Reading Crawley: glycin, sheen and dichroic fog

Pixophrenic · May 20, 2019

Geoffrey W. Crawley wrote in BJP 1960, issue of Dec 15: "Promicrol, by using glycin which as noted earlier has a slight solvent effect, in excess of sodium sulfite has a very high rate of physical development. Glycin, by itself, with modern films, provokes dichroic fog as soon as the concentration of sulfite rise above eight times its own concentration... the energized glycin does not provoke dichroic fog in the excess sulfite, a "sheen" however is produced similar to that given by borax alkalinity unrestrained"

Now, I know from practice, that a concoction with the following composition: metol 1.0 g/L, hydroquinone 0.5 g/L, glycin 0.5 g/L, sodium sulfite 30 g/L, sodium carbonate anhyd 2.5 g/L (pH 10.3), develops film in about the same time as D-76 and accumulates fine silver when used, despite relatively low sulfite and glycin. However, I do not see any dichroic fog, neither in FP4 nor in Foma 100, despite sulfite/glycin ratio exceeding the one predicted by Crawley to invoke dichroic fog, and perhaps I am overlooking the "sheen". The questions I have:

1. What does "sheen" look like and is it a weaker manifestation of dichroic fog?

2. Is there solvent action of some kind in the above concoction, which, however, happens in the absence of >75 g/L sulfite?

3. Am I to conclude that glycin is "energized"?

4. How can I provoke dichroic fog in this concoction?

Thank you very much for any ideas. If a similar discussion has already taken place, I'd appreciate a pointer.

Lachlan Young · May 20, 2019

Modern films (since the 60's-70's I think) have had anti-dichroic stain agents incorporated in the emulsion(s).

Rudeofus · May 20, 2019

Can you provide some context for Crawley's use of the term "energized" ? Does it mean together with a primary development agent (Crawley's FX 11 uses 1.5 g Glycin and 125 g Sodium Sulfite per liter, but also contains Phenidone) ? Does it mean highly alkaline, such as your developer formula here ?

Photo Engineer · May 20, 2019

And Haist says that anyone using 3 developing agents is doing something wrong.

In addition, modern films are generally NOT subject to dichroic fog.

PE

Pixophrenic · May 20, 2019

Rudeofus said:
Can you provide some context for Crawley's use of the term "energized" ? Does it mean together with a primary development agent (Crawley's FX 11 uses 1.5 g Glycin and 125 g Sodium Sulfite per liter, but also contains Phenidone) ? Does it mean highly alkaline, such as your developer formula here ?

This is what I am trying to understand. It does not mean highly alkaline, but I do not understand what "energizes" glycin here. In Crawley's universe glycin has always a secondary role, the main agent in his developers is always metol or phenidone. However, glycin-only developers work well, albeit slowly, at pH around 11; at a pH step lower, glycin contributes little to the actual image in a composite developer with metol, but imparts other qualities, such as, I suspect in this case synergy with sulfite as solvent.

Pixophrenic · May 20, 2019

Photo Engineer said:
And Haist says that anyone using 3 developing agents is doing something wrong.

In addition, modern films are generally NOT subject to dichroic fog.

PE

In many formulas glycin is indeed added to a developer at a pH where it practically does not work. However, such developers are known to have exceptional keeping qualities, which is attributed to glycin. Haist, BTW, offers no explanation why glycin contributes to the image in Edwal developers, which work at pH below 8. So, are you saying that no modern film can be used to "experience" dichroic fog?

Pixophrenic · May 20, 2019

Lachlan Young said:
Modern films (since the 60's-70's I think) have had anti-dichroic stain agents incorporated in the emulsion(s).

So, do you mean to say that Crawley's descriptions of glycin behavior in high sulfite are no longer valid?

Lachlan Young · May 20, 2019

Pixophrenic said:
So, do you mean to say that Crawley's descriptions of glycin behavior in high sulfite are no longer valid?

Most likely no. I'd go so far as to raise a question as to the extent to which glycin can be substituted by a suitable quantity of metol & the same results obtained. Working out what that substitution quantity would be & testing it is something I haven't got around to just yet.

Photo Engineer · May 20, 2019

Pixophrenic said:
So, do you mean to say that Crawley's descriptions of glycin behavior in high sulfite are no longer valid?

Try taking two identical photos and processing them in a developer at the same pH with and without glycin. Then compare for quality at the same contrast.

That should tell us all.

PE

Pixophrenic · May 22, 2019

Lachlan Young said:
Most likely no. I'd go so far as to raise a question as to the extent to which glycin can be substituted by a suitable quantity of metol & the same results obtained. Working out what that substitution quantity would be & testing it is something I haven't got around to just yet.

I think you are right about the results, but my initial question was if a combination of glycin and sulfite exhibits synergy in silver halide solvency? I am not talking about the end effect on grain, because I do not know. The above concoction could be made to exhibit "acutance" effects by substantially lowering the sulfite, but this is not what surprised me.

Pixophrenic · May 22, 2019

Photo Engineer said:
And Haist says that anyone using 3 developing agents is doing something wrong.

In addition, modern films are generally NOT subject to dichroic fog.

PE

Anchell and Troop attribute this saying to Bob Schwalberg: "One developing agent is best, two is okay, three is very suspect, and four the guy is definitely a jerk". This may be true, but does not apply to general situations where a developing agent is used in another capacity.

Photo Engineer · May 22, 2019

And, we have no proof from anyone except word of mouth that this type of formulation works.

When I formulated developers, I had to prove that it was better than its predecessor.

PE

KN4SMF · May 23, 2019

To me, there have always been 2 schools of thought on developers and all things photographic for that matter. There were all these obscure special formulas that were hightly touted and had its users. And then there was the Kodak formulas and standards. That said, there's one thing I know is that Kodak had scientists that had credentials as long as your arm who came from the cream of the crop of their scholastics, who came to work every day at 8am and worked, tested, retested exhaustively on every idea till that idea was either sent to the next level to go through the studies and tests all over again, and again, till (or if) they even made their way to the marketing board room.
All this said, if other formulas than Kodak were as good as Kodak, then why wasn't Kodak themselves selling it too?

MattKing · May 23, 2019

There was a robust and very interesting photographic environment in areas other than North America. Even Kodak Limited, the UK subsidiary of Eastman Kodak, was significantly different from Eastman Kodak, and that made sense because the photographic industry in the UK was very inventive and quite fiercely independent.
And of course Germany was a huge source of photographic innovation.
So don't discount something different from Kodak just because Eastman Kodak didn't sell it, especially if one of the other Kodaks did.

KN4SMF · May 23, 2019

I don't discount them at all. I too have always questioned why Kodak on Rochester offered no glycin developer products that I've ever heard of. When I think of glycin, I think of "push developers". Somehow I get the idea that they didn't believe in pushing film, but rather in film being made at a certain speed and putting their energies into batch consistency and quality control to keep it that way. Then they printed their disclaimer on the package, which was totally needless to the point of absurdity. I never ONCE in the pre- bankruptcy days ran across a Kodak Rochester that wasn't perfect. And Lord knows they got their share of my money. In my darkroom there was D76 or Microdol. Usually Microdol. For printing there was Dektol, ISB, and Kodak Fixer. I thought ACU-1 was pretty neat outside the Kodak realm. And I liked Ilfobrom F paper. But the foreign brands were not typically available in my area and when they were and I tried them, I thought they were second class. I especially disliked Agfa products. Now my point of view may give context. Maybe ignorant, or not. But they invented most things in the first place.

MattKing · May 23, 2019

KN4SMF said:
But they invented most things in the first place.

Or they bought the businesses of those who did invent them .
Don't get me wrong, I am a life-long Kodak user. I was brought up with all things Kodak - my father worked for Canadian Kodak from before I was born until his retirement when I was in my mid 20s.
But I've come to learn that there were a bunch of different Kodaks and a robust non-Kodak environment which has/had a lot going for it.
And I can assure you, there were things that went wrong with Kodak products long before the more recent debacle with 120 film and its backing paper.

Pixophrenic · May 23, 2019

Photo Engineer said:
And, we have no proof from anyone except word of mouth that this type of formulation works.

When I formulated developers, I had to prove that it was better than its predecessor.

PE

There is no need, as I think you, PE, of all people, do not doubt that a combination of a certain amount of metol and a minimal amount of sulfite, when adjusted to pH 10.3 will develop film. Taking the notion of pH out of consideration would be problematic, as some combinations of metol and sulfite would result in pH where metol is almost inactive. This particular concoction minus glycin is not my invention, it is very close to a favorite developer of Baron von Huebl, who is only known in North America for his "Huebl paste", a concentrated glycin developer. Thus it certainly worked and was used to develop countless plates in the Austrian cartographic service in the time predating D76 formulation. This developer is not particularly stable, so I added glycin. The surprise then was that it exhibited solvent action but no dichroic fog as promised by Crawley.. I am not sure that if I post some negatives you would be convinced that it works, but please let me know.

Pixophrenic · May 23, 2019

KN4SMF said:
T
All this said, if other formulas than Kodak were as good as Kodak, then why wasn't Kodak themselves selling it too?

IMHO, from a historical perspective, Eastman Kodak can be distinguished by a minimalist approach to developers. This is understandable, as in the 1920s to produce a good quality metol, hydroquinone and sulfite in large quantity was no small feat. The convoluted history of metol-sulfite developers proves that. Kodak also succeeded in driving p-aminophenol developers completely off the market, where these ruled before D-76.

Ian Grant · May 23, 2019

Photo Engineer said:
And Haist says that anyone using 3 developing agents is doing something wrong.

In addition, modern films are generally NOT subject to dichroic fog.

PE

I had a discussion about this in the early 1980's with a senior Ilford photo-chemist over a business lunch, he'd been involved in Ilford's manufacture of the Crawley formulated Paterson chemistry before the move to Mobberly. Chemistry manufacture was outsource around then. They didn't understand why Crawley sometimes used three developing agents in some of his developer, there were anomalies in the fixers as well.

Both Kodak and Ilford used 3 developing agents in commercial replenished D&P developers in the 1930's these were essentially MQ developer and a small amount of Pyrogallol was used as an Oxygen scavenger.

Pixophrenic said:
IMHO, from a historical perspective, Eastman Kodak can be distinguished by a minimalist approach to developers. This is understandable, as in the 1920s to produce a good quality metol, hydroquinone and sulfite in large quantity was no small feat. The convoluted history of metol-sulfite developers proves that. Kodak also succeeded in driving p-aminophenol developers completely off the market, where these ruled before D-76.

That last statement is contradicted by the facts. Kodak Ltd released a p-Aminophenol based developer to compete with Rodinal, Certinal (Ilford), Vytol, Azol, and a few others. Kodinol was based on GEK Mees work while at Wratten & Wainwright, somewhere I have the paper he wrote around 1908/9 about p_Aminophenol and some other developing agents.. I'm not sure when Kodinol was released probably in1930's, it was definitely available before WWII and I think production ceased in the early 1960's, that's when Ilford dropped Certinal. There was a major recession in the UK in the early 1960's which caused many companies to close or cease chemistry production, reduce ranges etc.

So quite the opposite from around 1908 onwards there were a growing number of Rodinal type developers from many manufacturers and these expanded after the release of D76. However this was mostly outside North America. Eastman Kodak never manufactured or sold Kodinol, it was a Kodak Ltd product sold in Europe, India and other British Colonies.

Ian

Photo Engineer · May 23, 2019

Pixophrenic said:
There is no need, as I think you, PE, of all people, do not doubt that a combination of a certain amount of metol and a minimal amount of sulfite, when adjusted to pH 10.3 will develop film. Taking the notion of pH out of consideration would be problematic, as some combinations of metol and sulfite would result in pH where metol is almost inactive. This particular concoction minus glycin is not my invention, it is very close to a favorite developer of Baron von Huebl, who is only known in North America for his "Huebl paste", a concentrated glycin developer. Thus it certainly worked and was used to develop countless plates in the Austrian cartographic service in the time predating D76 formulation. This developer is not particularly stable, so I added glycin. The surprise then was that it exhibited solvent action but no dichroic fog as promised by Crawley.. I am not sure that if I post some negatives you would be convinced that it works, but please let me know.

I did not say it won't work. I was saying that there is no proof that it is BETTER.

It may aid in keeping, but that is also true as Ian noted that Pyrogallol is / was used to improve keeping of some developers.

PE

Pixophrenic · May 23, 2019

Ian Grant said:
I had a discussion about this in the early 1980's with a senior Ilford photo-chemist over a business lunch, he'd been involved in Ilford's manufacture of the Crawley formulated Paterson chemistry before the move to Mobberly. Chemistry manufacture was outsource around then. They didn't understand why Crawley sometimes used three developing agents in some of his developer, there were anomalies in the fixers as well.

Both Kodak and Ilford used 3 developing agents in commercial replenished D&P developers in the 1930's these were essentially MQ developer and a small amount of Pyrogallol was used as an Oxygen scavenger.

That last statement is contradicted by the facts. Kodak Ltd released a p-Aminophenol based developer to compete with Rodinal, Certinal (Ilford), Vytol, Azol, and a few others. Kodinol was based on GEK Mees work while at Wratten & Wainwright, somewhere I have the paper he wrote around 1908/9 about p_Aminophenol and some other developing agents.. I'm not sure when Kodinol was released probably in1930's, it was definitely available before WWII and I think production ceased in the early 1960's, that's when Ilford dropped Certinal. There was a major recession in the UK in the early 1960's which caused many companies to close or cease chemistry production, reduce ranges etc.

So quite the opposite from around 1908 onwards there were a growing number of Rodinal type developers from many manufacturers and these expanded after the release of D76. However this was mostly outside North America. Eastman Kodak never manufactured or sold Kodinol, it was a Kodak Ltd product sold in Europe, India and other British Colonies.

Ian

Thanks, Ian. I stand corrected. I did mean North America with regard to p-aminophenol developers. With regard to three compounds in a Kodak developer, I suspect that in HC-110 catechol, a third developing compound, is also used as an antioxidant and it imparts its characteristic color to it.

Pixophrenic · May 23, 2019

Photo Engineer said:
I did not say it won't work. I was saying that there is no proof that it is BETTER.

It may aid in keeping, but that is also true as Ian noted that Pyrogallol is / was used to improve keeping of some developers.

PE

Thanks, this is a good note. A contemporary developer of this kind may be Moersch Finol (catechol/pyrogallol/CD2). And I was not implying that my concoction is better than anything commercial. It is not a competition, I was pointing to a chemical anomaly, and then again, possibly only with regard to Crawley's writings.

Lachlan Young · May 23, 2019

Pixophrenic said:
The surprise then was that it exhibited solvent action

How are you measuring this 'solvent action'?

Pixophrenic · May 23, 2019

Better to say how I observed it. After developing a clip upwards from six shots plus leader in 250 ml, later on there appear floating specs of metallic silver that eventually settle on the bottom. They may be filtered away, but after the next clip they would appear again.

Lachlan Young · May 23, 2019

Pixophrenic said:
Better to say how I observed it. After developing a clip upwards from six shots plus leader in 250 ml, later on there appear floating specs of metallic silver that eventually settle on the bottom. They may be filtered away, but after the next clip they would appear again.

Did you test it without the glycin & not observe the same effect? Did you analyse the image to see if it had any effect on the grain, or if it was merely reducing the threshold at which it would produce silver sludge? If I'm reading your account correctly, your working solution has about the same sulfite content as D-76 diluted 1+2 as opposed to a seriously clean-working developer like PQ Universal which has perhaps a third of that sulfite content at working strength - and even less when diluted further for film use.

If glycin induces sludge at a level below the point at which the sulfite has a useful grain solvency effect, I can see why it fell out of use...

Reading Crawley: glycin, sheen and dichroic fog

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Reading Crawley: glycin, sheen and dichroic fog

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