Controling Sepia toning.... how?

[brian steinberger]

Ralph,

Thank you for your correction (in pointing out the loss of highlights). How about then.... bleach it partially and redevelop it FULLY in Sepia, then follow it up with Selenium? That way, whatever the portion of silver that got bleached get toned in sepia, and the portion that wasn't bleached will be selenium toned. At no step there will be un-toned and undeveloped silver.

PS. Brown direct toner is on order...

Yes this will work and exactly what I do. I also find that selenium after sepia also seems to boost the color a bit of the sepia tones, especially with MGWT. So be careful, some colors can get out of control. You may need to try a more dilute selenium or even a different developer if you'd like to keep your lower values more neutral tone.

 

[Thomas Bertilsson]

Speaking of which, just what is the useful life of toner? I mix my own and store it in a dark glass bottle, then mix working solutions by adding 50 ml of "lye" to diluted toner at about 1 to 10. My only metric has been that it either tones or it doesn't (using test strips), but I'm never sure ahead of time. Anyone? Anyone? Bueller?

Not sure, John... I just use it until it doesn't do the job anymore. I don't really count. I keep more toner on hand than I need at any given moment, so it's easy to just mix new on the fly if necessary.
I believe Wolfgang Moersch claimed once that his MT-3 vario toner would do 30-50 8x10 prints. I print on 11x14 for the most part, which would give me about half of that capacity, 15-25 prints.

Ferris out

 

[RalphLambrecht]

Yes this will work and exactly what I do. I also find that selenium after sepia also seems to boost the color a bit of the sepia tones, especially with MGWT. So be careful, some colors can get out of control. You may need to try a more dilute selenium or even a different developer if you'd like to keep your lower values more neutral tone.

Let me play the devil's advocate here for a moment.

If a print is 'fully' redeveloped (sepia toned), how can any subsequent selenium toning work at all?

As was said, sulfide and selenium toners convert metallic silver into much more inert silver sulfide and silver selenide, respectively. But selenium does not convert silver sulfide. So, why does it subsequent selenium toning work (and we know it does)?

I think, one possible answer is that 'full' sulfide toning is not as 'full' as we like to believe. But if it was previously bleached, what is the not fully redeveloped compound then?

 

[Ian Grant]

Ralph, other toners can convert Silver Sulpide etc, even with a fully toned image, the most common is Gold toning after sepia (sulphide & thiourea) to form red tones.

The Silver can be replaced by Gold, Platinum, Palladium etc and that can happen with Selenium as well.

Ian

 

[Philippe Grunchec]

Convert or plate, that is the question!

 

[RalphLambrecht]

Ian

The indication here is:

silver + sulfide > silver sulfide
silver sulfide + selenium > ? (no idea what this would be)

But I believe it's more like this:

silver + sulfide > silver sulfide + (residual) silver

then adding selenium gives you:

silver sulfide + silver selenide + (still some residual) silver

In other words, no toning process is fully complete!

 

[Ian Grant]

Philippe. With Gold toning of sepia toned images the Silver is replaced.

Ralph, indirect sepia toning is to completion if the image was fully bleached, too much light during washing etc before toning might allow a little of the silver to print out. You could easily test this by cutting a toned print in half rebleaching & fixing on half and comparing.

Ian

 

[RalphLambrecht]

With Gold toning of sepia toned images the Silver is replaced.

Ian

Ian

Let's stick to sulfide and selenium for now. Are you saying that selenium replaces silver in silver sulfide, or is it as I assume that selenium just forms silver selenide with the residual silver?

 

[Thomas Bertilsson]

Ralph, both Brian and I don't fully bleach the print. We just bleach back a little bit, so that when we re-develop the print all we do is warm up the highlights. We fully re-develop the silver that was returned to silver halide form, but since it was only a partial bleach in a weak bleach bath, the whole picture doesn't exhibit the typical sepia tone.

There is plenty of unbleached silver gelatin left for the selenium to tone. The combination of the two make for a very beautiful color rendition.

Think of it as the sulfide / thiourea toner being a 'top down' type of toner, where we go after the highlights and some of the mid-tones to be bleached back and fully re-developed in sepia, to form a picture that consists of both silver and silver sulfide.
Then think of the selenium as being a 'bottom up' type of toner, affecting the shadows mostly, converting some of the silver into silver selenide.

That process can be done in reverse also, by first toning in selenium toner, then bleaching back the highlights, and finally re-developing in sepia. Or, if you want to get really funky, bleach, re-dev in sepia, then bleach again, re-dev again, and then selenium. Or do selenium as the middle step. They all yield different results.

I go for the effect, and take more than reasonable care in making sure all steps are properly executed. I am not worried about archival standards, since any bleach back done is completely re-developed.

- Thomas

 

[RalphLambrecht]

Ralph, both Brian and I don't fully bleach the print. We just bleach back a little bit, so that when we re-develop the print all we do is warm up the highlights. We fully re-develop the silver that was returned to silver halide form, but since it was only a partial bleach in a weak bleach bath, the whole picture doesn't exhibit the typical sepia tone.

There is plenty of unbleached silver gelatin left for the selenium to tone. The combination of the two make for a very beautiful color rendition. ...

Thomas

I fully understand that, and it makes a lot of sense to do it that way. However, if you just want a 'hint of sepia', to take the edge of the print and warm it up a bit, I find it easier to use direct sulfide toning, possibly followed by selenium toning. The OP must try both methods and hopefully add both to his darkroom repertoire.

 

[Ian Grant]

Sorry for the confusion Ralph the Gold/Sepia comment was for Philippe but you replied inbetween.

Well with straight Selenium toning there's a point where the Silver is totally replaced by Selenium, it's why Thiosulphate is needed in KRST, so this isn't a plating effect as Philippe was asking, neither is the conversion of Silver Sulpide with a Gold toner using Thiocyanate as the silver solvent.

So with a a Sepia toned image there's possibly very slight straight Selenium toning of any printed out image particularly if the image is bleached then washed in daylight. However there's also an interaction between Selenium and Sulphide which is exploited in Flemish toners, etc an Ilford IT-3.

It's possible to convert Silver Sulphide to other compound so it's not an unchangeable compound. So some can be converted by Selenium toner, but the amount and degree is very dependent an how fine the grain is of the paper emulsion and the original type of emulsion & development effects that.

Ian

 

[RalphLambrecht]

Ian

Thanks for that clarification. I'll dig into Haist a bit more over the next few days to understand some more details.

 

[nworth]

With selenium toning, silver is replaced by silver selenide, similar to what happens with sulfide toning where silver gets replaced by silver sulfide. Both are highly stable. When you partially bleach, tone in sulfide, and then tone in selenium, the process becomes a bit more complicated. The bleached part of the image is quickly converted to silver sulfide. The unbleached image is also attacked by the sulfide and is converted more slowly and incompletely. The selenium toner, if allowed to go to completion, converts most of the remaining silver to selenide and then fixes out any remaining silver salts. This allows you some considerable control, depending on the amount of bleaching, the length of time in the sulfide beyond what it takes to convert the bleached image, the strength of the selenium toner, and the time in the selenium toner.

 

[RalphLambrecht]

nworth

Very good explanation! So, what would you say are the possible compounds in a sulfide and selenium-toned silver image?

silver, silver-sulfide, silver-selenide, ... anything else?

 

[Philippe Grunchec]

Ian, I thought gold would plate, not convert.

 

[nworth]

nworth

Very good explanation! So, what would you say are the possible compounds in a sulfide and selenium-toned silver image?

silver, silver-sulfide, silver-selenide, ... anything else?

A good question. The actual products of toning processes might still make an acceptable dissertation topic, and quantifying them would get into some interesting instrumentation methods. The obvious, in addition to the above, would be silver thiosulfate complex salts from the selenium toner and various sulfur and selenium compounds adsorbed onto the image and absorbed into the gelatin. Those are why a good washing is required after the toning. (How much is good enough?) I would also expect some sulfides and selenides of trace metals in the paper or possibly the water supply, but these would be very minor. Since most sulfides and selenides are quite insoluble, they probably will do no harm.

 

[Philippe Grunchec]

Is it possible to use a thiocarbamide toner as a direct toner?

No one seems to have mentioned the use of a sulfite sodium "stop bath": would it also work with a thiocarbamide toner (direct or indirect)?

 

[RalphLambrecht]

... No one seems to have mentioned the use of a sulfite sodium "stop bath": would it also work with a thiocarbamide toner (direct or indirect)?

You don't want a toner stop with indirect toning, because you'd like the toning as complete as you can get it.

 

[Philippe Grunchec]

Thank you, Ralph! What would be your answer to my other question? Thanks in advance!

 

[RalphLambrecht]

Is it possible to use a thiocarbamide toner as a direct toner? ...

I see no reason why not, but wouldn't expect much tonal change.

 

[Marco B]

Ralph:

I have had fully sepia toned (full bleach + redevelop), and almost full selenium toned prints (harder to judge, as there is no bleach step as I used it) subsequently ran through a selenium toner or sepia toner respectively. Toning times for the second toner were deliberately exaggerated long to ensure any remaining silver would be converted and any effect on existing
toned parts of the images could be judged.

I can assure you:

- a fully sepia toned image (silver sulphide) IS NOT converted to silver selenide by selenium toner, the images remain as they are.
- a fully selenium toned image IS NOT converted to silver sulphide by a sepia toner, the images are again unaffected by the second toner.

I actually ran a whole bunch of tests using different papers (Ilford, Kentmere) and different amounts of double toning of sepia and selenium, going from fully sepia toned, as judged by a full bleach, to almost full selenium toned (judged by eye) with about 6 steps in between, and the results were consistent.

As you also more or less say: it is the remaining untoned silver and possible remaining bleach products like silver halide or silver ferricyanide that is converted in a subsequent toning bath.

Anyway, this is not a statement about the effects of any other types of toners (gold), I haven't tried it so can't comment, or that silver sulphide and silver selenide are wholly immutable. Like Ian Grant suggests, there might well be some chemical substances capable of attacking both, but another consideration in that respect is if the paper base or gelatine would survive such conditions...

Is it possible to use a thiocarbamide toner as a direct toner?

I see no reason why not, but wouldn't expect much tonal change.

I have attempted this just once in experiments. Any toning effect of a working strength thiocarbamide / thiourea (same substance, different names), is painfully slow to the point of non-existent without a pre-bleach. With "working strenght", I mean the concentrations as designated by the manufacturers of two bath bleach / redeveloper sepia toners for making the redeveloper solution.

I don't know if a higher concentration solution would possibly make a viable direct toner...

 

[RalphLambrecht]

Marco

Thanks for sharing. Your conclusions make sense to me.

 

[Marco B]

By the way, my test also highlighted what others here on APUG having been saying too.

BIG WARNING for anyone doing double toning involving selenium toner as the first toning bath and a subsequent bleach of a second toner to be applied afterwards:

- Ensure you properly wash the print after the selenium toner, preferably using HCA or Washing Aid, to wash out any remaining hypo from the selenium toner.

Hypo (fixer) forms part of the chemical cocktail of most selenium toners. If you don't wash it out properly prior to the second sepia toner bleach bath, the fixer will bleach out some of the silver halides formed in the bleaching process, leading to especially highlight detail loss.

I could clearly see this effect in my tests. If I quickly rinsed the selenium toned prints, there was highlight loss due to fixing out of formed silver halides, if I properly washed them prior to bleaching, it was OK.

 

[RalphLambrecht]

Does someone know how Michael Kenna gets his so subtle tones? I met him very recently... but did not dare to ask!

I just send him an email to ask him.

I did an answer from Michael, but it was not clear to whether he uses direct or indirect toning. I did ask for further clarification and get back to you.

 

[Philippe Grunchec]

Is he back from Moscow?