Sepia Toners

RalphLambrecht · Mar 11, 2010

CBG said:
From people's comments here, it sounds like the stink is not as bad as I have occasionally read. Stinky, but not intolerable.

So, the stories I have seen of people being driven from their houses by the smell may be a bit exaggerated?

One can get used to it, which might be one of it's dangers. Adequate ventilation is a must due to it's toxidity. I have a large darkroom fan exhausting to the outdoors, and it works fine. I minimize the fumes by having a sheet of glass on top of the tray whenever possible.

naugastyle · Mar 11, 2010

I use the odorless thiourea sepia toner, so I'd say there's no significant smell.

Brown toner is definitely not a pleasant smell but it can easily minimized. I don't tone outside or at home, not an option where I live. I work in a basement darkroom where it's also not really safe to open the outside door (far away, not in my sightlines). But I have ventilation, and I open the doors of the darkroom itself just to enlarge the indoor space in which the fumes have to circulate.

dancqu · Mar 11, 2010

Has Me Wondering?

Stuart said:
You can also use direct toner as indirect toners
ei: bleach before you tone. So they are just as
versatile if not more so.

Bleach before you tone. Those are the directions
on my envelope of Kodak Sepia Toner. That toner
uses sodium sulfide not the polysulfide.

So with direct toning would not sodium sulfide work
also? I know that the IPI has toned microfilm with
an extremely dilute sodium sulfide solution. The
result was much improved LE. Polysulfide is
nothing more than sodium sulfide with
additional sulfur added. Dan

RalphLambrecht · Mar 12, 2010

dancqu said:
Bleach before you tone. Those are the directions
on my envelope of Kodak Sepia Toner. That toner
uses sodium sulfide not the polysulfide.

So with direct toning would not sodium sulfide work
also? I know that the IPI has toned microfilm with
an extremely dilute sodium sulfide solution. The
result was much improved LE. Polysulfide is
nothing more than sodium sulfide with
additional sulfur added. Dan

It is my understanding also that sodium sulfide toners are only used for indirect toning and polysulfide toners can be used for direct and indirect toning, but I don't know why that would be. Maybe Tim Rudman knows more about this. I know people have used odorless thiourea toners for direct toning with the desired visual effects, but I don't know how archival that is. Since thiocarbamide turns image silver into silfer sulfide as well, I think, it should make for a stable image. Again, Tim may be able to clarify.

Ian Grant · Mar 12, 2010

You can direct tone with Sodium Sulpide for image permanence but Polysulpde was more popular and gives more colour shift.

Ilford actually recommend for their IT-1 Sulphide Sepia toner - "Colder tones can be obtained by immersing the washed black-and-white print for 5 minutes in the sulphide bath before bleaching. Prints are then washed, bleached and darkened in the normal way."

Ian

Marco B · Mar 12, 2010

RalphLambrecht said:
It is my understanding also that sodium sulfide toners are only used for indirect toning and polysulfide toners can be used for direct and indirect toning, but I don't know why that would be. Maybe Tim Rudman knows more about this. I know people have used odorless thiourea toners for direct toning with the desired visual effects, but I don't know how archival that is.

I can't speak for sulfide toner as a direct toner, but I have attempted to tone an image directly using a thiourea based toner, so without bleaching it first in ferricyanide.

All I can tell you is any toning effect is veryyyyyy sloooooowww, at least at the "normal" concentration for using thiourea in combination with a pre-bleach of ferricyanide. Even after 20 minutes or so, there wasn't a visible color shift on my Ilford Warmtone, which normally is extremely fast in toning.

So speed of toning may be the main reason why some type of toners use a pre-bleach, and others don't...

Rolleiflexible · Mar 12, 2010

Kodak Sepia I and II -- difference?

To take this thread briefly in a slightly different
direction -- can someone explain the difference
between Kodak Sepia I and II toners? I have
tried both and prefer the II, both for tone and
for its seemingly less acrid small. I assume they
are both sodium sulfide toners -- can anyone
elaborate on the differences?

Anon Ymous · Mar 12, 2010

Sanders, the only difference seems to be the composition of the bleaching bath:

MSDS data from the Sepia I toner:
Weight % Components - (CAS-No.)
50 - 55 Potassium bromide (7758-02-3)
45 - 50 Potassium ferricyanide (13746-66-2)

MSDS data from the Sepia II toner:
Weight % Components - (CAS-No.)
85 - 95 Potassium ferricyanide (13746-66-2)
5 - 15 Potassium bromide (7758-02-3)

The actual toning bath was a solution of Na2S for both versions.

rmolson · Mar 12, 2010

toning for $165

Am I the only one who thinks that a book on toning for $165 is just a little bit beyond the pale?

PVia · Mar 13, 2010

Try Freestyle for the toning book...!

I see them in there from time to time, that's where I got mine, slightly corner bumped for $15.

Vlad Soare · Apr 14, 2010

Update:
I've tried Moersch MT3 (thiourea based), and I've also mixed a 1% solution of sodium sulfide (as per the Agfa 221 recipe).
The sulfide solution does smell, but much less than I expected. It's something I can live with. The smell is strongest when I insert the toned print into the washing tray, but even then it's far from being as annoying as I thought it would be.
On the paper I'm now using (mostly Fomabrom Variant, but also graded Fomabrom) the sulfide gives very beautiful and clean sepia tones. However, although the tones given by MT3 were clearly different (especially in a direct comparison), the difference is small, and I think I could get the same tones with MT3 if I played a little with the NaOH concentration.
So, for the time being I'm going to use both, and I'll decide later on which one I like best.

Is it possible to get different tones with a sulfide solution? Raising the pH (like you do with a thiourea toner) will probably not work, since the sulfide solution is already close to pH 14. How about dilution? Or temperature? Or maybe thiourea is the only toner capable of giving various tones?

PVia said:
except for making sure the sodium hydroxide solution is in a glass bottle (it can sometimes eat through a plastic bottle after a few months)

Paul, are you sure it's not the other way around? As far as I know, concentrated solutions of sodium hydroxide tend to react with glass to form sodium silicates.

Vlad Soare · Apr 14, 2010

There's something I don't get. I keep reading that thiourea toners must be discarded after use, that the concentrates have a long life, but once mixed they deteriorate beyond use within a few hours. Well, it's been almost three weeks since I mixed my MT3 (variant D - 50ml toner plus 130ml activator), and it's still working normally. Images toned today and those toned when the solutions were fresh are indistinguishable. The toning time is also unchanged - it completes in about ten seconds, maybe even less.
Mr. Moersch says that the toner can be kept indefinitely, and should be simply replenished when it gets depleted from use.
What's the catch? What am I missing? :confused:

RalphLambrecht · Apr 14, 2010

VladSoare

Can you please post a copy of the Agfa 221 recipe? Is it a direct toner?

Some literature recommends against the use of sodium sulfide, due to a potential sludge build-up, but Agfa Viradon is using it. Kodak recommended potassium polysulfide and used it in Kodak Brown Toner (KBT). Interestingly enough, I have the sludge build-up with Viradon but not with KBT. Also, keep in mind that thiourea does not give the strong archival protection, which sulfides do.

Marco B · Apr 14, 2010

VladSoare said:
There's something I don't get. I keep reading that thiourea toners must be discarded after use, that the concentrates have a long life, but once mixed they deteriorate beyond use within a few hours.

A few hours... Sorry, but this made me laugh, I have kept working solutions of two bath bleach / redevelop thiourea based toner for maybe half a year or so without issues. Yes, some calcareous deposit will form, but the solution is still working. Of course, solution stored in (almost) full bottles during non-usage.

RalphLambrecht said:
Also, keep in mind that thiourea does not give the strong archival protection, which sulfides do.

Ralph, what is this based on? Is it because some of the silver in a bleach / redevelop ferricyanide toner is turned into in a silver / ferri/ferrocyanide complex next to the formation of Ag2S, instead of only Ag2S, as with a straight polysulfide without a pre-bleach??

Ralph, I also see you stating in one of your previous post that thiocarbamide also produces Ag2S, and should thus be equally stable to sulfides, which contradicts your latest post...

By the way: thiourea and thiocarbamide are the same thing, just with a different name used for it.

Vincent Brady · Apr 14, 2010

nworth said:
Check Tim Rudman's book on toning.

There is another book by Tony Worobiec "Toning and Handcolouring Photographs" which is very informative. But Tim's book is the bible on toning.

Marco B · Apr 14, 2010

VladSoare said:
Is it possible to get different tones with a sulfide solution? Raising the pH (like you do with a thiourea toner) will probably not work, since the sulfide solution is already close to pH 14. How about dilution? Or temperature? Or maybe thiourea is the only toner capable of giving various tones?

What I am suspecting, but I haven't actually seen this confirmed in articles, is that the heightening of the pH in a bleach / redevelop thiourea (or sulfide toner), actually causes more of the formed silver / ferri/ferrocyanide complex to be broken down and also converted to Ag2S.

Silver / ferri/ferrocyanide by itself is a light yellow coloured substance, as can be witnessed during the bleach. It is formed next to AgBr during the bleach, this latter substance being somewhat light sensitive. The silver / ferri/ferrocyanide is probably pretty stable though, but not in highly alkaline environments, see the referenced article here:

http://81.207.88.128/science/photo/toners/toner.pdf

It thus may explain the more yellowish tones of a plain thiourea redeveloper, without added NaOH, as the substance remains partly in the final toned print, while heightening the pH using NaOH, may help in converting it to Ag2S as well. Please note that this is just my theory based mainly on what Wilco wrote in the above article and other stuff I read.

By the way, according to Wilco though, these metal cation complexes with ferri/ferrocyanide are quite stable by itself, and in fact, it is what cyanotypes and some other toners for silver images are based on!

See also this site by Wilco about the ferrocyanide toners:

http://81.207.88.128/science/photo/toners/ferrocyanide.html

Marco

RalphLambrecht · Apr 14, 2010

Marco B said:
...Ralph, what is this based on?...

Thiourea toning is far more complex than straight sulfide toning, but if you have Tim Rudman's toning book, check pages 94 to 96. He has a pretty good explanation there. It has partially to do with the fact that thiourea redevelops some silver back into silver halides of smaller grain size. This is also responsible for a change in reflection properties, and consequently, a color change, which has nothing to do with chemical toning or protection. Smaller grain size also means larger surface area, and larger surface area means more opportunity for environmental attack.

Grant Haist states in his book that thiourea can create poorly soluble silver compounds, which will decompose in the presence of light and moisture. This will mostly happen in alkaline environments, so, developer carry-over into the fixer is an issue.

Marco B said:
...Ralph, I also see you stating in one of your previous post that thiocarbamide also produces Ag2S, and should thus be equally stable to sulfides, which contradicts your latest post...

I didn't mean to confuse. It's true, thiourea also converts metallic silver to silver sulfide. Please, don't get me wrong. It's not that thiourea gives no protection. It does, but my statement is that it gives less protection than polysulfide toning, which is the strongest protection you can get from any one toner, especially if toning is not done to completion.

Toning in thiourea is far better than no toning at all, but don't expect the archival properties of sulfide toning. By the way, don't expect that from selenium toning either.

clayne · Apr 14, 2010

RalphLambrecht said:
Toning in thiourea is far better than no toning at all, but don't expect the archival properties of sulfide toning. By the way, don't expect that from selenium toning either.

Ralph, what do you know about the differences between individual sulfide toners? KBT uses potassium polysulfide (+ sodium carbonate), whereas Viradon uses sodium polysulfide. Any real-world differences between these two formula? I've often wondered why Viradon is capable of slightly different tones than KBT but at the same time afflicted with the residue issues. I've always considered the dried chalky residue to be a consequence of not using distilled water - however it still appears to be somewhat random from print to print. But aside from that I'm curious if potassium vs sodium makes any actual difference in toning results.

CBG · Apr 15, 2010

RalphLambrecht said:
... Can you please post a copy of the Agfa 221 recipe? ...

I haven't used this but the formula I found is:

Agfa 221 Sepia Toner

Solution 1
Water 125 F . . . . . . . . . . . . . . 750cc
Potassium Ferricyanide . . . . . . . 50.0g
Potassium Bromide . . . . . . . . . . 10.0g
Sodium Carbonate (mono) . . . . . .20.0g
Water to . . . . . . . . . . . . . . . . .1.0L

Solution 2
Sodium Sulfide. . . . . . . . . . . . . . 45.0g
Water to. . . . . . . . . . . . . . . . . . 500cc

For use dilute 1 part Solution 2 with 8 parts water.

Prints should be washed thoroughly and then bleached in solution 1 until the black image is converted to a very light brown, about 1 minute. Print should then be washed for 10 minutes and redeveloped in solution 2, about 1 minute. Wash and dry normally.

Vlad Soare · Apr 15, 2010

Yup. That's the formula I used. Mine states 90g of sulfide per liter, which is, of course, the same.
A 1+8 dilution means 90g per 9 liters, so 10g per liter of working solution. I didn't bother to mix the concentrate first; I mixed the working solution directly.

The formula doesn't mention whether those 45g per half liter of concentrate are anhydrous. I assumed so, and because mine is trihydrated (59%) I used 17g per liter instead of 10. It seems to be extremely active. The print tones in a split second, just as it touches the solution. Does this mean it's too concentrated, or is this its normal way of working?
I believe the most common form of sodium sulfide is nonahydrate (ca. 32%), and from what I've read it seems to me that the anhydrous form is quite nasty. So it would make sense to use hydrated states in formulae, not anhydrous. But I couldn't find this information anywhere.

Does any of you happen to know whether the sodium sulfide in the above formula is anhydrous or not?

What I am suspecting, but I haven't actually seen this confirmed in articles, is that the heightening of the pH in a bleach / redevelop thiourea (or sulfide toner), actually causes more of the formed silver / ferri/ferrocyanide complex to be broken down and also converted to Ag2S.

Silver / ferri/ferrocyanide by itself is a light yellow coloured substance, as can be witnessed during the bleach. It is formed next to AgBr during the bleach, this latter substance being somewhat light sensitive. The silver / ferri/ferrocyanide is probably pretty stable though, but not in highly alkaline environments, see the referenced article here:

http://81.207.88.128/science/photo/toners/toner.pdf

It thus may explain the more yellowish tones of a plain thiourea redeveloper, without added NaOH, as the substance remains partly in the final toned print, while heightening the pH using NaOH, may help in converting it to Ag2S as well. Please note that this is just my theory based mainly on what Wilco wrote in the above article and other stuff I read.

Thanks Marco, I think this makes sense.

RalphLambrecht · Apr 15, 2010

Thanks, I know this formula as Ansco 221.

CBG · Apr 15, 2010

I'm guessing this naming Agfa Ansco ... is more of the Agfa/Ansco/Orwo/GAF/WhateverWhoever mess.

Ian Grant · Apr 15, 2010

CBG said:
I'm guessing this naming Agfa Ansco ... is more of the Agfa/Ansco/Orwo/GAF/WhateverWhoever mess.

This is an Agfa Ansco/GAF formula, the German Agfa/Orwo formulae for toners like this are far higher numbers, in addition the German toners are separate - one for the Bleach bath another for the toner and they never use Monohydrated Sodium Carbonate in any of their formulae.

Agfa 503
Water 200ml
Potassium Ferricyanide 10% soln 500ml
Potassium Bromide 10% soln 100ml
Sodium Carbonate (anhyd - wasserfrei) 10% 200ml
(Makes a total of1 litre)

This is almost the same bleach as Agfa Ansco 221

Agfa 510
Sodium Sulphide 5g
Water to 1 litre

Agfa use 4 different bleaches and then a choice of 4 toners, plain Sulphide, selenium Sulphide, and two different Thiourea(Thiocabamide) so there's plenty of combinations giving quite different sepia tones. They also use 10% solutions so you can vary the bleach as you make up your working solutions.

Interestingly throughout the Agfa Ansco formulae the substitution of Sodium carbonate Monohyrate for Anhydrous has been mis-calculated in the wrong direction using less rather than more.

Ian

Stefan Findel · Apr 15, 2010

clayne said:
I've always considered the dried chalky residue to be a consequence of not using distilled water - however it still appears to be somewhat random from print to print. But aside from that I'm curious if potassium vs sodium makes any actual difference in toning results.

Clayne, you may have very hard tap water. Here is what I do: Use distilled or filtered (Brita filter) water to make toner. After toning, place print for one minute in water, then for 15 seconds in a 1% acidic solution (stop bath), then wash as usual. That should take care of any white deposits.

BTW: I never use distilled water when called for, I find Brita-filtered water to work fine.

Stefan

RalphLambrecht · Apr 15, 2010

clayne said:
Ralph, what do you know about the differences between individual sulfide toners?...

I know, I don't know enough. Kodak Brown Toner (KBT) is using potassium polysulfide as the active ingredient, and Viradon 'new' (post 2000) is using sodium polysulfide. Viradon 'old' had some selenium added, so does or did Kodak's Poly-Toner. Kodak' T-8 formula calls for Polysulfide or 'liver of sulfur', which is a not precisely specified mixture of several sulfides but mainly potassium polysulfide.

I believe, the addition of sodium carbonate and sodium hydroxide in KBT serves as a pH buffer. The pH of KBT is around 11. Viradon seems to be much higher (up to 14 pH), but the older Agfa MSDS and newer MSDSs are in conflict and list varying pH values. I don't know if different pH values have a significant effect on toning or color.

Grant Haist voices a concern about sodium polysulfide being agressive on paper fibers in his book but does not go into detail. Both compounds are pretty 'nasty' anyway.

Tim Rudman shows a pictorial comparison between KBT and Viradon 'new', but I have never experienced a difference as dramatic as he shows. Then again, I'm not using the paper he chose for the comparison.

Sorry, can't be of more help.

Sepia Toners

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