Reading Crawley: glycin, sheen and dichroic fog

Pixophrenic · May 24, 2019

Lachlan Young said:
<snip>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...

I looked up some literature and I think it is incorrect to call this "incipient sludge". In historical terms, actual developer sludge is much more than finely divided silver. I found that Champlin, not that he is likely to serve as an authority to you, also warns against dichroic fog if excess sulfite is used in a typical glycin-only developer (glycin-sulfite-carbonate, i.e. Kodak D78) and says that sulfite can be added in only as much as the weight of glycin. This is a far stricter requirement than Crawley's. Now, if it is true that the improvement of emulsions made them resist silver complexing with the surface (which in my understanding produced the dichroic mirror), today one should be able to use glycin and sulfite in reckless abandon and not get the dichroic fog. I did not encounter anyone online or otherwise complaining of dichroic fog in Edwal 12, which has 3 times the sulfite I used and 10 times the glycin. I was never compelled to try Sease developers from which it is apparently derived.

On the second part of your question, as I said, this developer is lifted from a book of Baron von Huebl of 1918, and I did test it separately several months ago. From the metol concentration it is more like D-76 1:1, but its sulfite concentration is that of a tank developer like DK50, as well as the pH which is close to that of a tank developer. I did not analyze the image yet, but perhaps I should now do a more accurate comparison and use a microscope. Asking the question I expected to get the answer that sulfite-glycin solvent synergy is common knowledge, but it appears to be not that simple, since the evolution of the emulsions is involved.

Ian Grant · May 24, 2019

When I first began making images seriously in the late 1960's the issue of Dichroic fogging was mentioned frequently in magazines and a few books, however all mentions referred to it occurring with Kodak films.

Now at that time some Kodak professional developer data-sheets (that came in the box) gave different development times and recommended film speeds for Tri-X depending on where the emulsion was made and coated, the US, Canada, or the UK. Slower films it seems weren't an issue. Now these differences in Tri-X were down to the gelatin supplies.

Ron - PE has told us a few times Eastman Kodak began having issues with their Gelatin supplies due to radio active contamination from the fall out from US atmospheric nuclear tests, this lead to special techniques to "clean" the gelatin. In the long term it actually brought very much tighter control to emulsion manufacture and eliminated differences between emulsion manufacture at their coating plants.

I know that Kodak dropped Kodatol, (DK20) because of Dichroic fog and replaced it with of Microdol, but then later also had big issues in the US with Dichroic fog and Microdol so replaced it with Microdol-X. There wasn't the same issue here in the UK and it was 2 or 3 years before Kodak Ltd switched to making Microdol-X.

Ian

Tom Kershaw · May 24, 2019

In terms of dichroic fog, I've heard it suggested that the Perceptol substitute formula, while being suitable for ILFORD films may cause issues with Kodak products, and that this may be possibly be related to why ILFORD recommends against pre-soaking.

Tom

Ian Grant · May 24, 2019

Tom Kershaw said:
In terms of dichroic fog, I've heard it suggested that the Perceptol substitute formula, while being suitable for ILFORD films may cause issues with Kodak products, and that this may be possibly be related to why ILFORD recommends against pre-soaking.

Tom

I've heard that numerous times but always anecdotal and never with any evidence to back it up, and most likely no practical experience in terms of seeing it.

Back in the 1970's I was having issues with Dichroic fogging but this was with an applied process and our own emulsion, upping the Sulphite in the dilute developer completely cured the issue.

Ian

Tom Kershaw · May 24, 2019

I've never seen dichroic fog on any film processed by myself. ILFORD or Kodak, but then I've only been processing film since 2002/03. I haven't used Perceptol or the substitute for a long time but recall excellent results with Pan F Plus, diluted 1+3.

Tom

Lachlan Young · May 24, 2019

Ian Grant said:
I know that Kodak dropped Kodatol, (DK20) because of Dichroic fog

You wouldn't happen to have a source for that? The Henn & Crabtree articles on D-23/25 & Microdol refer to a 'scumming in deep tanks' problem in heavily used DK-20, but not to dichroic fog.

Photo Engineer · May 24, 2019

All manufacturers had problems with radiation when atmospheric nuclear tests were still in vogue. This was not confined to Ek. Dichroic fog was present in many films, but I only saw it once (AFAIK) back in the '50s on some film or other. I don't remember the film nor the conditions.

In addition, Lachlan has the correct explanation for the change referenced.

PE

KN4SMF · May 24, 2019

In this thread I saw DK-20 mentioned. Having never heard of it and curious I searched it where some thread somewhere said it was a high contrast developer and later replaced by Microdol. That in itself sent up red flags because Microdol isn't a high contrast developer. So I found the formula posted below and despite my limited knowledge of chemistry, this sure as heck doesn't look like a high contrast developer at all. What's going on here?
Kodak DK-20
High contrast film developer
Water 125F/52C 750 ml
Metol 5 g
Sodium Sulfite (anhydrous) 100 g
Balanced Alkali 2 g
Potassium Thiocyanate 1 g
Potassium Bromide 0.5 g
Cold water to make 1000 ml
Mixing Instructions: Add chemicals in specified sequence.
Dilution: Use undiluted.
Usage: Starting point dev time: 20 mins (tank), 16 mins (tray)

Ian Grant · May 25, 2019

Kodak list DK20" as an "Extra Fine Grain Developer" in numerous publications, it was sold prepackaged as Kodatol or DK20. Most errors in formulae come from the Photo Lab Index publications which are the most unreliable source available but unfortunately used as a primary reference for most other US publications. Only manufacturers published formulae can be a primary source.

Lachlan Young said:
You wouldn't happen to have a source for that? The Henn & Crabtree articles on D-23/25 & Microdol refer to a 'scumming in deep tanks' problem in heavily used DK-20, but not to dichroic fog.

There have been many references to DK20 and Dichroic fog over the years it'll be in books I have, Mason page 148 for instance 2nd Ed. Crawley mentions Dichroic fog in deep tank use with developers like DK20 as the developer becoming exhausted, that would be with replenishment. It's assumed Ilford ID-48 was similar to DK20 but the formula has never been published.

The following text from the Ilford "Technical Information Sheet P10 - Fine grain Development" states:
Developers containing silver halide solvents: Certain fine grain formulae contain silver halide solvents such as hypo and thiocyanate. These depend for their action on the fact that some of the silver dissolved during development is redeposited in a very fine form to reinforce the final image. Ilford ID-48 Developer is of this class.

P10 is suggesting adding 40g Ammonium Chloride to a litre of working strength ID-11 (at that time 1965 Kodak and Ilford didn't recommend using D76/ID-11 1+1 or 1+3), alternately 10g of Ammonium Chloride added to a litre of ID-2 at 1+2, Developing times double and 50% extra exposure is needed. This is 4 years before Ilford released Perceptol but shows the way Ilford research was thinking.

One problem with a replenished Metol based solvent developer is Bromide build up, but add to that the Silver, DK20 recommended replenishment was on a top up basis not bleed so faster Bromide build up and collapse. Interesting the 1944 Kodak Formulary gives no limits to replenishment a 1949 Kodak Chemicals and Formulae states replenish until 25% of the original developer has been replaced.

Ian

Ian Grant · May 25, 2019

A quick check and almost all references to DK-20 after about 1953/4 mention the Dichroic fog issue with higher speed films like Tri-X and HP3. Microdol was released around 1951 in the UK and its use was recommended instead of DK-20 by Kodak. Kodak adverts claim lower fog levels, cleaner working no sludge in hard water areas and extremely fine grain comparable to PPD fine grain developers.

Later Kodak publications like Kodak J-1 list DK-20 as one of the developers no longer in general use, and adds "that some of these developers may not yield satisfactory results with modern films".

Ian

Lachlan Young · May 25, 2019

Ian Grant said:
A quick check and almost all references to DK-20 after about 1953/4 mention the Dichroic fog issue with higher speed films like Tri-X and HP3. Microdol was released around 1951 in the UK and its use was recommended instead of DK-20 by Kodak. Kodak adverts claim lower fog levels, cleaner working no sludge in hard water areas and extremely fine grain comparable to PPD fine grain developers.

Later Kodak publications like Kodak J-1 list DK-20 as one of the developers no longer in general use, and adds "that some of these developers may not yield satisfactory results with modern films".

Ian

Cheers for these references - I reckoned that if Microdol could cause dichroic fog without the addition of chlororesorcinol as an anti-stain agent, then there was no reason the similarly highly solvent DK-20 should be any different - the main question I had was over the tendency of so many sources no not give useful references to manufacturer's advice/ data & how it changed over the years. The critical point seems to be the advent of the new higher speed films in the early 50's - which, as you say, post-dates the advent of DK-20 & Microdol.

Ian Grant said:
Interesting the 1944 Kodak Formulary gives no limits to replenishment a 1949 Kodak Chemicals and Formulae states replenish until 25% of the original developer has been replaced.

That's a surprisingly low replenishment limit - and it certainly shows the extent to which there was ongoing research & feedback going on - and why Microdol came about!

For what it's worth, apparently David Douglas Duncan used Super-XX in replenished DK-20 for his iconic 'This Is War' book/ concurrent Life Magazine stories.

Ian Grant · May 25, 2019

Lachlan Young said:
Cheers for these references - I reckoned that if Microdol could cause dichroic fog without the addition of chlororesorcinol as an anti-stain agent, then there was no reason the similarly highly solvent DK-20 should be any different - the main question I had was over the tendency of so many sources no not give useful references to manufacturer's advice/ data & how it changed over the years. The critical point seems to be the advent of the new higher speed films in the early 50's - which, as you say, post-dates the advent of DK-20 & Microdol.

That's a surprisingly low replenishment limit - and it certainly shows the extent to which there was ongoing research & feedback going on - and why Microdol came about!

For what it's worth, apparently David Douglas Duncan used Super-XX in replenished DK-20 for his iconic 'This Is War' book/ concurrent Life Magazine stories.

Well in Kodak J-1 the historic information on DK-20 suggests the need for bleed replenishment (although it doesn't use that term). I'd forgotten that Tri-X production had halted during WWII, so Kodak's fastest film was Supper-XX at the time Kodak switched from DK-20 to Microdol. DK.20 was one of the recommended developers for Tri-X in 1939/40.

Microdol came from the same Henn and Crabtree research as DK20 introduced in 1938, I have the pre-WWII paper somewhere, it's about a decade since I looked at it. 1951 was the year Kodak started to have issues with radioactive fallout from atmospheric Nuclear tests, there's plenty on-line about how Kodak detected and knew about the fallout which was kept from the public.

While Ron - PE states that all film companies had issues with radiation from the fallout this was of far greater magnitude at Eastman Kodak in the early 1950's. That can be seen in the maps showing the levels of background radiation in the US. Ultimately that had an effect on the Bovine Gelatin in North America.

I guess the question would be why newer versions of Eastman Kodak films started suffering Dichroic fogging in Microdol, this would be the early days of washed de-activated gelatin for emulsions. Long before I first read anything by Crawley there were warnings in books and magazines about Dichroic fog and predominantly Kodak films. An assumption would be that the Gelatins used by Ilford and Kodak were treated differently.

It's worth noting that when I did research into Monobaths in the late 1970's Thiosulphate or Thiocyanate in the monobath would cause Dichroic fogging when the balance of the formula was changed in certain ways.

Ian

Photo Engineer · May 25, 2019

The use of 40 g/l of Ammonium Chloride / Liter is a HUGE level of solvent and could cause serious problems. There are two solvents at play here, neither to be dismissed at this level.

Kodak used 2 types of gelatin for making film. In the '20s and up to the '40s (all dates approximate), Kodak used oxidized purified gelatin, where earlier they had used straight gelatin with no special treatment. All of these were noodle washed. After the '40s, they used phthalated gelatin in the pptn to facilitate washing. In the '60s, when diafiltration and reverse osmosis became popular, the emulsions were filtered as a wash step.

During this same period, the emulsions underwent major changes in addenda that improve reciprocity and latent image keeping along with plain keeping. One of the additional effects was to reduce or eliminate the dichroic fog in high solvent developers. This was a must, especially for MP processes which used high solvent developers for reversal processing.

PE

Ian Grant · May 25, 2019

Photo Engineer said:
The use of 40 g/l of Ammonium Chloride / Liter is a HUGE level of solvent and could cause serious problems. There are two solvents at play here, neither to be dismissed at this level.

PE

Well Microdol, Microdol-X, and Perceptol , all use a high level of Sodium Chloride, the P10 technical sheet is similar to some of the Kodak data like Henn & Crabtree's notes on D23, D25, & DK20, more about indicating possibilities.

Ammonia salts. can be used to achieve great warmth in Warm tone developers and this is down to finer grain, but it's not used commercially. There's issues with Ammonia fumes.

Ian

Photo Engineer · May 25, 2019

Sodium Chloride yes, as only one ion is a solvent but Ammonium Chloride is a double whammy! And to boot, the developer will smell bad due to released Ammonia, and will also vary in effect rapidly due to the Ammonia loss into the air and the resulting pH shift.

PE

Pixophrenic · May 27, 2019

I am glad that my questions generated such an informative thread, so here is something in lieu of an accurate comparison, plus and minus glycin.
Half a liter of the developer mentioned in the original post was prepared omitting glycin. It was left overnight in a 500-ml beer bottle with a latched cap, and next day split into two portions of 250 ml. One was supplemented with glycin, introduced as a 5% solution in 5% sodium sulfite. A clip featuring the same subject with bracketed exposure was produced, including also a Stouffer wedge shot on a lightbox with two stops overexposure. Both clips were developed for 6.5 minutes at 20 C, agitation 5 seconds every minute, followed by citro stop and Ilford Rapid fixer, eco wash and Photo Flo rinse. The results are on attached images and I think the effect of glycin addition is fairly obvious. As you can see, despite as accurate as possible reproduction of conditions, the images, although not materially different, are slightly weaker with glycin addition. As much as can be seen in my imperfect reproduction, glycin does not produce substantially smaller grain, but makes it sharper. The change in density cannot be explained, IMO, by the fact that glycin is an acid, and its addition shifts the developer pH from 10.4 to 10.3 in this batch. And finally, no trace of dichroic fog, although I think that fogged leader in the case of glycin addition displays what may pass for sheen, but I do not know how to reproduce it.

Rudeofus · May 27, 2019

One thing which is striking is shadow detail: it looks like it's the same, despite the vastly different contrast.

Alan Johnson · May 27, 2019

I believe Crawley used the word "sheen" to describe the appearance of the dry dichroic fog, as here:
https://www.issuu.com/piticu/docs/photographic_chemicals_and_solution/259

Pixophrenic · May 28, 2019

Alan Johnson said:
I believe Crawley used the word "sheen" to describe the appearance of the dry dichroic fog, as here:
https://www.issuu.com/piticu/docs/photographic_chemicals_and_solution/259

Thank you, Alan, for the reference. It contains one of the best treatments of the issue of dichroic fog I have seen so far. It follows from the text that fixer is as much to blame as the developer. In fact this book separates surface silver deposition produced by developer and that by fixer, and from silver precipitation in the emulsion depth which produces stain. However, I think sheen is the description of a weaker version of surface dichroic fog, which is not truly dichroic, but only seen in reflected light. Also, it occurred to me that traditional glycin-only developers, working at pH 11 or above (as FX2 and D-78) would be prone to produce dichroic fog in the fixer, as strongly alkaline developer is carried over in thick emulsion into a partially spent fixer. It is not, IMO, a specific property of glycin, but rather its developer being very alkaline.

Reading Crawley: glycin, sheen and dichroic fog

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