Wait... so selenium toning does not improve archival properties?

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Bill,

Thanks for posting the link. This is the study I was referring to above. This quote says it all, and is, I think, applicable to papers as well as microfilms:

"Gold and selenium treatments provide protection against peroxide attack [the aging test] only in proportion to the degree to which the heavy metal is substituted for the original silver image. In the absence of sulfiding agents, even very high degrees of gold or selenium substitution do not provide complete protection. In actual practice, when used as recommended, the metal components of gold and selenium toners for microfilm do very little to protect against oxidation; their effectiveness is almost entirely due to the sulfiding action of other constituents of the toner formulas.

Also worth reading is the section entitled, "Selenium Without Sulfiding Ineffective."

Interesting above was the reference to an earlier version of KRST that contained polysulfides. The original version of Viradon was such a toner as well. Kodak Polytoner was also a mixed sulfide/selenium toner. The sulfides in these would have indeed helped print permanence. Practices like the split toning that Bob Carnie does will also provide protection.

In my research of these older selenium formulas, I came across a lot of old threads on the (now defunct?) Pure Silver forum with posts by Richard Knoppow, Ryuji Suzuki and Tim Rudman. In these discussions, the idea of mixing selenium toner with new Viradon or Kodak Brown Toner in order to create a direct toner that was similar to these older sulfide/polysulfide/selenium toners was mentioned. Is there anyone here doing this? I'd really be interested in knowing more about this.

Best,

Doremus
 
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LarsAC

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Carbon Toner from Moersch is Sulfide with Selenium. It is great stuff.

In some Kodak publications, there was a recipe for mixing brown toner with selenium toner to achieve the same. The Darkroom cookbook has a recipe for flemish toner which is Sulfide with Selenium also. Maybe from the recipe you can infer how to mix existing toner solutions, in case you know what you are doing safety-wise.

Lars
 

Bill Burk

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I'm intrigued by this paragraph in the article I posted:

Sulfiding Treatments
...only a small amount of the sulfiding agent is needed. For example, sodium sulfide solutions of 0.1 grams per liter... are completely effective.

Because I am happy with the print color as-is, I currently tone in KRST 1:20 just a few minutes to "protect" my prints. I'm not looking for tone/density change.

I've got room in the sink, and have enough air circulation, I could see making a sodium sulfide bath following the KRST.

What's the difference between Polysulfide and Sodium Sulfide?

I've got a pound of Sodium Sulfite. Is that totally unrelated/useless for the purpose?
 

LarsAC

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Yes, sulfite is different from sulfide and will not help. Sulfide can indeed be used very diluted and will work even stronger. This is why toning continues in a water wash bath.

Lars
 

Bob Carnie

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Yes, sulfite is different from sulfide and will not help. Sulfide can indeed be used very diluted and will work even stronger. This is why toning continues in a water wash bath.

Lars
Yes this continuing of toning really can cause problems for workers like me who tone and then put them in a water bath(even with circulation) many a print has gone too far for my liking.

It kind of reminds me of the dry down effect which one has to adjust for in printing.
 

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I would love to find a solution to this problem btw .--- Ian Grant where are you..
 

Photo Engineer

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Bob Carnie

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You can use a fairly strong alkali bath as a stop bath for the sulfide toner. Can look up a recipe id that's what you are after.

Lars
Yes this information would be great, as I do see this problem and when I print or tone its not just a few but quite a few prints and I have been bitterly disappointed many times.
I would like to also know would the wash time need to be increased after this alkali bath?
 

faberryman

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I think a search on "Douglas W. Nishimura" will give you good reading about how vulnerable our silver images are...

Here's an example article, seems very plain to me. Selenium Toning isn't going to protect your silver from red spots.

http://cool.conservation-us.org/byorg/abbey/an/an12/an12-5/an12-507.html

The article refers to preserving film, though I suppose it is equally applicable to prints. The problem with using polysulfide is that it is a brown toner, so that while it may preserve prints, it also turns them brown. Not a problem with film though.
 

Photo Engineer

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Look up some papers by Reilley. I believe he discusses this problem or refers to some papers by others. Kodak has reported that the newer KRST is less effective and tests show this to be the case. I have information about this from both Troop and Nishimura (via Troop).

PE
 

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Oren Grad

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Twelve years ago, I posted on the Large Format forum a summary of findings on print image stability reported in Christopher Gmuender's RIT master's thesis. It's still there, in case anybody is interested:

http://www.largeformatphotography.i...Paper-toning-and-permanence-experimental-data
Overall, my own interpretation of all of the information I've seen is that the long-standing belief, that 2 minutes of toning with KRST 1:20 or 1:40 at room temperature is strongly protective of the image silver in a FB print, is most likely not correct today. It may or may not have been true in the past; I don't know enough to hazard an opinion on that, but in any case that's not any use in making decisions about how to print today.

If permanence is the primary consideration and near-certainty about adequate protection of image silver is required, one can tone to completion in selenium. But I did some experiments with that some years back, and consistently strongly disliked what it did to the appearance of the print. YMMV.
 
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Bill Burk

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I remember that article and the followup where you pointed out the author had washed the Sistan... so funny.
 

Bill Burk

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How brown would a print be after being toned in a "sodium sulfide solution of 0.1 grams per liter"?
 

Ian Grant

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I would love to find a solution to this problem btw .--- Ian Grant where are you..

Here :D Missed the posts on this.

Ole has mentioned a mixture of selenium toner and brown toner before. I have mixed up and used the formula published by Kodak as a polytoner substitute. It worked well and gave the expected results at different times and dilutions mentioned in Kodak dataguides. I didn't particularly like the colors produced on Ilford WT, but that is personal taste.

http://imaging.kodakalaris.com/sites/prod/files/files/resources/CIS268.pdf

This is forming Flemish Toner which is quite fast acting and gives a large colour shift. It's meant for Bromide papers , the shift will be far greater with a Warmtone paper.


How brown would a print be after being toned in a "sodium sulfide solution of 0.1 grams per liter"?

Well normally Polysulphide toners like Ilford IT-7 Liver of Sulphur Toner are 1.75g per litre and you tone by inspection for around 8 minutes at 27ºC (82ºF). So not that fast acting and you need to raise the temperature slightly.

Sodium Sulphide toners are bleach and a re-developing toner so a 0.1% solution used as a direct toner for say 2 minutes @ 20permenaceC should give an almost unnoticeable colour change while adding to the archival permanence. Again it'll depend on the paper WT will be the ones that react the most, also dev times are important. I use deve times (and exposure) to control and increase the warmth of WT papers, you can't do this with Bromide papers.

Ian
 

Bob Carnie

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So I am glad Ian got on this .. I was going to say that I use 32grams per 10 litres so about 3.2 times the strength of what is being discussed and it really turns the print fast depending upon how much bleaching is done first.

Ian are you suggesting that going to .1% solution I can tone without change and there will be protection, even though no visible change.. this is new and interesting concept as when I do sepia selenium I on Ilford warmtone the prints go warmer than I would like -
 

Doc W

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This whole thread leaves me scratching my head. After all these years of photographers toning in selenium in order to preserve prints, it now seems that this was bogus. Not being a chemist, and having to rely on what I read in (supposedly) reliable books, I find this rather depressing! It makes me wonder what else folks like me have been told (and believed) over the years that is not reliable.

On the plus side, the very first prints I made (in 1970) still look just fine and will no doubt outlast me. They were printed on Agfa fb paper and washed for half an hour in a basement sink with absolutely no other equipment and no toning at all. So much for archival methods. :laugh:
 

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Gerald C Koch

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This whole thread leaves me scratching my head. After all these years of photographers toning in selenium in order to preserve prints, it now seems that this was bogus. Not being a chemist, and having to rely on what I read in (supposedly) reliable books, I find this rather depressing! It makes me wonder what else folks like me have been told (and believed) over the years that is not reliable.

On the plus side, the very first prints I made (in 1970) still look just fine and will no doubt outlast me. They were printed on Agfa fb paper and washed for half an hour in a basement sink with absolutely no other equipment and no toning at all. So much for archival methods. :laugh:

The best way to achieve archiaval permanence is thorough washing. In this case there is no change in image tone.
 

john_s

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The best way to achieve archiaval permanence is thorough washing. In this case there is no change in image tone.

Although we have read that a miniscule amount of thiosulphate left in the emulsion can improve permanence because, iirc, it becomes sulphide. I will look for a reference.
 

Ian Grant

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So I am glad Ian got on this .. I was going to say that I use 32grams per 10 litres so about 3.2 times the strength of what is being discussed and it really turns the print fast depending upon how much bleaching is done first.

Ian are you suggesting that going to .1% solution I can tone without change and there will be protection, even though no visible change.. this is new and interesting concept as when I do sepia selenium I on Ilford warmtone the prints go warmer than I would like -

That's the theory, and what's claimed by many people. What's not disputed is that even a slight direct toning in Sodium Sulphide will greatly increase archival permanence. We (well I) are more concerned about how colour/tone changes.

I think it needs experimenting with as there will definitely be differences between papers. There's questions of which you do first Sulphide or Selenium toning, either way the Sulphide needs to be minimal. I print in fits and bursts and am in a lull otherwise I'd do some testing. I've a huge backlog of other work which I must get finished first.

Too strong a Sulphide solution and you'll react with the Selenium and effectively form Flemish Toner and see huge colour shifts.

Ian

Chocolate brown.
Only with indirect toning and a bleach stage, you won't see that with direct toning.
 

michaelorr

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This thread has been fascinating to follow.
I have now looked in Tim Rudman book Toning and discovered he has a chapter on toning for permanence. Since copyright does not prohibit small snippets of text, i will type here. It seems to resolve some of the confusion about tone shifts or not, and how permanent toning and possibly "to completion", noted in this thread, and the knowledge and experiences that have likewise been spoken of here by the posters.

From c. 2003 Amphoto, pg.159
< start >
Selenium Toning
This is still the commonest toner in use for archival treatment of prints. Its popularity stems from the mistaken belief that, like some of the much more expensive gold toners, selenium toning can provide excellent print protection with little or no colour shift, even on warm-tone papers when used at high dilutions. Although a number of myths about archival selenium toning have now been refuted, it does remain a valuable archival toner, but the following points should be borne in mind.

Selenium toner converts the image-silver into red/brown coloured silver selenide, which is a highly stable substance that resists attack by chemicals and pollutants very effectively.

Selenium does not tone evenly through all the image tones simultaneously. It works first in the the darkest tones - in the finer grains of the darkest tones to be precise - and then works up through the tonal range, eventually converting the lightest tones last. It only tones grains below a certain size - the largest, coarsest grains remain largely unaffected. These are the least vulnerable to deterioration as a result of attack from external agents.

On warm-tone papers, selenium toner produces a significant red-brown colour shift. On cold-tone papers the color shift is not seen. The explanation for this is due largely to the masking effect of the coarse cold-tone black grains that resist conversion. The apparent ability of the selenium to give archival protection to cold-tone papers without colour shift is due to the fact that it is the finer grains that are vulnerable to chemical attack. Although these are converted, the larger, more stable, black grains mask their colour. See also comments above regarding co-incidental sulphiding1.

It has also been demonstrated that selenium toning is less effective for a given time of toning, when the selenium toner is used diluted with hypo-clearing agent (HCA) instead of water, and is more effective for a given toning time if these steps are undertaken separately. The role of HCA, when used prior to selenium is to prevent staining, not to enhance toning efficiency. The only advantage of combining HCA with selenium n one solution is to shorten the process. A toner stores well and can be kept almost indefinitely for future use. Dilute working strength HCA has a very short active life of a day or less in an open tray. It should then be discarded. Mixing the two wastes selenium toner.

All selenium toners (except the rare oderless variety) contain a significant amount of ammonium thiosulphate - rapid fixer. Treatment with HCA is therefore advised before and after selenium toning, followed by a full wash.

Advice that selenium toning at high dilutions of 1+20 or more will give good image protection wihtout colour shift on chlorobromide (warm) papers should no longer be followed. Toning for permanence should be at 1+9 or stronger for at least three minutes at 68F (20C) and colour change on these papers is usually inevitable, if full protection is to be achieved. An alternative approach sometimes employed to give protection without significant colour shift is to follow dilute selenium toning with Sistan treatment (see below)2. I am not aware of any hard data on the effectiveness of this combination

Notes:
1. Selenium and gold toning only provided protection in proportion to the conversion (selenium) or coating (gold) that took place, and even at high levels of toning protection was incomplete. Some of the protection given by selenium and gold toning actually came from the incidental sulphiding from other constituents.
2. Sistan is a silver image stabilizer made by Agfa. Made principally from potassium thiocyanate, and also containing a substance known as 'POP' - polyoxyethylated octyl phenol - which is probably added as a wetting agent.
<end>

I have printed a series of charts from @Nicholas Lindan for Ilford MGIV FB WT in D-72 and Ansco 130, without and with selenium toning 1+9 for 20 minutes. Not that this addresses the change in color, but it seems the reflectance density is reaching the same top levels. It does provide one toning time example in practice. In his support files at http://www.darkroomautomation.com/support/index.htm .
 
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