
 
Bill, I have the FDC beside me. On pages 57 & 117 the mention of Schneour is very ambiguous because you don't say who he is and his name only ever crops up in relation to you & Rodinal. Gerald Koch, who's opinions I respect is the source of the(there was a url link here which no longer exists).

If Elie Schneour has definitive data on Rodinal where is it ? I could have done spectrographic analysis on Rodinal & other developers lf but in fact it's quite difficult to determine what's in a compouded developer. I had two Varian AA Spectrometers in the lab I ran, and access to other instruments as we worked closely with 2 or 3 other labs specialising in different testing methods, however as Ron (PE) could confirm some elements or salts are difficult to detect and measure. Getting a full analysis done is extremely expensive.

I'd request you don't turn threads like this on APUG into the ill tempered and bitter threads that you've taken part in so many times before on various forums.

I don't doubt that the formula published by Agfa themselves in Andresen's book is the closest formula to Rodinal that Agfa has ever published. (Which is the formula in the FDC). Other people may have been closer to the mark.

Ian
 
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Ian, you are correct about cost to an extent and correct about difficulty to an extent. At EK, analysis of any processing solution or emulsion (or coating for that matter) was routine and a snap. I got back analyses on all of my processing solutions before and after use if they were experimental. In fact, such analyses are essential for determining how to work out seasoning and balance (see my post on steady state).

As an additional factor here, analysis is essential for patent infringement work and thus all competitor products are analyzed in great detail. This extensive work reduces the cost to being minimal.

PE
 
Another factor with Rodinal would be the tests show what's in the developer once matured, rather than the chemistry used to make it.

So the early Andresen published formula and both R09 & modern Rodinal would show Sulphite while in fact the first uses Metabisulphite and wouldn't test for the full hydroxide content that would need to be added.

Again it would be almost impossible to determine what form the p-Aminophenol was in when added.

Ian