The Ins and Outs of D-76 -- (The Film Developing Cookbook)

Lachlan Young · Dec 29, 2019

138S said:
Another thing is printing that image on VC paper optically. I guess you realize that you would need a complex masking in the enlarging or an special development of film, or both.

Go and look at Michael Kenna's night work. It's almost all regular 400 speed films (predominantly regular Tri-X) processed in D-76 at a standard time (12 mins I recall - a CI of about 0.7 or what used to be recommended as 'N' for diffusion/ cold cathode). Your approach is giving you difficulty because you are likely underexposing and by the sounds of it underprocessing too. It should take about 1 roll of film and a contact sheet to learn the necessary - 12 mins in Xtol 1+1 & a set of exposures of a stop greater than the last (say 3, 6, 12 mins etc) would seem like a good starting point - the contact print should tell you whether you are within half a grade of where you need to go - there should be an eminently printable neg somewhere in the set. Some papers can be tricky in terms of dumping shadow values at a higher grade - MGIV for example - Classic etc is much better. Main thing to remember is that night images are hard to truly overexpose - and that the approach of the least possible exposure and least possible processing are really facets of trying to minimise grain on 35mm, not necessarily get the best possible tonality in a relatively small enlargement off 8x10. What really matters is making the best possible print, then understanding what your processes were to get there, rather than attempting to analyse that-which-does-not-exist-yet in the hopes of making a 'correct' negative.

138S · Dec 29, 2019

Ian, thanks for the explanation.

Ian Grant said:
Autophen (Ilford's commercial PQ variant of ID-II/D76) could be replenished just by topping up add-infinitum,

It can be pointed that Xtol is also replenished up add-infinitum, as overflows provide also a high enough evacuation rate of by-products.

Ian Grant said:
Developers like D94/D94a are for reversal processing and need a higher level of Bromide because of the Thiocyanate or DTOD both Silver solvents.

OK, but D94 is a very, very high Br content developer that it also has Metol in the formulation, so superadditivity remains, and we are talking about a high-energy developer, so in that ultra high KBr formulation Metol works.

in D-94 pH is near 12.8, in D-96 pH is 8.6

Probably this is related to when Metol works with high KBr or not, given the REDOX of Metol.

Ian Grant said:
developers switched to Phenidone

Yes, there are many reasons to switch to Phenidone:

"It has five to ten times the developing power as Metol. It also has low toxicity and, unlike some other developers, does not cause dermatitis upon skin contact.[1]"

Combined low toxicity with 1/10 dose makes it a good candidate, safe and cheap. PQ combo has a tendence to fog generation, fortunately BZT exists.

Rudeofus · Dec 29, 2019

138S said:
D-96 is formulated with 0.4gr/L of KBr, while D-94A (Metol Hidroquinone also) is formulated with 7gr/L of KBr, 17 times more. With D-94A even the replenisishment contains some KBr because the bleed removes too much of it.

Kodak D-94A (formula: Metol 0.6g, Sodium Sulfite 60g, HQ 20g, NaBr 7g, DTOD 0.42g, NaOH 20g) is a completely different animal compared to D-96 or D-76. It is a superactive high contrast developer well suited for reversal processing, but nothing one would want for B&W negative development. Note: you won't find a "normal" B&W negative developer with 5+ g/l bromide in its working solution. A switch from MQ to PQ type developer, on the other side, would likely lead to very similar results, maybe 1/3 - 1/2 more speed, and greatly reduced sensitivity to bromide.

PS: I am realistic enough to accept, that your management would NEVER support a switch from established MQ to experimental PQ formula, so my argument may be moot from the onset.

138S said:
Of course, but life limitation of the fixer comes from silver content, when silver is at 1gr/L (archive) or 2gr/L (commercial) bromide still it's not a problem, so first you have to do to extent chem usage is removing silver. I geuss that we all understand that.

With the waste regulations as described, and 750 gallons of photographic liquid around, I would have thought, that silver recovery is a nobrainer. Which puts the limitation of fixer capacity squarely back into the bromide/iodide corner. Are the hazmat regulations less strict with (potentially silver ion containing) fixer than with developer?

Rudeofus · Dec 29, 2019

138S said:
IOK, but D94 is a very, very high Br content developer that it also has Metol in the formulation, so superadditivity remains, and we are talking about a high-energy developer, so in that ultra high KBr formulation Metol works.

in D-94 pH is near 12.8, in D-96 pH is 8.6

Probably this is related to when Metol works with high KBr or not, given the REDOX of Metol.

Reduction potential rises with developer pH, but only up to a point. The real reason, why D-94 needs such high levels of bromide, is the DTOD as pointed out by Ian. It's the combination of high HQ, high pH and relatively high DTOD content, which makes D-94 a very unusual developer, and one quite unsuited for normal B&W development.

Ian Grant · Dec 29, 2019

138S said:
Ian, thanks for the explanation.

It can be pointed that Xtol is also replenished up add-infinitum, as overflows provide also a high enough evacuation rate of by-products.

No it can't with Xtol you have to discard some good working stock to replenish, this is called Bleed replenishment. Autophen just needed topping up no bleed except with machines designed specifically for Bleed replenishment.

138S said:
OK, but D94 is a very, very high Br content developer that it also has Metol in the formulation, so superadditivity remains, and we are talking about a high-energy developer, so in that ultra high KBr formulation Metol works.

in D-94 pH is near 12.8, in D-96 pH is 8.6

Probably this is related to when Metol works with high KBr or not, given the REDOX of Metol.

It's not a Fine grain still film developer so is irrelevant here when discussing D76.

Ian

Kino · Dec 29, 2019

Rudeofus said:
Kodak D-94A (formula: Metol 0.6g, Sodium Sulfite 60g, HQ 20g, NaBr 7g, DTOD 0.42g, NaOH 20g) is a completely different animal compared to D-96 or D-76. It is a superactive high contrast developer well suited for reversal processing, but nothing one would want for B&W negative development. Note: you won't find a "normal" B&W negative developer with 5+ g/l bromide in its working solution. A switch from MQ to PQ type developer, on the other side, would likely lead to very similar results, maybe 1/3 - 1/2 more speed, and greatly reduced sensitivity to bromide.

PS: I am realistic enough to accept, that your management would NEVER support a switch from established MQ to experimental PQ formula, so my argument may be moot from the onset.

With the waste regulations as described, and 750 gallons of photographic liquid around, I would have thought, that silver recovery is a nobrainer. Which puts the limitation of fixer capacity squarely back into the bromide/iodide corner. Are the hazmat regulations less strict with (potentially silver ion containing) fixer than with developer?

Absolutely no chance of a developer change.

And, I didn't make it clear, there IS fix sliver recovery, but no wash water treatment.

138S · Dec 29, 2019

Lachlan Young said:
Go and look at Michael Kenna's night work.

I love Kenna works... but this is another style, working with high contrast, many silhouttes and deep blacks with slight detail, a bit in the opposite side of the image I posted.

Lachlan Young said:
Your approach is giving you difficulty because you are likely underexposing and by the sounds of it underprocessing too.

It is not my approach, it is one of the approaches I may use, and it's not mine, I learned it from Steve Sherman, after I made those histograms for him he made me a gift, the material he delivers in his workshops, videos and recipes.

Not underexposing, not underprocessing...

This is: Exposing for the shadows to get the right detail, developing for normal contrast... but selectively compressing highlights in the development to make them printable. What you would do with an HLM done in the development, for a similar effect.

EMA is not about flat negatives or not flat negatives, you can compress or not the scene range like in ZS, but you have the choice to solve the highlight depiction in the development instead performing a difficult burning in the split grade.

138S · Dec 29, 2019

Ian Grant said:
It's not a Fine grain still film developer so is irrelevant here when discussing D76.

Rudeofus said:
Reduction potential rises with developer pH, but only up to a point. The real reason, why D-94 needs such high levels of bromide, is the DTOD as pointed out by Ian. It's the combination of high HQ, high pH and relatively high DTOD content, which makes D-94 a very unusual developer, and one quite unsuited for normal B&W development.

Of course, D-94 is for reversal as you pointed, it was just to show that Metol can also be in a formulation with ultra High KBr, if the formulation has the suitable strong pH.

So you are right in that Br interferes with Metol, just pointing that it also depends on pH and may be other things.

It would be interesting to know how Metol sensitiveness to Br changes with pH.

Rudeofus · Dec 29, 2019

138S said:
Of course, D-94 is for reversal as you pointed, it was just to show that Metol can also be in a formulation with ultra High KBr, if the formulation has the suitable strong pH.

So you are right in that Br interferes with Metol, just pointing that it also depends on pH and may be other things.

It would be interesting to know how Metol sensitiveness to Br changes with pH.

It's the DTOD which puts the Metol into gear at this high pH in D-94A, and ideally without much of a speed loss. You can bring up Kodak D-82 as a working developer with Metol, high pH and loads of KBr, but that's also a developer you don't want to get anywhere near your normally exposed film. Note, that D-82 has an order of magnitude more Metol in its formula compared to D-94(A). The next stage (even more bromide, even higher pH) would be D-8, which doesn't even bother with Metol any longer, and I wonder, whether the bromide starts acting as solvent at 30 g/l.

Rudeofus · Dec 29, 2019

Kino said:
Absolutely no chance of a developer change.

You complain about difficulties, yet all the relevant parameters are cast in stone. This makes your job both very easy, and very unstable

138S · Dec 29, 2019

Rudeofus said:
It's the DTOD which puts the Metol into gear at this high pH in D-94A, and ideally without much of a speed loss. You can bring up Kodak D-82 as a working developer with Metol, high pH and loads of KBr, but that's also a developer you don't want to get anywhere near your normally exposed film. Note, that D-82 has an order of magnitude more Metol in its formula compared to D-94(A). The next stage (even more bromide, even higher pH) would be D-8, which doesn't even bother with Metol any longer, and I wonder, whether the bromide starts acting as solvent at 30 g/l.

Yes... D-82 per 1L

14g Hidroquinone
14g Metol
8.8g KBr
etc
... and caustic stuff for an strong pH, sulfite at 52g

Old High energy recipe for speed increase...

It looks Br is bad for Metol in the usual pH conditions, as you pointed, but we have those caustic exceptions for insane high energy.

D-94, as a reversal developer, it also requires insane energy for contrast plus solvent effect to drill in the highlights for a lower DMin. Destroying film in reversal BW testing is my speciality

Now what I do is H log and D aligning graphs of Provia, TX reversal and my calibrations, this was a flawed test last weekend, showing positive an reversal calibration, there is a silver reserve that's difficult to develop in the first developer and if it's not cleared it delivers fog. In that game we always end in high energy for contrast.

I found a good strategy is calibrating the reversal to nail provia sensitometric gradient, from the H shift in the curves vs provia the good ISO can be calculated, so after the calibration is ok one goes to shot in the street like if it was (ISO corrected) provia and the slides are nailed.

Lachlan Young · Dec 29, 2019

138S said:
This is: Exposing for the shadows to get the right detail, developing for normal contrast... but selectively compressing highlights in the development to make them printable. What you would do with an HLM done in the development, for a similar effect.

You don't need to compress the highlights or make a mask with that kind of negative if you know your way around selective fogging. You just need a piece of diffusion material under the lens and your hands - you print shadows harder than might be sensitometrically 'correct' and then help the highlights in with a directed flash/ fog exposure - Grade 00 will tend to affect the shadows less. It's old hat amongst printers, especially those who had to get lots of prints out the door. And you can make suitable negatives just fine with D-76 and continuous agitation.

If you've ever had to try to get good separation back into over compressed highlights, you'll understand why the less you compress them the better.

Rudeofus · Dec 29, 2019

138S said:
It looks Br is bad for Metol in the usual pH conditions, as you pointed, but we have those caustic exceptions for insane high energy.

There are 14g Metol working against these 8+ grams of bromide ... and Metol loves to stick to silver ....

Kino · Dec 29, 2019

Rudeofus said:
You complain about difficulties, yet all the relevant parameters are cast in stone. This makes your job both very easy, and very unstable

Thank you for grasping what management cannot; they insist that "something must be done, but we can't touch a thing."
Retirement looms and I await in great anticipation...

138S · Dec 29, 2019

Lachlan Young said:
You don't need to compress the highlights or make a mask with that kind of negative if you know your way around selective fogging.

There are several ways to overcome the same challenge, you can burn more the highlights in the print or you can build a lower density in the negative selectively highlights which also will throw more light on the paper. Or we can do both.

With the right visualization and the right technique we can craft a negative that allows to print highlights directly like we want without manipulation, or at least with less manipulation.

Look, I'm not saying to make a general tonal compression, this is about shouldering the response selectively in the highlights to obtain directly the print we want.

The beauty of that process is it's minimalism, a pill replacing surgery. Of course advanced print manipulation makes sense absolutely, but we cannot overlook what we can do in the negative crafting.

Lachlan Young said:
If you've ever had to try to get good separation back into over compressed highlights, you'll understand why the less you compress them the better.

Ideally highlights should be more or less compressed in the negative to just obtain directly the print we want without manipulation, as we miss in nailing that we have to manipulate.

Of course another choice is taking all linear and later manipulating until we have what we want, departing from a flexible negative is not a bad choice as we keep our options open, but also there is nothing wrong in solving tonality (or a share of it ) in the negative crafting, if we know what we want.

beemermark · Jan 8, 2020

Ian Grant said:
It's often forgotten that the way D76 is used today is often quite different to it's original origins as a replenished D&P and motion picture developer. It was never designed for amateur use diluted at 1+1 or 1+3.

Not sure how/why the use of D76 used today is different than it's original purpose. The 1st edition of the Leica Manual by Morgan & Lester published 1935 gives D76 as one the few developers for 35mm film. Which only makes sense since 35mm film used in still cameras was motion picture film rolled into cassettes.

I bought packaged D76 for years (still do once in awhile), I also roll mine own. I see no difference in the developed negatives. D76 is a rather simple formula so it's difficult to see where it could be changed to much in a package form.

Ian Grant · Jan 8, 2020

beemermark said:
Not sure how/why the use of D76 used today is different than it's original purpose. The 1st edition of the Leica Manual by Morgan & Lester published 1935 gives D76 as one the few developers for 35mm film. Which only makes sense since 35mm film used in still cameras was motion picture film rolled into cassettes.

I bought packaged D76 for years (still do once in awhile), I also roll mine own. I see no difference in the developed negatives. D76 is a rather simple formula so it's difficult to see where it could be changed to much in a package form.

It differs because they weren't suggesting using D76 dilute at 1+1 or 1+3, always stock solution and in most cases replenished. My pre-WWII Leica book says "use Undiluted" and 8-10 rolls of film per litre. What they don't mention is the need to increase development times, that was in the ID-11 & Microphen (ID-68) instructions when I first started along with replenishment rates..

Ian

MattKing · Jan 8, 2020

It also differs because the early motion picture film was designed to be printed on to projectable film, not paper, so was designed for a different contrast than film designed for paper prints.

Ian Grant · Jan 8, 2020

MattKing said:
It also differs because the early motion picture film was designed to be printed on to projectable film, not paper, so was designed for a different contrast than film designed for paper prints.

Well I think (know) that by the early 30's Europeans photographers and particularly Germans were evolving new ways of working epitomised by Hans Windisch in "Die Neu Foto Schule", and also Leica publications.

This involved changing the way negatives were over exposed and developed to much higher densities than we do today, by cutting exposures and development they achieved finer grain and better sharpness with 35mm films. There was still a degree of uncertainty with exposures and a stop safety factor was added to the film speeds, but meters ere becoming available, Gossen advertised in Die Neu Foto Schule. The film industry would have been more advanced in terms of meters, but large not very portable.

Print film emulsions wouldn't have been much different to printing papers.

Ian

138S · Jan 8, 2020

Ian Grant said:
The film industry would have been more advanced in terms of meters, but large not very portable.

In the film crew (https://en.wikipedia.org/wiki/Film_crew) there was a "Unit still photographer" man (https://en.wikipedia.org/wiki/Unit_still_photographer), the "Leica man". He made shots for the marketing and publicity of feature films... but for costly, important or challenging scenes there was the choice to make bracketed pre-shots with the "Leica" and developing in the place, so cinematographer could have a reliable reference, I cannot say how often this was used, but Leica's film could be developed/fixed and inspected before drying, so in some 10 min (while Director instructing the actors) the cinematographer would better predict the result when a doubt was there.

Kino · Jan 8, 2020

Even though it was a great image developer, D-76's adoption had much more to do with the sound track than the image.

Apples and Oranges: D76 should be discussed discreetly as still image developer OR as a motion picture developer, as the use determines succinctly different rationale for deployment and use.

billtroop · Jan 15, 2020

The reason for the two known supplements are 1 to chelate minerals in hard water and 2 to preserve the ingredients in single powder packages.

No known manufactured version of D-76 by Kodak contains additional buffering.

The known supplements do not have any known effect on HQ or pH.

The rise in pH does not occur in the package but only once the solution has been mixed.

Kino said:
About half-way through the 2nd Edition of "The Film Developing Cookbook" by Bill Troop and Steve Anchell and am really learning a lot.

The section on D-76 kinda stopped me dead in my tracks.

I never knew there were so many variants and that the fresh stuff I mixed was different enough from Kodak's mix to have a real impact on image quality.

So if I am reading this right, Kodak added their "supplements" to prepackaged D-76 to overcome the tendency to rise in PH over time when stored in powdered form and "activate the Hydroquinone", which was otherwise inactive.

Huh?

Why have HQ at all in the formula if it is not "activated".

Did they mean enhance the effect of HQ?

What am I missing?

billtroop · Jan 15, 2020

To be a little more exact, although I am basing this on memory, the original ASA standard had a 2.5x safety factor and after 1960 this was reduced to 1.25x. The papers of Loyd Jones, well worth reading today, and which formed the basis for that standard, were concerned with how to find the minimum exposure for an acceptable print.

Ian Grant said:
Well I think (know) that by the early 30's Europeans photographers and particularly Germans were evolving new ways of working epitomised by Hans Windisch in "Die Neu Foto Schule", and also Leica publications.

This involved changing the way negatives were over exposed and developed to much higher densities than we do today, by cutting exposures and development they achieved finer grain and better sharpness with 35mm films. There was still a degree of uncertainty with exposures and a stop safety factor was added to the film speeds, but meters ere becoming available, Gossen advertised in Die Neu Foto Schule. The film industry would have been more advanced in terms of meters, but large not very portable.

Print film emulsions wouldn't have been much different to printing papers.

Ian

Ian Grant · Jan 15, 2020

Kodak's own MSDS data indicates the increased buffering compared to the original published formula and there's no disputing that.

Ian

Rudeofus · Jan 16, 2020

Ian Grant said:
Kodak's own MSDS data indicates the increased buffering compared to the original published formula and there's no disputing that.

If you refer to this MSDS here, then there is a mention of 0.1 - 1% Boric Anhydrid in the materials list, a compound which is not part of the original formula. Interestingly, this compound is not listed in the working solution ingredient list, which puts it below 0.1% of the working solution, which means below 1g/l.

If you compare this to D-76 variants with improved buffering, e.g.D-76d contains a lot more Boric Acid than these measly 1g/l. I would therefore assume, that this <1g/l addition of Boric Acid serves some other purpose than an increase in buffering. Boric Acid Anhydrid is known to dissolve very slowly, and I wonder whether it is used to delay the release of Sodium Sulfite into solution, such that it doesn't arrive in quantity before the Metol is fully dissolved.

The Ins and Outs of D-76 -- (The Film Developing Cookbook)

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