B&W Reversal with Hydrogen Peroxide

[YoIaMoNwater]

Well folks, this bleach works very well, and solves all of the problems we've seen with other bleaches except emulsion damage with some films. I have run a roll of Fomapan 400 in it today and obtained good results. I decided to write up a Photrio resource for others to benefit from here, including the full, working formula with all amounts including the citric acid.

https://www.photrio.com/forum/resources/b-w-reversal-bleach-—-hydrogen-peroxide-edta-citric-acid.448/

Here's the roll I developed today:

View attachment 265184

I still have not tried the etidronic acid/HEDP that I got from Suvatlar in Germany. I will reserve some time to experiment further with that to see if it works better to handle emulsion damage. In the meantime I think it's worth celebrating some victory over most of the other issues we've seen.

cc @Raghu Kuvempunagar, @Donald Qualls, @YoIaMoNwater, @falotico, and most especially @kentanghk who all helped out here!

Hey hey hey, that looks pretty damn good! I just ordered some Fomapan 400 to try this in the future.

I tried reversal with 1:6 Rodinal today with some film leaders from Rollei Superpan 200 and TMax 400 but got bad results. The first failed attempt was probably due to the fact I didn't wash after each step so the bleach wasn't complete (only around the edges of the film did it bleach while the rest was still pretty dark) and the second trial I used 2x KMnO4 and resulted in the emulsion falling off the film base. Both attempts had 0.2% and 0.4% sodium thiocyanate in the first developer, since I thought this could help to clear the base for TMax400. It's worthy to note that 0.4% sodium thiocyanate did resulted in better bleaching in the first trial.

I'm tempted to give ths H2O2 bleach a try too but also to test if DTT can help to clear the highlights.

 

[Helinophoto]

OOohh, yes I confused the two, Sodium Carbonate and bicarbonate
(I have both)

I tried to find some data on LPD as a film-developer, but came up short, so then I thought about the D-76 ^^

Thanks for the tips, I will see if I can source these things locally first. There are several examples of photographers being caught in "sting operations", because the customs-office found liquid Tetenal slide developer to be GHB (I kid you not, https://translate.google.com/transl...tkontoret-og-sikta-for-narkosmugling/63300815), while others are questioned if they are planning some kind of terror attack.

The paranoia reached astronomical heights here and has remained so after the 2011 terror-bombings. (The terrorist used an ANFO type home-made bomb, which put a whole slew of chemicals on the banned list or antiterror trigger-list, then there is the ISIS threat and so on and so on).

 

[relistan]

Hey hey hey, that looks pretty damn good! I just ordered some Fomapan 400 to try this in the future.

Thanks! It came out great. I have scanned some of the frames now and will post below. Fomapan 400 is not the greatest film, but it does seem quiet forgiving to this process! I think in 120 it might be pretty great. Interested to see how it comes out when you try it!

I tried reversal with 1:6 Rodinal today with some film leaders from Rollei Superpan 200 and TMax 400 but got bad results. The first failed attempt was probably due to the fact I didn't wash after each step so the bleach wasn't complete (only around the edges of the film did it bleach while the rest was still pretty dark) and the second trial I used 2x KMnO4 and resulted in the emulsion falling off the film base. Both attempts had 0.2% and 0.4% sodium thiocyanate in the first developer, since I thought this could help to clear the base for TMax400. It's worthy to note that 0.4% sodium thiocyanate did resulted in better bleaching in the first trial.

I'm tempted to give ths H2O2 bleach a try too but also to test if DTT can help to clear the highlights.

Sorry to hear you had some mixed results. Getting the right amounts of everything for each film stock seems to require a fair bit of tuning. If you have access to Ilford Multigrade paper developer, I have had very good luck with it as a first developer. For a bunch of films it seems to be aggressive enough at 1+5 to not need any solvent. I am now using 1.5g/L for Fomapan 400 with the new bleach. I don't have any thiocyanate to try. For the second developer I use Ilford Multigrade 1+9 for about 8 minutes.

Also interested in your DTT experiment!

I tried to find some data on LPD as a film-developer, but came up short, so then I thought about the D-76 ^^

I think somewhere in this thread I posted a link to Hans Dietrich's document and his D-76-based first developer. You could give it a try.

Thanks for the tips, I will see if I can source these things locally first. There are several examples of photographers being caught in "sting operations", because the customs-office found liquid Tetenal slide developer to be GHB (I kid you not, https://translate.google.com/transl...tkontoret-og-sikta-for-narkosmugling/63300815), while others are questioned if they are planning some kind of terror attack.

The paranoia reached astronomical heights here and has remained so after the 2011 terror-bombings. (The terrorist used an ANFO type home-made bomb, which put a whole slew of chemicals on the banned list or antiterror trigger-list, then there is the ISIS threat and so on and so on).

Good grief, that is ridiculous! E6 chemistry is industry standard stuff. And they said it came from "one of Germany's premier photography suppliers" so I am guessing it was from Fotoimpex or Maco. Just absolutely crazy to seize that as drugs at customs.

In any case the two chemicals you would be ordering from that place in France are nowhere near anything that should be detected as an issue, even by incompetent customs folks with meters. But, definitely look locally!

 

[relistan]

Here are a couple of frames from that roll that I posted on the Resource.

These are Fomapan 400 at EI200, Ilford Multigrade 1+5 with sodiudm thiosulfate 1.5g/L, peroxide/EDTA/citric acid bleach, Ilford Multigrade 1+9

 

[Helinophoto]

Good grief, that is ridiculous! E6 chemistry is industry standard stuff. And they said it came from "one of Germany's premier photography suppliers" so I am guessing it was from Fotoimpex or Maco. Just absolutely crazy to seize that as drugs at customs.

In any case the two chemicals you would be ordering from that place in France are nowhere near anything that should be detected as an issue, even by incompetent customs folks with meters. But, definitely look locally!

Yeah, AFAIK he had ordered from Maco in Germany.
So strange indeed, but, it is 10 years ago, one can hope they have changed out the testing-equipment with something more useful since then.
Then again, it's the government, which means that these things can take decades to change

 

[YoIaMoNwater]

Sorry to hear you had some mixed results. Getting the right amounts of everything for each film stock seems to require a fair bit of tuning. If you have access to Ilford Multigrade paper developer, I have had very good luck with it as a first developer. For a bunch of films it seems to be aggressive enough at 1+5 to not need any solvent. I am now using 1.5g/L for Fomapan 400 with the new bleach. I don't have any thiocyanate to try. For the second developer I use Ilford Multigrade 1+9 for about 8 minutes.

I was looking around online and I think my issue could also be the 2nd developer. Since Rodinal itself is very high pH and can cause emulsion swelling, this combined with the 2x KMnO4 bleach probably caused the emulsion to fall off the film base. Google tells me that the stock Rodinal has a pH of 14, which is absurdly high; in comparision, Microphen is at pH 8.8. If I have time I'm gonna check what the pH of my 1.3x Microphen vs 1:6 Rodinal are and repeat the experiment again but with normal amount of KMnO4.

 

[relistan]

I was looking around online and I think my issue could also be the 2nd developer. Since Rodinal itself is very high pH and can cause emulsion swelling, this combined with the 2x KMnO4 bleach probably caused the emulsion to fall off the film base. Google tells me that the stock Rodinal has a pH of 14, which is absurdly high; in comparision, Microphen is at pH 8.8. If I have time I'm gonna check what the pH of my 1.3x Microphen vs 1:6 Rodinal are and repeat the experiment again but with normal amount of KMnO4.

Ah, interesting thought. When I use Rodinal for regular purposes I used it 1+50. I wonder what the pH is of that as well. I assume it will be quite a lot lower than 1+6! I did not realize the concentrate was pH 14. If you didn't wash thoroughly and went from a very high alkaline pH to an a low acidic pH I can imagine that would make the emulsion pretty unhappy with the reaction that would occur inside it.

 

[Fragomeni]

I've been popping into this thread to review information over the past few months while experimenting with peroxide reversal and just have to say thank you to everyone who has contributed. This thread has become indispensable.

Ah, interesting thought. When I use Rodinal for regular purposes I used it 1+50. I wonder what the pH is of that as well. I assume it will be quite a lot lower than 1+6! I did not realize the concentrate was pH 14. If you didn't wash thoroughly and went from a very high alkaline pH to an a low acidic pH I can imagine that would make the emulsion pretty unhappy with the reaction that would occur inside it.

My understanding is that the later Agfa formula (reformulation) as was of higher pH than the original formula and Calbe's R09, I believe because Agfa included free Hydroxide in their later reformulation. I think it was Ian Grant who spoke on this in other threads several years back. I'll try to find a post and link it. If I recall correctly, it's the later Agfa formula with the Hydroxide that has a pH of 14 (concentrate) whereas the original formula as well as R09 without Hydroxide is just below 12. The working solutions would have lower pH. The formula containing Hydroxide goes down to 11.5-ish. Not sure about the non-Hydroxide formula. Other's may have a link to the old threads or may be able to correct me if any of these numbers are off.

On a different note, regarding some earlier info/experiences, I believe I've seen a few people report seeing a gain in film speed when using the peroxide and vinegar formula. Can anyone confirm this and what has the average increase in speed been for those finding that to be true? I'm consistently getting an increase of 2 stops using FP4 and the peroxide-vinegar formula. I have yet to try the version with EDTA and citric acid.

 

[Fragomeni]

Here is a post from 2010 where the pH of Rodinal/R09 are discussed. My memory of the numbers was correct: https://www.photrio.com/forum/threads/rodinal-ph.68971/

 

[esearing]

I tried to find some data on LPD as a film-developer, but came up short, so then I thought about the D-76 ^^

LPD works at 1:15 for 10minutes on FP4+ but I did not note the temperature or agitation scheme or print the negative.
Ansco 130 1:10 for 12 minutes @72* on HP5 is great for low contrast images.

 

[relistan]

On a different note, regarding some earlier info/experiences, I believe I've seen a few people report seeing a gain in film speed when using the peroxide and vinegar formula. Can anyone confirm this and what has the average increase in speed been for those finding that to be true? I'm consistently getting an increase of 2 stops using FP4 and the peroxide-vinegar formula. I have yet to try the version with EDTA and citric acid.

Glad you made it this far!

Yeah, I was getting 1 stop speed boost with Multigrade as a developer on Fomapan 400 with the Vinegar/peroxide bleach. I normally would shoot it at EI200 but was fine at 400. It will depend on the developer and times and other factors. Keep in mind you are working the exposed film much harder in this process. But that bleach is a fairly effective blix so the whole negative is quite a bit thinner than with a more traditional bleach. The citric acid/EDTA bleach is also a blix but quite a bit weaker. I was seeing more or less box speed on Fomapan 400. You still get some emulsion damage, though quite a bit less. It looks like you are shooting 6x12(?) though so you may not notice

 

[Fragomeni]

Glad you made it this far!
…The citric acid/EDTA bleach is also a blix but quite a bit weaker. I was seeing more or less box speed on Fomapan 400. You still get some emulsion damage, though quite a bit less. It looks like you are shooting 6x12(?) though so you may not notice

That’s interesting about the EDTA version yielding results closer to box speed than the acetic acid/vinegar version. I’m on a road trip currently but just got ahold of a small bottle of EDTA (disodium) from a random lab supply store I passed by so will probably five the updated formula with some of my rolls. I’d rather not give up the extra speed but I’m curious if I can get a result without a golden hue. If I can get that then I guess it just because a question of which is more important to me — probably speed in my case (I actually kind of like the golden hue anyway).

And yes, that test was done on 6x12. I’m using this process mostly with 612 and 6x9. Emulsion damage hasn’t been an issue. I maintain temperatures between 30C-40C, never really going down to 20C until the final wash. I’m not sure if that has been helping to reduce potential damage. I’ve been consolidating my notes and will share in a post on my website when I have that complete. Thanks for your confirmation about the film speed.

 

[YoIaMoNwater]

That’s interesting about the EDTA version yielding results closer to box speed than the acetic acid/vinegar version. I’m on a road trip currently but just got ahold of a small bottle of EDTA (disodium) from a random lab supply store I passed by so will probably five the updated formula with some of my rolls. I’d rather not give up the extra speed but I’m curious if I can get a result without a golden hue. If I can get that then I guess it just because a question of which is more important to me — probably speed in my case (I actually kind of like the golden hue anyway).

And yes, that test was done on 6x12. I’m using this process mostly with 612 and 6x9. Emulsion damage hasn’t been an issue. I maintain temperatures between 30C-40C, never really going down to 20C until the final wash. I’m not sure if that has been helping to reduce potential damage. I’ve been consolidating my notes and will share in a post on my website when I have that complete. Thanks for your confirmation about the film speed.

The golden hue is probably from the residual silver stain, which if I recall does not appear with the EDTA formula.

 

[Fragomeni]

The golden hue is probably from the residual silver stain, which if I recall does not appear with the EDTA formula.

Yea, my understanding is that it’s from the silver but I would have expected a good sodium sulfite bath to clear most or all of that away. The sulfite certainly reduces it but doesn’t eliminate it in my experience.

I need to read through this thread again to see if anyone left notes about using EDTA with the vinegar formula (as opposed to with citric acid in the later formula) along with the sulfite clearing bath. In the vinegar version of the formula, the vinegar and peroxide combine to become peracetic acid, which makes sense why it’s a little rougher on the emulsion— peracetic acid being more corrosive than either the dilute peroxide or vinegar/acetic acid alone. But it seems like the paracetic acid may for some reason be what causes the speed gain so maintaining that while getting the clearing action of the EDTA would be ideal if possible. If anyone knows where in this thread or elsewhere this might be answered please let me know. I’m sure it must have been tried while folks were working out what became the EDTA/citric acid version. Regarding the differences between acetic acid vs citric acid in the formulas, does anyone know why acetic acid (contributing to the resulting peracetic acid) might contribute to a speed gain where citric acid does not? I’m not sure what the resulting compound is when the citric acid combines with the peroxide but if I’m not mistaken, acetic acid and citric acid are fairly similar with the primary difference being that citric acid is tribasic where acetic acid is monobasic. I wish PE was still around. My bet would be that he would know exactly how to explain it. (Cheers to the man and the legend)

 

[relistan]

Yea, my understanding is that it’s from the silver but I would have expected a good sodium sulfite bath to clear most or all of that away. The sulfite certainly reduces it but doesn’t eliminate it in my experience.

I need to read through this thread again to see if anyone left notes about using EDTA with the vinegar formula (as opposed to with citric acid in the later formula) along with the sulfite clearing bath. In the vinegar version of the formula, the vinegar and peroxide combine to become peracetic acid, which makes sense why it’s a little rougher on the emulsion— peracetic acid being more corrosive than either the dilute peroxide or vinegar/acetic acid alone. But it seems like the paracetic acid may for some reason be what causes the speed gain so maintaining that while getting the clearing action of the EDTA would be ideal if possible. If anyone knows where in this thread or elsewhere this might be answered please let me know. I’m sure it must have been tried while folks were working out what became the EDTA/citric acid version. Regarding the differences between acetic acid vs citric acid in the formulas, does anyone know why acetic acid (contributing to the resulting peracetic acid) might contribute to a speed gain where citric acid does not? I’m not sure what the resulting compound is when the citric acid combines with the peroxide but if I’m not mistaken, acetic acid and citric acid are fairly similar with the primary difference being that citric acid is tribasic where acetic acid is monobasic. I wish PE was still around. My bet would be that he would know exactly how to explain it. (Cheers to the man and the legend)

Sorry if that was not clear: there is no reduction in speed from the Citric acid/EDT bleach. Fomapan 400 is not a 400 speed film (per Foma's own datasheets), so shooting it at 400 is a ~1 stop increase. Also keep in mind that the developer has much more to do with speed increase than the bleach. However, the bleach can make the speed worse by blixing too much and leaving you with a thin negative. Leaving it in the bleach too long in the acetic acid/peroxide bleach will take quite a lot away. The unpredictable nature of the bleach speed is also very annoying.

The leftover yellow "staining" from the acetic acid bleach is not actually staining, as discussed earlier in the thread. It's fine grains of silver that get evenly deposited across the film. This is why it doesn't clear with a sulfite bath. The EDTA and citric acid in the the bleach we formulated on this thread chelate that silver and prevent it from re-depositing on the film. You still need to use a sulfite bath with this bleach to get rid of the actual staining.

Peracetic acid _can_ damage the emulsion, but the majority of what you see is damage from bubbles of oxygen splitting off the peroxide when catalyzed by the silver and then tearing the emulsion on the way out. The faster the bleach goes, the bigger the bubbles are that form and the more damage, within reason. So slowing it down a bit actually produces better results. Also, chelating any free silver as much as possible before it has time to further catalyze the breakdown of the peroxide seems to help a lot. The acetic acid bleach is worse at this. Stabilizers for peroxide also help from the patent literature. HEDP is recommended as a peroxide stabilizer in the Konica patent. I began testing with this but have not revisited it.

In your negatives you are definitely seeing some emulsion damage. But because they are so big you probably don't see it on scans. Do a detailed scan and zoom to the highest resolution and you will definitely see it. Some films do better than others. Temperature seems to have very little impact from all the testing I did. Which is further reinforced by the fact that none of the patents out there talk about temperature as a controlling factor in emulsion damage.

I need to read through this thread again to see if anyone left notes about using EDTA with the vinegar formula (as opposed to with citric acid in the later formula) along with the sulfite clearing bath.

Yes, we did test it. No it doesn't work well. You get weird swirl lines all over the film.

 

[relistan]

The golden hue is probably from the residual silver stain, which if I recall does not appear with the EDTA formula.

This is correct.

 

[Raghu Kuvempunagar]

Can bleach increase the speed of a film in reversal processing? Intriguing!

 

[Donald Qualls]

If the bleach (or an additive in first developer, such as the thiosulfate I've added in the past) dissolves some of the undeveloped halide, this will lighten the final positive -- which is effectively an increase in film speed.

 

[Raghu Kuvempunagar]

If the bleach (or an additive in first developer, such as the thiosulfate I've added in the past) dissolves some of the undeveloped halide, this will lighten the final positive -- which is effectively an increase in film speed.

If the bleach in reversal processing dissolves some of the undeveloped halide in the shadows, i.e. if it acts like a blix, it will do so through out the image and thereby wiping out the critical highlights. In other words, what is gained in shadows is lost in the highlights.

 

[Donald Qualls]

In other words, what is gained in shadows is lost in the highlights.

This is true, though in my experience a one stop increase doesn't affect highlights noticeably. I've found with the process I used some years ago, with a few grams of thiosulfate in the first developer, Tri-X was better at EI 800 than even at EI 640 -- and I had good detail in skies with clouds as well as shadows.

 

[YoIaMoNwater]

Can bleach increase the speed of a film in reversal processing? Intriguing!

If the bleach in reversal processing dissolves some of the undeveloped halide in the shadows, i.e. if it acts like a blix, it will do so through out the image and thereby wiping out the critical highlights. In other words, what is gained in shadows is lost in the highlights.

This depends on the type of film used in reversal. Thicker film emulsions such HP5 seems to handle blown highlights better than thinner ones like Rolleis. Which makes sense since the amount of leftover silver halides after bleach is what is used to become the positives.

 

[relistan]

I am pretty sure as I said a few posts back that what you are seeing with speed gain has nothing to do with the bleach and everything to do with the very aggressive developers being used. AFAICT the only thing the bleach can do is to make the positive thinner all around as @Raghu Kuvempunagar also said. @Donald Qualls also implied this when speaking about using thiosulfate as an accelerator in the first developer. You can make the negative a little thinner with a solvent like thiosulfate or thiocyanate, but you also make it possible to develop a lot more of the silver and thus can pick up more of an image where it was faint. From reading Haist's explanation and my own experience I believe that what Donald describes is more or less what is happening.

 

[relistan]

This depends on the type of film used in reversal. Thicker film emulsions such HP5 seems to handle blown highlights better than thinner ones like Rolleis. Which makes sense since the amount of leftover silver halides after bleach is what is used to become the positives.

I think this is correct also. You are seeing the effect of developing more of the latent silver.

 

[Raghu Kuvempunagar]

A bleach when acting like a blix can definitely lighten the deep shadows by removing the halides. But it can't possibly create detail where there is none. Any shadow detail appearing in the final slide must also be present in the film right after the first development. All subsequent steps in reversal processing can subtract detail (if adequate care isn't taken) and can't possibly create detail that the first development didn't produce. So one can easily verify the presence of shadow details by fixing the film after first development and checking the shadow areas with a loupe or using densitometer. If there's any speed increase, it'll be visible in the negatives.

 

[relistan]

A bleach when acting like a blix can definitely lighten the deep shadows by removing the halides. But it can't possibly create detail where there is none. Any shadow detail appearing in the final slide must also be present in the film right after the first development. All subsequent steps in reversal processing can subtract detail (if adequate care isn't taken) and can't possibly create detail that the first development didn't produce. So one can easily verify the presence of shadow details by fixing the film after first development and checking the shadow areas with a loupe or using densitometer. If there's any speed increase, it'll be visible in the negatives.

Agreed. I’m not sure if that’s a reply to me, but you are saying the same thing.