Kodak Polytoner and alternative sepia/sulfide toners

[koraks]

If it has lost the deep oranage colour, then it is mostly gone.

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]

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.

Ammonia is released in alkaline solutions of Ammonium salts which does indicate the presence of Ammonium Thiosulphate as you suspected.

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:
View attachment 405487
.

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]

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.

 

[Raghu Kuvempunagar]

View attachment 405488

Yes, the colour does indicate the formation of Polysulphides. You may want to do a clip test with it and also with other two concentrates.

 

[koraks]

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]

I tried a scrap of film with your preparation and it certainly does act as a toner.

Good to hear this.

I've not tried the others yet. I have in mind to do some testing but IDK if it'll be for today.

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]

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]

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.

 

[Guillaume Zuili]

This is done with the second bottle, so the one I prepared using sulfur and persulfate:
View attachment 405495
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.

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

 

[koraks]

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

Thanks; no, none at all; it's really clean-working.

 

[skahde]

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.

 

[koraks]

Adding selenium toner is also on my to-do list. Yes, please share your notes if you can find them!

 

[skahde]

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]

Adding selenium toner is also on my to-do list.

CONCENTRATED SELENIUM TONER AND PROCESS OF MAKING

https://patentimages.storage.googleapis.com/fc/60/0d/e153da2c061202/US2382683.pdf

"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."

 

[Raghu Kuvempunagar]

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

 

[koraks]

please read this before you try making any of these

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]

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.

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]

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.

 

[RalphLambrecht]

How do you use brown towner". Direct or indirect?

I never use it indirekt. I'm uncertain about the redevelopment process and find direkt toning much easier to control.

 

[Keith Tapscott.]

Perhaps Adox will offer an Agfa Viradon substitute if there is enough interest.

 

[skahde]

I have to report that a full scan of my harddrive only found Kodak's known Publication the above recipe for making your own is obviously cited from but not my own notes. I attach it here anyway.
In Essence and from memory it was T8 with Selenium-Toner Concentrate added to the working-solution. As I could not get selenium-powder and also didn't want to mess with it, this was a viable solution.
The selenium toner-concentration should be chosen as for normal selenium-toning while aiming for more purple darks i.e. in the ballpark around 1+9 rather than 1+19.
I still have prints on my wall toned with this solution which I like quite a lot, nice, delicate brown-purple tone.

 

[koraks]

Thanks @skahde, I think that's about as specific as it needs be. Very much appreciate your digging in your archives to locate the data you had on this!

 

[Guillaume Zuili]

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.

Same concerns than you about the selenium powder.
About adding store-bought selenium, why Kodak didn't propose that solution ? Too simple or I suspect the Ammonium Thiosulphate might be the issue.
I do wax lyrical about polytoner !!!

 

[Rudeofus]

Same concerns than you about the selenium powder.
About adding store-bought selenium, why Kodak didn't propose that solution ? Too simple or I suspect the Ammonium Thiosulphate might be the issue.
I do wax lyrical about polytoner !!!

There may be a substantial difference, whether you use this substitute directly or indirectly. Used directly the Ammonium Thiosulfate probably doesn't hurt at all, whereas it could make indirect toning a gamble.

 

[Arthurwg]

Yes, I had six bottles of polytoner and now down to my last, about three quarters full. Now if I could only get Agfa Classic Matte paper...