A Lye-r 's Tale: Dilutions Of Grandeur

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thronobulax

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In another thread, @Ian-Barber had an extended conversation about higher dilutions of D-23. This led me to be curious about really high dilutions of both D-23 and DK-50. @Raghu Kuvempunagar suggested this would be possible by addng 0.5g/l of lye (Sodium Hydroxide or NaOH) to the highly dilute developers to jack up their alkalinity. I caution the reader - full concetrate lye is nasty stuff and yields unpleasant chemical burns and should only be handled if you know how to work properly in a lab, with good ventilation and bodily protection..

I did a variety of tests in 3 formats: 35mm, 120 9x6, and 9x12 sheets. Not all developers were tried in all formats, nor were all dilutions. All tests were done using 3 min prewet, 2min initial continuous agitation, standing, 10-15 sec agitation at 31 min, and completed development at 60min, nominal 68F (semistand development).

So, the following should be understood to be provisional results subject to more testing:

  1. D-23 1:3 and DK-50 1:3 both work fine without any lye being added and yielded well managed negatives.
  2. D-23 1:9 and DK-50 1:5 with 0.5g/l of lye added also produced well managed negatives.
  3. D-23 in either dilution seemed to give better sharpness than the DK-50 in either dilution. That is, reducing solvent effects for higher acuity seemed more evident with dilute D-23 than DK-50.
  4. DK-50 in any of the dilutions produced noticeably less developer compensation effects than did the D-23.
  5. Highly dilute D-23 makes grain really visible in 35mm - at least it did with Kodak XX film. Since I've never tried the film with my more usual development practice, I cannot yet comment on whether or not it's the film or the developer, but I strongly suspect it's the latter.

Next up will be to try the higher dilutions of D-23 and DK-50 see how much difference the lye actually makes.
 
I probably should note also that both DK-50 and D-23 at 1:3 produced very fine negatives and excellent sharpness, in this particular case with Fomapan 200, so it's questionable whether the additional effort of even higher dilution plus lye really makes enough difference to be worth the effort.

I do want to try higher dilutions - say 1:5 with both developers, without adding lye to see what happens.

My reason for all this fiddling is that Pyrocat-HD starts to show lower contrast beyond dilutions of 1.5:1:200. The quest here is to:

  1. Achieve the midtone contrast of semistand AND
  2. Rein in highlights by compensating effect AND
  3. Achieve optimal sharpness AND
  4. Maintain overall desired contrast range
This is very much still in the experimental stages. There may be an X,Y for X:Y:Z for Pyrocat-HD that gets what I am after. I do think for almost all practical purposes, 35mm works best with Pyrocat-HD simply because the stain hides grain so effectively.
 
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I don't think your last point is correct. When you use Pyrocat Hd at a dilution of 2+2+100 (i.e. a stronger solution, and therefore maybe more stain) you get noticably more grain than you do at 1+1+100.
And why does the grain hiding feature of Pyrocat HD make it the best developer for 35mm ? I actually like grain in a print. I don't want to hide it.
As it happens I agree that Pyrocat HD is an excellent developer. But there are others that are just as good, and easier to obtain.

I know that you enjoy doing all this testing. But you do make it sound as though you are trying to achieve something that nobody else has so far managed to do. The reality is that several off-the -shelf developers will easily achieve the four qualities that you list. Perceptol at 1+3 is one. And it will deliver them with a normal development routine of one agitation every half minute. No need for all that semi-stand stuff.
 
thronobulax said:
I caution the reader - full concetrate lye is nasty stuff and yields unpleasant chemical burns and should only be handled if you know how to work properly in a lab, with good ventilation and bodily protection..
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Chemicals must be handled with due care but adding 0.5 of lye to a developer working solution isn't as complicated as you make it! I have a bottle of Lye pellets and usually 3 pellets make 0.5g. Protective gear that you use for Pyrocat-HD should be sufficient to handle Lye at the quantity recommended.
 
Alan Clark said:
And why does the grain hiding feature of Pyrocat HD make it the best developer for 35mm ? I actually like grain in a print. I don't want to hide it.
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Isn't using a fine-grain developer like Perecptol going to negate this?
 
Ian. Yes, Perceptol is a fine grain developer. But that is when it is used as a stock solution or maybe at 1+1. At a dilution of 1+3, the chemical that eats away at the grain - and also the sharpness - is diluted. The grain comes back a bit but is very crisp and sharp. And there is a real increase in image sharpness.
When I say I like grain, what I mean is that I like a hint of it - to give some structure and character to the print. I'm talking about 35mm here, of course. I don't see grain in prints from 120 or large format negatives.
 
Alan Clark said:
Ian. Yes, Perceptol is a fine grain developer. But that is when it is used as a stock solution or maybe at 1+1. At a dilution of 1+3, the chemical that eats away at the grain - and also the sharpness - is diluted. The grain comes back a bit but is very crisp and sharp. And there is a real increase in image sharpness.
When I say I like grain, what I mean is that I like a hint of it - to give some structure and character to the print. I'm talking about 35mm here, of course. I don't see grain in prints from 120 or large format negatives.
Click to expand...

It is said that Perceptol is D-23 + sodium chloride. If that's true, then at a dilution of 1+3, Perceptol is probably not very different from D-23 1+3 due to the dilution of sodium chloride.
 
Raghu, I am no chemist, but I believe Perceptol contains another ingredient that you haven't mentioned.
I can understand why people get something out of buying raw chemicals and mixing their own developers. But personally, I really like the convenience of buying a top-quality developer, off the shelf, ready packaged.
 
Raghu Kuvempunagar said:
It is said that Perceptol is D-23 + sodium chloride. If that's true, then at a dilution of 1+3, Perceptol is probably not very different from D-23 1+3 due to the dilution of sodium chloride.
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I have heard this mentioned before so if it is true, then D-23 1+ 3 is a much more economical choice than the ready-made Perceptol
 
@Alan Clark Is it the sharpness of Percetol that you like, never used it personally but briefly looking, it's not a low-cost developer compared to others.
 
Alan Clark said:
I don't think your last point is correct. When you use Pyrocat Hd at a dilution of 2+2+100 (i.e. a stronger solution, and therefore maybe more stain) you get noticably more grain than you do at 1+1+100.
Click to expand...

I should have been more specific. Pyrocat-HD at the dilution I use (1.5:1:200) tends to generally exhibit low grain and the stain acts to hide grain further which is most notable in 35mm.

Alan Clark said:
And why does the grain hiding feature of Pyrocat HD make it the best developer for 35mm ? I actually like grain in a print. I don't want to hide it.
As it happens I agree that Pyrocat HD is an excellent developer. But there are others that are just as good, and easier to obtain.
Click to expand...

I prefer to minimize grain except in the rare case where it's actually an aesthetic tool to be consciously manipulated. You do not. One is not better than the other, we just have a different way of working.


Alan Clark said:
I know that you enjoy doing all this testing. But you do make it sound as though you are trying to achieve something that nobody else has so far managed to do. The reality is that several off-the -shelf developers will easily achieve the four qualities that you list.
Click to expand...

I have never said, suggested, intimated, or even silently thought that I was doing new science here. But I long ago realized that most internet "experts" are not, and doing my own experimentation would provide far better insights, not to mention being a considerably valuable learning experience. The past few years of experimentation have taught me more about how how film actually works than any amount of theorizing could have.

Alan Clark said:
Perceptol at 1+3 is one. And it will deliver them with a normal development routine of one agitation every half minute. No need for all that semi-stand stuff.
Click to expand...


Again, there are many ways of working, no one of which is absolutely better than the other. In my experience, you can get to the first 80% of desired outcomes with "off the shelf" solutions. But the last 20% requires a much greater degree of fiddling and tuning. If you are getting your desired outcomes with your workflow, blessings be upon you.

I would be interested in seeing one of your images done in Perceptol that demonstrates the four goals I mentioned about absent post scanning manipulation. I say that because my desired output medium is a silver print not a display, so my interest is getting those four qualities laid down on a physical print which means they need to be present in the negative.
 
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Alan Clark said:
Raghu, I am no chemist, but I believe Perceptol contains another ingredient that you haven't mentioned.
I can understand why people get something out of buying raw chemicals and mixing their own developers. But personally, I really like the convenience of buying a top-quality developer, off the shelf, ready packaged.
Click to expand...

And that's an entirely reasonable approach. I would point out that cooking your own chemistry is dramatically less expensive than buying it premade - at least that so here in the US where bulk chemistry is readily available and relatively cheap.
 
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Raghu Kuvempunagar said:
Chemicals must be handled with due care but adding 0.5 of lye to a developer working solution isn't as complicated as you make it! I have a bottle of Lye pellets and usually 3 pellets make 0.5g. Protective gear that you use for Pyrocat-HD should be sufficient to handle Lye at the quantity recommended.
Click to expand...

I sort of feel obligated to put standard warnings into my postings on the off chance that someone new to this all decides to go down one of the experimental paths I am describing. I see people doing things with chemicals of all kinds that are the least worrisome and, at worst, terrifying.

Lye can absolutely be handled carefully in a small lab without incident, but it does take extra care.
 
Raghu Kuvempunagar said:
It is said that Perceptol is D-23 + sodium chloride. If that's true, then at a dilution of 1+3, Perceptol is probably not very different from D-23 1+3 due to the dilution of sodium chloride.
Click to expand...

I would point out that in my recent round of testing D-23 1:3 produced very sharp images. Similarly, D-23 1:9 with lye added was very sharp.

Hoping to post print scans soon.
 
Ian-Barber said:
@Alan Clark Is it the sharpness of Percetol that you like, never used it personally but briefly looking, it's not a low-cost developer compared to others.
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Ian, It's not just the sharpness. When I use it with 35mm FP4+ I find that the prints have a magical tonality about them, that I really like. This justifies the cost, for me.
I like to photograph in hazy sun. To control the negative highlight density I give the film, like everyone else, reduced development. This brings the highlight density down. But it also brings the mid-tones down too, and they can look too dark in the finished print. To counteract this I give the film a stop extra exposure, and this - in theory - brings the mid-tones back up to where you want them. A few years ago I did a whole series of experiments with different developers to try to work out what worked best. I used FP4 - in 35mm because differences show up best in normal sized enlargements from 35mm. I waited for my "best" light - hazy sunshine. set the camera up on a tripod, rated the film at 64 ISO and exposed two rolls of film on the same subject. Then I went through the laborious process of cutting bits off the film and developing each piece in different ways in different developers. I used Pyrocat HD - at 1+1 +100, with regular agitation. I also tried it more dilute, with semi-stand development. I used Rodinal in various dilutions. And Perceptol, Xtol and ID11 in different dilutions.
I learned a lot. Rodinal - highly acclaimed as a compensating developer - turned out to be third rate. Drab mid-tones, and lack of shadow detail. Xtol was sharp and grain-free, but the tonality was not good enough - the mid and upper -mid tones were simply too dark. ID11 at 1+3 was excellent. Really sharp. Fine and very crisp grain. And lovely bright mid-tones. Very close to Pyrocat HD and Perceptol 1+3, but these last two seemed to have an extra "something" The prints shone! I was using a lot of Pyrocat at the time but when my supply dried up I switched to Perceptol for 35mm FP4. I have since discovered that it gives outstanding results with 35mm HP5 as well. In 120 and large format I find IID11 at 1+2 works excellently, so I only actually use Perceptol for 35mm films.
 
OK, here are some example images. These are all scans of 8x10 silver prints on a very mediocre scanner. Post scan manipulation limited to try to duplicate the physical print as closely as possible.

All of these were prewet for 3 min, continuously agitated for 2 min, and semistand developed for a total of 60 min with one 10-15 sec agitation at 31 min. Temps were a nominal 68F with developer time adjusted by a temperature compensating timer. All were exposed at box ASA.

4x5 Fomapan 200 DK-50 1+3 - 127mm f/4.7 Ektar

https://www.tundraware.com/Photogra.../media/large/20230525-1-14-Firmly_Planted.jpg

This image was shot in very flat light with almost no SBR to speak of. Notice the very strong local contrast and excellent edge sharpness throughout. (The wind was blowing some of the leaves around hence not everything is perfectly sharp.)

9x6 Agfapan APX 100 DK-50 1+4 Sodium Hydroxide 0.5g/l - 90mm f/3.5 EBC Fujinon

https://www.tundraware.com/Photogra...er/media/large/20230602-1-05-Falling_Down.jpg

Further dilution does hold sharpness fairly well, though it's hard to compare this smaller format and lens with the larger format of the the prior image. This was shot in a glade that was in the shadow with very flat light on the tree itself but with very bright light filtering through from the upper right. I had to burn a lot on the right to get this to some reasonable level of detail. This suggests that this developer/dilution combination doesn't really compensate the highlights very effectively, though it does manage to hold the detail.

35mm Kodak Double-X 5222 D-23 1+9 Sodium Hydroxide 0.5g/l - 50mm f/3.5 Uncoated Elmar

https://www.tundraware.com/Photography/MyPhotographs/Silver/media/large/20230608-1-12-Tickets.jpg
https://www.tundraware.com/Photogra...er/media/large/20230608-1-14-No_Spin_Zone.jpg

These are handheld with a Leica IIIf and the negs where somewhat overexposed (I'd never used Double-X in 35mm before so I wasn't quite sure what to expect). Both images show very good management of large dynamic range, but the grain jumps out. At least in 120, Double-X in Pcat isn't particularly grainy, so I attribute this primarily to the format/developer combination.

12x9 Fomapan 100 D-23 1+9 Sodium Hydroxide 0.5g/l - 127mm f/4.7 Ektar
Wonderful dynamic range management and very sharp. (The line toward the bottom left of center is a single weed stalk!)

Observations

It's hard to be definitive because there are variables of lens, format and film type at play here. But I have provisionally concluded (to be amended as I learn more) that:

  1. DK-50 at higher dilutions is produces good edge sharpness but much less highlight compensation compared to Pcat or D-23.

  2. I find the images done in D-23 preferable to those done in DK-50. They're generally slightly sharper and the highlights are managed better.

  3. I prefer less grain than more, so for 35mm - at least for me - these high dilutions are nonstarters. I likely will stick with Pyrocat-HD for this format.

  4. D-23 in high dilution produces very fine results with large format film. When I first looked at the 9x12 image, I though it had some sort of defect in it. When I looked closer, it turned out that the line toward the bottom left of center is a single weed stalk!
Next Up

Comparing D-23 1+9 without adding lye - how much difference does it really make?

Comparing D-23 1+9 to Pyrocat-HD to see if there is clear winner when best sharpness is desired.
 
I’m not part of this particular conversation, but may I comment?
These subjects are so varied that it must be impossible to distinguish any differences attributable solely to variations in the developing process.
There are other factors too. These are scans from prints, but the printing process doesn’t seem to be standardised either. (“…burn a lot…”)
There’s also the unknown factor of the “mediocre scanner” and its software.
As always, there’s the final threshold of the differing screens we are using to view the results.
I don’t doubt that these experiments are useful and interesting in your own quest for an optimum system of development. I applaud your ambition. I wish you well. …and I rather like the images you’ve shown, anyway.
 
David makes the point that I was going to make myself. Too many variables.
When I did the experiment described above I made 72 identical exposures of the same subject, in the same light, with the same film. The same subject made it easy to spot differences in the final prints, and these differences could only come from differences in developer and/or the way the developer was used.
 
David M said:
I’m not part of this particular conversation, but may I comment?
These subjects are so varied that it must be impossible to distinguish any differences attributable solely to variations in the developing process.
There are other factors too. These are scans from prints, but the printing process doesn’t seem to be standardised either. (“…burn a lot…”)
There’s also the unknown factor of the “mediocre scanner” and its software.
As always, there’s the final threshold of the differing screens we are using to view the results.
I don’t doubt that these experiments are useful and interesting in your own quest for an optimum system of development. I applaud your ambition. I wish you well. …and I rather like the images you’ve shown, anyway.
Click to expand...

You are part of any conversation you wish to join ;)

I certainly agree that this isn't a rigorously controlled body of tests. I used to do exactly that - much more formal testing - taking dozens of the same image and then changing only one variable to see the changes, using a densitometer to check my work, and so on. This mostly led to too much time spent on dead ends, not to mention taking many boring test shots and no "real" pictures. I found that trying to make real pictures with broad changes helped me circle in on the things of interest by discarding what wasn't of interest and then I could go more deeply. Similarly, I pretty much never do test strips in the darkroom. I make a rough print to get me in the general area of expression and then tune to desired outcome.

This recent foray was more intended to do a quick look at highly dilute D-23 and - possibly DK-50 and to discard anything that I obviously didn't like ... a filter, if you will, for the gross cases. Based on this quick survey, I will no longer pursue more rigorous testing of highly dilute development with 35mm, I don't think DK-50 offers anything particularly compelling here, and I think D-23 highly dilute is worth testing in more controlled depth.

I do think that there is value in more formal, controlled testing when someone is first starting out. It gets one to at least passable negatives early on which then serves as a base for further exploration.
 
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