Toning and Permanence

Ed Buffaloe's cite, The Unblinking Eye, has a concise and well written article on archival processing. In that article, I came across the following:

"Doug Nishimura indicates (in a letter to Jennifer Scott) that complete protection with Kodak Selenium Toner requires a dilution of not more than 1:9, and a toning period of 3 to 5 minutes at 68º. Some fine art photographers find this depth of toning not to their taste."

What is interesting to me personally about this is that the paper I use, Ilford MGIV Fiber, requires almost exactly this dilution and toning period to get a discernible increase in DMax. While there is, to my eye, almost no change in image color, is it possible that, after all, I have been toning sufficiently for archival permanence? To put this another way, for an area of the picture to be protected by the toning, must there have been a visible change in density and/or image color? Do any of this forum's scientist contributors have an opinion on this?

I also found, in the same article, some information on Agfa Sistan:

"Other Treatments: Agfa makes a product called Sistan, and Fuji makes a similar product called AG Guard, which is used to treat prints after washing. Thomas Wollstein has corresponded with Agfa regarding Sistan, and tells us that Sistan contains potassium thiocyanate and a wetting agent--it works by converting oxidized silver ions in the emulsion to a stable, insoluble salt. Robert Chapman states that Sistan “...precipitates any silver ion formed by oxidation in the form of silver thiocyanate (AgSCN). Silver Thiocyanate is colorless and virtually light-insensitive.” But Sistan only works as long as the thiocyanate stays in the emulsion, so Agfa recommends that Sistan be used as a final treatment, after washing and before drying--if it is washed out, archival benefits are probably lost.

According to Doug Nishimura, “before any silver deterioration can occur, silver must be oxidized into silver ion. Even air and moisture can act as a strong enough oxidizing combination to cause damage.” He notes that “...there is always a small amount of ionic silver in equilibrium with silver metal in a photographic image.” But, whether the ionic silver already exists in the emulsion or is caused by pollutants, thiocyanate combines with it, thereby stabilizing it as an inert salt which will not cause image degradation. Sistan is said to be fully compatible with toning treatments. I should note that Dupont 6-T Gold Toner contains potassium thiocyanate, and Kodak GP-1 contains sodium thiocyanate, but I do not know if either is in sufficient quantity to be as effective as Sistan is alleged to be--also, prolonged washing would negate any benefit derived therefrom. Robert Chapman states that, though he has inquired several times, Agfa has not provided him with substantive documentation to prove the effectiveness of Sistan. He allows, however, that “..it makes sense on theoretical grounds.” Other sources on the world-wide-web hint that Sistan may not be effective over the long term, but there is no hard data to back this up either."

Obviously, then, for those who want the effectiveness of the treatment demonstrated before adoptiong it Sistan would not fill the bill.

I am surprised so few people here and elsewhere have asked what the contaminant is. Apparently there is a substance which can be present in such small amounts that it doesn't show up in Kodak's production line assays, yet which affords silver images the protection always attributed to selenium and gold. The real question should be why is nobody bottling it and selling it.

Optical brighteners are not necessarily evil. Some may in fact help preserve the image as by definition they absorb UV light. That said, the one I know about - TiO2 - catalyses a number of organic decompositions, and photocatalyses even more. A standard treatment to remove organic contaminants is to pass water over a Ti02 support illuminated with UV.

Finally, a comment on archives: like many state funded institutions it is much easier to get money for sexy new equipment than for upgrading existing stock or for day to day operations and salaries. The library here, and a couple of county archives I know, have received money for swanky digibacks from private foundations that they would never have been able to raise for more mundane but arguably more useful purposes such as adding climate control to all the storage areas. It's the 'machine that goes ping' syndrome.

Struan, is Ti02 an optical brightener? and if so, is it the one that's used in modern papers? I only knew of it as a pigment.

It is used as a brightener in many if not all RC silver gelatin papers, and it would not surprise me to find it in inkjet papers too - although I have no confirmation of that.

Again: it is not evil incarnate, but with the benefit of hindsight, it came as no surprise to me to see it fingered for at least part of the RC bronzing problem.

PS: it is used in RC papers because of its high specular reflectivity. It doesn't have the strength of fluorescence of phosphorescence that optical brighteners in, say, washing powder have (which is why it is used in blackberry-powered solar cells, but that's another story).

Interesting. I remember reading that Ti02 wasn't the most stable pigment in oil paints .. that it yellowed over time. which was suprising, since titanium is so nearly innert. aparently zinc oxide is more stable in paint.

I've been working on varnishing my inkjet prints and was wondering why the varnish seemed to reduce the surface brightness of the paper (yellowing it slightly). the varnish is supposed to be acrylic based and crystal clear. then this thread made me realize--it has UV blockers, so the optical brighteners aren't getting their magic juice.

>>>>For example, I know you can buy walker evans prints, made from the original negatives, from the library of congress for dirt cheap. i'm sure these are rc, if they're not digital already. But the walker evans prints in the collection at MoMA are fiber based, and were printed by walker, or by someone he hired a long time ago. let me know if i'm missing something.<<<<<<<<

okay--the art museum piece is the original, or as close to it--it's the real mccoy, the "artifact". the LOC, or any other archive for that matter, is a reproduction. Chances are it won't come off the original negative, but will come off a duplicate of the neg, or a copyneg of a print--or some combination of the two meaning, it could be many times removed. It might be a good reproduction of an original print, but it's not the same thing by any stretch of the imagination.

Art museums do not generally print for their collection. They collect by purchasing, donation or loans....there's a fundamental difference here---a case of miscommunication between you and I. I'm talking about records, in that these are copies and duplicates of existing photographs or they are original photographs that were shot for the purpose of documenting an object or a building or even an event to support some broader idea.

It's just completely different, but the original records are treated with the same care as the artifact--only they're duplicated in an effort to preserve them and as a way of disseminating the information to the patron base--which now in the age of the internet means that a state museum or a county historical society often serves a much wider audience than many of them ever imagined. It is both exciting in some ways, and unrealistic in others--but like Struan's comment about fundraising and basic priorities--I can't even begin to go there in talking about this, it's just too close to home...just no comment really. Times change--you gotta go with the flow, or find something else to do.

I got a slip of paper about my retirement today. seems like I have about 15 some odd years to go before full retirement. Tell you what--in 2020, when I'm living off my pension, and not selling Grit door to door to supplement it--I'll get back to y'all about selenium toning when I'm tooling around in my own darkroom, assuming of course there's still some photo papers being made, and I'm not too senile or burned out to remember how to use the stuff.

"But I've not seen an OBA free gelatin silver paper in the past decade. Is there a commercially available gelatin silver paper that is actually free of optical brighteners? I doubt it."

As best I can determine, Azo does not contain optical brighteners.

if fortezo contained them, it sure didn't look like it.

I'll eat my words.

As far as I can tell, doing some research on the web, recent Kodak fiberbase papers with a 'C' finish are OBA free. Don't know about Azo.

Apparently the Cachet/Maco papers are OBA free.

From what I've read, it's possible for a paper to look like it's oba free but still have OBA's in the paper base.

But it doesn't constitute a high horse from which to dismiss those who are in fact the experts on the topic, or photographers who are willing to consider their case.

Paul, I am not the only one who saw these inconsistencies, Ken pointed them out too. Quoting an expert does not give the right to get on your high horse and proclaim you are the holder of the "truth." I have tried to tell you that "anecdotal" experience which I choose to call reality goes contrary to what was presented here. Bottom line I suppose these prints that were toned in selenium but were in fact protected by some magical sulfur compound must be brown not black as is the case of Se toning. Funny thing, I have yet to see brown microfilm too....Unfortunatelly I dont think Kodak is interested in finding this magical sulfur compound any longer.

It does not matter to me in any case Paul, you choose to beleive this person and take his word as the word of god, whatever floats your boat, I am sure as a chemist you are very capable of making your own conclusions.....

Jorge, why does everything have to come down to extremist black vs. white interpretations of what people say?

For what it's worth, in my lexicon, calling something "the best information available to date" does not equal "the word of god." Calling something "annecdotal" does not equal "wong."

However, if I have to make a bet, I'll more likely bet on an evidence-based, well supported source than on an annecdote. If it's an annecdote or personal experience that holds weight with me, it will get me to start asking questions, not just sumarily dismissing everything that disagrees with me.

It's one of those weird, post-middle ages prejudices I can't seem to get out of my head, that's all.

Jorge, why does everything have to come down to extremist black vs. white interpretations of what people say?

I guess because in the absence of visual cues, we have to take words at their face value.

In any case I did a gooogle search and in most cases where selenium was put in question they all cite Nishimura's research, when you are the only source of something even when you are wrong you are right and are still the expert, Wilhelm is another good example.

When I was in college doing graduate work, I worked as a TA for the physical chemistry dept. At the time we had oral final exams in the graduate dept. So before my one of my exams the professor that I worked for saw I was nervous, and this was his advice, he said:

Did you study?....yes
did you pepare the subject you are going to present? ....yes.

So then trust what you know and relax

So in the same vein, while to you it might seem silly that I question Nishimura's hypothesys, I have to trust what I know, and that is that the "anecdotal" reference (right or wrong) gives evidence to facts that challange the response posted by you.

As Ken said, I suspect the answer lies in the middle somewhere, also as he said, I suspect Kodak was less than forthcomming with Nishimura on their research and results. I beleive the inclusion of ammonium thiosulfate as part of KRST has a big role in the permanence properties of selenium toning, but apparently it is something that has not been researched. In the end, unlike you, if I was doing silver printing I would still use selenium toning for increased Dmax and permanence regardless of what Nishimura beleives, I have seen prints processed this way that are 60 years old, this is good enough evidence for me.

In the end as I said, while I tried to stay away from this thread I saw it as a way to discredit a well stablish clasic process in the hopes of elevating ink jet posters so that someone with little scientific traning like the pirnting tech can say, yeah well my ink jet posters are just as lasting as silver or pt/pd printing. I thought this needed to be challagned, I have done so, I am done with this. I wish you well.

Thanks to Paul for seeking out and posting Doug Nishimura's observations.

I've ordered a copy of Christopher Gmuender's master's thesis from the RIT library. If folks here are interested, I can prepare a brief summary of his methods and findings after it arrives and I've had a chance to review it. Perhaps that would be a useful supplement to the Nishimura comments if those are going to be archived on the static page as a reference.

I think we understand each other a bit better now, Jorge.

You said, "So in the same vein, while to you it might seem silly that I question Nishimura's hypothesys, I have to trust what I know, and that is that the "anecdotal" reference (right or wrong) gives evidence to facts that challange the response posted by you."

It doesn't seem silly at all that you should question his (or anyone's) hypothesis. I think it's healthy. Your earlier posts sounded more like an outright dismissal, not a line of questioning. That is what I took issue with.

"I have seen prints processed this way that are 60 years old, this is good enough evidence for me."

this may be just be evidence that your goals are different from Nishimura's (and from those of some other people here as well). His research was based on how to preserve things to the standards of a historical archive--which calls for much more than 60 years without visual degradation. The world is full of 60 year old prints made in all kinds of ways that still look great. Nishimura was charged with the question of how best to preserve things for several hundred years.

"I saw it as a way to discredit a well stablish clasic process in the hopes of elevating ink jet posters so that someone with little scientific traning like the pirnting tech can say, yeah well my ink jet posters are just as lasting as silver or pt/pd printing"

Well, I started this thread, and that sure wasn't my goal. I don't know what could have made you think otherwise. This was about helping people who wish to continue making silver prints make the best decisions on how to preserve them, if that's important to them. the reseach I cited has nothing to do with inkjet, platinum, or any other printing process or turf war. It has to do with what toners best resist oxidation.

I'd love to see a thread (somewhere else!) about different pigment inks' resistance to oxidation, and how they compare to various other photographic processes. Unfortunately, i have not seen any research yet that addresses this. In the mean time, all we have is this lonely little thread, about toners for silver.

Oren: yes please.

Paul: I have seen anecdotal statements that there are salt(s) in carbon inkjet inks that are needed for the ink droplets to aquire a charge and be deflected by the print head. Supposedly these could increase the rate at which the paper degrades, making even carbon-ink prints less long-lived than charcoal drawings or traditional carbon prints. This makes sense to me, but I've no feel for the scale of the 'problem' and I've not seen references to any research.

Me, I'm going to learn how to draw in silverpoint and chalk. Or use digital output to enamel on glass.

"In the end as I said, while I tried to stay away from this thread I saw it as a way to discredit a well stablish clasic process in the hopes of elevating ink jet posters so that someone with little scientific traning like the pirnting tech can say, yeah well my ink jet posters are just as lasting as silver or pt/pd printing. I thought this needed to be challagned, I have done so, "

Paulr,

I think it's obvious that there are so many variables in the printing process with silver, or even with outdated niche methods like pt/pd, that what has been defined as an archival process (silver-selenium) many not end up being as archival as many presume. Some early responses in this thread were appearing as an outright dismissmal and needed clarification.

Fine art injet printing, carbon or otherwise, may very well end up being as archival as silver. There are so many different tests out there that it is difficult to choose one over the other as being accurate. In the end....no one can say with certainty because of all the variables.

Really, nothing in this thread has been "challenged." It seems that quite often those that become defensive about using niche methods are really simply lacking the experience of using new materials. Afterall, the entire basis of scientific analysis is established upon the idea of experimentation. Those who have not had any experience with new materials can really not offer anything other than opinion....making their assertions without value. I ran across people like this quite often doing my graduate work.

In the end we choose the materials that we enjoy working with. Silver is still a viable option as is inkjet. ....and I believe that output from both, when properly stored, will be around for generations......and this is based upon good quality tests.

Straun, I have heard about the salt issue as well. I am waiting for a response from my supplier of carbon pigment ink as to this issue. I'll see what they come back with.

All the best.

"I am waiting for a response from my supplier of carbon pigment ink as to this issue. I'll see what they come back with."

this could be worth a new thread if they tell you anything interesting. Jon Cone brought up another possible inkjet issue ... the coatings that do such a nice job of receiving inks also do a nice job of receiving atmospheric pollutants. i think a lot remains to be learned about various papers and coatings.

"the coatings that do such a nice job of receiving inks also do a nice job of receiving atmospheric pollutants. i think a lot remains to be learned about various papers and coatings."

Paul,

These coating are of course an issue. Many of the Resin Coated papers designed to receive and encapsulate dye based inks use coatings that are of questionable archival quality. That said, acid free cotton rag matte papers would be a good option for pigment, or carbon pigment inks. These are the papers that don't use optical brighteners....yet still are great for both color & B&W output.

I'll let you know what response I get from the "Carbon Guys."

Iodide treatment is only weakly effective. It's inadequate to completely protect the image from standard peroxide attacks, while polysulfide toning is sufficient.

Efficacy of selenium treatment is dependent on the emulsion and developer, not only on the toner solution. It is not very easy to determine whether selenium treatment is adequate or not for ALL silver-gelatin material used today. Several studies indicated that selenium is effective with some emulsions but not in others, all at the same concentration and same treatment time. It is also known that selenium treatment may protect dark areas better than light areas, which may be left unprotected. These are the problems with selenium. Polysulfide treatment does not leave this problem.

There is a product called Ag Guard. I have some detailed discussion here:
http://www.silvergrain.org/wiki/index.php/Ag_Guard

This product is well tested by Fuji people, and the result is very promising, especially when polysulfide cannot be used, or when full toning with selenium is undesirable. However, this product is not available outside Japan. I have been making a image protecting agent similar to this and also has very good image protecting action. It's been showing pretty good protection by bleach (immersion) tests and peroxide fuming tests. I should be able to report more details in near future.

Quote:

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Originally Posted by Jorge Gasteazoro

In any case I did a gooogle search and in most cases where selenium was put in question they all cite Nishimura's research, when you are the only source of something even when you are wrong you are right and are still the expert, Wilhelm is another good example.

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There are some other independent studies by a Danish group, a German group, et al., and also myself. Nishimura is not alone on the unreliable protection of selenium treatment, although not many people may agree on his "sulfur impurity" theory. I think he only mentioned this theory as one possibility to account for his observations and he did not intend to establish this as a fact or anything.

Quote:

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I beleive the inclusion of ammonium thiosulfate as part of KRST has a big role in the permanence properties of selenium toning, but apparently it is something that has not been researched.

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The inclusion of ammonium thiosulfate is to accelerate selenium toning reaction.

So wash well, but not too well is the thing. I wonder whether I should continue to use washing aid in the development process.

Thank you