Modern Staining Developers for Enlarging

I have been using PMK for the last few years with good overall results. While I occasionally print on graded paper, I usually use Ilford’s Multigrade papers. Most of my work is with medium format with only modest enlargements. I have not experienced the ‘flat highlights’ problem that is attributed to PMK; I assume that since I print with a condenser enlarger that the collier effect counteracts the effect of PMK’s ‘dye mask’(image specific stain) on variable contrast paper.

With the potential of Ilford cesing production, I am forced to rethink my film development procedures. I have experimented with Forte papers but the resulting prints are grittier than ones printed on Ilford papers. My assumption is ‘dye mask’ created by PMK is more transparent to the sensitizing dyes used in the Forte papers than Ilford’s.

I gave PyroCat HD a casual trial last year. Evaluating the prints for overall quality I felt that PyroCat produced sharper but grainier prints than PMK. Evaluating the negatives under magnification the actual grain size was similar for both PMK & Pyrocat; since the Pyrocat prints looked grainier I deduced that it produced less usable ‘dye mask’ for silver printing than PMK did. The PyroCat negatives printed similarly on both brands of papers; which leads me to believe that other Pyro formulas are better suited to the characteristics of eastern block papers.

Recently there have been a number of new staining developer formulas published. Are any of them optimized for enlargement quality negatives? Also, does TEA as an accelerator provide any benefits over carbonate or metaborate accelerators other than the obvious benefit of a single solution developer?

Josef Guay said:

With the potential of Ilford ceasing production, I am forced to rethink my film development procedures. I have experimented with Forte papers but the resulting prints are grittier than ones printed on Ilford papers. My assumption is ‘dye mask’ created by PMK is more transparent to the sensitizing dyes used in the Forte papers than Ilford’s.

I gave PyroCat HD a casual trial last year. Evaluating the prints for overall quality I felt that PyroCat produced sharper but grainier prints than PMK. Evaluating the negatives under magnification the actual grain size was similar for both PMK & Pyrocat; since the Pyrocat prints looked grainier I deduced that it produced less usable ‘dye mask’ for silver printing than PMK did. The PyroCat negatives printed similarly on both brands of papers; which leads me to believe that other Pyro formulas are better suited to the characteristics of eastern block papers.

Recently there have been a number of new staining developer formulas published. Are any of them optimized for enlargement quality negatives? Also, does TEA as an accelerator provide any benefits over carbonate or metaborate accelerators other than the obvious benefit of a single solution developer?

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Can I assume that your Pyrocat-HD/PMK comparison was on VC paper? If so your findings are opposite of what Steve Simmons reported in his article in the current issue of View Camera. In my own tests I have found that both developers give results that are virtually identical in terms of grain and sharpeness, but most of my comparisons are made based on printing on AZO, other graded silver papers and with alternative processes, not VC.

I agree with you that the dye mask produced by Pyrocat-HD is less efficient than that produced by PMK with VC papers. But with graded papers the Pyrocat grain mask is more effective than that of PMK. And for alternative printing the grain mask of Pyrocat-HD is much, much more effective. And for scanning the Pyrocat-HD grain mask appears to be at least as effective as that of PMK because it gives very clean, almost grain free scans.

Your comments about a possible difference in the reaction of Ilford and Forte papers to the color of the stain of different pyro formulas are very interesting. Maybe others will just in and comment on this. I would like to be helpful but am not working any more with VC papers and projection printing and don't have anything useful to add. Well, I could theorize but results from actual tests or prints are always more interesting.

As for the TEA, no, in my opinion it does not provide any benefits over carbonate or metaborate accelerators other than the convenience of single solution and stability. The key to a good developer is to have a good balance of reducer(s), accelerator, and restrainer if needed. The formulas that I have prepared with TEA work at a pH of about 9.3, slightly lower than the pH of 9.6 of PMK, and quite a bit lower than the 10.9 of Pyrocat-HD. According to some theory the lower pH should give finer grain but I did not find that to be the case in recent tests I did with a pyrogallo/metol developer in TEA.

In fact, there are some real problems with the Pyro/TEA formulas if you use them at other than the standard dilution because this will result in very large changes in pH and in the activity of the working solution.



Sandy

jdef said:

Sandy posted while I was still typing, but he makes some interesting points.



"As for the TEA, no, in my opinion it does not provide any benefits over carbonate or metaborate accelerators other than the convenience of single solution and stability."


That is probably true, but for me, those are important benefits.


"The formulas that I have prepared with TEA work at a pH of about 9.3, slightly lower than the pH of 9.6 of PMK, and quite a bit lower than the 10.9 of Pyrocat-HD."


Sandy, I'm not sure why the Ph is so important to you. Could you please explain why it is? I know that the Ph of a developer has an effect on its activity, and a developer with low Ph could have inconveniently long developing times, which is definitely not the case with the TEA developers I'm using, but is there something else that makes a higher Ph important?

"In fact, there are some real problems with the Pyro/TEA formulas if you use them at other than the standard dilution because this will result in very large changes in pH and in the activity of the working solution."

That's an interesting claim. I spent the better part of yesterday testing various developers with Technical Pan, and one of the clear winners was Pyro-TEA @ 1:200 for 10 min. @ 70F, the standard dilution being 1:50. Pyro-TEA and Technical Pan is a fantastic combination, by the way, and I imagine that it would be useful for other high contrast, fast developing films as well. Could you expand on your problems with Pyro/TEA developers and non-standard dilutions?

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You misunderstood my point about pH. High pH is not desirable in theory. In fact, to the contrary as much of the literature suggests that *low* pH is better than high pH if small grain structure is desired. My point was that I could find no difference in grain with the various developers ranging from pH of 9.3 to 10.9.

When you dilute a Pyro/Tea formula there is a much greater change in pH than when you dilute PMK or Pyrocat-HD by an equal amount. Just test it yourself and you will see. This is a potential source of trouble, especially when you are trying to get as much contrast as possible out of an emulsion because if the developer exhausts too quickly because it is too energetic there will be oxidation and greater B+F.

Technical Pan is a high contrast film and one would expect that a much less energetic solution would work best with it. But I am not sure what you mean by clear winners? What other developers did you use for the comparison tests, and at what dilution and temperature? And on what do you base your conclusion that Pyro-TEA at 1:200 was the winner? Densitometry, comparison of print from different developers, or visual evaluation of the results of the negatives?

Sandy

The Callier Effect does not affect dye images, according to what I have read. I suppose you could test this assertion by printing one of the C-41 monochrome films both ways. The color of the stain image does affect contrast on VC paper differently than on graded paper.

jdef said:

Sandy, thanks for clearing up my Ph confusion. I've never used Pyrocat or PMK, so I have no basis for comparison with those developers. As for diluted TEA developers, I think Patrick has already addressed that and suggested that the addition of sulfite would equalize those differences.

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I missed what Pat said about adding sulfite to equalize the differences in diluted TEA formulas. How much and at what dilutions? I would personally consider this a major complication to have to add extra sulfite to a pyro staining developer because the sulfite will almost certainly affect the intensity of the stain, and printing contrast of the negative.

In a broader sense I have looked rather carefully at the advantages and disadvantages of the one solution pyro formulas based on TEA as compared to two solution formulas in which the A solution is stored in propylene glycol, and determined that for my own purposes, which involves developing film both for the relatively low CI needed for silver papers and the higher CI needed for alternative work, the two part formula offers quite a bit more flexibility. Using TEA as the accelerator, with pyro or pyrocatechin in combination with either metol or phenidione, has resulted in unacceptablly long development time to reach the needed contrast, and quite a bit more B+F than I get with Pyrocat-HD.

Sandy

I'm not sure what I may have said about adding sulfite to PQ-TEA or CAT-P-TEA. Well, I'm 77 years old. It was probably for the purpose of activating the synergism. Pyrocat HD and PMK both have a little sulfite. Too much reduces the stain. In the case of PQ-TEA, 1 gram/liter of working solution is enough. As you add more, the developer begins to take on the characteristics of many other PQ developers. No stain, lots of contrast, etc.

It's no great strain to add a pinch of sulfite to the working solution, or a bunch of it to the B solution. It is not required for keeping the A solution if you mix that in glycol.

Another thing I have found is that TEA is a good substitute for the B solution of PMK. I have used it in the same amounts I would have used for the Kodalk solution. If you mix your own, the Kodalk solution is sometimes a matter of concern judging from the many posts I have seen asking what to do when it won't all dissolve.

Anything I say here is only a suggestion, and my feelings won't be hurt If any of you find a better way. They might be hurt if you don't tell us about it.

jdef said:

As for your purposes, I don't really see what you have to gain by experimenting with other developers. Your developer seems to do everything you want it to, and very well. If it aint broke etc.. I like single solution developers, and for me, PCP-TEA is very promising.

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I may have nothing to gain in a real sense but I enjoy experimenting, both for its own sake and to see what happens.

Pyrocat-HD is a very good formula but there are some things I would like to improve. For example, with minimal and semi-stand development it gives very enhanced adjacency effects and outstanding apparent sharpness. I would actually like to be able to get those qualities in a staining developer using rotary processing so that is one of the avenues I will look at with Pyrocat. One of my previous goals was to adjust it so that the stock solutions would be as stable as those of PMK. Well, thanks to Pat Gainer I now already know how to do that.

I can appreciate the advantages of a single solution developer. In theory it should be faster and simpler to mix a working solution from a one stock solution than from a two stock formula. Unfortunately the viscosity of TEA in my own experiments worked against that simplicity because in order to measure it accurately I have found it necessary to heat the solution. By the time I have finished doing that I could have already easily mixed the working solution from a two part formula with Stock A in glycol. So in practice I have found that it takes more time to mix a working solution from the one part TEA solution than with the two part formulas.I could store the TEA solution at a higher temperature to reduce viscosity of course, but that brings with it some complications as well.



Sandy