Who is actually making new formulas? What have you made!?

removed account4 · Jan 17, 2021

earlz said:
I'm currently testing a developer that might give similar results and tray life without the hard to source (internationally) glycin component

Have fun with that,
I don't keep my Sumatranol130 in an open tray but in a big dollar store tupperware vat .... I use it to process film and make prints, then pour it back in the vat. I develop c41/e6 with it (so the film is b/w but stained from the coffee to mask the orange or yellow masks ) and pour it back in the vat... I've gotten more than 6months of life out of the vat ( and even leaving the developer unused for a month or 2 or 3 ) ... hundreds of prints and rolls and sheets of film through it ... the 130 is about 20cc/L of stock ansco 130 ... maybe its 1.5 - 2 gallons of developer total... usually when I hit 6 months I get rid of 1/2 or 2/3 of it and make another couple liters. what I have in the vat now is 2 years old and I last used it a few months ago and it worked fine ... I wish it didn't last so long, I've like 30-40lbs of green coffee in my garage.

BainDarret · Jan 17, 2021

john_s said:
Ryuji Suzuki, who used to post here, devised some ascorbate developers including print developers:

https://web.archive.org/web/20070720203755/http://silvergrain.org/wiki/Silvergrain_formulae

I've been using DS-1 for most of the past year. I find I get about a half stop speed boost over D-76 and get finer grain. I use it with HP5+ and Rollei IR 400. I keep it in wine bags and I find it's good for about a month before it starts to slowly lose strength. I also make a version of D-72 (Dektol) using 1.6x Ascorbic acid to replace Hydroquinone and up the carbonate by about 10%. This gives me the deepest blacks I have ever been able to achieve. It lasts a couple of months in wine bags.

Mike

albada · Jan 17, 2021

BainDarret said:
I've been using DS-1 for most of the past year. I find I get about a half stop speed boost over D-76 and get finer grain. I use it with HP5+ and Rollei IR 400. I keep it in wine bags and I find it's good for about a month before it starts to slowly lose strength. I also make a version of D-72 (Dektol) using 1.6x Ascorbic acid to replace Hydroquinone and up the carbonate by about 10%. This gives me the deepest blacks I have ever been able to achieve. It lasts a couple of months in wine bags.
Mike

"Deepest blacks" means you have a worthwhile developer. After making your changes described above, I get the following formula:

Water (warm)	500 ml
Metol	3.1 g
Sodium Sulfite (anhy)	45 g
Ascorbic Acid	19.2 g
Sodium Carbonate (anhy)	74 g (88g for monohydrate)
Potassium Bromide	1.9 g
Cool water to make	1000 ml

Can you confirm that this is the formula you use?

BainDarret · Jan 17, 2021

said:
"Deepest blacks" means you have a worthwhile developer. After making your changes described above, I get the following formula:

Water (warm) 500 ml
Metol 3.1 g
Sodium Sulfite (anhy) 45 g
Ascorbic Acid 19.2 g
Sodium Carbonate (anhy) 74 g (88g for monohydrate)
Potassium Bromide 1.9 g
Cool water to make 1000 ml
Can you confirm that this is the formula you use?

I have tinkered with the formula a little and am currently using the following to make 2L batches:

Water 125F/52C 1500 ml
Metol 6 gr
Sodium Sulfite 90 gr
Ascorbic Acid 38 gr
Sodium Carbonate 200 gr
Potassium Bromide 4.4 gr
Water to make 2000 ml

I use it to develop Ilford MG RC Warmtone diluted 1 part developer and 3 parts water.

john_s · Jan 17, 2021

BainDarret said:
I have tinkered with the formula a little and am currently using the following to make 2L batches:

Water 125F/52C 1500 ml
Metol 6 gr
Sodium Sulfite 90 gr
Ascorbic Acid 38 gr
Sodium Carbonate 200 gr
Potassium Bromide 4.4 gr
Water to make 2000 ml

I use it to develop Ilford MG RC Warmtone diluted 1 part developer and 3 parts water.

I'd consider mixing this without the ascorbic acid, and add it at the last minute. It's very quick to dissolve.

Is the image tone noticeably warm with that paper? Have you found development time to be reasonably short? I do batches of prints in a Nova and I prefer to get them done reasonably quickly. I currently use ID-78, initially to get the supposed warm tones with MGWT, but the warmth is very subtle anyway.

albada · Jan 17, 2021

BainDarret said:
I have tinkered with the formula a little and am currently using the following to make 2L batches:
Water 125F/52C 1500 ml
Metol 6 gr
Sodium Sulfite 90 gr
Ascorbic Acid 38 gr
Sodium Carbonate 200 gr
Potassium Bromide 4.4 gr
Water to make 2000 ml
I use it to develop Ilford MG RC Warmtone diluted 1 part developer and 3 parts water.

Do you know whether your carbonate is anhydrous or monohydrate? Given the large quantity in your formula, I would guess monohydrate, but I could easily be wrong.

BainDarret · Jan 18, 2021

john_s said:
I'd consider mixing this without the ascorbic acid, and add it at the last minute. It's very quick to dissolve.

Is the image tone noticeably warm with that paper? Have you found development time to be reasonably short? I do batches of prints in a Nova and I prefer to get them done reasonably quickly. I currently use ID-78, initially to get the supposed warm tones with MGWT, but the warmth is very subtle anyway.

The image tone is fairly neutral, I use selenium toner to achieve the final look of the print. I tray develop for about 90 seconds.

BainDarret · Jan 18, 2021

albada said:
Do you know whether your carbonate is anhydrous or monohydrate? Given the large quantity in your formula, I would guess monohydrate, but I could easily be wrong.

The carbonate seems to be monohydrate. I started using Photographers Formulary Sodium Carbonate Mono before switching to PH UP a swimming pool additive that works identically to the Formulary carbonate. Much cheaper at about $25 CAD for 5 kilograms.

Rudeofus · Jan 18, 2021

BainDarret said:
I've been using DS-1 for most of the past year. I find I get about a half stop speed boost over D-76 and get finer grain. I use it with HP5+ and Rollei IR 400. I keep it in wine bags and I find it's good for about a month before it starts to slowly lose strength. I also make a version of D-72 (Dektol) using 1.6x Ascorbic acid to replace Hydroquinone and up the carbonate by about 10%. This gives me the deepest blacks I have ever been able to achieve. It lasts a couple of months in wine bags.

Ryuji spent years investigating Fenton's reaction and ascorbates, and based on this research he published a couple of very capable formulas. DS-1 does not take advantage of any of these insights, therefore even Ryuji lists it under "obsolete formulas". As its name DS-1 tells, this must have been one of the earlier experimental ascorbate formulas which Ryuji published. It does not contain anything to protect the ascorbate against Fenton's reaction, and its shelf life will vary a lot, even if you mix it with distilled water.

BainDarret · Jan 18, 2021

Rudeofus said:
Ryuji spent years investigating Fenton's reaction and ascorbates, and based on this research he published a couple of very capable formulas. DS-1 does not take advantage of any of these insights, therefore even Ryuji lists it under "obsolete formulas". As its name DS-1 tells, this must have been one of the earlier experimental ascorbate formulas which Ryuji published. It does not contain anything to protect the ascorbate against Fenton's reaction, and its shelf life will vary a lot, even if you mix it with distilled water.

I looked up Fenton's Reaction and what I found goes beyond my ability to comprehend due to my lack of scientific education. ;-]
I have been getting predictable and repeatable results using these Ascorbic acid formulae. I like what I see and trust my eyes. There may come a time when there are storage issues and I will then have to change my methods. I understand others may get different results.

Alan Johnson · Jan 18, 2021

The Fenton reaction is an oxidation. No oxygen, no oxidation. Will keep in full sealed bottles.
https://www.photrio.com/forum/threads/metol-ascorbate-keeping-properties.75541/

BainDarret · Jan 18, 2021

Alan Johnson said:
The Fenton reaction is an oxidation. No oxygen, no oxidation. Will keep in full sealed bottles.
https://www.photrio.com/forum/threads/metol-ascorbate-keeping-properties.75541/

Thanks for the link and explanation. I use distilled water for making up developer, I try not to introduce air when mixing and I find the wine storage bags work well at keeping out oxygen. Even so I will probably switch to batch developing with day old developer mix. I use the developer full strength one shot, I should mention.

Rudeofus · Jan 18, 2021

Fenton reaction is oxidation (and thereby inactivation) of a reducer catalyzed by metal ions such as Iron. These metal ions can enter the developer through the water used to make it, or through other ingredients containing them as impurities. If your tap water is particularly rich in Iron and/Copper, then switching to deionized water will help with the problem, but will not solve it completely. Sodium Sulfite is said to be a prolific source of trace metal ions, and it is contained in almost any photographic developer you will want to use, including DS-1. The things, which make Fenton reaction so evil for ascorbate developers is that you do not see whether it has gone bad (no discoloration or precipitates) and that it can strike within a very short time frame.

The reason I know all this is, because Ryuji wrote about these things, and his later developers took advantage of the knowledge he gained and shared along his journey.

grainyvision · Jan 18, 2021

Rudeofus said:
Fenton reaction is oxidation (and thereby inactivation) of a reducer catalyzed by metal ions such as Iron. These metal ions can enter the developer through the water used to make it, or through other ingredients containing them as impurities. If your tap water is particularly rich in Iron and/Copper, then switching to deionized water will help with the problem, but will not solve it completely. Sodium Sulfite is said to be a prolific source of trace metal ions, and it is contained in almost any photographic developer you will want to use, including DS-1. The things, which make Fenton reaction so evil for ascorbate developers is that you do not see whether it has gone bad (no discoloration or precipitates) and that it can strike within a very short time frame.

The reason I know all this is, because Ryuji wrote about these things, and his later developers took advantage of the knowledge he gained and shared along his journey.

Another thing to keep in mind is that sulfite does not appear to preserve ascorbate, in fact it's believed (depending on pH) to potentially be the opposite, ascorbic acid will instead sacrifice itself to preserve sulfite. Either way, the way the reaction works, even very small amounts of metal ions can cause a surprisingly fast degradation of the developer. Hydroquinone is subject to the same effect though, yet is quite simple to preserve in a moderately acidic solution, even without or with minimal sulfite (though my experience with no sulfite is using oxalic acid, another reducing agent that seems to preserve it at acidic pH). Anyone with more chemistry knowledge know why ascorbic is so difficult to preserve? It seems to decay to CO2 or some other odorless gas at very acidic (<4) pH, while at basic pH it will discolor to orange in my experience.

There's a paper out there also that says solutions containing oxalate will preserve ascorbate at weakly (~6) acidic pH, but I've not really been able to confirm this myself despite messing with it to some extent

Rudeofus · Jan 18, 2021

earlz said:
Another thing to keep in mind is that sulfite does not appear to preserve ascorbate, in fact it's believed (depending on pH) to potentially be the opposite, ascorbic acid will instead sacrifice itself to preserve sulfite.

The notion, that sulfite eats up the oxygen and thereby protects developers is a bit too simple. Hydroquinone will happily react with Oxygen in the presence of sulfite, but it will quickly form HQMS instead of hanging around as autocatalytic semiquinones. Sulfite eats some Oxygen, too, but its main purpose in PQ and MQ type developers is prevention of autocatalytic destruction of HQ.

Things are very different with ascorbates: they do not form radicals with a tendency towards autocatalytic self destruction. They are, on the other side, sensitive to tiny amounts of Iron or Copper, and sulfites won't prevent this. Iron and Copper act as catalysts for oxidation of ascorbates.

String sequestering agents are added to many photographic developers, including those made from PPD derivatives and HQMS, but AFAIK ascorbates are destroyed by Fenton reaction much, much faster than the other developers. I have read articles, in which an ascorbate solution deteriorated within less than an hour in the presence of Iron or Copper. And, at the chance of repeating myself: most developers show very visible signs of oxidation, but ascorbate doesn't.

earlz said:
There's a paper out there also that says solutions containing oxalate will preserve ascorbate at weakly (~6) acidic pH, but I've not really been able to confirm this myself despite messing with it to some extent

This is most surprising, because oxalate is one of the final decomposition products of ascorbate, yet you can't even store ascorbate in acidic solution.

laingsoft · Jan 18, 2021

Rudeofus said:
Fenton reaction is oxidation (and thereby inactivation) of a reducer catalyzed by metal ions such as Iron. These metal ions can enter the developer through the water used to make it, or through other ingredients containing them as impurities. If your tap water is particularly rich in Iron and/Copper, then switching to deionized water will help with the problem, but will not solve it completely. Sodium Sulfite is said to be a prolific source of trace metal ions, and it is contained in almost any photographic developer you will want to use, including DS-1. The things, which make Fenton reaction so evil for ascorbate developers is that you do not see whether it has gone bad (no discoloration or precipitates) and that it can strike within a very short time frame.

The reason I know all this is, because Ryuji wrote about these things, and his later developers took advantage of the knowledge he gained and shared along his journey.

Interesting that this reaction haunts me to this day. My first lab job was working on a chemical filter that was based around an electrofenton reaction.

Sufficient amounts of EDTA and storage in amber glass bottles in large enough quantities (at least a liter) should do enough to halt any significant amount of photofenton occurring. In turbid water you typically can't go much father than a meter or so deep before light stops penetrating to the iron particles in a photofenton water treatment plant. Likewise the reaction is only really sensitive to UV and a tinge into blue, so dark amber glass bottles will stop almost all of that from reaching your solution.

Alan Johnson · Jan 18, 2021

On a Pourbaix diagram it is likely that the lines for ascorbate would fall below those shown for sulfite and it would be theoretically impossible for it to be regenerated by sulfite making it difficult to preserve. I have never seen such a diagram for ascorbate and it has likely never been measured .

grainyvision · Jan 18, 2021

Rudeofus said:
The notion, that sulfite eats up the oxygen and thereby protects developers is a bit too simple. Hydroquinone will happily react with Oxygen in the presence of sulfite, but it will quickly form HQMS instead of hanging around as autocatalytic semiquinones. Sulfite eats some Oxygen, too, but its main purpose in PQ and MQ type developers is prevention of autocatalytic destruction of HQ.

Things are very different with ascorbates: they do not form radicals with a tendency towards autocatalytic self destruction. They are, on the other side, sensitive to tiny amounts of Iron or Copper, and sulfites won't prevent this. Iron and Copper act as catalysts for oxidation of ascorbates.

String sequestering agents are added to many photographic developers, including those made from PPD derivatives and HQMS, but AFAIK ascorbates are destroyed by Fenton reaction much, much faster than the other developers. I have read articles, in which an ascorbate solution deteriorated within less than an hour in the presence of Iron or Copper. And, at the chance of repeating myself: most developers show very visible signs of oxidation, but ascorbate doesn't.

This is most surprising, because oxalate is one of the final decomposition products of ascorbate, yet you can't even store ascorbate in acidic solution.

The paper name is "INHIBITION, lNDUCTION AND THE CHAIN REACTION THEORY, 11: Inhibition by Oxalate" if you're interested (available on The Science Hub wink wink). It seems that it requires a fairly large surplus of oxalate, a small amount of ascorbic aicd and kept at weakly acidic pH to be most effective as a preservative. Ascorbic acid does decay into several radicals, but these radicals are significantly more stable than hydroquinone's. They are actually capable of being observed and kept in solution for a while. The most common one is dehydroascorbic acid, which is relatively stable at a pH of ~4. Notably, the radical can be reduced back into ascorbic acid. This appears to potentially be how oxalic acid preserves it. Ascorbic acid does not otherwise seem to decay into anything else directly and instead must first be oxidized to DHAA before further oxidation occurs... so prevent DHAA from hanging around and maybe you can make ascorbic acid a lot more stable. I can't recall if DHAA can cause changes in ascorbic acid like hydroquinone's radicals can (ie, hydroquinone radicals can oxidize hydroquinone, part of the thing that makes lith developers so unstable). There's another radical as well that forms when the pH of the solution is below the natural pH of ascorbic acid. DHAA itself goes on to further form other irreversible oxidation products, iirc a chain of 3 or 4 radicals before it finally gets to oxalate... and oxalate can be oxidized eventually to plain CO2 and water. I've observed this reaction in some poor lith developer formulations that incorporated oxalate and ascorbic acid, but I'm unsure of how it actually occurred. I only know the bottle of my solution would become pressurized with an odorless gas and ascorbic activity would decrease.

Another paper focused on ascorbic acid decay and oxidation is "OXIDATION OF ASCORBIC ACID AND REDUCTION IN VITRO AND IN VIVO*". It's of course more of a biology paper, but covers experiments in solution as well in media and either way I found rather interesting.

Also ascorbic acid definitely can form colored products. Try adding some ascorbic acid to water and then some lye and you'll see it turn quickly into a deep orange.

laingsoft · Jan 18, 2021

If I'm remembering correctly, Mason talks about oxalic acid as a physical developing agent in his book. If that's the case, AA + Oxalic acid seems like a recipe for fogged film.

grainyvision · Jan 19, 2021

laingsoft said:
If I'm remembering correctly, Mason talks about oxalic acid as a physical developing agent in his book. If that's the case, AA + Oxalic acid seems like a recipe for fogged film.

why would it result in fogging? in my experience oxalate seems to have no or very minimal effect on normal silver halide development including developers with ascorbate, even at massive amounts of oxalate such as 50g/L. I've only done minimal testing on film with such a formula, but with paper I've never had a problem I could pinpoint to oxalate

Rudeofus · Jan 19, 2021

Alan Johnson said:
On a Pourbaix diagram it is likely that the lines for ascorbate would fall below those shown for sulfite and it would be theoretically impossible for it to be regenerated by sulfite making it difficult to preserve. I have never seen such a diagram for ascorbate and it has likely never been measured .

If ascorbate ever fell below sulfite, it would be a fogging developer like dithionite, which it isn't.

grainyvision · Jan 19, 2021

Rudeofus said:
If ascorbate ever fell below sulfite, it would be a fogging developer like dithionite, which it isn't.

I'm not chemistry minded enough to understand the diagram, but ascorbate is a very fog prone developer when at a pH high enough that it can work alone. Benzotriazole is the only thing that can prevent the fog that comes with it, starts to become active at pH 11, but only really becomes reasonable at pH 12 or above

Tom Kershaw · Jan 19, 2021

I'm curious to know what mixing temperatures others are using for ascorbic acid based developers?

Anon Ymous · Jan 19, 2021

Tom Kershaw said:
I'm curious to know what mixing temperatures others are using for ascorbic acid based developers?

25°C or thereabouts is ok. Lower is probably fine, since I add phenidone predissolved in propylene glycol.

Tom Kershaw · Jan 19, 2021

Anon Ymous said:
25°C or thereabouts is ok.

Thanks.

Who is actually making new formulas? What have you made!?

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