Kodak Polytoner and alternative sepia/sulfide toners

[Arthurwg]

I'm famous for stinking my whole building...!
My friends did this to make fun of me
View attachment 403727

Matt, I know of this substitute but I dont want to play with selenium powder.

I wonder why you can't use liquid selenium.

 

[Renato Tonelli]

I have some: one full bottle and one 3/4 full or so. Had them for decades; I used some last month for some printing tests (still good).
I would be willing to sell them but how do you ship this stuff (it's classified as Hazardous)? and at what cost?!?

 

[Guillaume Zuili]

I have some: one full bottle and one 3/4 full or so. Had them for decades; I used some last month for some printing tests (still good).
I would be willing to sell them but how do you ship this stuff (it's classified as Hazardous)? and at what cost?!?

pm sent

 

[Arthurwg]

Seems that Moersch MT4 is unavailable at the moment.

 

[Guillaume Zuili]

Seems that Moersch MT4 is unavailable at the moment.

Freestyle stopped importing it a long time ago (MT5 as well) which is a shame. And it’s not possible to ship it from europe. Tried from fotoimpex. No go.

 

[RalphLambrecht]

Me too. Down to my last bottle. But there are recipes on-line to make it yourself. But I think you need Kodak Brown toner, also difficult to find.

I suggest looking for'black salt' in oriental food stores. it can be used as a polysulfide toner replacement.

 

[MattKing]

I suggest looking for'black salt' in oriental food stores. it can be used as a polysulfide toner replacement.

AKA, Kala Namak - see here: https://www.photrio.com/forum/resources/kala-namak-sepia-toner-for-indirect-toning.451/

 

[Robert Ley]

Just checked my stock of DR chemicals and I have a full gallon of Kodak Brown toner that i picked up many years ago and never used so I don't know whether it has ever been opened.
Have no idea if it is still good, I suspect that it is and am wondering if one or more members would want some or all of it.
PM me if interested.

 

[Arthurwg]

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

 

[AnselMortensen]

Direct

 

[Guillaume Zuili]

Kodak Brown toner never dies. Stinks like hell !

 

[Raghu Kuvempunagar]

Liver of Sulphur is difficult to procure in some locations. Someone posted a simple DIY formula for making Polysulphide toner starting with the more easily available Sodium Sulphide and Sulphur. I tried it once for toning my B&W slides and was happy with the results. YMMV.

https://www.photrio.com/forum/threads/kodak-polytoner.195916/#post-2622723

 

[koraks]

Someone posted a simple DIY formula for making Polysulphide toner starting with the more easily available Sodium Sulphide and Sulphur. I tried it once for toning my B&W slides and was happy with the results.

Neat! That's easy enough to try. Sodium sulfide I had on stock anyway, and I also had a little bit of sulfur that I kept from a jar of sulfured out fixer (who knows when some elemental sulfur comes in handy, eh?)

This is in 150ml, so a little stronger than in the post you linked to. Just mixed and shaken, hence the cloudy appearance. What's interesting is that the solution turns quite bright yellow within a few seconds of mixing, even though elemental sulfur as such isn't water soluble. So something's happening alright. I reckon things will go faster if it's heated up, so maybe I'll put the bottle in a beaker of hot water later on, see what happens.

 

[xtol121]

@koraks I’d be excited to see results if you plan on testing it at all!

 

[Raghu Kuvempunagar]

Neat! That's easy enough to try. Sodium sulfide I had on stock anyway, and I also had a little bit of sulfur that I kept from a jar of sulfured out fixer (who knows when some elemental sulfur comes in handy, eh?)
View attachment 405476
This is in 150ml, so a little stronger than in the post you linked to. Just mixed and shaken, hence the cloudy appearance. What's interesting is that the solution turns quite bright yellow within a few seconds of mixing, even though elemental sulfur as such isn't water soluble. So something's happening alright. I reckon things will go faster if it's heated up, so maybe I'll put the bottle in a beaker of hot water later on, see what happens.

Heating as well as agitating definitely speeds up the reaction. A similar process for a more concentrated Polysulphide synthesis is discussed in Haist, Modern Photographic Processing, Vol 2:

"The effectiveness of polysulfide for toning was recognized as early as 1913 by J. Desalme, 26 · 28 who prepared a sodium polysulfide solution by adding, slowly, 6 g of sulfur to 50 ml of boiling water containing 50 g of sodium sulfide. When the sulfur is dissolved, dilute to one liter for the toning bath (30 min immersion is required, followed by thorough washing in water). Desalme also noted that sodium sulfide may be converted to a polysulfide by adding hydrogen peroxide or some per-salt, such as am monium persulfate."

 

[Guillaume Zuili]

Good that you moved that thread.
Funny that I was also the OP on the other one. Now I know that I have almost 3 more years of Polytoner.
I'm also going to try that simple formula. The more choices the better.
Koraks please shows some results later on.

 

[koraks]

@koraks I’d be excited to see results if you plan on testing it at all!

You bet! Not sure when or how, but I certainly intend to give it a go. What I'm not sure about is how to figure out if the result is any different from toning in plain sodium sulfide. Any ideas on this, @Raghu Kuvempunagar ?

Desalme also noted that sodium sulfide may be converted to a polysulfide by adding hydrogen peroxide or some per-salt, such as am monium persulfate."

Well, more good news - I have a jar of sodium persulfate here (somewhere....). I bought it for etching PCB's, but prefer ferric chloride, so it's not seen much use. Any suggestions on the ratio between persulfate and sodium sulfide?

Good that you moved that thread.

You got it! And I will report back at some point.

Edit: half an hour later, while looking for (and finding) the persulfate, the polysulfide conversion seems mostly complete with only a few clumps of sulfur floating around. Note how the color has changed to a less vivid ocher:

 

[koraks]

Since this thread and the one linked to by @Raghu Kuvempunagar in post #40 were pretty much about the same thing anyway, and this is now turning into a continuation of that older thread, I've merged them into a single discussion.

 

[Raghu Kuvempunagar]

Well, more good news - I have a jar of sodium persulfate here (somewhere....). I bought it for etching PCB's, but prefer ferric chloride, so it's not seen much use. Any suggestions on the ratio between persulfate and sodium sulfide?

Unfortunately the ratio is not mentioned in Haist who cites two publications of J. Desalme in the British Journal Of Photography:

26. J. Desalme, "Toning by Sulphuration," Brit. J. Phot., 60: 157 (1913).
27. J. Desalme, "Direct Sulphide Toning," Brit. J. Phot. Almanac, p. 661 (1914).

You may want to check with @Ian Grant who might have copies of this journal.

 

[koraks]

Not to worry - some haphazard experimentation gets us somewhere, I'm sure:

From left to right, all the same bottle:

• 2.5g sodium sulfide in tap water
• Immediately after 1g of sodium persulfate to it. Solution remains clear, but the powdered persulfate at the bottom already starts to react
• After shaking the bottle, tones shift to more orange. Solution is still cloudy at this point.
• This is after adding another gram of sodium persulfate
• Let it sit for a minute or two and it clears right up.

Here's the preparation compared to the bottle I made with Na2S and plain sulfur. The concentrations are different. I suspect the molecular weight distribution of the polysulfides are also different in the bottles. But I figure the functional properties are probably about the same:

Maybe if I add a little more persulfate the bottle on the right turns darker. IDK.

 

[Raghu Kuvempunagar]

From left to right, all the same bottle:

• 2.5g sodium sulfide in tap water
• Immediately after 1g of sodium persulfate to it. Solution remains clear, but the powdered persulfate at the bottom already starts to react
• After shaking the bottle, tones shift to more orange. Solution is still cloudy at this point.
• This is after adding another gram of sodium persulfate
• Let it sit for a minute or two and it clears right up.

Here's the preparation compared to the bottle I made with Na2S and plain sulfur. The concentrations are different. I suspect the molecular weight distribution of the polysulfides are also different in the bottles. But I figure the functional properties are probably about the same:

Maybe if I add a little more persulfate the bottle on the right turns darker. IDK.

Fantastic!

Since you're in the mood to experiment, let me suggest another synthesis process which I adapted from a patent:

Sulphur: 40 g
Potassium Hydroxide: 10 g
Boiling water: 100 ml
Shake vigorously for at least 10 minutes.
Let the mixture stand for 24 hours.

Filter the liquid and add water to make volume 1 l.

This also gave me good results but the keeping quality was low. Might have something to do with the reaction continuing after the formation of Poylsulphides. Not sure if 24 hours are strictly needed for the Polysulphides to form. Nice thing about this process compared to the other two is there is no need to work with Sodium Sulphide.

 

[koraks]

Since you're in the mood to experiment

Apparently! (There goes my Sunday, LOL)

I adjusted the concentration and the absolute amounts a little to fit a small bottle that was sitting on my workbench.
This is 4.0g sulfur + 1.0g sodium hydroxide in some 40ml of really hot water:

Note how something is definitely happening where the sulfur and the hydroxide meet.

After vigorous shaking for a minute or two.

If the sulfur is allowed to settle, the solution can be seen to already have turned yellow/orange. So it appears to be working alright.

I've put it on the stirrer now and I'll put a hot water jacket around it to keep things going at least in the first half hour or so. I'll probably forget about it for the rest of the afternoon!

the keeping quality was low

I'm surprised at this. How does it deteriorate? Does it sulfur out, basically? Or does it break down into plain sodium sulfide? I would have expected a polysulfide solution to be stable.

 

[Raghu Kuvempunagar]

I adjusted the concentration and the absolute amounts a little to fit a small bottle that was sitting on my workbench.
This is 4.0g sulfur + 1.0g sodium hydroxide in some 40ml of really hot water:

Note how something is definitely happening where the sulfur and the hydroxide meet.


I'm surprised at this. How does it deteriorate? Does it sulfur out, basically? Or does it break down into plain sodium sulfide? I would have expected a polysulfide solution to be stable.

No sulphurisation happened in my case. The orange solution eventually (i.e. after a month) turned clear and I suspect that Polysulphides, in this particular concoction, eventually got oxidised to Thiosulphate and other usual suspects. I would be curious to know if this is going to happen in your case too.

 

[koraks]

Sounds like a slow way of making fixer, LOL. I bet it stains to high heaven as well!

I would be curious to know if this is going to happen in your case too.

You'll have to remind me of this in a month or so. I wonder about the other two bottles as well, the ones I made with sodium sulfide. I'd expect those to be liable to the same modes of deterioration, no?

 

[Raghu Kuvempunagar]

Sounds like a slow way of making fixer, LOL. I bet it stains to high heaven as well!


You'll have to remind me of this in a month or so. I wonder about the other two bottles as well, the ones I made with sodium sulfide. I'd expect those to be liable to the same modes of deterioration, no?

No idea about the Persulphate based process as I never tried that. The first one did do well for a few months before it got used up. Fortunately, you can tell if the solution has gone bad by looking at the colour. If it has lost the deep oranage colour, then it is mostly gone.

Stain it might not as some Sulphide toner formulations do have Thiosulphate in them which is probably needed for them to work well as direct toners.