Modern Staining Developers - a discussion

[Raghu Kuvempunagar]

I was simply asking your views on whether the £23 bottle of alkali stop bath at 38 pence a roll would be a worthwhile purchase for you. I will take it that you do not wish to answer

Well.. you also asked me "do you think the alkali stop bath works better than a water stop for staining developed". Isn't that a question best answered by someone who has had the opportunity to use both stops extensively and compared the results? John Finch (or Peter Hogan) could be that guy.

As far as using an alkali stop for my own work is concerned, if I find a need for it, I'll formulate one based on the ideas given in Haist vol 1 chapter 12 and use it.

 

[pentaxuser]

Thanks Raghu. I now know your answer which was all I was asking

pentaxuser

 

[Alan Johnson]

That would be a very creative reading of Henry as his results show something rather different in terms of the relationship between sharpness and sufficient agitation for even density (and which agrees with the publication record).

While zero agitation will increase sharpness, it comes at a cost of extremely uneven development - once sufficient agitation is given for even development, the differences between almost all agitation methods/ intervals declines to well within the margin of error. If agitation really had meaningful effects on sharpness once over the threshold for even development, Kodak, Ilford etc would be recommending it at every turn (unlike someone like Sandy King or Barry Thornton - or for that matter Geoffrey Crawley - their analytical wherewithal is much more considerable and statistically significant - and done in concert with double blind visual/ perceptual testing) - instead, they found that it is much better to design emulsions that will react with the developer (in particular developer solvency) to deliver heightened sharpness while allowing for sufficient agitation to deliver very even development (this is really, really important when dealing with colour/ colour separations and getting even grey scales).

That 'bromide drag' you describe is essentially macro scale effects of development inhibiting agents being released from the emulsion(s) - in other words, the stuff that under adequate agitation conditions actually enhances sharpness.

I don't think Kodak and Ilford make Glycin and also Catechol based developers like FX-2 and Pyrocat /Prescysol so it is hardly surprising that they have no recommendations for them. Those that have formulated them do however suggest that reduced agitation provides increased sharpness,which conclusion is supported by some of the users on Photrio.

 

[Ian Grant]

I don't think Kodak and Ilford make Glycin and also Catechol based developers like FX-2 and Pyrocat /Prescysol so it is hardly surprising that they have no recommendations for them. Those that have formulated them do however suggest that reduced agitation provides increased sharpness,which conclusion is supported by some of the users on Photrio.

Both Ilford and Kodak (Ltd) made equivalents to FX2, they were Hyfin & HDD, as did Johnsons of Hendon. Johnsons also made many different Meritol based developer, Meritol was their proprietary fusion og Pyrocatechin and PPD. Johnsons were/are the oldest trading photographic company they supplied Fox Talbot and synthesised raw photo-chmicals up until the early 1960s including B&W and Colour developing agents, and colour couplers.

Gentlemen and Ladies (because who can say for sure with screen names),
We have received at least one suggestion that, as this thread has wandered significantly from anything related to the thread title, shouldn't most of the wanderings be in a different thread all their own.
Would anyone like to start that separate thread? We could put complementary links in both threads.
If there is a clear demarcation somewhere, we could probably start that thread with an edited version of an existing post here, and move everything after that there.

It might be better that you split the thread from post #279, to maybe one titled "A discussion of Modern Staining Developers"

Ian

 

[MattKing]

The creation of this thread is now complete, and has been effected by splitting off posts. from the pre-existing discussion regarding ZoneImaging.
And now back to our regularly scheduled program (said in my best BBC announcer voice).

 

[Lachlan Young]

I don't think Kodak and Ilford make Glycin and also Catechol based developers like FX-2 and Pyrocat /Prescysol

The available publication record/ patents etc makes it clear that they major research labs worked with all of these very extensively - and they seem to have been deeply researched in particular within basic emulsion research for colour materials. It is better to assume that the research labs looked at a given developer ingredient and dismissed it - then ask yourself why that might have been (almost always not going to be an economic reason - the scale of the market at the time would not have been a barrier to synthesis - in fact, if it was good enough they'd have worked very intensely to make it at scale and at lower cost - case-in-point: Phenidone).

Catechol has intermittently appeared in HC-110 as well - and Glycin in various uses by Ilford, Kodak, Agfa, M&B etc, etc, etc - but there seems to be a point somewhere 1955-70 where the industry collectively catches on to HQMS (and the commercial sensitivity of this knowledge - hence the rather piecemeal and haphazard disclosure of it over the years) and increasingly moves its attention away from the needlessly exotic to a far more remarkable, useful and commonplace (at least in terms of in-situ formation) component instead.

Agitation and its effects were very heavily studied microdensitometrically (and via perceptual testing) by the major research labs - with the pretty clear outcome that emulsion design was going to more consistently, controllably and effectively deliver better sharpness, especially as it opened up the ability to use more solvent developers to improve granularity and sharpness simultaneously - what has happened is that over the last 20-25 years various individuals have made names/ cults of themselves via rehashing old observations from the 1920s/30s (at the latest) that originally began to disintegrate when subjected to the level of analytical wherewithal the major research labs had at their disposal - nevermind the advent of the DIR coupler & consequent exploration of how that behaviour could be modelled within emulsions that were silver only (i.e. no dye couplers).

have you done tests to compare extreme minimal agitation with Kodak/Ilford recommended agitation? and in your experience have you found that there are no meaningful effects on sharpness?

All that I saw was results that could be achieved, equalled or bettered by more direct process control means (i.e. a reduction in process time) to match density - if there was sufficient agitation to get even development.

Sharpness manipulation to the level that the various minimal agitation claimants/ profiteers suggest is actually much more about lowering overall density to the point that a given neg will print on a much harder grade of paper - which will inherently increase visual microcontrast/ sharpness (this is not new knowledge). You can exceed their claimed outcomes to the point that your result will look (to use the SPSE handbook words) 'Masky' or 'dupey' with excessively enhanced edge effects via quite conventional means too (hint: MTFs add up).

 

[john_s]

....

Catechol has intermittently appeared in HC-110 as well - and Glycin in various uses by Ilford, Kodak, Agfa, M&B etc, etc, etc - but there seems to be a point somewhere 1955-70 where the industry collectively catches on to HQMS (and the commercial sensitivity of this knowledge - hence the rather piecemeal and haphazard disclosure of it over the years) and increasingly moves its attention away from the needlessly exotic to a far more remarkable, useful and commonplace (at least in terms of in-situ formation) component instead.

Kodak Alaris current MSDS for HC-110 shows Catechol as an ingredient (under an alternative name, 1,2-Benzenediol)

 

[Raghu Kuvempunagar]

Kodak Alaris current MSDS for HC-110 shows Catechol as an ingredient (under an alternative name, 1,2-Benzenediol)

But it is present in too little a weight percent (0.1 - < 1) to play a role as a significant developing agent once the concentrate is diluted into working solution. It was suggested, IIRC, by @Pixophrenic in a previous discussion on this subject that Catechol plays the role of a preservative in HC-110.

 

[Ian Grant]

But it is present in too little a weight percent (0.1 - < 1) to play a role as a significant developing agent once the concentrate is diluted into working solution. It was suggested, IIRC, by @Pixophrenic in a previous discussion on this subject that Catechol plays the role of a preservative in HC-110.

Both Ilford and Kodak used low levels of Pyrogallol in pre WWII MQ deep tank developers as an Oxygen scavenger, because of the high level of Sulphite there's no staining.

Ian

 

[Alan Johnson]

Lachlan, you say that old observations (I presume referring to effect of reduced agitation) began to disintegrate when subject to the level of analytical wherewithal that major research labs had.
Why is this not mentioned in The Theory of The Photographic Process, Mees and James, or in Photographic Processing Chemistry, LFA Mason?
Can you cite one paper to support your claim?

 

[Ian Grant]

When Haist and Mason wrote their books stand development was largely a newspaper darkroom technique for push processing underexposed films.

Mason does state that care must be taken with High Acutance Developers and agitation, too much nullifying the effects of localised exhaustion, too little reducing the gamma. The instruction sheet for Hyfin warned about excessive agitation, I can't find that sheet at the moment, but the recommended agitation was less than with other developers.

The idea of using these developers at much greater dilutions only realty tool off via the Internet. I'd add Rodinal here as well, alongside Pyrocat and 510 Pyro.

Ian

 

[Lachlan Young]

Lachlan, you say that old observations (I presume referring to effect of reduced agitation) began to disintegrate when subject to the level of analytical wherewithal that major research labs had.
Why is this not mentioned in The Theory of The Photographic Process, Mees and James, or in Photographic Processing Chemistry, LFA Mason?
Can you cite one paper to support your claim?

The SPSE handbook (which is published about the time that C-41 and E-6 are deep in R&D - and thus highly commercially sensitive) discusses agitation and sharpness effects in considerable detail, making the point that evenness of development negates the highest sharpness effects that can be achieved through zero agitation (there's even MTFs of 1+10 DK-50 used without agitation). However, this is not the whole picture - and the effects of iodide placement are hinted at in the handbook and elsewhere at that time. If you read Ron's commentary on emulsion design, you'll see that building emulsions to have the right degree of developer solvency sensitivity to enhance sharpness via developer solvency acting on iodide (and a lesser extent bromide) was brought into action essentially from the point that it was released it had an effect (1950s +/-) and controlled crystal growth became ever more achievable. By the time you start to find materials/ theses from Kodak or Ilford people a decade or two after the first publication of the SPSE handbook (which is mainly the disclosable science of 1966-69 rather than a few years later), you start to get specific lines about developer solvency causing release of what are defined as 'development inhibition agents' from the emulsions - which is a desirable outcome - as opposed to extremely non-solvent developers. While it isn't difficult to find their published/ patented work on these matters with appropriate search terms, I'm not overly desperate to simply hand out the names of the more recently retired Ilford and Kodak scientists involved as I really don't want to be responsible for people with agitated bees in their bonnet tracking them down and stuffing their inboxes with demands that they prove themselves against the various amateur-hour individuals who are rehashing stuff that was questionable with primitive emulsions and pointless with highly controlled and intentionally engineered ones. You can find a surprising amount in the usual places, plus looking in certain institutions' thesis repositories (hint, you might find important information from the Gilman & Willis era that builds on disclosures from the Henn/ Haist era).

When Haist and Mason wrote their books stand development was largely a newspaper darkroom technique for push processing underexposed films.

It probably worked better because those older emulsions had buried (or more buried) iodide. And it also tends to get forgotten that even the thickness of even the 'thin' Schleussner/ Adox/ Efke emulsions was thicker than many 400 speed emulsions today. Getting DIR-like effects from conventional silver halide emulsions seems to have been an explicit aim of Delta technology - the other consequence of Delta seems to have been that it allowed for a thin single layer emulsion to be used even for faster films (which opens up some interesting questions about contexts for colour materials - and there are hints that Fuji may have exploited this with their seemingly remarkably similar Epitaxial Sigma Crystal technology in some late-analogue era materials).

Mason does state that care must be taken with High Acutance Developers and agitation, too much nullifying the effects of localised exhaustion, too little reducing the gamma. The instruction sheet for Hyfin warned about excessive agitation, I can't find that sheet at the moment, but the recommended agitation was less than with other developers.

This seems to have been what the literature demonstrates the research labs were trying to navigate a way around - but what they seem to have found was getting the iodide close enough to the surface (in the 'shell') for the solvency (potentially even quite low solvency) to access it, a balance of carefully chosen grain sizes and relative accessibility of those structures to the developer - and that the developer should ideally have some degree of solvency - with developing agent choices ideally being able help enhance sharpness in ways that were controllable at will (hence PQ in preference to M alone in preference to MQ in descending order of desirability for developing agent caused inhibition/ adjacency effects) and pH being balanced either to borate buffering range for fine grain or carbonate/ bicarbonate for maximum sharpness. From what I can tell, Ilford, Kodak - and presumably all the others - seem to have picked up on this around the same time, with published materials starting to dribble out more noticeably from the mid 70s onwards.

A bit of anecdata here: I've found that full strength ID-11 seems to actually make noticeably seemingly visually sharper 4x5 negs (i.e. low frequency sharpness effects) with current issue Ilford materials - probably because of the stronger level of developer access to the emulsions releasing more of iodide placed for exactly that purpose.

 

[Alan Johnson]

It's just possible that Lachlan is not impressed by by amateur tests and since since all the tests on Pyro and Pyrocat have been done by amateurs they have no chance.
Anyhow, my thread "Scans retain developer properties" does suggest that Pyrocat HD might have an edge.
Sorry I cannot link to it directly.

 

[MattKing]

Anyhow, my thread "Scans retain developer properties" does suggest that Pyrocat HD might have an edge.
Sorry I cannot link to it directly.

I can: https://www.photrio.com/forum/threads/scans-retain-developer-properties.156243/

 

[Ian Grant]

As I said at the time I agree with your findings there. That's been my experience from 18 years of using Pyrocat HD

Someone has asked me to write something detailed about staining developers, their history through to modern use, there were two articles published in the 1940s on Modern uses of Pyro developers. Ilford published a Phenidone Pyrogallol formula in the 1940s and if you switched from using Pyrogallol to Pyrocatechin it's close to a concentrated form of Pyrocat.

It's not a co-incidence that LP Clerc's seminal mid to late 1930s book "Photography" adds to the title "Theory and Practice". Sometime experimental practice comes before the Theory, other times Theory informs the experimental work, it's a two-way dialogue.

There was a time 5 decades ago when I could understand and explain what was going on at the molecular and subatomic level of complex biochemical reactions, when I looked at the fixing process it was easy to understand the intricate and convoluted series of intermediary equilibrium complexes formed.

With developers Ilford's research in the 1950s was at the cutting edge, they were the first company to analyse developer exhaustion, in their case it was a PQ version of D76/ID-11. Unlike D76/ID-11 a PQ version doesn't collapse due to Bromide build up, as Phenidone is not inhibited by Bromide build up like Metol. So they released Autophen with two different replenishers for top up or bleed, and one lab kept a line going for years, just replenishing. Kodak learnt from this for Xtol which was fine-tuned to get the best from Tmax emulsions, and be self replenishing.

But moving away from Replenished developers, sometimes the practice and cumulative experience is worth far more than theory. And more importantly it's the results that count.

Ian

 

[john_s]

....... various amateur-hour individuals who are rehashing stuff that was questionable with primitive emulsions and pointless with highly controlled and intentionally engineered ones......

Funny that I have better results by not following the manufacturers' instructions (exposure and development times, agitation).

Probably something wrong with me.

 

[Lachlan Young]

It's just possible that Lachlan is not impressed by by amateur tests and since since all the tests on Pyro and Pyrocat have been done by amateurs they have no chance.

No, the very short answer is that I've had hands-on experience with outcomes from various staining and very low solvency developers & wanted to know why they didn't seem to produce better results (in terms of image content capacity/ transmission) than conventional processes with good process control did. Or to put it another way, why the major manufacturers' developers seemed to deliver better results (once you zero out the variances for your own aim contrast etc) than the various staining developers that have fandoms/ hinterlands that seem heavily populated with reflexive contrarians desperately concerned about silver content (rather than curve shape - which is the bit that actually has an impact) and the like. It quickly became apparent to me that the manufacturers' R&D was streets ahead of whatever sort of poorly controlled/ designed 'experiments' were being done to try and claim that the big manufacturers were essentially lying to their customers about everything (they aren't - it's just that they sometimes were terrible at communicating why certain changes happened and often unwilling to challenge the nonsense that appeared in the media/ online for fear of revealing commercially sensitive knowledge) and that often the bigger problems came about in terms of R&D attempting to explain adequately to sales/ marketing what was important about the product & should thus be explained in the documentation.

Funny that I have better results by not following the manufacturers' instructions (exposure and development times).

None of the manufacturers say that they're anything other than starting points - the whole point of the standards used is that they give a meaningful set of comparisons to work from. It doesn't help that for various cultural reasons there are several different aim contrasts preferred by different manufacturers for their recommended processing times (as opposed to the ISO aim contrast).

 

[Raghu Kuvempunagar]

All that I saw was results that could be achieved, equalled or bettered by more direct process control means (i.e. a reduction in process time) to match density - if there was sufficient agitation to get even development.

A bit of anecdata here: I've found that full strength ID-11 seems to actually make noticeably seemingly visually sharper 4x5 negs (i.e. low frequency sharpness effects) with current issue Ilford materials - probably because of the stronger level of developer access to the emulsions releasing more of iodide placed for exactly that purpose.

Thank you.

The SPSE handbook (which is published about the time that C-41 and E-6 are deep in R&D - and thus highly commercially sensitive) discusses agitation and sharpness effects in considerable detail, making the point that evenness of development negates the highest sharpness effects that can be achieved through zero agitation (there's even MTFs of 1+10 DK-50 used without agitation).

Was hoping to find a discussion on minimal agitation techniques and/or diluted staining developers in the SPSE handbook but all I could find was the following:

Section 17.5.2 page 956: "developing with a dilute developer without agitation accentuates the [adjacency] effect."

Section 9.5.2: "development should therefore be under relatively still conditions, because agitation minimizes the [adjacency] effect."

Further, "adjacency effects disappear at full development, but normally one does not develop fully."

And "the same factors that promote adjacency and interimage effects often make uniform processing over the area of the film more difficult."

None of this is new information to many here.

 

[Ian Grant]

Thank you.



Was hoping to find a discussion on minimal agitation techniques and/or diluted staining developers in the SPSE handbook but all I could find was the following:

Section 17.5.2 page 956: "developing with a dilute developer without agitation accentuates the [adjacency] effect."

Section 9.5.2: "development should therefore be under relatively still conditions, because agitation minimizes the [adjacency] effect."

Further, "adjacency effects disappear at full development, but normally one does not develop fully."

And "the same factors that promote adjacency and interimage effects often make uniform processing over the area of the film more difficult."

None of this is new information to many here.

There is one other factor not mentioned, over exposure can negate edge effects. Adox and EFKE warned about over exposure.

Ian

 

[Lachlan Young]

Was hoping to find a discussion on minimal agitation techniques and/or diluted staining developers

The most likely answer is that the agitation problems fall under those outlined above (i.e. if they're getting truly even development, then it's not 'minimum agitation'), dilution has been tested to death in developer series (you can find papers that indicate that the major research labs had more than outflanked anyone going on about highly diluted developing agents - Crawley wasn't being original, merely rehashing research disclosures of the mid-late 50s without actually quite getting 2+2 to equal 4 over time) - and with the best will in the world, the various staining developers that have more-or-less-usable function aren't any sharper than something like dilute Perceptol (PQ can potentially go sharper than that) with worse granularity overall. And as for staining developers, don't assume that absence in the SPSE handbook means conspiracy - all the available circumstantial evidence suggests the opposite - they had been found irrelevant and largely only useful in situations for which the tanning of unhardened gelatin was needed - to quote from Lee's patent (3,453,109) "Still another object is to provide a tanning development method wherein the staining propensities of conventional quinone-producing developing agents are avoided. " and "This invention also avoids the staining propensity of the well-known tanning agents which produce quinones to cause the localized hardening of the gelatin. These quinones cause highly colored stain on film, paper, hands, equipment, etc. " which altogether strongly suggests that the effects of those stains/ couplers had been thoroughly investigated and found to be troublesome for various reasons (there was a recent case-in-point involving Fomapan and Pyrocat) - if they produced genuinely useful imagewise effects that couldn't otherwise be better engineered into the emulsions there's little doubt that they'd have received the same attention PPD did. I have heard of a dihydroxybenzene being used experimentally as a non-persistent coupler - but that was far more grounded in resolving an actual scientific problem that could lead to a granularity/ sharpness improvement rather than creating a marketing opportunity that'll merely stain your film without adding anything that process controls and Beutler (or Ilfosol 3) can already do or better.

 

[ags2mikon]

There are all kinds of developers out there. When someone claims the developer he champions has magical properties, ask to see his prints.

Just like church. Some of us are holy rodinal church members others are first xtol, others are church of perceptol and some of us are agnostic and will use whatever works the best at the moment.

 

[Raghu Kuvempunagar]

the various staining developers that have more-or-less-usable function aren't any sharper than something like dilute Perceptol (PQ can potentially go sharper than that) with worse granularity overall.

merely stain your film without adding anything that process controls and Beutler (or Ilfosol 3) can already do or better.

If I understood the discussion on FX-1 and Pyrocat-HD here, it was not claimed that Pyrocat-HD is much sharper than FX-1 or Beutler:

"In a metol developer it is hard to beat FX-1 for absolute sharpness. Beutler should come close. FX-2 is almost as sharp and provides nicer tonal renditions."

"For a pyro type developer PMK, Pyrocat-HD and WD2D+ give excellent sharpness with good tonal rendition and much finer grain (from grain masking by the stain) than Rodianl or FX-1."

I think the claim made, implicitly, was that for an acutance developer, Pyrocat-HD gives a good balance of tonality, fine grain and acutance. Isn't this what long terms users of Pyrocat-HD have also been saying based on their experience?

If dilute Perceptol gives the same or better balance of tonality, fine grain and acutance than Pyrocat-HD, then it is definitely worth considering. What is the dilution you recommend?

 

[john_s]

Then there's the effect of stained negatives with VC papers, perhaps not investigated much by the real professionals because VC papers took over the market rather later then when most investigation was taking place.

The stain is often a help, sometimes a hindrance.

 

[Lachlan Young]

If I understood the discussion on FX-1 and Pyrocat-HD here, it was not claimed that Pyrocat-HD is much sharper than FX-1 or Beutler:

"In a metol developer it is hard to beat FX-1 for absolute sharpness. Beutler should come close. FX-2 is almost as sharp and provides nicer tonal renditions."

"For a pyro type developer PMK, Pyrocat-HD and WD2D+ give excellent sharpness with good tonal rendition and much finer grain (from grain masking by the stain) than Rodianl or FX-1."

I think the claim made, implicitly, was that for an acutance developer, Pyrocat-HD gives a good balance of tonality, fine grain and acutance. Isn't this what long terms users of Pyrocat-HD have also been saying based on their experience?

If dilute Perceptol gives the same or better balance of tonality, fine grain and acutance than Pyrocat-HD, then it is definitely worth considering. What is the dilution you recommend?

The point is that none of them have magical mystery effects that can't be achieved by simpler & more direct means. I have seen evidence that Kodak (and by inference of the nature of the disclosure, Ilford and everyone else had likely done the same) seem to have completely outflanked FX-1's formulation and then MTF, granularity and perceptually tested the results - from what I could tell from the results, it was significantly worse in visual granularity, high frequency sharpness was no better than D-76, and whatever low frequency benefits there were could probably be more usefully achieved through emulsion adjustment for interaction with D-76. PQ seems to be able to deliver better sharpness at higher frequencies (in comparison) - and quite frankly, it isn't hard to deliver better high frequency detail rendering than Rodinal, especially if you have some degree of development inhibition going on. At best, these staining developers may be a fragment better in one aspect, but significantly worse in others, than D-76 (and about equivalent to 1+2 or 1+3 diluted Perceptol/ Microdol-X - indeed, in the diluted form, there seems to be some evidence that Henn felt Microdol-X was a low pH Rodinal equivalent) - and overall worse than a well designed PQ type developer could be. Ilfosol 3 (as opposed to Microphen or DD-X) seems aimed at this. However, this obsession with sharpness via development is only a fragment (a pretty insignificant one) of overall image information capacity/ transmission - and a lot of it belies a terrible lack of basic process controls among those who preach a relentless stream of things-they-read-about-in-Ansel-Adams-and-similar-weekender-oriented-tech-manuals.

 

[Sidd]

Well this is supposed to be DiXactol Ultra

DiXactol Ultra (type) Developer

Stock Solution A
Sodium Sulphite 3 g
Glycin 2 g
Pyrocatechin 10 g
Phenidone 0.2 g
Sodium Metabisulphite 5 g
Water to 100 ml

Stock Solution B
Sodium Hydroxide 10 g
Distilled water to make 100 ml


To make a standard working solution, mix 1 part A with 1 part B with 100 parts water.
Develop: 6 mins @ 20ºC

So Part A is acidic like Pyrocat, change Part B to Potassium Carbonate and who knows what it's called . . . . . . . .

The Sodium Sulphite in Part A is completely unnecessary, the Metabisulphite forms Sulphite in an Alkali solution once mixed

Probably the sulphite is required to dissolve Glycin, I have read somewhere in this regard.

I am new to Photrio, and this is my first post, I am hoping earnestly you people will accept me to participate in the discussions on developers and other things.