Advice on my Two Bath Developer

[Raghu Kuvempunagar]

Karl, regarding carry over, the next time you develop a roll of film using either of your 2 bath formulations, immerse a film strip in part B immediately after the second bath is over for your roll. Alternatively, add 20ml of part A to part B and do a similar exercise. Check if the film strip darkens after a few minutes. If it does then it means that the carryover part A itself acts as a developer and therefore highlights will continue to build density (ie no developer exhaustion in the highlights). If the film strip doesn't darken then your 2 bath developer works like a conventional 2 bath developer.

 

[relistan]

Karl, regarding carry over, the next time you develop a roll of film using either of your 2 bath formulations, immerse a film strip in part B immediately after the second bath is over for your roll. Alternatively, add 20ml of part A to part B and do a similar exercise. Check if the film strip darkens after a few minutes. If it does then it means that the carryover part A itself acts as a developer and therefore highlights will continue to build density (ie no developer exhaustion in the highlights). If the film strip doesn't darken then your 2 bath developer works like a conventional 2 bath developer.

Yes, good point, this is a good test. I will try it out. I have both developers and can easily try it.

In the meantime, here is another shot from this weekend. This is 2B-4 3 mins A, 3 mins B with ADOX HR-50/Scala 50 from my Leica M2. There is some light piping at the bottom because apparently I was not cautious enough with the film when loading. It has a clear PET base.

 

[Raghu Kuvempunagar]

Karl, good work, both pics are quite nice.

 

[Alan Johnson]

Hi Alan, I am not sure what point you are making here. Are you suggesting that I am using too much ascorbic acid? I am happy with the results so far. Also, not sure about what to conclude from the comparison. First I'm certainly not as experienced as Ryuji, but furthermore DS-12 is not a two bath developer and I explained that I think effective two baths need to have a higher concentration of agents to work with thinner emulsion films. This developer works nicely on Fomapan films, for example, where as Barry Thornton's really doesn't work well at all with them in my experience. You get pretty thin negatives on a single pass.

@Raghu Kuvempunagar @Alan Johnson Are you saying there is something specific about carryover into the second bath with a phenidone/ascorbate developer? I used Diafine for years without seeing major issues. It's a phenidone/hydroquinone 2 bath. Shouldn't the build up of bromide largely counteract that? This is how that normally works. And once you have too much bromide, you get drag. So there is a spot where you want to get rid of it, but it ought to be 6-10 rolls I should think. Unless you are saying there is something specific about ascorbic acid developers here, or because an extremely minute amount of developer is still effective?

On the first point I was just checking that the concentrations of Salicylic acid and TEA used in the DS-12 concentrate would also be about right in 2B-4 and not completely irrelevant to your case, that's all.
On the second point, Raghu's quote comes from an old thread where I tried to make a 2-bath vit-C developer but found the P-C combination is so active that even the small amount carried over from the A bath on the surface of the film (~20ml) and dispersed in the B bath was quite a good developer and produced significant development in addition to that absorbed in the emulsion. This would mean that development would not stop in the highlights when the developer in the emulsion is used up. You could check this as mentioned by Raghu in post 117.
If there is development in the diluted carry over in bath B you have to take a view on whether this is in an amount to be acceptable.

 

[relistan]

Karl, good work, both pics are quite nice.

Thanks, Raghu!

On the first point I was just checking that the concentrations of Salicylic acid and TEA used in the DS-12 concentrate would also be about right in 2B-4 and not completely irrelevant to your case, that's all.
On the second point, Raghu's quote comes from an old thread where I tried to make a 2-bath vit-C developer but found the P-C combination is so active that even the small amount carried over from the A bath on the surface of the film (~20ml) and dispersed in the B bath was quite a good developer and produced significant development in addition to that absorbed in the emulsion. This would mean that development would not stop in the highlights when the developer in the emulsion is used up. You could check this as mentioned by Raghu in post 117.
If there is development in the diluted carry over in bath B you have to take a view on whether this is in an amount to be acceptable.

Ah I see Alan, thanks for clarifying.

@Raghu Kuvempunagar and @Alan Johnson It looks like Alan was right: I just tested both bath Bs from 2B-1 and 2B-4 and the verdict is 2B-1 is completely fine. 5 minutes, no real development. HOWEVER 2B-4 is NOT. With 20ml of developer in B, it develops film to a nice dark black Which makes me wonder... have I just been getting away with it because I was not running full rolls? I was cutting 5-8 shots from the camera while testing. The roll of ADOX HR-50 was the only full roll I have run and it's a VERY thin emulsion. EDIT: Actually that only had 20 frames on it, had been previously cut.

 

[relistan]

Thinking about this, this might be an insurmountable problem with trying to use ascorbic acid in a two bath developer. Because I shot a lot of PC-Glycol, for instance, and it uses an extremely minute amount of developing agents. You'd get near that easily with any developer that has enough present in the first bath to allow proper development in the second. I guess there might be an argument you need a much, much weaker bath A and that this would work. Given how dilute PC-Glycol is, though, I imagine this is a dead end.

 

[Alan Johnson]

Relayer succeeded with effortless superiority , using a PC A-bath and a Borax B-bath, see post 15 here:
https://www.photrio.com/forum/threads/diafine-revisited-ascorbate-version.78123/#post-1072668
I gave up, but it may be possible to improve Relayer's formula.

 

[relistan]

Relayer succeeded with effortless superiority , using a PC A-bath and a Borax B-bath, see post 15 here:
https://www.photrio.com/forum/threads/diafine-revisited-ascorbate-version.78123/#post-1072668
I gave up, but it may be possible to improve Relayer's formula.

Ah, so that one works OK regarding carryover? That's good news at least.

I'm not following. All other things being equal I would be very surprised if PC was more active than PQ. The PQ combination should be at least as superadditve as PC.

Sorry, reacting a bit from frustration after some weeks working on and with this developer and not figuring out about the carryover. I think you are right. And Alan says that Relayer's developer doesn't have this problem.

However all other things are not equal. If I remember 2B-1 correctly it has half the Phenidone concentration of 2B-4. There are other differences but that's a big one.

It does, exactly twice as much. That was in order to get enough density and a smooth enough gradation (which I think I've nailed now). I know you know this but, Ascorbic acid and hydroquinone don't behave the same at all. I had an earlier iteration of this developer with half as much phenidone and somewhat less ascorbic acid and added a bit at a time until density looked right to me. It's possible that the important thing is actually the proportions and I could keep that and drop it in half.

I'm also still not sure why you need bath B to be so alkaline but that's another story.

I didn't post all the variations that I tried because I learned from the hydrogen peroxide bleach thread that if I post all the experiment that I did then people are not nice about it if things don't go well. So I've been heavily filtering what I posted. I tried several variations of a borax B developer with different A baths and was not able to get a decent looking negative. I know this was a problem with my work and not that borax won't do the job. I am sure there are other things I can tune but I have gotten very good results with the more alkaline baths and so I stuck with that. I have some ideas why borax didn't work and what to do about it, but I want to do some more research before posting something.

 

[Raghu Kuvempunagar]

Sorry, reacting a bit from frustration after some weeks working on and with this developer and not figuring out about the carryover. I think you are right. And Alan says that Relayer's developer doesn't have this problem.

Unlike your 2B-4, Thornton's 2 bath developer is not a true divided developer as substantial development takes place in the first bath and therefore the second bath doesn't need to do the heavy lifting. It seems inevitable that in a true divided developer, part A needs to be concentrated enough and part B has a high enough pH for the second bath to do develop film to the right contrast. This implies that the carryover will be a developer by itself. How does Relayer's developer avoid this? It might be instructive to compare it first with PC-Glycol and then with PG-110B.

300ml of 1+50 dilution working solution of PC-Glycol has 6ml of the concentrate which translates into 0.6g Ascorbic Acid and 0.015g Phenidone. Now, 300ml of part B of Relayer with 20ml of carryover part A has 0.2g Sodium Ascorbate and 0.004g Phenidone. Close enough to PC-Glycol 1:150 dilution which might act as a low contrast developer with Metaborate as the accelerator. So the key difference seems to be that Relayer uses lower pH Borax as the accelerator.

Now let's compare Relayer with a low contrast PC Borax developer (PG110B by Jay Defehr). 300ml working solution of PG-110B at dilution 1:100 contains 0.3g Ascorbic Acid and 0.03g Phenidone. Notice the significantly higher proportion of Phenidone in PG110B but is said that activity level for PC combination is more or less the same for ratios 1:40 to 1:10. This raises a little bit of doubt about carry over not being a weak developer by itself in the case of Relayer, but not something that can't be tested by experiments.

 

[Alan Johnson]

Yes, the carry over from Relayer's developer does cause a faint image. I thought it insignificant (10 years ago).
But my test was done with a 500ml developing tank.
https://www.photrio.com/forum/threads/diafine-revisited-ascorbate-version.78123/#post-1072667
Use of Borax, giving lower pH, may be a key factor but I never tested using Metaborate or Carbonate with Relayer's developer.

 

[Raghu Kuvempunagar]

Not clear why Jay never followed this 2 bath work up.

Even this 2 bath developer suffers from the carryover problem.

 

[gorbas]

I think you can significantly reduce the carry over by transferring just film on the reel and centre core from A to B, but you need 2 tanks and total darkness for it.

 

[Alan Johnson]

That this carry over problem occurs with the smaller molecule ascorbate and not with the larger molecules metol (Thornton's) and hydroquinone (Diafine) suggests that transfer through the solution to the emulsion surface may be controlled by diffusion (Stokes Einstein equation). If the pH is increased there are more ions, maybe they get into the emulsion from the solution and develop it faster. So the lower pH Borax may work better.

Edit-this is wrong, ascorbate is actually the heaviest molecule, see post by relistan below.

 

[relistan]

Unlike your 2B-4, Thornton's 2 bath developer is not a true divided developer as substantial development takes place in the first bath and therefore the second bath doesn't need to do the heavy lifting. It seems inevitable that in a true divided developer, part A needs to be concentrated enough and part B has a high enough pH for the second bath to do develop film to the right contrast. This implies that the carryover will be a developer by itself. How does Relayer's developer avoid this? It might be instructive to compare it first with PC-Glycol and then with PG-110B.

300ml of 1+50 dilution working solution of PC-Glycol has 6ml of the concentrate which translates into 0.6g Ascorbic Acid and 0.015g Phenidone. Now, 300ml of part B of Relayer with 20ml of carryover part A has 0.2g Sodium Ascorbate and 0.004g Phenidone. Close enough to PC-Glycol 1:150 dilution which might act as a low contrast developer with Metaborate as the accelerator. So the key difference seems to be that Relayer uses lower pH Borax as the accelerator.

Now let's compare Relayer with a low contrast PC Borax developer (PG110B by Jay Defehr). 300ml working solution of PG-110B at dilution 1:100 contains 0.3g Ascorbic Acid and 0.03g Phenidone. Notice the significantly higher proportion of Phenidone in PG110B but is said that activity level for PC combination is more or less the same for ratios 1:40 to 1:10. This raises a little bit of doubt about carry over not being a weak developer by itself in the case of Relayer, but not something that can't be tested by experiments.

Thanks, Raghu this is useful data. It seems that it's much easier to make a divided developer like 2B-1 vs a true two bath in general due to the different emulsion thicknesses of various films and the ensuing difference in both carryover and diffusion rate. And then the leftover-carryover issue that I had not previously considered.

The interesting thing is that the alkalinity of Diafine's bath B is around the same as that for both of my developers. So it does hint that the problem is something specific about ascorbic acid.

I think you can significantly reduce the carry over by transferring just film on the reel and centre core from A to B, but you need 2 tanks and total darkness for it.

Good point. You would only have the carryover contained in and on the film. But then this would be a very difficult development process.

That this carry over problem occurs with the smaller molecule ascorbate and not with the larger molecules metol (Thornton's) and hydroquinone (Diafine) suggests that transfer through the solution to the emulsion surface may be controlled by diffusion (Stokes Einstein equation). If the pH is increased there are more ions, maybe they get into the emulsion from the solution and develop it faster. So the lower pH Borax may work better.

Hmm, yes emulsion swell would be quite a bit higher with this level of alkalinity. How can you tell how big a molecule is? I looked at molecular weight and in that case ascorbic acid actually has the highest mass of the group.

Maybe a solution could be to start out with restrainer in the bath B? It would also have to diffuse into the emulsion to work, but might offset a certain amount of build-up in that bath? I think with PQ or MQ two baths you don't need that since carryover effect is more neutralized by bromide build-up. But since such a small amount of ascorbic acid seems to be enough, maybe that's required.

... which also reminds me that 2B-4 has a lot less restrainer because I determined I didn't need it to keep the fog down.

 

[gorbas]

Good point. You would only have the carryover contained in and on the film. But then this would be a very difficult development process.

Karl, long, long time ago when I was regular user of 2 baths developers I always developed it "regularly" in tank, pour in, pour out, but recently with BT2B I started to transfer reels to second tank in total darkness and I like it. I think that way film is much faster and more evenly submerged in bath B. I turn lights after first minute agitation and securing the lid. Also I made decision to keep film in both baths for 5 min. If I see any bad effect I will resort to shorter times. 3 minutes time in pour in, pour out situation is just too short for my taste.
Sorry, I'm staying away from your chemical discussion. My knowledge of chemistry is close or equal to 0.

 

[Raghu Kuvempunagar]

The interesting thing is that the alkalinity of Diafine's bath B is around the same as that for both of my developers. So it does hint that the problem is something specific about ascorbic acid.

Different developer agents (and their supper additive combinations) have different range of pH where they are most active. So I don't know if it is prudent to compare alkalinity of Diafine part B with that of PC developers. Anyway, the point I was making on pH in my earlier post was specific to PC developers (and hence the comparison of Relayer with PC-Glycol and PG110B). It appears to me that Relayer's trick of using Borax as a relatively low pH alkali for PC might have helped in making the carryover a relatively weak and non-consequential developer. Reducing the pH further would have risked reduced development and a higher pH would have made carryover problematic.



And Alan did confirm that carryover in Relayer's 2 bath developer does act as a (weak) developer by itself despite using Borax in part B.

 

[relistan]

Different developer agents (and their supper additive combinations) have different range of pH where they are most active. So I don't know if it is prudent to compare alkalinity of Diafine part B with that of PC developers. Anyway, the point I was making on pH in my earlier post was specific to PC developers (and hence the comparison of Relayer with PC-Glycol and PG110B). It appears to me that Relayer's trick of using Borax as a relatively low pH alkali for PC might have helped in making the carryover a relatively weak and non-consequential developer. Reducing the pH further would have risked reduced development and a higher pH would have made carryover problematic.



And Alan did confirm that carryover in Relayer's 2 bath developer does act as a (weak) developer by itself despite using Borax in part B.

Sorry I wasn't dismissing that point about ph affecting carryover effectiveness in a PC two bath. I think you make a good point. I was trying to say that this alkalinity thing might indeed be specific to ascorbic acid two baths. I think you are probably on to something.

EDIT: I realized I have a mixed up bath B with borax sitting in a bottle from previous testing with borax. So I poured 300ml into a container and added 20ml of 2B-4 bath A. Very nearly identical results to 2B-1 with the high pH bath B! Which is to say there was not much real development. So @Raghu Kuvempunagar this indeed looks worth pursuing. Thanks!

 

[relistan]

Karl, long, long time ago when I was regular user of 2 baths developers I always developed it "regularly" in tank, pour in, pour out, but recently with BT2B I started to transfer reels to second tank in total darkness and I like it. I think that way film is much faster and more evenly submerged in bath B. I turn lights after first minute agitation and securing the lid. Also I made decision to keep film in both baths for 5 min. If I see any bad effect I will resort to shorter times. 3 minutes time in pour in, pour out situation is just too short for my taste.
Sorry, I'm staying away from your chemical discussion. My knowledge of chemistry is close or equal to 0.

I appreciate your contributions to the discussion! This is an interesting idea. I may experiment with that, too.

 

[Alan Johnson]

Starting from Relayer's formula you could try 20ml of various A solutions in 500ml of his B solution to determine what does not give too much carry over development.
But there are many ways of proceeding.

 

[relistan]

Starting from Relayer's formula you could try 20ml of various A solutions in 500ml of his B solution to determine what does not give too much carry over development.
But there are many ways of proceeding.

I looked in my notes to see what that borax bath was that I tested above. It was this formula:

• 800ml water
  
• Borax — 20g
• Sodium sulfite — 35g
• Water to 1L

pH was recorded as 9.25 with my pH meter.

Already at this pH there was a huge cut in development vs the existing bath B from 2B-4 (pH 11). But the question is after a few rolls of film, would that still be true. Part of me thinks that intentionally aeriating the crap out of bath B after finishing a roll is a good idea. I also am starting to think that intentionally putting sulfite in there is not a good idea, although with ascorbic acid this might not matter.

 

[Raghu Kuvempunagar]

I looked in my notes to see what that borax bath was that I tested above. It was this formula:

• 800ml water
  
• Borax — 20g
• Sodium sulfite — 35g
• Water to 1L

pH was recorded as 9.25 with my pH meter.

Already at this pH there was a huge cut in development vs the existing bath B from 2B-4 (pH 11).

You may want to replace Ascorbic Acid in part A by equivalent amount of Sodium Ascorbate and use Borax in part B. As Ascorbic Acid is acidic, some of the Borax could be spent on neutralizing it and thereby reducing the pH around the film surface. By using Sodium Ascorbate, you can avoid this. [Edit] But pH of part A might go up and consequently there could be some development in the first bath itself.

 

[Raghu Kuvempunagar]

Ryuji who did a lot of work on Ascorbic Acid developers had the following insight to offer:

"Based on my experiments, vitamin C developers are very good in two rather extreme conditions. (1) high concentration of reductants, low pH, moderate sulfites. This condition is in agreement with what's described in XTOL patent. (2) low concentration, low sulfites, high pH. This is more like Ilfosol-S and original Gainer formula."

Don't know how exactly to translate this insight to 2 bath developers, but it's definitely something to think about.

 

[relistan]

You may want to replace Ascorbic Acid in part A by equivalent amount of Sodium Ascorbate and use Borax in part B. As Ascorbic Acid is acidic, some of the Borax could be spent on neutralizing it and thereby reducing the pH around the film surface. By using Sodium Ascorbate, you can avoid this. [Edit] But pH of part A might go up and consequently there could be some development in the first bath itself.

What I was wondering is: with bicarbonate in B I assume that ascorbate is getting formed. With only borax, what happens to the ascorbic acid? Does it form a compound that can still reduce? This was my theory about why maybe the borax bath didn't work well for me. I was thinking it was only leaving the phenidone to do most of the work. But then maybe that's not right at all. I was going to do more research on this before bringing it up, but maybe you already know. I guess relayer's developer is just borax, so that must be wrong.

 

[Donald Qualls]

You'll still get ascorbate. In fact, you'll get ascorbate in the presence of any dissolved ions in sufficient quantity (add table salt, you'll get an equilibrium mix of Na+, Cl-, and ascorbic acid <-> sodium ascorbate and HCl). Ascorbate forms in any conditions that allow the ascorbic acid to ionize (assuming you didn't just start with sodium ascorbate for pH reasons).

 

[Raghu Kuvempunagar]

Alan,

When you tested Relayer's PC 2 bath developer, did you observe any development in the first bath? I could be wrong but pH of ~7 might enable some development at least when the agitation is continuous. I believe Phenidone's pH threshold is somewhere in the ballpark.

@relistan: did you notice any developing in part A of your developer which has a pH similar to Relayer?