Paper developer with long shelf life

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Ian Grant

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When I find my Morgan and Morgan, or if somewhere here has the time, I'll look up that Agfa/Adox formula and see if it's composition (ADOX MCC/Adox developer) is listed for making yourself.

That's one of the things that made that collection even more notable to me, over the last forty plus years; the ability to read for yourself old formulas.

The AgfaMCC formula was never published, also be aware that a high percentage of the formulae in the Morgan & Morgan publications are incorrect. The Agfa Neuto WA Warmtone developer is very similar to Ilford ID-78. MCC is probably similar to ID-62.

Ian
 

snusmumriken

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I love it when my deveveloper turns brown. It still works beautfully.
I have noticed that it never goes darker beyond a point. That point is session number three, and it stays the same color for all subsequent sessions, even at session 500.
I suppose this is the usual amazeballs? But just in case it might mislead someone ...

Besides the developing agent lost by oxidation, and any inhibiting effect of its breakdown products on development, the capacity of any working solution is finite. For instance, Ilford state that the capacity of 1 litre of 1+9 working strength Multigrade Developer is 100 sheets of 10x8 RC or 50 sheets of 10x8 FB. On that basis you might make it to 500 sessions if you develop only one RC postcard per session!
 

koraks

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But just in case it might mislead someone ...

I think what was left out of @NB23's post, but as he did mention earlier, is that he apparently does replenish the developer. I can confirm that when doing so, the developer doesn't darken any further at some point and remains stable. Due to replenishment, capacity is also maintained.
 

snusmumriken

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I think what was left out of @NB23's post, but as he did mention earlier, is that he apparently does replenish the developer. I can confirm that when doing so, the developer doesn't darken any further at some point and remains stable. Due to replenishment, capacity is also maintained.
Ah, OK, thanks for pointing that out.
 
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Yes, that's the best way to go IMHO: work with stock solution or even a concentrated version of it. I use self mixed D-72 (aka Dektol) as stock solution, with weekly print sessions interrupted by lith or color development sessions. I mix 2 liters at once, and use it over the course of 3-6 months. It rarely fails after that time (have seen it, but only after many, many more months). I mostly have to replenish, when carryover reduced the 2 liters to less than 1 liter.

Background: Concentrated aqueous solutions dissolve a lot less Oxygen than diluted ones or pure water, therefore you get much less oxidation in stock solution. Another factor may be Carbon Dioxide: a stock soluion has much stronger buffering, therefore equal amounts of dissolved Carbon Dioxide will affect pH much less.

The shelf life of Dektol is really hard to beat.
 

Philippe-Georges

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The shelf life of Dektol is really hard to beat.

Yes, and idem E-72, which is a Hydrochinon/Metol free version of it.

BTW, A.A. worked with Dektol...
 

Philippe-Georges

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Background: Concentrated aqueous solutions dissolve a lot less Oxygen than diluted ones or pure water, therefore you get much less oxidation in stock solution. Another factor may be Carbon Dioxide: a stock soluion has much stronger buffering, therefore equal amounts of dissolved Carbon Dioxide will affect pH much less.

If you blow some Dust-Off in the bottle just before closing it, then de Oxygen will be chased as the Methane gas, it's the propellant in D-O, is heavier.
 

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Yes, and idem E-72, which is a Hydrochinon/Metol free version of it.

Really? I'm interested because although I have a decent supply of HQ left and I'm also not too worried about toxicity and environmental load, I'm in principle in favor of replacing it with something more benign and even easier to obtain if possible. But given the problem of the Fenton reaction I'd be surprised to hear that E72 is as stable as Dektol. How long have you kept the concentrate and working stock solutions, and under which conditions?
 

eli griggs

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The AgfaMCC formula was never published, also be aware that a high percentage of the formulae in the Morgan & Morgan publications are incorrect. The Agfa Neuto WA Warmtone developer is very similar to Ilford ID-78. MCC is probably similar to ID-62.

Ian

Thanks.

I had no heard of the Morgan and Morgan having bad data before today.

Is there a thread listing the mistakes I could turn to?

I would have thought that with yearly updated sheets and addendum, mistakes would have been corrected in timely fashion, up to the last year published.

Best Wishes and Godspeed to you and yours,

Eli
 

Philippe-Georges

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Really? I'm interested because although I have a decent supply of HQ left and I'm also not too worried about toxicity and environmental load, I'm in principle in favor of replacing it with something more benign and even easier to obtain if possible. But given the problem of the Fenton reaction I'd be surprised to hear that E72 is as stable as Dektol. How long have you kept the concentrate and working stock solutions, and under which conditions?

Well, I can keep the work solution running for easily a month, even more, it all depends on how 'good' I treat my chemicals😉
Topping off is important in the way that it is actually a kind of replenishing for the 10% of the volume.
But I always blow some Dust-Off just before closing the bottle, regardless it is the work or the top-off bottle.
I learned that cleaning the bath with some hot water to prevent old developer drying in after use, is good practice too.
 
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john_s

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Thanks.

I had no heard of the Morgan and Morgan having bad data before today.

........

Eli

I bought the Morgan and Morgan loose leaf compendium in the mid 1970s. I avidly went through it while on the train back home (20 minutes). I was dismayed to find several really obvious mistakes before I got home. Very disappointing. I resorted to the big Ilford book then, and had no problems with it.
 

albada

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Really? I'm interested because although I have a decent supply of HQ left and I'm also not too worried about toxicity and environmental load, I'm in principle in favor of replacing it with something more benign and even easier to obtain if possible. But given the problem of the Fenton reaction I'd be surprised to hear that E72 is as stable as Dektol. How long have you kept the concentrate and working stock solutions, and under which conditions?

Here's the formula for the paper developer, E-72:

E-72 by Chris Patton
Dekol-type developer substituting ascorbic acid for hydroquinone and Phenidone for metol.

Water (125°F/52°C) ......... 750 ml​
Phenidone ........................ 0.3 g​
Sodium sulfite (anhy) ....... 45 g​
Ascorbic Acid ................... 19 g​
Sodium carbonate (mono) ..... 90 g (77 g Sodium carbonate anhy)​
Potassium bromide ........... 1.9 g​
Water to make ................... 1000 ml​

USING THE DEVELOPER: Dilute between 1:1 and 1:4, with 1:3 for normal contrast.
For 1+3, 2 minutes works well.
NOTE: 3.0 g of metol may be substituted for the Phenidone.
Formula #81, The Darkroom Cookbook, 2nd Edition, Stephen G. Anchell, p.192

Note the lack of a sequestering agent, leaving it defenseless against the evil Mr. Fenton.
 

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For those who want to home-brew something without Metol, which can cause dermatitis, I suggest starting with ID-62. Here is its formula:

ID-62 Ilford "Universal" PQ Developer (like D-72, but uses Phenidone)

Start with 750 ml warm water (125f or 52c).

sodium sulfite (anh) ......... 50 g​
hydroquinone ................... 12 g​
phenidone ........................ 0.5 g​
sodium carbonate (anh) ... 60 g​
potassium bromide ........... 2 g​
benzotriazole .................... 0.2 g​
Water to ............................ 1 litre​

To use: Photographic papers - Dilute 1+3 (can be 1+2 or 1+1 for higher contrast)

Forte 203, which was recommended for Polywarmtone, is ID-62 without Benzotriazole (a PQ version of and gives slightly warmer results, Ilfords's Warm tone version of ID-62 is ID-78).
Ilford first published ID-62 (with no number) in mid 1950s w/o benzo, but later added benzo and named it ID-62.
Without benzo, it's a little warmer.

For use with enlarging papers: dilute 1:3 and develop 1.5-2 minutes.
For use with contact print papers: dilute 1:1 and develop 45-60 seconds.
For tray development of films and plates: dilute 1:3 and develop 2-4 minutes.
For tank development of film: dilute 1:7 and develop 4-8 minutes.

A formula similar to ID-62 has been published without the Benzotriazole. If this is made up, it can be used as a Cool tone type of developer, and by adding additional Bromide becomes like ID-78 warm tone developer, or by adding Benzotriazole solution like ID-62 more neutral (blue tones).

Most of the material above was taken from Ian Grant's website, lostlabours.co.uk.
 

Philippe-Georges

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Here's the formula for the paper developer, E-72:

E-72 by Chris Patton
Dekol-type developer substituting ascorbic acid for hydroquinone and Phenidone for metol.

Water (125°F/52°C) ......... 750 ml​
Phenidone ........................ 0.3 g​
Sodium sulfite (anhy) ....... 45 g​
Ascorbic Acid ................... 19 g​
Sodium carbonate (mono) ..... 90 g (77 g Sodium carbonate anhy)​
Potassium bromide ........... 1.9 g​
Water to make ................... 1000 ml​

USING THE DEVELOPER: Dilute between 1:1 and 1:4, with 1:3 for normal contrast.
For 1+3, 2 minutes works well.
NOTE: 3.0 g of metol may be substituted for the Phenidone.
Formula #81, The Darkroom Cookbook, 2nd Edition, Stephen G. Anchell, p.192

Note the lack of a sequestering agent, leaving it defenseless against the evil Mr. Fenton.

In a previous post, I attached the original page, as published by Chris Patton him self, as a pdf, that's my reference.
But in addition, I add 10cc of a saturated K Br (Kalium Bromide) solution, which isn't mentioned in the C. Patton paper.

So, to be clear, I made a data sheet of the modus operandi I apply, here it is, sorry for it is in Flemish/Dutch...
 

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Philippe-Georges

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Note the lack of a sequestering agent, leaving it defenseless against the evil Mr. Fenton.

Correct if I am wrong, but isn't a sequestering agent is needed to compensate for hard- and metals containing tab water?
Then, is it indicated to use demineralised water?

PS: I understand that your referring to "Mr. Fenton" is tongue-in-cheek, but can you please elaborate?
 

albada

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Correct if I am wrong, but isn't a sequestering agent is needed to compensate for hard- and metals containing tab water?
Then, is it indicated to use demineralised water?

PS: I understand that your referring to "Mr. Fenton" is tongue-in-cheek, but can you please elaborate?

Side-note: In your previous post, you mentioned "Kalium". I've wondered what language used a K-word for Potassium. Now I know. Thank you.

The Fenton reaction is a catalytic reaction of iron ions with ascorbate. It will cause your developer to die, even if you used distilled water, because the iron comes from impurities in the chemicals used in the developer. Because it's catalytic, even a small amount of iron will eventually destroy all ascorbate. For some lucky people, the stock solution will last a long time, and for others, it might only last a few days. Kodak solved this problem by adding the sequestering agent DTPA to its XTOL developer. According to their patent, they added 1 gram of DTPA per litre of working solution.

With no DTPA, I would recommend mixing E-72 immediately before use, and discarding it after the session.

Pat Gainer solved this problem by dissolving all chemicals in TEA in his PC-TEA developer. With no water, there can be no Fenton reaction in his concentrate.
 

Philippe-Georges

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Side-note: In your previous post, you mentioned "Kalium". I've wondered what language used a K-word for Potassium. Now I know. Thank you.

The Fenton reaction is a catalytic reaction of iron ions with ascorbate. It will cause your developer to die, even if you used distilled water, because the iron comes from impurities in the chemicals used in the developer. Because it's catalytic, even a small amount of iron will eventually destroy all ascorbate. For some lucky people, the stock solution will last a long time, and for others, it might only last a few days. Kodak solved this problem by adding the sequestering agent DTPA to its XTOL developer. According to their patent, they added 1 gram of DTPA per litre of working solution.

With no DTPA, I would recommend mixing E-72 immediately before use, and discarding it after the session.

Pat Gainer solved this problem by dissolving all chemicals in TEA in his PC-TEA developer. With no water, there can be no Fenton reaction in his concentrate.

Thank you for elaborating, this proves again that I am not too old to learn!
I must be lucky as I can keep E-72 in stock solution, made in water, for months, perhaps it is due to me using reagentia grade products from Sigma-Aldrich?

And yes, Pat Gainer is a smart man, I learned a lot by reeding his writings!

BTW: albada, does your forumname refers to the viewfinder type?
 

koraks

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perhaps it is due to me using reagentia grade products from Sigma-Aldrich?

No, even ultra-pure vitamin C is inherently prone to the Fenton reaction.

What might explain your success is a combination of the following factors:
* Surprisingly little iron in the water you use.
* Replenishment of the developer before it wears out.
* Use of a dilution that happens to have sufficient safety margins for you not to notice the problem, combined with sufficient frequency of replenishment (i.e. not having the unused working stock developer sit around for many weeks).

And yes, Pat Gainer is a smart man, I learned a lot by reeding his writings!

Was; I'm afraid he passed away a couple of years ago. He sure is missed, also on this forum where he used to be a helpful member and kind person all around.
 

Ian Grant

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Thanks.

I had no heard of the Morgan and Morgan having bad data before today.

Is there a thread listing the mistakes I could turn to?

The problem was so bad, and had a longer lasting effect, because so many US published books copied the formulae from.
It was a mixture of typos, incorrect calculations of comparative weights of compounds like Sulphites and Carbonates which can be found as anhydrous or crystalline, in the case of Sodium Carbonate monohydrate form as well.

I remember buying an Amphoto book of formulae in the mid 1970s and being shocked at the mistakes, these carried through various other publications to the Darkroom Cookbook 2nd edition. I contacted Steve Anchell pointing out some errors, and he asked me to cross-check every formulae which I did with primary sources which I cited, that's manufacturer's own published data, often multiple publications from Ilford, Agfa Ansco, Orwo (Agfa), Gevaert, Kodak, Dupont/Defender, etc.

What was interesting was virtually every error was first published in the Morgan & Morgan Photo Lab Index, and people had been assuming it was the definite guide. The errors are in the realm of 30%.

I guess the two formulae that initially caught my eye was a formulae that was obviously a PQ version of D76/ID-11 that was claimed to be Microphen, but I knew that the published version of Microphen was ID-68a bit different, the formula the Lab Index listed was actually for Autophen. The other was ID-78 which Ilford had sold as a Warm tone developer in powder form, every US publication listed 0.4g (per litre) Potassium Bromide I knew the correct weight was 4.5g, essentially it's the warm tone version of ID-62 with no Benzotriazole and increased Bromide.

So after that I was quite sceptical and began finding more errors. Finally, I picked up some Lab Index supplements years later and realised that was where the errors had come from originally, then I obtained a full copy. Ir wasn't sold here in the UK.

Ian
 

eli griggs

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The problem was so bad, and had a longer lasting effect, because so many US published books copied the formulae from.
It was a mixture of typos, incorrect calculations of comparative weights of compounds like Sulphites and Carbonates which can be found as anhydrous or crystalline, in the case of Sodium Carbonate monohydrate form as well.

I remember buying an Amphoto book of formulae in the mid 1970s and being shocked at the mistakes, these carried through various other publications to the Darkroom Cookbook 2nd edition. I contacted Steve Anchell pointing out some errors, and he asked me to cross-check every formulae which I did with primary sources which I cited, that's manufacturer's own published data, often multiple publications from Ilford, Agfa Ansco, Orwo (Agfa), Gevaert, Kodak, Dupont/Defender, etc.

What was interesting was virtually every error was first published in the Morgan & Morgan Photo Lab Index, and people had been assuming it was the definite guide. The errors are in the realm of 30%.

I guess the two formulae that initially caught my eye was a formulae that was obviously a PQ version of D76/ID-11 that was claimed to be Microphen, but I knew that the published version of Microphen was ID-68a bit different, the formula the Lab Index listed was actually for Autophen. The other was ID-78 which Ilford had sold as a Warm tone developer in powder form, every US publication listed 0.4g (per litre) Potassium Bromide I knew the correct weight was 4.5g, essentially it's the warm tone version of ID-62 with no Benzotriazole and increased Bromide.

So after that I was quite sceptical and began finding more errors. Finally, I picked up some Lab Index supplements years later and realised that was where the errors had come from originally, then I obtained a full copy. Ir wasn't sold here in the UK.

Ian

That's really good to know as I've thought of the Morgan and Morgan as the last word on many topics.

Godspeed and Best Wishes for the Holidays and Thank You for setting me straight about these formula,
Eli
 

albada

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BTW: albada, does your forumname refers to the viewfinder type?

Yes! In the 14 years that I've participated in this forum, you are the first to point out the meaning of my name.

Regarding the OP's desire for a "paper developer with long shelf-life":
I'm planning to mix ID-62 (see formula above in post #64), but I want to dissolve the two developers (phenidone and hydroquinone) in propylene glycol (PG). If I keep the PG solution refrigerated or frozen, and the stock solution at room temperature (hot in summer), I'm hoping that both will last over a year.
Has anyone tried this?

BTW, @relistan is putting developers in PG with his new PC-512 developer (here's the link to that thread).
 

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Ethol LPD. I also keep working solution and continue to reuse.

Same experience. My current LPD batch is 2 year old and I only replenish it after every print session. Not sure it will last forever but close...
 

Philippe-Georges

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Yes! In the 14 years that I've participated in this forum, you are the first to point out the meaning of my name.

That forum name stroke me from you first posting in this thread but the discussion about the paper developer took 'the upper hand'.
The viewfinder of my Linhof Technorama 617 is an Albada system...

This afternoon I am about to mix a new B bath for the FX-55 film developer the Pat Gainer way, in Glycerol with TEA.
But I wonder if I couldn't mix E-72 as a two bath so it could be standing ready for immediate mixing/using (and long lasting)?
Up to now, now I kept all the different components ready wighted out in small containers (some of them 35mm film roll containers) and the Phenidone as a 1% mixture in Isopropyl Alcohol (and measure this with a syringe), which I think is the less stable part in this flow.
 

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BTW, @relistan is putting developers in PG with his new PC-512 developer (here's the link to that thread).


Yes, developing agents last a long time in propylene glycol, as Gainer found. I have had a batch of PC-Glycol last 3 years in a partially filled bottle with some small exposure all that time to ultraviolet as well. It works well! I like the freezer idea you used with Mocon and will be doing that from now on.
 
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