Reuse of Pyrogallol developer

Silverhalide Emulsions / Chemistry.
jrburns47
Posts: 164
Joined: Mon Sep 14, 2015 2:48 pm
Location: Oyster Bay, NY

Re: Reuse of Pyrogallol developer

Post by jrburns47 »

Hi Martin,
Thank you for your thoughtful reply. I can see that we’re thinking along similar lines. It’s possibly important to differentiate between the different old glass plate emulsions of Ilford SP696T, Agfa 8E75HD and HRT BB640. The old HRT BB640 results are almost a moot point since I only have about 6 of the old plates remaining for testing. Also please note this conversation only relates to white light transmission holograms. The old HRT BB640 plates are very different visually, after processing, from the old Agfa & Ilford plates, resulting in an almost clear plate with a bright image when properly exposed. The caveat is that, although all my tests have used FeEDTA bleach, the Ilford & Agfa 8E tests used catechol based developers whereas the BB640 used the BB640 ascorbic acid, sodium hydroxide developer. As everyone I think knows, the old BB plates are and were a dramatic improvement over the old Agfa and Ilford plates.

I have also been asking this question about the efficacy of using graded alcohol dry as a final process after a pre-exposure TEA presensitizing and also about isopropyl vs ethanol. I had a good discussion with Dinesh who has had success using isopropyl whereas I’ve always used ethanol. My feeling, based on a long ago run series of tests on the effect of various hardeners on freshly mixed Knox gelatin, was that isopropyl, unlike ethanol & methanol, had the possibility of leading to a crazing or milkiness of gelatin. Dinesh said he had not experienced that in the context of isopropyl graded alcohol drying of silver halide exposures.

I plan to do some testing, i.e., TEA presensitizing & alcohol graded dry. I don’t see why it shouldn’t work.

An additional question is whether a graded alcohol dry helps prevent printout. The anecdotal evidence is possibly. If not, then the desirability of a dilute dichromate bleach anti printout rinse after non-fixed rehalogenating bleaching and washing, as suggested by John Wiltshire, may preclude a graded alcohol drying process. The question there being whether a graded alcohol drying process might negate, or possibly enhance, the anti printout benefit of the dilute dichromate bleach rinse.

In recent discussions with both Dinesh and Mike Medora, I also suggested that it could be the red sensitizing dye in the various old red sensitive emulsions that may have caused the massive loss of apparent sensitivity over decades. I came to the possibility of this conclusion because the similarly old Ilford SP695T and Agfa 8E56HD plates, that I’ve used over the last several years, most recently this last May/June, are much closer to their original sensitivity. I don’t really know if, other than their sensitizers, the old red vs.green Agfa & Ilford glass plate emulsions were the same for their respective brands. Maybe your co-author, John Wiltshire might know.

Other than the massive several orders of magnitude loss of sensitivity, all the different old red sensitive plates are providing good holograms if they receive sufficient exposure and appropriate darkroom processing.

My end objective is to arrive at an optimized visual and archival exposure and processing regime, particularly for the large quantity of old Ilford plates that I have. Although I’ve gotten good results on 4x5” plates, the 12x16” plates will definitely need presensitizing of some sort in order to avoid unrealistically long exposures. Although I’ve gotten good results without obvious defects, the very brightest results all have some sort of issue which almost looks like dissolving gelatin but may be something else entirely such as chemical staining or something about the BIPS layer that Ilford used on these plates or something else entirely. Sometime in the next few weeks I’ll post videos of those odd results.

I’m also planning to try the sodium formate presensitizing suggested by Bill Altschuler based on his experimental holography results giving a 5X increase in sensitivity. His original work for holography was derived from the work of Jacqueline Belloni on photographic emulsions.

If I’m fortunate enough to use up all my existing stock of old materials, I plan to move exclusively to the amazing BB materials😊!

I still hate squeegees but am resigned that I probably need to acquire this skill. Peter Miller has promised to visit and give me some hands on squeegee training🥳!
Din
Posts: 401
Joined: Thu Mar 12, 2015 4:47 pm

Re: Reuse of Pyrogallol developer

Post by Din »

Martin wrote: Sun Feb 20, 2022 8:30 am
Incidentally, in regards to the shelf-life of outdated, very old holographic AgX materials I wondered about the lifetime of the sensitizing dye (provided there's no AgX fogging). Would it be possible to spectrally re-sensitize these old materials?
If you knew the original dye used by the manufacturer, I can't see why not, assuming there was only one dye and not some mixture of dyes. Of course, it's not just the dye(s), but the dye(s) concentration. However, the exposure characteristics of the film are based on the type and concentration of the dye(s), so a different concentration, or different dye(s) will give different exposure characteristics. Another factor is grain size, since, presumably, the energy transfer between the dye and the grain is a surface phenomenon.
Joe Farina
Posts: 803
Joined: Wed Jan 07, 2015 2:10 pm

Re: Reuse of Pyrogallol developer

Post by Joe Farina »

jrburns47 wrote: Sun Feb 20, 2022 9:47 amMy feeling, based on a long ago run series of tests on the effect of various hardeners on freshly mixed Knox gelatin, was that isopropyl, unlike ethanol & methanol, had the possibility of leading to a crazing or milkiness of gelatin.
For what it's worth, I've definitely noticed this with respect to dye-sensitized DCG. Under some circumstances, ethyl alcohol will prevent milkiness (or crazing, or the "branching" effect) when compared to isopropyl. For the ethyl alcohol source, I go to the liquor store for the high-proof version of Everclear.
Din
Posts: 401
Joined: Thu Mar 12, 2015 4:47 pm

Re: Reuse of Pyrogallol developer

Post by Din »

Joe Farina wrote: Mon Feb 21, 2022 6:56 am
jrburns47 wrote: Sun Feb 20, 2022 9:47 amMy feeling, based on a long ago run series of tests on the effect of various hardeners on freshly mixed Knox gelatin, was that isopropyl, unlike ethanol & methanol, had the possibility of leading to a crazing or milkiness of gelatin.
For what it's worth, I've definitely noticed this with respect to dye-sensitized DCG. Under some circumstances, ethyl alcohol will prevent milkiness (or crazing, or the "branching" effect) when compared to isopropyl. For the ethyl alcohol source, I go to the liquor store for the high-proof version of Everclear.
I found many years ago that the white crazing on dcg (we called them "whities") was due to insufficient hardening of the plate. Once I pre-treated the plate to increase hardening, the whities disappeared. But, it would seem that ethyl alcohol has a greater hardening effect than IPA. Why, I don't know, but I suspect it has something to do with the bonding that polymerises the gelatin.
Martin
Posts: 131
Joined: Sat Apr 04, 2015 2:36 am

Re: Reuse of Pyrogallol developer

Post by Martin »

jrburns47 wrote: Sun Feb 20, 2022 9:47 am As everyone I think knows, the old BB plates are and were a dramatic improvement over the old Agfa and Ilford plates.
Indeed - putting apart SHSG processing.
jrburns47 wrote: Sun Feb 20, 2022 9:47 am An additional question is whether a graded alcohol dry helps prevent printout.
Never heard that. Maybe alcohol dehydrated layers provide better protection from humidity...
jrburns47 wrote: Sun Feb 20, 2022 9:47 amMaybe your co-author, John Wiltshire might know.
John Wiltshire is not my co-author, you seem to be mistaking me for Martin Richardson.

quote=jrburns47 post_id=72654 time=1645368477 user_id=4407]I plan to move exclusively to the amazing BB materials😊![/quote]

They're nice.
jrburns47 wrote: Sun Feb 20, 2022 9:47 amI still hate squeegees but am resigned that I probably need to acquire this skill.
That's been another reason I used to prefer film materials. They're very easy to handle in that respect - as long as the emulsion is well hardened.
Martin
Posts: 131
Joined: Sat Apr 04, 2015 2:36 am

Re: Reuse of Pyrogallol developer

Post by Martin »

Din wrote: Sun Feb 20, 2022 9:48 am If you knew the original dye used by the manufacturer, I can't see why not, assuming there was only one dye and not some mixture of dyes. Of course, it's not just the dye(s), but the dye(s) concentration. However, the exposure characteristics of the film are based on the type and concentration of the dye(s), so a different concentration, or different dye(s) will give different exposure characteristics. Another factor is grain size, since, presumably, the energy transfer between the dye and the grain is a surface phenomenon.
How about simply have a bathing step like the one in Jeff's diffusion method? It essentially consists of a halide (say, KBr) + a spectral dye solution. You may add ascorbate to enhance speed. See also https://holographyforum.org/wiki/DIY_Silver_Halide_Film
Martin
Posts: 131
Joined: Sat Apr 04, 2015 2:36 am

Re: Reuse of Pyrogallol developer

Post by Martin »

Joe Farina wrote: Mon Feb 21, 2022 6:56 am
jrburns47 wrote: Sun Feb 20, 2022 9:47 amMy feeling, based on a long ago run series of tests on the effect of various hardeners on freshly mixed Knox gelatin, was that isopropyl, unlike ethanol & methanol, had the possibility of leading to a crazing or milkiness of gelatin.
For what it's worth, I've definitely noticed this with respect to dye-sensitized DCG. Under some circumstances, ethyl alcohol will prevent milkiness (or crazing, or the "branching" effect) when compared to isopropyl. For the ethyl alcohol source, I go to the liquor store for the high-proof version of Everclear.
We all know, pouring "alcohol" into water involves heat release. Could it be then that IPA is generating more heat than ethanol or methanol mixed with water?
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