So I've recently been messing with a really crazy developer formula which produces a unique warmtone print. Specifically, it'll give dark brown-olive blacks and brown or sometimes orange highlights and midtones. I'm really not a fan of how every modern warmtone developer produces a deep olive green kind of warmtone, so the browns and reds are what I'm more looking for. I've not been able to figure out how to get that though until now (excluding lith prints of course), at least not without bleaching and redev or toning.
I began adding ammonium thiocyanate. Normally very much of this at all will very easily cause fogging, any level above 0.05g/L without care will produce fog in my tests. However, the fogging can be prevented with benzotriazole. In my tests, my developer could go all the way up to 2g/L without fog or dichroic fog/sludging if matched with 0.3g/L BZT. Beyond this level though, dichroic fog and sludging begin to appear which can not be prevented with BZT.
Anyway, the formula I tried is this: GVPX1 (not in mixing order)
* 3g glycin
* 6g ascorbic acid
* 25g sodium sulfite
* 20g potassium carbonate
* 1.5g sodium hydroxide
* 40ml triethanolamine 99% (source: photographer's formulary)
* 2g ammonium thiocyanate
* 0.3g benzotriazole
* 0.2g potassium bromide
* 2g sodium chloride
* top to 1L with water
The idea here is to make an extremely solvent developer which will give very fine grain on a print, translating to brown warm tones. This it actually does work really well for... but the developer quickly changes after just a few prints and shifts from brown to green or neutral tones. The developer otherwise seems stable keeping development action after 1 day in an open tray, but changes quickly with each sheet of paper developed. I'd estimate I got maybe 6 sheets of 8x10 from it before it lost the effect. Specific papers I've confirmed will give this effect include Ilford MGV RC, Ilford MGFB, and Arista.EDU Ultra FB (more subtle, cold brown)
The biggest problems I have are the depth of blacks, development time requirement, and the very small print capacity. The blacks can be a bit of a challenge as I believe I'm getting "veiling" in large blocks of shadows which modern papers are specifically designed to prevent apparently. It's not a problem with all subjects, but with low key subjects it can be a pretty ugly look. Increasing pH using carbonate doesn't do much to fix it, increasing pH with sodium hydroxide does fix it quite well, or at least eliminates the effect. Development times range from 3-8 minutes. This developer tends to look best though when not 100% developed to completion, rather I tend to pull when blacks look dark enough and shadows have enough density. Again, adding hydroxide speeds up development, but since hydroxide is so powerful it requires very careful balancing to avoid going overboard with. This is another capacity issue.
Finally, the small print capacity is especially weird. When freshly mixed there's a very mild ammonia smell which dissipates after a few minutes. The first 3 or 4 prints developed in this will cause the developer to release more ammonia smell, sometimes it can be a bit much honestly. This doesn't happen when just sitting in the tray. However, after 10 prints, the smell when developing is almost completely gone. By this point as well, there is no longer a good brown tone and the color has shifted to green or neutral.
In addition, the developer itself would very quickly get dark with all of the silver being taken off the paper. It's quite nearly a monobath to be honest. This doesn't seem to affect actual developer performance nor cause staining as long as you're careful not to push any silver into the image area.
When the developer seemed dead to get the brown tone, I tried adding 2g more ammonium thiocyanate. The next print had a significant amount of silver sludging, BUT was beyond brown and into the red tones. After 4 prints, it was still somewhat red, but more subdued. This may have been due to pH adjustments though.
Now, why I'm posting all this here. Does someone who knows more about the chemistry happening here have any hints on fixing any of these problems, especially the print capacity? My rough guess is that the ammonium in solution is less important than the thiocyanate for giving the specific color I'm looking for. However, I don't understand why the ammonium seems to quickly get used up. I do have some ammonium chloride and it's cheap to order online (aquarium chemical), but I'd rather not have to be replenishing the ammonium salt every 3 prints, especially since chloride brings it's own problems to be using for replenishment. I could use some kind of dirty household ammonia, but don't have a good source of concentrated stuff, and honestly had rather not handle it in a limited ventilation darkroom anyway. I just want some way of keeping the ammonium in solution somehow. My target for replenishment is more like 20 8x10 prints per liter unless I reformulate things to be a bit more economical.
Example on MGV RC and MGFB
I began adding ammonium thiocyanate. Normally very much of this at all will very easily cause fogging, any level above 0.05g/L without care will produce fog in my tests. However, the fogging can be prevented with benzotriazole. In my tests, my developer could go all the way up to 2g/L without fog or dichroic fog/sludging if matched with 0.3g/L BZT. Beyond this level though, dichroic fog and sludging begin to appear which can not be prevented with BZT.
Anyway, the formula I tried is this: GVPX1 (not in mixing order)
* 3g glycin
* 6g ascorbic acid
* 25g sodium sulfite
* 20g potassium carbonate
* 1.5g sodium hydroxide
* 40ml triethanolamine 99% (source: photographer's formulary)
* 2g ammonium thiocyanate
* 0.3g benzotriazole
* 0.2g potassium bromide
* 2g sodium chloride
* top to 1L with water
The idea here is to make an extremely solvent developer which will give very fine grain on a print, translating to brown warm tones. This it actually does work really well for... but the developer quickly changes after just a few prints and shifts from brown to green or neutral tones. The developer otherwise seems stable keeping development action after 1 day in an open tray, but changes quickly with each sheet of paper developed. I'd estimate I got maybe 6 sheets of 8x10 from it before it lost the effect. Specific papers I've confirmed will give this effect include Ilford MGV RC, Ilford MGFB, and Arista.EDU Ultra FB (more subtle, cold brown)
The biggest problems I have are the depth of blacks, development time requirement, and the very small print capacity. The blacks can be a bit of a challenge as I believe I'm getting "veiling" in large blocks of shadows which modern papers are specifically designed to prevent apparently. It's not a problem with all subjects, but with low key subjects it can be a pretty ugly look. Increasing pH using carbonate doesn't do much to fix it, increasing pH with sodium hydroxide does fix it quite well, or at least eliminates the effect. Development times range from 3-8 minutes. This developer tends to look best though when not 100% developed to completion, rather I tend to pull when blacks look dark enough and shadows have enough density. Again, adding hydroxide speeds up development, but since hydroxide is so powerful it requires very careful balancing to avoid going overboard with. This is another capacity issue.
Finally, the small print capacity is especially weird. When freshly mixed there's a very mild ammonia smell which dissipates after a few minutes. The first 3 or 4 prints developed in this will cause the developer to release more ammonia smell, sometimes it can be a bit much honestly. This doesn't happen when just sitting in the tray. However, after 10 prints, the smell when developing is almost completely gone. By this point as well, there is no longer a good brown tone and the color has shifted to green or neutral.
In addition, the developer itself would very quickly get dark with all of the silver being taken off the paper. It's quite nearly a monobath to be honest. This doesn't seem to affect actual developer performance nor cause staining as long as you're careful not to push any silver into the image area.
When the developer seemed dead to get the brown tone, I tried adding 2g more ammonium thiocyanate. The next print had a significant amount of silver sludging, BUT was beyond brown and into the red tones. After 4 prints, it was still somewhat red, but more subdued. This may have been due to pH adjustments though.
Now, why I'm posting all this here. Does someone who knows more about the chemistry happening here have any hints on fixing any of these problems, especially the print capacity? My rough guess is that the ammonium in solution is less important than the thiocyanate for giving the specific color I'm looking for. However, I don't understand why the ammonium seems to quickly get used up. I do have some ammonium chloride and it's cheap to order online (aquarium chemical), but I'd rather not have to be replenishing the ammonium salt every 3 prints, especially since chloride brings it's own problems to be using for replenishment. I could use some kind of dirty household ammonia, but don't have a good source of concentrated stuff, and honestly had rather not handle it in a limited ventilation darkroom anyway. I just want some way of keeping the ammonium in solution somehow. My target for replenishment is more like 20 8x10 prints per liter unless I reformulate things to be a bit more economical.
Example on MGV RC and MGFB
