Diluting D-76 variants

Pentode · Nov 28, 2020

I have been using D-76 diluted 1:1 as a one-shot developer for years. I haven’t used it straight since, probably, the 1990s and I’ve never replenished it.

D-76 was originally intended to be a replenished developer but it is very commonly used 1:1 and the same holds true for D-23.

I’ve recently become tired of having to mix a gallon of D-76 at a time and I’m ordering bulk chemicals so I can mix from scratch. This will also open me up to the possibility of trying some of D-76’s close relatives; Adox Borax MQ, Ansco 17/Agfa 44, Eastman Kodak Fine Grain (H76) and also D-23, which I’ve never used. All of these were originally intended to be replenished.

My questions to those who have mixed these formulae from scratch is this: Have any of you used these D-76 derivatives diluted 1:1? Is there any good reason why I shouldn’t or couldn’t?

I’m curious to try these other formulae but it seems to me that the only way to make a fair comparison would be to use them in the same way I use D-76, and that would be 1:1, one-shot.

What do y’all think?

Pentode · Nov 28, 2020

michael_r said:
I've experimented with D-23 and Haist's D-76 variant at 1+1 (and 1+3). To answer your question directly, there is no reason why you couldn't or shouldn't. They behave the same way when diluted as D-76 or virtually any general purpose solvent developer does when diluted. That is, you get a slight increase in sharpness, with the penalty of slightly increased graininess. There really is not much more to it.

Thanks, Michael. That was my assumption, but I figured it couldn’t hurt to ask.

MattKing · Nov 28, 2020

I understand that the commercial packages of D-76 contain ingredients that help deal with water quality variations. The mix your own recipes may not. If you are using the developer 1+ 1, you may need to exercise more care with the water you use - both to mix the stock, and to dilute it.

Pentode · Nov 28, 2020

MattKing said:
I understand that the commercial packages of D-76 contain ingredients that help deal with water quality variations. The mix your own recipes may not. If you are using the developer 1+ 1, you may need to exercise more care with the water you use - both to mix the stock, and to dilute it.

Thanks, Matt. I had planned to mix my stock solutions with distilled water, something I never bothered to do with commercial D-76 because of the sequestering agents you mentioned.
I would do my dilution with regular tap water as I’ve always done as NYC tap water has proven to be well-behaved for diluting other developers. I would, of course, compare those results with my previous use of commercial D-76 just to be sure.

Anon Ymous · Nov 29, 2020

Pentode said:
Thanks, Matt. I had planned to mix my stock solutions with distilled water, something I never bothered to do with commercial D-76 because of the sequestering agents you mentioned.
I would do my dilution with regular tap water as I’ve always done as NYC tap water has proven to be well-behaved for diluting other developers. I would, of course, compare those results with my previous use of commercial D-76 just to be sure.

I live in an area with very hard water, in the 250 to 300 mg/l range and scratch mix all my chemicals. This hardness results in cloudy solutions. Any developer that contains sulfite or carbonate will definitely form some precipitate. The solution to this is to use a sequestrant, just like the commercial chemicals use, or use distilled water for everything, including dilution. The fact that you didn't notice anything bad when diluting your developer with tap water doesn't tell us anything about it. You can easily get an idea how problematic your tap water is by mixing a small amount of sodium sulfite with it. 2g in 100ml of water is enough. If this solution stays clear after some time, then your tap water is soft. Mine becomes cloudy within minutes. Now, obviously you can use distilled water for everything, but this can become a nuisance, because you need to store a large amount of it, which takes space. Since you will be buying chemicals, try to source some sodium hexametaphosphate. You typically add 2g/l for D76 and up to 6g/l for a print developer like D72. Add this to the water before adding any of the chemicals in the formula.

Alan9940 · Nov 29, 2020

I mix my own D-76 using distilled water and dilute 1:1 for use. The only "relative" I've used is D-23 which I use straight. Both are fantastic formulas that have provided quite consistent and nice results.

Ian Grant · Nov 29, 2020

The buffering of D76 changed probably because it makes it more stable dilute. In a Patent one example developer is ID-11 (un-named) with the Borax raised to 3gms and an inclusion of 3.5gm Sodium Tripolyphosphate that's possibly the current commercial form of ID-11.

It's possible the current D76 uses 4gm Borax and 2gm Boric acid for the buffering. For greatest stability dilute you could use ID-166/D76d which takes the buffering to 8gm Borax and 8gm Boric acid.

Ian

Donald Qualls · Nov 29, 2020

I haven't used D-76 since college (the photography class darkroom had it, I think; I'm almost certain that's what we had in my high school's darkroom) -- so roundly forty years, maybe forty-five. I have used home-mixed D-23 with replenishment the last time I had a darkroom, and got good results for several months (and then I was pushed out of my darkroom), though I've never tried it diluted as one-shot. I'd suggest if you're interested in replenishment and mixing your own, D-23 is a great place to start. The stock solution has only three ingredients, and one of those is water (mix both the stock and the replenisher with distilled or deionized water, please); the replenisher, DK-25R, has one more (sodium metaborate, which can be replaced with correct proportion of sodium hydroxide and borax; not hard to find or expensive). Results are very similar to D-76, but you'll see loss of about 1/3 stop of film speed and slower working compared to D-76 stock (D-23 replenished is roughly similar times to D-76 1+1).

The only easier way to get into replenishment is Xtol, which is commercially sold and is its own replenisher, but D-23 and DK-25R are almost as easy to mix as commercial Xtol, last as well, and are significantly cheaper (though won't deliver the sharpenss or speed you get with Xtol).

Home-mixed D-76 is well known to get stronger for a few days after mixing, as the pH changes -- Ian's post immediately above covers ways to deal with that. D-23 doesn't do that; you can use it as soon as the stock solution is cool. As a bonus, hydroquinone is apparently restricted in some locations (Europe?), and D-23 has none.

Pentode · Nov 29, 2020

Thanks everyone for your thoughtful replies.

Anon Ymous said:
The fact that you didn't notice anything bad when diluting your developer with tap water doesn't tell us anything about it. You can easily get an idea how problematic your tap water is by mixing a small amount of sodium sulfite with it. 2g in 100ml of water is enough. If this solution stays clear after some time, then your tap water is soft.

While I've never performed such a test, NYC drinking water is typically soft. I am, of course, at the mercy of the water people and whatever they decide to do to the water in terms of treatment, but every time they've sent me the test results in the mail (every couple of years) the water is soft and it has certainly always behaved that way. Using distilled water would remove any and all doubt, but my darkroom is extremely tiny and it's also much, much easier to control the temperature with tap water than with distilled.

Ian Grant said:
The buffering of D76 changed probably because it makes it more stable dilute. In a Patent one example developer is ID-11 (un-named) with the Borax raised to 3gms and an inclusion of 3.5gm Sodium Tripolyphosphate that's possibly the current commercial form of ID-11.

It's possible the current D76 uses 4gm Borax and 2gm Boric acid for the buffering. For greatest stability dilute you could use ID-166/D76d which takes the buffering to 8gm Borax and 8gm Boric acid.

I'm far from a chemist by even the most generous definition, Ian, but I assume the buffering is designed to compensate for the changes in behavior D-76 is infamous for early in its life. I have to admit I've never noticed any changes, but I've only used the commercial product which, as you say, might be buffered and I've only used it diluted which, I would assume, would make the effects less noticeable anyway. Along this same line of thinking, would Adox Borax MQ, Ansco 17 or any of the other MQ variants be prone to the same changes in activity that D-76 is known for?

Donald Qualls said:
I'd suggest if you're interested in replenishment and mixing your own, D-23 is a great place to start.

To be honest, Donald, replenishment isn't really on my radar for the moment. That's why I was interested to know how those other formulae would behave diluted. I'm not ruling the possibility of replenishment out for the future but, for now, it's not something I want to get involved with.

Donald Qualls said:
Home-mixed D-76 is well known to get stronger for a few days after mixing, as the pH changes -- Ian's post immediately above covers ways to deal with that. D-23 doesn't do that; you can use it as soon as the stock solution is cool. As a bonus, hydroquinone is apparently restricted in some locations (Europe?), and D-23 has none.

Grant Haist's D-76 variant (H-76 or really just Eastman Kodak Fine Grain Developer circa 1932) is another way around that phenomenon, among others. If I were to play with D-23 it's more likely I'd try it in order to see what the results were like and not because it's easier to work with - although I won't complain if it's easier to work with! Here in New York Hydroquinone is still readily available (for now) so that's not a concern yet.

Something I'm curious about in regards to D-76's habit of changing activity after mixing: Does this happen regardless of whether it sits in the bottle or is being used to develop film? In other words, can I just mix it a few days in advance and let it stabilize or do the changes only occur after it's been put to use?

Again, thanks for all the help. PHOTRIO can really be an amazing resource sometimes.

Ian Grant · Nov 29, 2020

Pentode said:
I'm far from a chemist by even the most generous definition, Ian, but I assume the buffering is designed to compensate for the changes in behavior D-76 is infamous for early in its life. I have to admit I've never noticed any changes, but I've only used the commercial product which, as you say, might be buffered and I've only used it diluted which, I would assume, would make the effects less noticeable anyway. Along this same line of thinking, would Adox Borax MQ, Ansco 17 or any of the other MQ variants be prone to the same changes in activity that D-76 is known for?

Any MQ Borax developer needs a few hours between mixing and use ideally.

Ian

Ian Grant · Nov 29, 2020

michael_r said:
Which reminds me, did we ever figure out what exactly boric anhydride is?

Regarding D-23, it was formulated to essentially duplicate the development properties of D-76. I found this to be the case.

According to Eastman Kodak Research Henn & Crabtree formulated D23 to give rather finer grain than D76 (rather was Kodak's term) with only a slight speed loss. D25 was to give exceptionally fine grain but with a stop speed loss.

Both were designed to be softer working than D76.

Ian

Ian Grant · Nov 29, 2020

michael_r said:
Not according to Haist. Source please. And what does “softer working” mean?

D-25 is another story.

The original source was Eastman Kodak Research Laboratory, an Abstract by Henn & Crabtree published in the BJP in 1945/6 and then abridged in the 1946 BJP Almanac. It appears Kodak Research Harrow had adapted/ammended the article to data for British made Kodak films. Whn I first used Tri-X and a Kodak developer the developer instructions gave speed and times for Tri-X made in the US. Canada and the UK, and they differed.

Soft working - Kodak's term, just means a lower contrast developer

Kodak Chemicals & Formulae, 1949. (Kodak Ltd not EK).

Kodak Reference Handbook, 1945, so Kodak Limited say Soft Working. EK say Low Contrast which D23 is.

Haist maybe contradicting Henn & Crabtree who were the experts in this field, the Microdol formula is in a pre WWII Henn & Crabtree Research Abstract and passed over in favour of Kodatol (DK-20) until there were issues with Dichroic fog and Eastman Kodak B&W films after the war. Here in the UK DK-20 remained a bit longer as did the later switch from Microdol to Microdol-X. British made Kodak films didn't suffer the same Dichroic fog issue, not sure about the Canadian Kodak films.

Ian

Pentode · Nov 29, 2020

Ian Grant said:
Any MQ Borax developer needs a few hours between mixing and use ideally.

Whenever I mix a stock solution from powdered chemicals (with the exception of coffee developers) I always mix at least a day before I plan to use them so I guess I'm okay as far as that's concerned.
Do all the changes in activity take place within that first few hours?

Lachlan Young · Nov 29, 2020

michael_r said:
Not according to Haist. Source please. And what does “softer working” mean?

D-25 is another story.

From Henn & Crabtree in Popular Photography, September 1945, pg.105., "The activity of D-23 and D-76 are very similar; they produce about equal emulsion speed and graininess and both developers possess good keeping qualities." Nowhere do they suggest that it's softer or finer grained than D-76 - but they do suggest that a great many of the PPD etc fine grain developers were not actually delivering better performance than D-76/ D-23 - and if you stripped them of all their inactive components at the pH used, you ended up with D-23 anyway. D-25 they regard as offering much finer grain, and Microdol (introduced in the October 1945 issue) as offering both finer grain and faster developing times than the very lengthy D-25 times.

RalphLambrecht · Nov 30, 2020

Pentode said:
I have been using D-76 diluted 1:1 as a one-shot developer for years. I haven’t used it straight since, probably, the 1990s and I’ve never replenished it.

D-76 was originally intended to be a replenished developer but it is very commonly used 1:1 and the same holds true for D-23.

I’ve recently become tired of having to mix a gallon of D-76 at a time and I’m ordering bulk chemicals so I can mix from scratch. This will also open me up to the possibility of trying some of D-76’s close relatives; Adox Borax MQ, Ansco 17/Agfa 44, Eastman Kodak Fine Grain (H76) and also D-23, which I’ve never used. All of these were originally intended to be replenished.
I always and only use D76H diluted 1+1
My questions to those who have mixed these formulae from scratch is this: Have any of you used these D-76 derivatives diluted 1:1? Is there any good reason why I shouldn’t or couldn’t?

I’m curious to try these other formulae but it seems to me that the only way to make a fair comparison would be to use them in the same way I use D-76, and that would be 1:1, one-shot.

What do y’all think?

twelvetone12 · Nov 30, 2020

I mix my D76 from scratch (I just made a new batch last week) and I find it easy to do and works very well. I generally use it 1+1 with good results. I also make sure I make as much as I need to use the stock solution as quickly as possible.

Ian Grant · Nov 30, 2020

michael_r said:
Not according to Haist. Source please. And what does “softer working” mean?

D-25 is another story.

There appears initially to be a contradiction between Kodak's (EK & Kodak Ltd) suggested use of D23 and what Henn & Crabtree and later Haist say about D23.

Kodak are saying that D-23 gives finer grain than D76 when use as a Low-contrast/Soft working developer, but if you extend development it takes longer to increase the contrast and graininess rises.

Ian

Diluting D-76 variants

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