Replenishing D-76

Don_ih said:

DK76 is claimed (on Digital Truth, and in some book I have somewhere) to be equal to D76. I don't think it's more active. Instead of 2g/L Borax, it's 2g/L sodium metaborate. But I haven't tried it. I could make it and see, I guess. But I still probably wouldn't notice. Who cares about fine grain? Use bigger film.

Kodak possibly doesn't recommend dilutions higher than 1:1 because of minimum recommendations of stock/roll. You can't fit 250ml of stock in a 500ml tank if the dilution is greater than 1:1.

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Borax has a pH pf 9.5, Sodium Metaborate is pH 10.5, that's a very significant difference in alkalinity, so activity. Crabtree & Henn mention this increased activity when the formulae were first published in research papers.

Remember that Sodium Metaborate is formed by adding Borax and Sodium Hydroxide.

Ian

Ian Grant said:

Borax has a pH pf 9.5, Sodium Metaborate is pH 10.5, that's a very significant difference in alkalinity, so activity. Crabtree & Henn mention this increased activity when the formulae were first published in research papers.

Remember that Sodium Metaborate is formed by adding Borax and Sodium Hydroxide.

Ian

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Well, all I can say is mix up both and try them out. Those are not the only ingredients in the formula. Grain is going to be impacted by the massive amount of sodium sulfite in there.

Replacing 2g borax with 2g metaborate will make the the formula more active. Since the development time would be shortened for a given gradient, all other things being equal one would usually expect coarser grain. Of course any difference might or might not be noticeable depending on the film and magnification.

It's worth noting that Kodak's research into fine grain developers was comparatively late compared to Agfa and Ilford. they poublished a paper in 1938 on Fine Grain Developers and Methods of Determing the Graininess of Photographic Plates.

The developers they tested were D76 11, Agfa Atomal 7.5. kodak Ultrafine 7.5, Tetenal Ultrafine SF 8, Sevewet (PPD) 8, the numbers refer to their measurement of grain size, so D76 was the grainiest.

This is at a timewhen Crabtree & Henn were testing various variations of D76, DK76a is the same as DK76 but with no Hydroquinone, It's likely Kodak Ultrafine was DK20, although D23 & D25 were also included in the same research papers.

In terms of B&W emulsions Kodak were lagging behind Agfa & Ilford in the 1930s, only introducing their first modern emulsions in 1939, that included Plus-X Super-XX, Tri-X, and Ortho-X, while Ilford had released Fine Grain Panchromatic (FP) and Hypersensitive Panchromatic (HP) in the early 1930s and FP2 & HP2 in 1938, HP3 in 1941.

Ron Mowrey (PE) stated that Kodak only caught up and surpassed Ilford when they released Tmax 100 & 400 in the mid 1980s.

Ian

I debated starting a new thread on this, but figured since the discussion was heading along these lines it was appropriate to ask this here.

The "Cookbook"(which admittedly I'm not wild about some of the chemistry explanations in) seems critical in general of replenished developers, and of replenished D76 in particular. It goes so far as to say(paraphrasing) that the only reason to replenish D76 is to save money, and that the developer will always give best results used one shot.

As I said, the appeal to me of replenished D76 in particular is the claims of consistent performance once "seasoned" appropriately, and that it gives-as discussed in this thread-results more like the best attributes(IMO) of both diluted and straight D76.

With that said, the Cookbook does cite one concern with replenished D76 as being the rise in pH as replenished, and in particular that this could cause the pH to rise enough that the hydroquinone starts acting as a developing agent(where it seems that its role in conventional D76 is the superadditivity/regeneration of metol).

Has anyone here who uses D76 replenished monitored the pH through a batch? If so, is the drifting upward of pH a real concern?

If it is, is it worthwhile to adjust the pH back down? If doing that, what would be best to use? My first thought would be boric acid. pH rise presumably is going to primarily be from the additional borax the replenisher adds, especially since the formula I'm seeing in the Cookbook(and a few other places I saw with a quick check) uses 20g/L for D76R. With that in mind, any acid added to lower the pH would have the effect of setting up a borate buffer system, but using boric acid would avoid adding any additional(potentially unwanted) anions. Would something like sulfuric acid work too? As best as I'm aware, sulfates don't contribute much if anything to developer chemistry, although there's also a lot about the subject I don't know...

Also, as a secondary question, I've seen references with other developers to seasoning by developing a certain number of rolls of film(often 5) before adding any replenisher. This may have been in reference to X-tol, and I can't find it now. With that said, for anyone using replenished D76, does this advice hold, or should one start replenishing with the first roll developed?

Milpool said:

Replacing 2g borax with 2g metaborate will make the the formula more active. Since the development time would be shortened for a given gradient, all other things being equal one would usually expect coarser grain.

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While it's very nice to say that, why not go mix some up and see if that's the case? (as in, how much more active and coarser the grain. Also, would a developing time reduction still result in coarser grain? There is some reason the Kodalk variation of D76 exists.)

I used replenished ID-11 for quite a few years, for mush of that time 3 of us shared the same deep tank. A lot of film, mostly 5x4 and 120, would be processed and then there was a point where you noticed a slight change in the negatives. ID-11/D76 collapses due to Bromide build-up, causing Metol to be inhibited.

Autophen which was Ilford's PQ version of ID-11 was designed and sold for large scale Photofinishing labs and could be replenished, and didn't collapse and could last years.


Ian

Like Ben, I'm looking to try replenished D-76 for the other qualities derived that I've read about. Plus, the whole concept really appeals to me in that I can setup my tanks, fill the developer tank from a jug, develop, toss in some replenisher (as required), empty the tank back into the storage container. And, I can potentially do this process for 6 - 12 months. Not trying to be lazy here, but this seems a WHOLE lot easier than setting up, processing, then draining my Jobo!

Recently, I watched a YT video where the photographer just re-used the developer (D-76, no replenishing) and increased development time a bit, as needed. IIRC, the developer was tossed when it started turning a color (yellow?) According to this photographer, her father was a photo journalist and that's the way he taught her to process film. She claimed (and others, too, appartently) that reusing the developer this way made her negatives "glow." Can't say I've ever seen a glowing negative, but there ya have it.

I am currently using Replenished Acufine, the directions on the can says that 1 quart of stock can be replenished by 1 quart of replenisher. I have a gallon of stock and on my first quart of replenisher, I am assuming that it last as long as I add fresh replenisher up the gallon. With D76, same recommendation? In the 70s I knew fine arts photographers were replenished D76 fans to the point of being a cult. One claim that twice a year he dumped 1/2 of the replenished stock and added fresh D76, had his tank going for years.

Ben Hutcherson said:

Would something like sulfuric acid work too? As best as I'm aware, sulfates don't contribute much if anything to developer chemistry

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Yes, I'd expect so. Or just acetic acid (acetate) or citric acid (citrate). I don't think any of these will interfere significantly. Sorry, haven't tried it, so just a wild guess.

Ben Hutcherson said:

With that in mind, any acid added to lower the pH would have the effect of setting up a borate buffer system, but using boric acid would avoid adding any additional(potentially unwanted) anions. Would something like sulfuric acid work too? As best as I'm aware, sulfates don't contribute much if anything to developer chemistry, although there's also a lot about the subject I don't know...

Also, as a secondary question, I've seen references with other developers to seasoning by developing a certain number of rolls of film(often 5) before adding any replenisher. This may have been in reference to X-tol, and I can't find it now. With that said, for anyone using replenished D76, does this advice hold, or should one start replenishing with the first roll developed?

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Once a developer like ID-11/D76 starts to collapse, it's due to the Bromide build up so adjusting pH is a waste if time.

Yes keep a little for seasoning, without you get a harshness compared to when seasoned or a few rolls have been processed.

Alan9940 said:

Like Ben, I'm looking to try replenished D-76 for the other qualities derived that I've read about. Plus, the whole concept really appeals to me in that I can setup my tanks, fill the developer tank from a jug, develop, toss in some replenisher (as required), empty the tank back into the storage container. And, I can potentially do this process for 6 - 12 months. Not trying to be lazy here, but this seems a WHOLE lot easier than setting up, processing, then draining my Jobo!

Recently, I watched a YT video where the photographer just re-used the developer (D-76, no replenishing) and increased development time a bit, as needed. IIRC, the developer was tossed when it started turning a color (yellow?) According to this photographer, her father was a photo journalist and that's the way he taught her to process film. She claimed (and others, too, appartently) that reusing the developer this way made her negatives "glow." Can't say I've ever seen a glowing negative, but there ya have it.

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Once seasoned you see a noticeable increase in negative quality, finer grain, better speed, and a longer tonal range, which you get also when used 1+1 and particularly 1+2.

The huge benefits of replenishment are speed of use, very economic, consistent results, and as mentioned above the negative quality. But the same can be said of Xtol.

Ian

Ian Grant said:

Once a developer like ID-11/D76 starts to collapse, it's due to the Bromide build up so adjusting pH is a waste if time.

Yes keep a little for seasoning, without you get a harshness compared to when seasoned or a few rolls have been processed.

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I can see bromide build up being a problem. In fact a while back I was experimenting with adding bromide as an anti-fog to try and salvage some found 70mm film(decided it was just wasting my time since I never could positively ID the film and realized base fog was so high that I doubted I'd get anything through it).

In any case, I definitely found a point where I added enough KBr that it just quit working. I was only playing with ~50mL at a time(developing film clips) and using a fairly concentrated KBr solution, but I definitely sensed that there was a "cliff" where too much just killed it completely.

With that said, I'm more focusing on this and other related comments in the Cookbook, and that's where my question about checking and adjusting pH came from

Ben Hutcherson said:

I can see bromide build up being a problem. In fact a while back I was experimenting with adding bromide as an anti-fog to try and salvage some found 70mm film(decided it was just wasting my time since I never could positively ID the film and realized base fog was so high that I doubted I'd get anything through it).

In any case, I definitely found a point where I added enough KBr that it just quit working. I was only playing with ~50mL at a time(developing film clips) and using a fairly concentrated KBr solution, but I definitely sensed that there was a "cliff" where too much just killed it completely.

With that said, I'm more focusing on this and other related comments in the Cookbook, and that's where my question about checking and adjusting pH came from

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Personally, I'm beginning to doubt a lot of Haist's writings, and I have read both recent volumes. Instead, I rely on LFA Mason's Photographic Processing Chemistry, edited by the head of Kodak Research, for Focal Press.
I don't know where your quote is from, but it does not match many years of use of D76/ID0-11 and other clones as an industry standard developer, by almost all professional photographers shooting B&W, for decades.

I would add that Haist couldn't even refer to the original Eastman Kodak Research precursor to D76 correctly, so clearly lacked full knowledge.

Haist quotes no primary sources, LFA Mason does. Anyone who has been to University know you HAVE to quote primary sources, and that's even more important to Post Grad qualifications, So in that respect Haist's books could be fiction, of course they are not, but then they are not verifiably accurate either.

Ian

Ian Grant said:

Personally, I'm beginning to doubt a lot of Haist's writings, and I have read both recent volumes. Instead, I rely on LFA Mason's Photographic Processing Chemistry, edited by the head of Kodak Research, for Focal Press.
I don't know where your quote is from, but it does not match many years of use of D76/ID0-11 and other clones as an industry standard developer, by almost all professional photographers shooting B&W, for decades.

I would add that Haist couldn't even refer to the original Eastman Kodak Research precursor to D76 correctly, so clearly lacked full knowledge.

Haist quotes no primary sources, LFA Mason does. Anyone who has been to University know you HAVE to quote primary sources, and that's even more important to Post Grad qualifications, So in that respect Haist's books could be fiction, of course they are not, but then they are not verifiably accurate either.

Ian

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This came from the Film Developing Cookbook 2e by Troop and Anchell.

I have found some of the chemistry in it somewhat questionable in a read through. The cookbook leans heavily on Haist and Crawley both, and yes it is certainly at best a tertiary source since it does not cite any primary sources. It's a relatively "fresh" reference also as it was published in 2020.

With that said, I am asking about it here because it is from at least a recognized/current source(and one cited often on here) and is contrary to a lot of this discussion.

I have started working through Haist's volumes, although put volume 1 aside for a little while because I got tired of reading about the wonders of monobaths.

I will find a copy of Mason as you've cited, but can you suggest some other good primary source material or some well-sourced secondary sources?

(and yes I'm well aware of the importance of primary sources-I do have some pieces of paper on my wall as well as a job title that says I know not just how to read and reference primary sources in chemistry, but also to write them when appropriate...)

Ben Hutcherson said:

This came from the Film Developing Cookbook 2e by Troop and Anchell.

I have found some of the chemistry in it somewhat questionable in a read through. The cookbook leans heavily on Haist and Crawley both, and yes it is certainly at best a tertiary source since it does not cite any primary sources. It's a relatively "fresh" reference also as it was published in 2020.

With that said, I am asking about it here because it is from at least a recognized/current source(and one cited often on here) and is contrary to a lot of this discussion.

I have started working through Haist's volumes, although put volume 1 aside for a little while because I got tired of reading about the wonders of monobaths.

I will find a copy of Mason as you've cited, but can you suggest some other good primary source material or some well-sourced secondary sources?

(and yes I'm well aware of the importance of primary sources-I do have some pieces of paper on my wall as well as a job title that says I know not just how to read and reference primary sources in chemistry, but also to write them when appropriate...)

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Haist is good but the best is James (get the 4th edition).

Reading Haist page 362-365 he also leans on Geoffrey Crawley's 1960 BJP articles. There's no mention of specific pH changes rather that after 7 weeks (49 days) activity has increased compared to fresh un-replenished developer. He states that D76d does not have this shift in activity of plain D76, the Boric Acid Borax combination is ab effective pH buffer.

Commercial D76 has been buffered with Boric Acid for many years and Australian packaging indicates the change to be 4g Borax and 2g Boric Acid. An Ilford Patent contains a reference developer indicating ID-11 buffering increased from 2 to 3 g Borax per litre.

Ian

Ian Grant said:

Reading Haist page 362-365 he also leans on Geoffrey Crawley's 1960 BJP articles. There's no mention of specific pH changes rather that after 7 weeks (49 days) activity has increased compared to fresh un-replenished developer. He states that D76d does not have this shift in activity of plain D76, the Boric Acid Borax combination is ab effective pH buffer.

Commercial D76 has been buffered with Boric Acid for many years and Australian packaging indicates the change to be 4g Borax and 2g Boric Acid. An Ilford Patent contains a reference developer indicating ID-11 buffering increased from 2 to 3 g Borax per litre.

Ian

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So in other words, the Cookbook is cherry-picking information from its main source and not accounting for commercial formulae changing to a buffered system.

The current SDS for Kodak D76 distributed in the US(assuming it's the same worldwide) lists Boric Anhydride as an ingredient along with sodum tetraborate. Of course I'd expect the anhydride to hydrolyze when dissolved in water to give boric acid, giving us the borate buffer.

So, now the question to me is-if formulating D76 at home, is it worthwhile to use a buffered formula and adjust the pH on initial mixing? Similarly, would it be desirable for the replenisher to be buffered to roughly the same pH as stock?

You don't need to adjust the pH. Unless you have very heavy throughput just the basic D76 is OK. If I went back to an MQ fine grain developer, I'd use Adox Borax MQ which I found gave finer grain, better sharpness, cleaner shadow details, and about a 1/3 stop faster than D76. It's closely related to the old ASA/BS standard developer for determining film speeds.

I did use Adox Borax MQ commercially for a few years and supplied a couple of local studios with it & the replenisher. It's very close to Agfa 487/Ansco 17. One of the disadvantages of D76 is it's nor a clean working MQ developer due to the silver solvency of a 10% Sulphite, it's not quite so simple because switch from Metol to Phenidone or Dimezone and that changes.

Ian

This (interesting) discussion reminds me of the often-repeated claim that D-76 changes activity during the first 24hrs after mixing. Seems to be an Internet case of circular confirmation. For sure, when I challenged that assertion on photrio, nobody came up with primary evidence (experimental or literature).
Could it be that it was born from the text quoted by @Ben Hutcherson in post #37. Itself based on writings of Haist, without proper primary sources. Plus a confusion between the "original" D-76, D-76d, and the commercial formula (see below)
FWIW I once measured the pH of D-76d during the first 48hrs and saw no change (yeees, buuut it's an effect more subtle than just pH...)
I now use the (possibly commercial) buffered version (4g borax 2g boric acid) after reading this and following posts: