Kodak Polytoner and alternative sepia/sulfide toners

koraks

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Raghu Kuvempunagar said:
If it has lost the deep oranage colour, then it is mostly gone.
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Well, the bottle I prepared with persulfate is less orange than the sulfide/sulfur preparation to begin with.

I don't think much was happening anymore with the sulfur/NaOH bottle, so I've added another gram of hydroxide in the hope of getting the remaining sulfur to react as well. I also re-heated the water jacket. It's now like this:

There's also strong ammonia smell then I open the bottle. That may seem odd, but keep in mind that the sulfur I used originated from sulfured out fixer - rapid fixer in this case. So there's some ammonia left in there, evidently.
 

Raghu Kuvempunagar

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koraks said:
There's also strong ammonia smell then I open the bottle. That may seem odd, but keep in mind that the sulfur I used originated from sulfured out fixer - rapid fixer in this case. So there's some ammonia left in there, evidently.
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Ammonia is released in alkaline solutions of Ammonium salts which does indicate the presence of Ammonium Thiosulphate as you suspected.



If I read your earlier post correctly, you used 40 ml water instead of 10 ml water. This could be the reason why the solution doesn't have a deep orange colour.
 

koraks

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Yes, correct, this is a lower concentration overall.
I've added more sodium hydroxide; it's now 5.0g NaOH to 4.0g sulfur. The solution is presently a fairly deep orange color. This was at around 1:1 weight ratio of both, after letting it sit for a few seconds to let the remaining sulfur settle down:


I'm not sure why, but I seem to need a lot more hydroxide to get all the sulfur to participate in the reaction. The solution is starting to clear now as I continue to add hydroxide. Looks quite similar to dichromate solutions in terms of hue and intensity.

Okay, at 5.2g NaOH to 4.0g of sulfur, the solution seems to have cleared up almost entirely:

The ammonia smell is pretty bad; I suppose I could probably get rid of it if I would leave the bottle open for a while.

Here's the three bottles I prepared together with the bit of remaining sulfur I 'harvested' from broken fixer:

The sulfur/hydroxide preparation is the darkest, but it's also the most concentrated.
 
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koraks

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I tried a scrap of film with your preparation and it certainly does act as a toner. I've not tried the others yet. I have in mind to do some testing but IDK if it'll be for today.
 

Raghu Kuvempunagar

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koraks said:
I tried a scrap of film with your preparation and it certainly does act as a toner.
Click to expand...

Good to hear this.


koraks said:
I've not tried the others yet. I have in mind to do some testing but IDK if it'll be for today.
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Sure, if and when you test, I'm sure many here including me will be interested in knowing your experience. And I'll try to remember to ping you after a month to check the condition of the last toner.
 

koraks

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This is done with the second bottle, so the one I prepared using sulfur and persulfate:

This is an old print on Fomabrom; it was in our hallway for a number of years, but I recently removed it to make space for the postcard exchange. The print was neutral, untoned; I don't recall with certainty what developer I used, but it was most likely ID68. I let the print sit for 20 minutes in the toner, undiluted, with virtually no agitation - so the toning isn't perfectly even. It's always hard to tell from a smartphone pic, but the print has toned to an attractive purple-brown that's typical for how this paper tones in strongly alkaline sepia.

The toner didn't stain or damage the print, although the emulsion feels really soft (unsurprisingly). The damage you see around the edges was pre-existing, which is also true for some small stains along the top edge.

This toner smells distinctly of sodium sulfide, so maybe that means not all the sulfide has converted to polysulfide. I'm not sure. I might try adding some more persulfate and see if it darkens. I have a feeling that might work.
 

Raghu Kuvempunagar

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That looks good! Thanks for doing the test and sharing the result.

Sulphide toners smell of Hydrogen Sulphide. So it is hard to say anything about the completion of the reaction by smell alone. But if colour is an indicator, you may be right about the need to add more Persulphate.
 
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Guillaume Zuili

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Looking great. Any scum or milky residue that you had to remove after the wash ?
 

skahde

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To make my own polytoner I dissolved and filtered 250 g of potassium-sulfide (pro balneo) in 500 ml. Filtered and buffered it and added a good amount of selenium-toner concentrate. Worked impessively well! If I find my notes, I can give amounts and concentrations.
 

skahde

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Harddrive searched: No results. Will try again tommorow, there is still a chance to find something. Otherwise I will have to try and recreate it.
 

Raghu Kuvempunagar

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koraks said:
Adding selenium toner is also on my to-do list.
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CONCENTRATED SELENIUM TONER AND PROCESS OF MAKING

"30 grams of sodium selenite are dissolved in 300 cc. of water (125° F.); 500 grams of ammonium thiosulfate, 75 grams sodium sulfite and 100 grams sodium bisulfite were dissolved in another quantity of water amounting to 500 cc. The sodium selenite solution was then added with constant stirring to the second solution. The volume was adjusted to make one liter and the pH of the mixture was then adjusted to 6.98 by the addition of sodium bisulfite. This concetrated solution precipitated none of its constituents during keeping over a substantial period of time. For use it is diluted with three parts of water at about 70° F. and will satisfactorily tone in the very short time of two to five minutes."
 
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Raghu Kuvempunagar

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Kodak Brown Toner

Weight % - Component - (CAS Registry No.)
70-80 Water (007732-18-5)
15-20 Potassium sulfide (001312-73-8)
5-10 Sodium carbonate (000497-19-8)
< 1 Sodium hydroxide (001310-73-2)


KODAK POLY-TONER

1. Begin with three 8-ounce bottles of KODAK Brown Toner, CAT No. 146 4452.
2. With constant agitation, add 67.4 grams of sodium carbonate, monohydrate, photographic grade. If a proper scale is not available, you can substitute two black plastic KODAK 35 mm Film containers, filled with sodium carbonate, monohydrate to approximately ¼ inch from the top.
3. With constant agitation, add 5.4 grams of selenium powder. If a proper scale is not available, you can substitute 1 teaspoon of powder.
4. With constant agitation, add 1.0 millilitres of sodium hydroxide, 50% solution. This step can be eliminated if making the “less precise” mix.
5. Agitate the mixture for a minimum of 30 minutes, then slowly add one additional bottle of KODAK Brown Toner, CAT No. 146 4452. Continue to agitate for at least 10 minutes.
6. Cover the solution to minimize evaporation and fumes, and let the solution stand for at least 12 hours with no agitation. Decant the solution through 0.45micron filter paper into a clean container. Change the filter paper halfway through if necessary to maintain a reasonable flow of solution. This process may take an hour.

p.s. please read this before you try making any of these: https://nj.gov/health/eoh/rtkweb/documents/fs/1727.pdf
 
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koraks

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Raghu Kuvempunagar said:
please read this before you try making any of these
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That's one of the key reasons why I've never done what you posted, although I've been aware of these formulas and a couple more for several years. Hence, my interest is mainly in what @skahde mentioned: adding a store-bought selenium toner concentrate to a DIY polysulfide toner. If that works, it would cut the unsafe corners from the process.
 

Raghu Kuvempunagar

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koraks said:
my interest is mainly in what @skahde mentioned: adding a store-bought selenium toner concentrate to a DIY polysulfide toner. If that works, it would cut the unsafe corners from the process.
Click to expand...

Store-bought selenium toner, at least the one made by Ilford and Kodak, has loads of Ammonium Thiosulphate in it whereas Kodak's Poly-Toner has none. So your DIY poly-toner might not behave exactly like Kodak's, but who knows. Sequential toning is another safer alternative.
 

koraks

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Exactly, that's my concern, hence my interest in what @skahde reported. I can imagine that the thiosulfate doesn't hurt in this context, but IDK for sure.
Sequential toning is what I've been doing so far and that works wonderfully; generally I use thiourea for the sepia step which is flexible and odorless. So technically I personally don't really have a compelling reason to try and improve my own toning process, although I always keep an eye out for alternative approaches. Part of the reason is also that sometimes people wax lyrical about polytoner and argue that its properties are unique, and the effect cannot be obtained in any other way. I'm very, very skeptical about these claims, but I'd still like to try it on for size and see what's up. My wish to try it is not so great that I'll go to the lengths of obtaining sodium selenite (which I found surprisingly difficult to get hold of here) and handling it.
 
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