A few phenidone dev/microfilm questions...

[cptrios]

Hi all -
I've mentioned some of this in a couple of other threads, but I figure it'd be worth its own post considering it doesn't totally fit into either. Hopefully it's not bothersome.

First things first: this isn't really a "fix my problem" post as much as it is me hoping someone can enlighten me about some fundamental developing mechanics. I've just started mixing my own chemicals, and I really don't know anything about what any of them are actually doing!

Anyway, I got my hands on some Kodak Imagelink, and after some ok-but-not-great efforts with HC-110 and Caffenol saw a bunch of shots from the somewhat legendary flickr member threepinner suggesting that H&W Control (recipe here) might be a good option. So of course I ordered some chemicals, because what could go wrong?

My first attempt (probably 3-4 minutes too long, considering I forgot that my water was at 22c) turned out rather heavily fogged. HW on the left, HC-110 in the middle, Caffenol on the right:

This seems to be in line with the experience of another poster but not with those of others elsewhere.
Today, I decided to try out the same developer with Copex Rapid. No fog at all, but I did get the same weird 'posterization' effect that I got with HR-Dev and the same film. Interestingly, though, the effect decreased as my EI increased; the frame shot at ISO 12 is rife with it but the one at 200 has none at all (and, with some PP, is pretty close to usable...cool!). Here's a crop from three frames, at ISO 50, 100, and 200:

The reason why I frame this question as being related to phenidone-based devs is that this writer had a similar issue when developing with POTA. I have no idea if it actually has anything to do with these two potentially unrelated issues!

Given the decreased effect with decreased exposure, the most obvious conclusion for me to jump to is that I overdeveloped the Copex, just like I'm sure I overdeveloped the Imagelink. It's also entirely possible that I didn't weigh out my chemicals perfectly, etc. But without further ado, here are my likely extremely stupid-sounding questions:

1. Is some aspect of the developer essentially finishing its job and then going to town on anything it can find? If so, what exactly is the process that's happening?
2. In the case of the Imagelink, and assuming the above is correct, is that base fog likely to be building throughout the process or is there a point at which it "kicks in?"
3. Possibly the stupidest-sounding question: could the fact that these were very short (6-7 frames) strips of film in full-strength 330ml-ish solutions have something to do with it?

Threepinner also has a recipe he's used that's just sulfite, carbonate, and metol. I'm going to give that a try later this week, but it seems like a shame to not use $30 worth of phenidone and hydroquinone (though I can't say I'm super excited by their toxicity).

But yeah, thanks for any answers you might offer. In the end I have enough film and chemistry to play around with times, etc., but I'd really love to know some of the science of what's actually going on here!

 

[Alan Johnson]

The streaking problem on document film that can occur with phenidone and its avoidance is discussed in The Film Developing Cookbook 2020 p130 onwards. The oxidized phenidone retards development but according to one theory I have seen differences in the thickness of the layers of a few atoms may cause some kind of interference pattern. FDC mentions that it may be avoided by adding small amounts of hydroquininone , pyrogallol or glycin. All of these are superadditive with phenidone and regenerate it.
Like you I have found that the H&W control formula with hydroquinone does not always work. The TDLC-102 formula with glycin is quite reliable though not long lasting. FDC says it is an intermittent problem with POTA,
For my work I am using metol rather than phenidone along with color developer in a formula I called CD4-LC.
Commercial developers from Spur and TD3 from Photoformulary do not show this problem.

 

[cptrios]

Thanks for that response Alan. I had actually come across your posts here and on Flickr re: CD4-LC, but ruled it out since CD4 seems to be very difficult to get here in the States at the moment. Maybe someday!

Do you have any theories about the fogging of the Imagelink? I'm going to try this metol formula when the metol I ordered arrives. TD-3 might be next, and I assume it'll work pretty well since Imagelink is supposedly quite similar to Tech Pan.

 

[Alan Johnson]

Appears from FDC p131 that Bill Troop spoke to TH James about the fogging problem and James said that its growth is never predictable. That was the situation in 2020, the only new thing I can add is that I managed to get some fog with Fuji Eterna RDS 4791 low ISO film in CD4-LC. Fog is thus not confined to phenidone and remains unexplained IMO, except that both phenidone and CD4 form oxidation products that block the emulsion surface.

 

[lamerko]

In the last attempt with H&W Control and Imagelink, I got something interesting - an overdeveloped negative (really a lot), but almost no fog. In it's test I had a pre-bath with some photoflo.

 

[cptrios]

Appears from FDC p131 that Bill Troop spoke to TH James about the fogging problem and James said that its growth is never predictable. That was the situation in 2020, the only new thing I can add is that I managed to get some fog with Fuji Eterna RDS 4791 low ISO film in CD4-LC. Fog is thus not confined to phenidone and remains unexplained IMO, except that both phenidone and CD4 form oxidation products that block the emulsion surface.

As annoying as it is, I kind of like the idea that some of these things remain mysterious after nearly 200 years of photography!

In the last attempt with H&W Control and Imagelink, I got something interesting - an overdeveloped negative (really a lot), but almost no fog. In it's test I had a pre-bath with some photoflo.

Oooh interesting. Did you also happen to try any in a pre-bath without photoflo? Maybe I'll do that myself in a little bit.

Edit: tried a 5min presoak in distilled water (nothing else). Identical fog, unfortunately. However, the exposures all look identical too, despite my reducing time from 15min to 11min. I wonder how much time it really needs?

 

[cptrios]

Ok, this time I tried replacing half of the sodium carbonate with borax, because I read that it had fog-reducing properties. I know it will lower the overall pH, but I haven't attempted to learn what exactly pH does to the developing process yet.

Unfortunately, the borax had no effect on the fog...but it did cause the same kind of swirling/streaking on Imagelink that the original formula does to Copex!

I think perhaps my next attempts will be #1 simply using a more dilute solution and #2 reducing the sulfite in the formula.

 

[lamerko]

I did another series of experiments and found some things.
First, the key in this developer is pH. For some reason, I'm getting a higher pH than it should obviously be. In this regard, there is an omitted detail in the formula - sodium carbonate is not anhydrous, but monohydrate. This requires an adjustment to the amount if you are using anhydrous. For pH, I aim for 9 - 9.5 (max).
For even development, shake the first 1:5-2 min constantly, then every minute. Not violent, but slow stirring.
It appears that low pH results in low contrast, little grain, and low base fog, and high pH results in high contrast, high amount of fog, and coarse grain.
Also something important - at high pH above 10.5 I get dichroic fog! It appears to be related to the phenidone.

 

[xkaes]

I hope you are keeping good notes.

I'd use the K.I.S.S. and try one film and one developer at a time. There is nothing really special about micro-film except that with any developer you have to drop the film speed and increase the development time. Each of these need to be varied by running controlled tests. That's much easier if you stick with one film and one developer. That's complicated enough. Throwing in other films, other developers, pH changes, dilutions, chemicals, etc. creates a real mess.

K.I.S.S.

 

[cptrios]

I did another series of experiments and found some things.
First, the key in this developer is pH. For some reason, I'm getting a higher pH than it should obviously be. In this regard, there is an omitted detail in the formula - sodium carbonate is not anhydrous, but monohydrate. This requires an adjustment to the amount if you are using anhydrous. For pH, I aim for 9 - 9.5 (max).
For even development, shake the first 1:5-2 min constantly, then every minute. Not violent, but slow stirring.
It appears that low pH results in low contrast, little grain, and low base fog, and high pH results in high contrast, high amount of fog, and coarse grain.
Also something important - at high pH above 10.5 I get dichroic fog! It appears to be related to the phenidone.

Ooh, interesting. I have indeed been using anhydrous. I'll have time later this week to try again, so I'll reduce the carbonate down to 3.83g. I'm very lucky that someone else is playing around with this film/dev who actually knows what they're doing re:chemistry!

I hope you are keeping good notes.

I'd use the K.I.S.S. and try one film and one developer at a time. There is nothing really special about micro-film except that with any developer you have to drop the film speed and increase the development time. Each of these need to be varied by running controlled tests. That's much easier if you stick with one film and one developer. That's complicated enough. Throwing in other films, other developers, pH changes, dilutions, chemicals, etc. creates a real mess.

K.I.S.S.

Hey, sometimes we luck into some weird film and want to get the most out of it! I'm mostly an HP5/HC-110 guy, but I am irrationally fascinated by hi-res films. I also find the unperforated aspect of the Imagelink really intriguing, since it opens up a bunch of interesting non-standard formats for potential DIY cameras. 30x30 square or 30x60 pano, to name two. And, of course, I am totally, definitely going to get around to building said cameras.

 

[xkaes]

Micro-film is quite popular with submini cameras because 16mm micro-film can easily give typical 35mm film a run for it's money.

 

[cptrios]

Alright, I've done a bunch more experimenting with some mildly interesting, if unsuccessful results. A couple more to come later today, but a question for you all:

I got some pH test strips (obviously not going to be the most accurate things around) so I could play around trying to hit the 9-9.5 level lamerko suggested. The standard H&W Control soup I used looks to be well over that, at around 12, but in testing step-by-step I found that just the distilled-water-sodium-sulfite mix is already at 11. After a quick Googling, it looks like that number should be more like 9. So...what gives?

 

[Milpool]

Alright, I've done a bunch more experimenting with some mildly interesting, if unsuccessful results. A couple more to come later today, but a question for you all:

I got some pH test strips (obviously not going to be the most accurate things around) so I could play around trying to hit the 9-9.5 level lamerko suggested. The standard H&W Control soup I used looks to be well over that, at around 12, but in testing step-by-step I found that just the distilled-water-sodium-sulfite mix is already at 11. After a quick Googling, it looks like that number should be more like 9. So...what gives?

In my experience the pH of a freshly mixed sodium sulfite solution can initially be as high as ~10 depending on the concentration but will gradually decrease.

The pH of H&W Control will be primarily dictated by the sodium carbonate and based on the developer formula the pH of the working solution is probably somewhere around 10.

 

[cptrios]

In my experience the pH of a freshly mixed sodium sulfite solution can initially be as high as ~10 depending on the concentration but will gradually decrease.

That did turn out to be the case! On Friday I mixed up a little batch with two modifications: half the carbonate, and a lower concentration of phenidone as suggested here (the original link is long-dead and the wayback machine is still being a bit wonky after the hack. I did make a pdf copy of it, though) in isopropyl added in at the time of mixing the stock solution.

First, I tried that straight, right after mixing everything. pH of the developer seemed to be around 12. The resulting negs had slightly less fog but were also noticeably thinner than the full-strength ones. The added bonus here was no streaking/swirling! Grain was on par with the other H&W Control tries and accutance/resolution were probably the 'best' I've gotten so far (though that could be down to better focus cameraside). A small crop at approximately 8500dpi:



Next, about an hour later, I mixed the same stock solution but added some ascorbic acid bit by bit until the pH seemed to be somewhere in the 9 range. The result was a huge pleasant surprise: no fog! The negs were still very thin, and shadows were blocked up (I might call it a full stop slower than the foggy strip overall), but grain was much finer. Seriously, I had to re-scan because I thought I had maybe missed focus. Accutance was definitely lower, but nothing a bit of USM can't handle. Really promising overall:



Then, I tried the final third of the concentrate today, planning on using the 'normal' H&W amount of phenidone but repeating the ascorbic acid thing. However, when I tested the pH, I found it had fallen to around 10, so I left out the acid. Again, no fog! Negs were a bit less thin, too. Speed was maybe 1/2 stop better than the previous test? Grain and accutance about the same (maybe not in this particular sample, but over the entire strip):



So, definitely interesting. I'm going to try two more things next: 1. Mixing the full-strength carbonate formula and lowering the pH with the ascorbic acid, and 2. Bumping the carbonate up a bit higher (from half) without the acid to try and find a happy medium between the foggy/streaky negatives and the too-thin ones. The fog isn't that detrimental, anyway, and it has the added benefit of masking the unfortunate spotting phenomenon that results from tiny granules of something or other on the reverse side of the film (threpinner pointed this out to me too). Actually, I think that the best overall result I've gotten so far has been the normal HW recipe but with a prebath in a very dilute sodium carbonate mixture. Still foggy, but no streaking. The only real problem is grain, which I don't really mind anyway.

 

[Milpool]

That did turn out to be the case! On Friday I mixed up a little batch with two modifications: half the carbonate, and a lower concentration of phenidone as suggested here (the original link is long-dead and the wayback machine is still being a bit wonky after the hack. I did make a pdf copy of it, though) in isopropyl added in at the time of mixing the stock solution.

First, I tried that straight, right after mixing everything. pH of the developer seemed to be around 12. The resulting negs had slightly less fog but were also noticeably thinner than the full-strength ones. The added bonus here was no streaking/swirling! Grain was on par with the other H&W Control tries and accutance/resolution were probably the 'best' I've gotten so far (though that could be down to better focus cameraside). A small crop at approximately 8500dpi:

View attachment 381467

Next, about an hour later, I mixed the same stock solution but added some ascorbic acid bit by bit until the pH seemed to be somewhere in the 9 range. The result was a huge pleasant surprise: no fog! The negs were still very thin, and shadows were blocked up (I might call it a full stop slower than the foggy strip overall), but grain was much finer. Seriously, I had to re-scan because I thought I had maybe missed focus. Accutance was definitely lower, but nothing a bit of USM can't handle. Really promising overall:

View attachment 381465

Then, I tried the final third of the concentrate today, planning on using the 'normal' H&W amount of phenidone but repeating the ascorbic acid thing. However, when I tested the pH, I found it had fallen to around 10, so I left out the acid. Again, no fog! Negs were a bit less thin, too. Speed was maybe 1/2 stop better than the previous test? Grain and accutance about the same (maybe not in this particular sample, but over the entire strip):

View attachment 381466

So, definitely interesting. I'm going to try two more things next: 1. Mixing the full-strength carbonate formula and lowering the pH with the ascorbic acid, and 2. Bumping the carbonate up a bit higher (from half) without the acid to try and find a happy medium between the foggy/streaky negatives and the too-thin ones. The fog isn't that detrimental, anyway, and it has the added benefit of masking the unfortunate spotting phenomenon that results from tiny granules of something or other on the reverse side of the film (threpinner pointed this out to me too). Actually, I think that the best overall result I've gotten so far has been the normal HW recipe but with a prebath in a very dilute sodium carbonate mixture. Still foggy, but no streaking. The only real problem is grain, which I don't really mind anyway.

Keep in mind using ascorbate to lower the pH does a lot more than that as it is superadditive with Phenidones (ie you now have three developing agents, two of which are superadditive with Phenidones).

A decrease in granularity when would seem to make sense based on a paper which came out of RIT many years ago, showing that a Phenidone-only developer (POTA in that case) was quite grainy and produces strong edge effects, and that both of these tendencies are lessened with the addition of HQ.

 

[cptrios]

Yeah, I figured - it's just the only thing I have on hand that would lower the pH (unless I want to start pouring apple cider vinegar into my developer!). Here's an extremely stupid question I have after reading through Anchell and Troop a bit: Is the entire point of the carbonate to raise the pH and make the phen/HQ more active? In that case, wouldn't using the original amount and then forcibly lowering the pH through whatever method be completely redundant? If so, it seems like the mild speed-boosting qualities of H&W Control are directly tied to the fog/grain tradeoff.

Meanwhile, just for fun - it looks like we've finally outresolved the 42mp sensor:

 

[Milpool]

Yeah, I figured - it's just the only thing I have on hand that would lower the pH (unless I want to start pouring apple cider vinegar into my developer!). Here's an extremely stupid question I have after reading through Anchell and Troop a bit: Is the entire point of the carbonate to raise the pH and make the phen/HQ more active? In that case, wouldn't using the original amount and then forcibly lowering the pH through whatever method be completely redundant? If so, it seems like the mild speed-boosting qualities of H&W Control are directly tied to the fog/grain tradeoff.

Meanwhile, just for fun - it looks like we've finally outresolved the 42mp sensor:
View attachment 381523

Yes, the carbonate is there to set and stabilize the pH. The pH is of H&W control is relatively high to keep developing times reasonable as the working solution is quite dilute. This is one way of formulating a developer of this type but not the only way. You could certainly try lower pH targets using different alkali compounds - or you could also add sodium bicarbonate to create a buffer with a pH closer to say 9.5. Higher alkalinity in and of itself is not what determines emulsion speed.

Another alternative to reduce high fog (typical of relatively alkaline special purpose low contrast Phenidone developers) would be to add small amounts of KBr until you observe a speed loss.

One thing to keep in mind is that the performance of a special purpose low contrast developer is often optimized for a specific film so the results can be quite variable.

 

[cptrios]

Yes, the carbonate is there to set and stabilize the pH. The pH is of H&W control is relatively high to keep developing times reasonable as the working solution is quite dilute. This is one way of formulating a developer of this type but not the only way. You could certainly try lower pH targets using different alkali compounds - or you could also add sodium bicarbonate to create a buffer with a pH closer to say 9.5. Higher alkalinity in and of itself is not what determines emulsion speed.

Another alternative to reduce high fog (typical of relatively alkaline special purpose low contrast Phenidone developers) would be to add small amounts of KBr until you observe a speed loss.

One thing to keep in mind is that the performance of a special purpose low contrast developer is often optimized for a specific film so the results can be quite variable.

I do definitely want to try out a little bit of KBr at some point, though I need to stop accumulating containers of chemicals! I think tomorrow I'll take a crack at replacing the carbonate with borax and see how that goes.

By the way, I just want to express my appreciation for everyone answering my annoying questions. This is fun for me, and I'm in danger of actually learning some stuff!

 

[cptrios]

So, after more trial and error, some interesting results. It seems like the fog is most directly connected to pH and the streaking is most directly connected to the interaction between the phenidone and the antihalation layer. I realized that my experiments with the lower phenidone concentration were actually MUCH lower; the standard recipe has 0.183g per one-roll quantity, while the other recipe I found wound up being 0.025g. Relevant results:

Half carbonate, 0.025g phenidone, pH 12ish: Medium fog, 'high' grain, high accutance, high detail
Half carbonate, 0.025g phenidone, pH lowered to 9ish with ascorbic acid: No fog, low grain, medium accutance, medium detail
Half carbonate, 0.05g phenidone, pH lowered to 9ish naturally after a few days (no idea why): No fog, low grain, medium accutance, high detail

Borax replacing carbonate, full phenidone, pH 11ish: Medium fog, medium-low grain, medium detail, streaking
Same but with pH lowered to 9ish with ascorbic acid (there was no natural drop in pH with this mixture): Same but with no fog
Same (acid) but with a prewash in very dilute carbonate solution to remove AH: Same but with no fog or streaking

So, under high magnification, the nicest of all of these had a pH between 9-10 and a bit less than a third of the original phenidone concentration. The lower phen concentrations also didn't require any prewashing. Speed is much better in the higher-phenidone soup, though, with the lower concentrations negatives being pretty thin with not much in the way of shadow detail. I'm sure there's a happy medium somewhere.