4-aminophenol+p-phenylenediamine color reveloper

Parodinal+hair dye, to be precise, but anyways.
I was able to go from pic 1 and 2 results to pic 3, but while tweaking the process I made an observation that I'm not sure is true. It seems like this color developer gives more color at Ph≈8, lower than normal. Could this be true?
The final goal is ersatz-E6 made only with components that can be easily bought in a pharmacy or a local shop, and unlike in case with color negative, slide can't be repeatedly bleached and developed to achieve better color, and according to PE hydrogen peroxide will ruin slide film, so I'll need to get as much color as possible in one go.

Wasn't too sure where to post this, maybe it belongs in Hybrid, since pictures above are scans.

I think the essence of what you're doing is analog processing; AFAIK the scans are just a means to communicate your findings. So I think this is the right place.

Sorry, can't answer your actual question, but I'm quite surprised you already got this far to be honest. In your place I would probably run some pH tests, with pH ranging from e.g. 6 to 10, while trying to compensate for activity by increasing color developer concentration. While not exactly bullet proof, it would say something about your finding that pH 8 is optimal. Or is this more or less what you did?

koraks said:

compensate for activity by increasing color developer concentration.

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I'm with you. With less optimized chemistry, you may need more molecules. I'd also question whether any superadditivity from the two developing agents contributes to dye formation. All the color developers I know of are single-agent types.

koraks said:

I think the essence of what you're doing is analog processing; AFAIK the scans are just a means to communicate your findings. So I think this is the right place.

Sorry, can't answer your actual question, but I'm quite surprised you already got this far to be honest. In your place I would probably run some pH tests, with pH ranging from e.g. 6 to 10, while trying to compensate for activity by increasing color developer concentration. While not exactly bullet proof, it would say something about your finding that pH 8 is optimal. Or is this more or less what you did?

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More or less, yes. I did several re-developments while ph was 10-11(hard to tell, because the indicator paper turns black) and when I snipped a small piece and blixed it, there was almost no dye. Then I brought the ph down with sulfuric acid and just after one dev cycle there was more dye than after previous 3.
How should I compensate for activity? Increase the concentration?

Donald Qualls said:

All the color developers I know of are single-agent types.

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You see, PPD produces only cyan and yellow dyes, and 4-aminophenol produces mostly magenta and some yellow. So in order to get a more or less full color palette you need both.

You may get better results than I did with color print film, but there is some useful comment from others:
I finished up using 4 bottles of cheap hair dye in 500ml to try to get the concentration up.

Alan Johnson said:

I finished up using 4 bottles of cheap hair dye in 500ml to try to get the concentration up.

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I heard somewhere that modern films don't 'like' when the concentration of color developing agent is too high.

LeoniD said:

More or less, yes. I did several re-developments while ph was 10-11(hard to tell, because the indicator paper turns black) and when I snipped a small piece and blixed it, there was almost no dye. Then I brought the ph down with sulfuric acid and just after one dev cycle there was more dye than after previous 3.
How should I compensate for activity? Increase the concentration?

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Ah, OK. Well, I'd recommend snipping a single piece of film into e.g. 4 strips and process each strip separately, every time at a different pH.

Compensating for loss of activity at lower pH will be a challenge because you'd have to figure out a compensation ratio. Yes, I'd do it either by increasing developer concentration for lower pH's or alternatively extend processing time. By how much...your guess is as good as mine.

Of course if your hypothesis is correct, there's probably an inverse U-shaped relationship between pH and developer activity. So perhaps it would be good to first do a 'ceteris paribus' test and just vary the color developer pH and keep the other parameters the same across all test strips.

Anyway, a test that first passes the same strip through developer of one pH and then the same strip through developer of a lower pH might give some clues but isn't a very reliable test, obviously. So to answer your question, you'll have to be more systematic in your testing.

LeoniD said:

I heard somewhere that modern films don't 'like' when the concentration of color developing agent is too high.

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Ok, I don't know what that's about, but I'd expect that within a reasonable range this shouldn't be a problem. And if it's an issue, compensate by extending development time and see what that does. But see above: perhaps start with the same process time and concentration, but only vary pH.

LeoniD said:

sulfuric acid

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I don't know if the sulfur would play a role. I'd sooner use something like nitric acid or even vinegar as acetate seems to be fairly innocuous in processing solutions (correct me if I'm wrong). In fact even hydrochloric acid is probably even a better idea to adjust pH downward with despite the formation of chlorides in your solution.

Sounds like you've got a lot more testing ahead! Keep us posted, your experiments are certainly interesting. Too bad PE isn't around anymore.

LeoniD said:

You see, PPD produces only cyan and yellow dyes, and 4-aminophenol produces mostly magenta and some yellow. So in order to get a more or less full color palette you need both.

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Ah, so you'll probably need to adjust the ratio between them to balance your colors, too. And may never get there if you have too much yellow before you get enough magenta, for instance.

koraks said:

use something like nitric acid

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This is likely the best pH adjuster, but it's a lot harder to come by than sulfuric (parts stores will reluctantly sell battery acid, or big box home improvement stores will have drain openers that are mostly H2SO4. There are floor cleaners that are mainly HCl (Janitor in a Drum was one brand), but Muriatic Acid is easy enough to get at the Big Box. Stop bath concentrate is pretty strong acetic acid, and is cheap and easy to get...

You're right about nitric acid being probably the difficult one to get. Funny thing; I once bought it in rather concentrated form (I think 20-30%) as a pH reducer for horticulture, specifically hydroponics. I severely doubt if the shop in question was legally allowed to sell it, let alone to consumers. I also doubt they were aware of this issue.

Donald Qualls said:

drain openers that are mostly H2SO4

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Here in Europe, drain opener is usually sodium hydroxide. I read years ago that it could also be H2SO4, and I scanned all drain openers I came by in stores. It never was. I had to resort to battery acid for this - which is of course an excellent source; it's a known concentration and (as of yet) omnipresent. It's amazing what useful stuff you can actually find in shops if you actually read the labels!

LeoniD said:

Wasn't too sure where to post this, maybe it belongs in Hybrid, since pictures above are scans.

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koraks said:

I think the essence of what you're doing is analog processing; AFAIK the scans are just a means to communicate your findings. So I think this is the right place.

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What koraks said!
I know I'm repeating myself, but you can always use scans to illustrate something.
It is the subject under discussion that determines where you should put your thread.
Sort of like the public library website, where you will likely find the books, e-books, DVDs and talking books about any subject all listed together under that subject.

koraks said:

drain opener is usually sodium hydroxide

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That's the case here, as sell, sometimes gelled with sodium silicate, other times mixed with some flake aluminum (increase the heat generated by dissolution, which is what really clears most clogs). But at the Big Box stores you can usually find the "industrial" variety that's sulfuric, and the MSDS for the product will have approximate concentrations. I agree, battery acid (known 30% strength) is easier for when you need to match formula, but sometimes parts stores don't want to sell it.

LeoniD said:

You see, PPD produces only cyan and yellow dyes, and 4-aminophenol produces mostly magenta and some yellow. So in order to get a more or less full color palette you need both.

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Hello, respected colleague. God bless you ..
Allow me to offer you a fraternal greeting.
Actually,,, I had a similar experience but it was a failure and I only used PPD and only got green, yellow and a little orange. At that time, he felt some sorrow and some despair, and I did not complete the experiments.
The experience was with (C41) films.
Let me know in what formula you have combined 4-aminophenol + PPD ,,,,Maybe I can enrich this research or contribute to it in some way.
God bless you

Nitric acid can be had by reacting root killing powder (Potassium Nitrate) and sulfuric acid. Please be careful, Nitric acid will cause nitrile gloves to burst into flames.

koraks said:

Anyway, a test that first passes the same strip through developer of one pH and then the same strip through developer of a lower pH might give some clues but isn't a very reliable test, obviously. So to answer your question, you'll have to be more systematic in your testing.

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Alright, got you. I wasn't initially planning to test dye formation/Ph ratio, it's just an accidental observation I made.

within a reasonable range this shouldn't be a problem

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Yeah, but 4 bottles per 500ml seems too much. I used equivalent of 2g of 4-aminophenol for 330ml and even this felt like too much.

I'd sooner use something like nitric acid or even vinegar

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Yeah, but I've run out of vinegar but had plenty of 35% sulfuric acid, and since H2SO4 is used in ECN-2 IIRC, I figured that it will not be too bad.

Donald Qualls said:

Ah, so you'll probably need to adjust the ratio between them to balance your colors, too.

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Yup. I'll need to add much more 4-aminophenol, because photos are too magenta, but I'll do it later. This process is too time-consuming. I tried developing one frame at ph 8 today tho, and it kinda looks like Lomo Metropolis when color-corrected.

Donald Qualls said:

but Muriatic Acid is easy enough to get at the Big Box.

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Here it's really easy to get sulfuric acid, it's sold without any questions, but HCl isn't used in any detergents, and as if it wasn't hard enough to get it, russians damaged the factory in Dnipro that was making it.

mohmad khatab said:

Hello, respected colleague. God bless you ..
Allow me to offer you a fraternal greeting.
Actually,,, I had a similar experience but it was a failure and I only used PPD and only got green, yellow and a little orange. At that time, he felt some sorrow and some despair, and I did not complete the experiments.
The experience was with (C41) films.
Let me know in what formula you have combined 4-aminophenol + PPD ,,,,Maybe I can enrich this research or contribute to it in some way.
God bless you

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Hi! I used Vision 3 500t films for these tests. The color developer vas prepared as follows:
30ml (probably shoul've used more) of parodinal without sodium sulfite were added to a beaker. Then half of 45ml hair dye tube was added and mixed until uniform consistency was obtained. After that I added the rest of the hair dye, mixed until uniform consistency and added the oxidizer bottle(45ml). The idea is that the dye coupler in the hair dye will react with 4-aminophenol (that can be easily added) first, so PPD is intact and can develop film. Then I brought the volume up to 300ml. and added H2SO4 until Ph was ~8.
The film was first developed in parodinal 1+50 for 7.5 min (not enough, 9 min would've been better) at ~21C, fixed, bleached and re-exposed to light.

LeoniD said:

since H2SO4 is used in ECN-2 IIRC, I figured that it will not be too bad.

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It is, but as the stop bath, not as a component of the developer. I don't know in what way the SO4 will interact with color development. Maybe its influence is negligible - or maybe it somehow in some concentrations promotes dye coupling? Your guess is as good as mine!

Btw, I considered using hair dye at some point for B&W development, but never got round to it and likely never will. I suppose the chemist would frown if I were to buy a bottle of hair dye. There's not all that much left to dye up there

koraks said:

I suppose the chemist would frown if I were to buy a bottle of hair dye. There's not all that much left to dye up there

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Tell him it's for your girlfriend...

Well, I can't keep abusing the poor woman for anything and everything photographic that I want!

You could always tell them the cat was wanting a new look

LeoniD said:

Here it's really easy to get sulfuric acid, it's sold without any questions, but HCl isn't used in any detergents, and as if it wasn't hard enough to get it, russians damaged the factory in Dnipro that was making it.


Hi! I used Vision 3 500t films for these tests. The color developer vas prepared as follows:
30ml (probably shoul've used more) of parodinal without sodium sulfite were added to a beaker. Then half of 45ml hair dye tube was added and mixed until uniform consistency was obtained. After that I added the rest of the hair dye, mixed until uniform consistency and added the oxidizer bottle(45ml). The idea is that the dye coupler in the hair dye will react with 4-aminophenol (that can be easily added) first, so PPD is intact and can develop film. Then I brought the volume up to 300ml. and added H2SO4 until Ph was ~8.
The film was first developed in parodinal 1+50 for 7.5 min (not enough, 9 min would've been better) at ~21C, fixed, bleached and re-exposed to light.

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Sorry, brother, I don't understand very well.
I don't know anything about hair dye..
I own a raw (PPD) component.
I also have an ingredient ( 4-aminophenol )
I also have HCL and sulfuric acid and I have a lot of chemical raw materials.
What should I do.
I want a formula to be a starting point

mohmad khatab said:

Sorry, brother, I don't understand very well.
I don't know anything about hair dye..
I own a raw (PPD) component.
I also have an ingredient ( 4-aminophenol )
I also have HCL and sulfuric acid and I have a lot of chemical raw materials.
What should I do.
I want a formula to be a starting point

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Well, I didn't use the raw components and the manufacturer doesn't disclose how much of PPD there is in 45ml of hair dye, but I'd start with 2g of PPD and 1g of 4-aminophenol, per 330ml of the developer. No idea what the Ph should be in this case, so I'd add potassium carbonate until Ph is somewhere around 9. IIRC, PE mentioned that sodium sulfite in low concentrations will help with dye formation by removing the excess oxidised color developing agent, so I'd add ~0.2-0.3g, again, per 330ml.
So the whole process would go like this

1) First dev.: Rodinal 1+50 or equivalent, approximately 9min at 20C.
2) Fix(non-hardening)
3) Bleach. Not blix and without formaldehyde or other chemicals that destroy the dye couplers. I used potassium ferricyanide+potassium bromide and a phosphate buffer, but ferric sodium or ammonium EDTA bleach will probably work fine too.
4) Re-exposure
5) Color dev
Repeat steps 3 through 5 until satisfactory amount of dye is formed. Then bleach and fix. AFAIK, the dyes formed by 4-aminophenol are Ph-sensitive, so I'd use a neutral fix and wash the film in sodium carbonate/bicarbonate/weak NaOH solution before the final wash.

That is where I would start if I tried to make this developer from the raw chemicals, but it 100% will need adjustments, maybe pretty major.

LeoniD said:

Well, I didn't use the raw components and the manufacturer doesn't disclose how much of PPD there is in 45ml of hair dye, but I'd start with 2g of PPD and 1g of 4-aminophenol, per 330ml of the developer. No idea what the Ph should be in this case, so I'd add potassium carbonate until Ph is somewhere around 9. IIRC, PE mentioned that sodium sulfite in low concentrations will help with dye formation by removing the excess oxidised color developing agent, so I'd add ~0.2-0.3g, again, per 330ml.
So the whole process would go like this

1) First dev.: Rodinal 1+50 or equivalent, approximately 9min at 20C.
2) Fix(non-hardening)
3) Bleach. Not blix and without formaldehyde or other chemicals that destroy the dye couplers. I used potassium ferricyanide+potassium bromide and a phosphate buffer, but ferric sodium or ammonium EDTA bleach will probably work fine too.
4) Re-exposure
5) Color dev
Repeat steps 3 through 5 until satisfactory amount of dye is formed. Then bleach and fix. AFAIK, the dyes formed by 4-aminophenol are Ph-sensitive, so I'd use a neutral fix and wash the film in sodium carbonate/bicarbonate/weak NaOH solution before the final wash.

That is where I would start if I tried to make this developer from the raw chemicals, but it 100% will need adjustments, maybe pretty major.

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I don't think I can do that experiment.
The experience seems to me largely ambiguous and not based on disciplined rules and cannot be built upon.
Maybe the fault is with me, maybe I didn't understand the experience correctly, maybe the problem is with me.

mohmad khatab said:

The experience seems to me largely ambiguous and not based on disciplined rules and cannot be built upon.

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Not really ambiguous. The amounts of developing agents I listed are guestimated on how much ЦПВ-1/CD-1 is used in a color dev. That is 1.15g for 0.5l. Bigger amount of developing agents is used because of their lower dye-formation activity. Then Ph-the optimal Ph for color dev. is 10, but here you have
A)more developing agent
and
B) 4-aminophenol, that is more of a BW developing agent, that is probably why at lower Ph I observed better dye formation.
Again, everything I listed, I would use as a starting point. The process most likely needs to be tweaked, and how it should be tweaked can only be determined after looking at the results. I would be very grateful for your tests as I currently don't have raw PPD