How archival is a straight print?

Donald Miller · May 18, 2006

jnanian said:
i have a suitcase of photographs that belonged to my grandmother that i am making copies of. some are from the late 1800s early 1900s into the 1920s. they all pretty much look like they were just printed.

is there a simple way to see if they were toned? if my prints look as good as these i'd like that. straight or toned, these look beautiful.

-john

My experience parallels John's experience. My family has photographs that are at least one hundred years old and they look as good as anything that I processed recently. I sincerely doubt that they were toned. Most are stored in albums and cardboard boxes that I know are not of archival materials...

I do believe, however, that knowledgeable collectors today will not buy untoned silver prints.

Toning to completion is the best archival procedure...some of the stuff that is shuffled out of darkrooms today is not archival...there is one well known LF format contact print photographer that advertises that he tones with Selenium at 1-128 dilution...primarily for tonal shift. As others have said this is a waste of toner for archival purposes...

blansky · May 18, 2006

What I haven't seen discussed here is what is done with the print and how it is displayed.

If a print is stored in your refrigerator or at 55 degrees it just may last forever, or until we nuke ourselves.

The anecdotal evidence that has been presented here most "store" their prints. In other words, they stick them somewhere in a dark place and look at them every few years.

On the other hand if you sell your prints, display or hang your prints, they probably will face a more rigorous lifestyle and may need extra protection.

Personally I tone almost every print, and probably overwash as well. I do this much for the same reason I change the oil in my car every 4000 miles. Because "in theory" it is a good idea.

I have no idea if it is or not but I attempt to do the most I can to preserve the print.

Michael

Jim Jones · May 18, 2006

Flotsam said:
I wash both my prints and myself in my shower. (Not simultaneously)
QUOTE]

Do you use selenium toner in the shower to promote longivity? It sounds risky to me!

Flotsam · May 19, 2006

Jim Jones said:
Do you use selenium toner in the shower to promote longivity? It sounds risky to me!

I don't think that even platinum would keep me looking like less of an old fart. Maybe Rudman should add a chapter to his book..."Toning to achieve personal archival permanence"

SeamusARyan · May 19, 2006

Flotsam said:
I don't think that even platinum would keep me looking like less of an old fart. Maybe Rudman should add a chapter to his book..."Toning to achieve personal archival permanence"

Thanks for making me laugh, doesn't happen often enough here

I think this has been intimated at in several earlier posts but I thought I ask outright if my thinking on print longevity is correct.

I believe the reason we currently have wonderful 150+ year old prints is that the majority of them have spent the most of their lives either in albums or boxes and have rarely seen the light of day, who here hasn't been to an exhibition of Talbot etc and seen an image or two under a blanket to save them from being damaged by whatever light is being used to display them and once the show is over you can be gaurenteed they go straight back into the dark and cool storage unit.

What I'd really like to hear is from some of the older (or children of ) photographers who perhaps were lucky enough to do a swap with Weston, White, Adams etc and have lived with the image on their wall for 50, 60, 70 years and to tell us how they look now. Obviously it would be nice to hear from someone who has a Talbot or Cameron on their wall but I'd imagine they've either been sold or taken down and stored properly, the same goes for the weston, white, adams prints.

lastly the use of the phrase "stored properly", we work in a visual medium so surely the prints we make are meant to be seen and enjoyed and bugger the long term consequences as oppossed to be being "stored properly"... how much enjoyment do any of you get from your "properly stored" images.

be well

Seamus
www.seamusryan.com

Ryuji · May 24, 2006

Flotsam said:
I've also heard that unless you selenium tone to the max (with perhaps undesired tone and contrast changes), the untoned silver will not get the archival benefit anyway. (Close only counts with Horseshoes and Hand Grenades ) So unless you are demanding the specific aesthetic benefits of toning, personally, I give it a pass.

Even a small amount of selenium or sulfide will act as a catalyst poison and has significant advantage over completely untoned image. Of course, the more conversion the better. So it's a matter of degree. It's always better to tone in polysulfide or selenium toner, even if very lightly, compared to no toning at all.

Ryuji · May 24, 2006

PhotoJim said:
Although I am inclined to agree that untoned prints will last longer than many think, we have to be wary of misleading samples. Any prints that were made a long time ago and were destroyed by incorrect processing will have likely been discarded by now. In essence, what you will see today are the best prints from that time, which are probably not the typical prints. It would be a little like going to a nursing home and inferring that people living into their 90s is quite common. The people who didn't make it to that age aren't there, obviously.

I agree with this opinion.

While there are several people who claim to have untoned old prints in mint condition, I can point out that it's very easy to make untoned print go bad if you put it in contact with air containing sufficient humidity and environmental pollutants. If you store the print in degrading cardboard, for example, you don't need automobile exhaust or coal burner to generate pollutants. Paints, adhesive, etc. can do the same. I personally have many old prints in mint condition, as well as many new prints that went bad quickly. I was pretty optimistic until I saw some of the latter examples happening in front of me. Since then, I tone everything other than scrap prints. Even postcards and snapshots I give away. These are not meant for archival permanence but I just don't want them to fade while being tacked up on my friend's fridge.

So I have been thinking about two different kinds of post-fixation treatments. One is for fine art prints that should last for 100 years. I have no question that polysulfide toning is the top candidate, as well as noble metal toning. The other is for making image more robust although archival quality is not necessary, like snapshots for casual display. I want them to last for 5 years in reasonably poor conditions. I am thinking that there can be a quick solution for this type of application, without going through toxic and stinky chemicals. I'm in middle of experimenting with several chemicals for this... will report when I find something worthwhile, but I already found a cheap chemical that seems highly effective in my accelerated peroxide fuming tests. Now it is in phase 2 fridge test...

Ryuji · May 24, 2006

Oren Grad said:
Unfortunately, research findings in recent years indicate that, contrary to long-standing dogma, light toning with selenium offers little protection. Some are convinced that this is attributable to an undocumented change in the Kodak Rapid Selenium Toner formula over the years - if I recall correctly, it may actually have been a sulfide contaminant that was providing the protection - but for most of us the details don't matter. The bottom line is that the product available to us today doesn't do what the conventional wisdom says it does.

Well, the problem is low density areas. High density areas are reasonably well protected even when KRST 1+19 is used just to increase Dmax. More of a mystery is that, until 1970s, KRST was effective in protecting all density areas, but after mid-late 1980s people started seeing specimens in which low density areas are degraded.

One theory is that the formulation of KRST changed at one point. If earlier KRST contained some sulfide, for example, low density areas would be protected by the sulfide. This theory is simple and also somewhat plausible but there are some questions that cannot be answered very well. For example, if you add a small amount of sulfide to KRST stock solution and let it sit for a few months, you probably lose the sulfide effect due to reaction with other ingredients in KRST.

I now have a different idea. The emulsion technology changed and this affects the way the image is toned. I made different kinds of emulsions, some of which are not too dissimilar to microfilm emulsions from 70s and 80s(I used them to make prints on paper support). As most people know, the world's first commercial tabular grain product was a Kodak microfilm. I don't know the exact formula but I tried to make something similar.

You know what, some split tone and others don't. This also depends on the print developer I used. I now suspect that the change in emulsion technology might have played a significant role in this problem.

You see, conservation scientists generally don't get into details of emulsion technology. They care whether the emulsion contained iodide, etc. but not much more. On the other hand, emulsion chemists may not care about the exact mechanism of how the emulsion formula affects the way the image is toned. There is no good study I know of that tried to bridge the two.

Anyway, my summary is: tone the image if it's important. If you don't like the toning effect, pull the print from the toner before the image hue changes much. It's still better than not toning at all.

(I personally use toner to make the color I like, so I have not much problem except extra work needed.)

tony lockerbie · May 24, 2006

Prints that I sell are always printed on fibre based paper and washed and fixed properly. I do not use RC paper for photos that will be displayed or framed.
The reason for this is because of bad experience that I have had with Rc papers that have been framed and have " silvered out" or " bronzed" after a very short time. The problem only seems to occur with prints that are framed as my family snaps that are on RC paper and in albums etc. do not show any deterioration.

I have made many enquiries about this but have been told that it must be my processing or whatever. This is not the case as I am very careful with the handling and have been printing for many years.

The safest thing to do is stick with a good fibre paper and use fresh rapid fixer and don't overwash. I sometimes use selenium but only really for a tone change rather than for archival issues.

Ryuji · May 24, 2006

tony lockerbie said:
Prints that I sell are always printed on fibre based paper and washed and fixed properly. I do not use RC paper for photos that will be displayed or framed.

The reason for this is because of bad experience that I have had with Rc papers that have been framed and have " silvered out" or " bronzed" after a very short time. The problem only seems to occur with prints that are framed as my family snaps that are on RC paper and in albums etc. do not show any deterioration.

What you described is a typical example of mirroring problem. It is a typical symptom of oxidative degradation of silver image, and it can be prevented by polysulfide, selenium or gold toning. It can also be prevented by using Fujifilm Ag Guard as the final rinse bath, and this is an effective product, but it is not available outside Japan.

On the other hand, even if you use fiber based paper, oxidative attacks can certainly take place. Mirroring, for example, can occur on FB paper as well.

unregistered · May 24, 2006

If you follow the proceedures listed on your hypo clear bath (I use Perma Wash myself) your print will be the standards listed on the bottle (they list the archival standards on the bottle and I don't have one right now). Also, storage and display contitions must be taken into account.

unregistered · May 24, 2006

Ctein has done extensive testing on prints that are framed and shown that RC prints actually degrade faster when "behind glass" than when they are not. I don't remember seeing any problems in his research on Fiber prints, and if processed archivally, shouldn't cause any problems without using toners.

Ryuji · May 24, 2006

Alexis Neel said:
Ctein has done extensive testing on prints that are framed and shown that RC prints actually degrade faster when "behind glass" than when they are not. I don't remember seeing any problems in his research on Fiber prints, and if processed archivally, shouldn't cause any problems without using toners.

That's because RC has a generator of oxidizing agents in the paper. FB doesn't. So RC is easier to go bad if framed. HOWEVER, I wouldn't take this to mean that FB is safe. FB can go bad when the oxidizing pollutants come from other sources, such as degrading paper, adhesive, exhaust gas, furnace, whatever. I have an example of dark stored print that developed blemish and mirroring in areas close to where I put some masking tape to reinforce the box from inside. Masking tape wasn't in contact to the affected print at all.

Oren Grad · May 24, 2006

Ryuji said:
What you described is a typical example of mirroring problem. It is a typical symptom of oxidative degradation of silver image, and it can be prevented by polysulfide, selenium or gold toning. It can also be prevented by using Fujifilm Ag Guard as the final rinse bath, and this is an effective product, but it is not available outside Japan.

Or Sistan. In Ctein's experiment with framed RC prints, light selenium toning and Sistan were independently protective.

James Glaze · May 24, 2006

I have silver prints of my parents honeymoon that date to about 1935. They were commercially processed on single weight paper. For many years they were stored in an album and in a basement (in the midwest) that was often damp. They look like they were processed yesterday! I always process to archival standards using selenium but when I look at these old prints I ask my self--why?

Ryuji · May 24, 2006

Oren Grad said:
Or Sistan. In Ctein's experiment with framed RC prints, light selenium toning and Sistan were independently protective.

Sistan can be effective in certain cases but it's less sure-fire. Once Sistan-treated prints are moistened (become wet, go through humidity cycles, etc.) the active ingredient of Sistan can be washed out. The problem is that the efficacy of Sistan treatment depends on rather precise amount of the active agent present in the coated layer. Fuji Ag Guard works with a very different mechanism and you can wash Ag Guard treated prints in running water and still see some useful level of protection effect.

Photo Engineer · May 24, 2006

Up until the mid 60s, Kodak and others added cadmium, mercury, copper and lead to B&W paper emulsions. AFAIK, no one did a comprehensive study of these metals on silver image stability. Concentrations of some of these were very high.

For a specific example, Mercury and Copper were used in the browner or warmer toned paper products. Of course there were other changes in the emulsions, but these two stand out as the preferred metal salts to be added to the emulsion for achieving a brown or warm toned paper.

After the mid 60s, organic salts and less toxic metal toners were used in paper emulsions by most all photo companies. Again, I doubt if there was any comprehensive study of these new addenda on image stability.

Many of the new organic salts contained sulfur in some form or another and were known to affect the final tone of the silver image. In fact, I believe that some of them were added to intentionally adjust the image tone to the correct 'hue'.

Due to the lack of intensive research on the stability of B&W products at all major companies since the mid 80s, I think that we will just have to wait and see how our prints hold up. In any case, they will probably hold up a lot better than digital. Note that I said 'intensive'. This does not mean that research has stopped, but rather that it has been less than comprehensive and all inclusive of products and conditions.

One of the most comprehensive recent studies of B&W prints was undertaken at Ilford by Beveridge and Cole. It was done in the mid 80s.

The methodology of testing B&W silver prints also is not as advanced as some of those used for color products and digital products, and some methods are not accepted by all as being authoritative.

(This information was provided in part by ICIS course "Image Permanence: Understanding, Measuring, and Predicting Print Life" by Dr. Jon Kapecki. It was also partly provided by discussions with Dr. Henry Wilhelm. Some portions were provided by conversations with Bill Troop and his references to Haist. The remainder of the comments are drawn from my own R&D work on image stability.)

The bottom line seems to be, "we don't know" and "we will have to wait to get the answers".

PE

Oren Grad · May 24, 2006

Ryuji said:
Sistan can be effective in certain cases but it's less sure-fire. Once Sistan-treated prints are moistened (become wet, go through humidity cycles, etc.) the active ingredient of Sistan can be washed out. The problem is that the efficacy of Sistan treatment depends on rather precise amount of the active agent present in the coated layer. Fuji Ag Guard works with a very different mechanism and you can wash Ag Guard treated prints in running water and still see some useful level of protection effect.

Point taken, but an observation and a question:

Observation: Until someone tells me how I can actually lay my hands on some AgGuard, any theoretical superiority of AgGuard compared to Sistan is of no practical significance.

Question: Can you cite any empirical evidence of Sistan failing because of humidity cycles? Can you cite specific examples of prints being treated with Sistan, being put through humidity cycles (not being dunked in water, which we know will wash it out), and then silvering out? Or are you simply speculating based on what we know of its mechanism of action? Nothing wrong with the latter - it may be all we have to go on - but if there is evidence I'd like to know about it.

srs5694 · May 24, 2006

Oren Grad said:
Observation: Until someone tells me how I can actually lay my hands on some AgGuard, any theoretical superiority of AgGuard compared to Sistan is of no practical significance.

I can't tell you how to do it with certainty, other than taking a vacation in Japan, but I've got two ideas about how you might try:

Contact Dead Link Removed which is an Internet mail-order outfit located in Japan that ships worldwide. I don't see AgGuard on their page, but you could ask them to add it to their lineup or see if they'd special-order it. Note that I've never bought from them, so I don't know how reliable they are. I've got them bookmarked, though, in case I hear of some Japanese product that's not available in normal US retail channels.
Go to eBay and use their Want It Now feature. I've never used this feature, but it enables you to create a post saying that you want something. Somebody with access to the thing you want might see your post and offer to sell it to you. Obviously, there are no guarantees here, but it's worth a try if you're interested in the stuff.

Oren Grad · May 24, 2006

In a recent thread here on RC permanence in which Ryuji was an active participant, it was mentioned that Ag Guard is out of production, though a quick check of the Fuji web site just now confirms that it's still listed (here, about two thirds of the way down the page, for anyone who wants to wade through the Japanese). I'd certainly appreciate being corrected and pointed to a source that will actually ship the stuff if that's not true.

Ryuji · May 25, 2006

Oren Grad said:
In a recent thread here on RC permanence in which Ryuji was an active participant, it was mentioned that Ag Guard is out of production, though a quick check of the Fuji web site just now confirms that it's still listed

It was Jerry Koch's errorneous information based on his misinterpretation of my posts to pure-silver. Fuji never announced discontinuation of Ag Guard. Fuji merely stopped internal manufacturing of the compound used for this product, but even this is not announced information. (I heard directly from the person in charge of chemical sales at Fuji.)

In the worst case Ag Guard may go. But I've studied the reports published by engineers who developed and tested this product, and the general idea is very closely described in those scientific papers (and patent).

I have some discussion info on my web site, and I've already started looking for possible replacements for this product. I've run the wet bleach test and accelerated peroxide fuming test, both with promising results. Now I have to confirm that it works in real life situation. I've been using it for my snapshot RCs.

The compound is closely related to agents used in machine processing chemistry to prevent staining (i.e., its parent compound has been used in photography for 70 years), and it's not toxic (at least in the qty I'm using), odorless, cheap, manufactured and traded as an industrial intermediate as well as an antioxidant in huge qty, colorless, reasonably soluble in water, and it's used just like PhotoFlo (or Ag Guard or Sistan).

The thing is that, once treated in this bath, the print can be immersed in 2% ferricyanide bleach and it'll take a lot longer time to fade, compared to untreated image. The treated image is similarly strong in peroxide fume. I'm beginning to feel that this treatment is very effective to make snapshots to withstand suboptimal storage/display conditions for a few years. However, it's not so easy to claim anything about the nature of this treatment in the time scale of 100 years. So I'm sticking with polysulfide for fine art prints.

Anyway, details of this project is currently only of scientific/technical interest and not for immediate application. But with further testing, I am hoping that this may be a very useful option for lith printers as well as untoned van dyke, kallitype and argyrotype prints. These prints change much of the image quality when toned in sulfur or selenium toners, and besides the Ag Guard, there's no very good option.

Ryuji · May 25, 2006

Oren Grad said:
Question: Can you cite any empirical evidence of Sistan failing because of humidity cycles? Can you cite specific examples of prints being treated with Sistan, being put through humidity cycles (not being dunked in water, which we know will wash it out), and then silvering out? Or are you simply speculating based on what we know of its mechanism of action? Nothing wrong with the latter - it may be all we have to go on - but if there is evidence I'd like to know about it.

I almost missed this one.

There is no good published test results using Sistan at ANY condition, as far as I know. People at IPI and possibly ENS Louis-Lumiere tested it and there are casual communications reporting their experiences. There is also a report authored by Fuji researcher who investigated thiocyanate (not the product) in this context in 1980s. There aren't much more on this subject.

So I've tested it. Humidity cycle is time consuming and labor intensive without a computer controlled, automated setup, and I'm yet to run an exact test for this.

But as you know thiocyanate is a hygroscopic compound and it is VERY soluble in a small amount of water.

The range of thiocyanate concentration for it to be very effective is rather narrow. If you use too much or too little, you're in trouble. In particular, if the concentration is higher than the optimal value, it's actually worse than no treatment.

Now, if you treat an absorbent paper with a soluble salt and dry. The concentration may be relatively uniform. But as you repeat humidity cycle, the concentration at the center of the sheet will be lower and the concentration near the edges will be higher. This is the problem.

Similar problem occurs in spray treatment of acid paper to make alkaline. Well, water-based approach is only one method and may not be the best option, but if you use soluble carbonate (like sodium carbonate) the same problem as above occurs with humidity cycles. So in reality calcium carbonate, which is only sparingly soluble, is used, to prevent migration during humidity cycles.

So, for final bath treatment like Sistan or Ag Guard, I'd much prefer compounds that are not very water soluble but highly argentophilic, being adsorbed on metallic silver surface with forming a barrier of dense assembly of the molecules, rather than a highly soluble compound floating between gelatin or cellulose molecules. Ag Guard is former, Sistan is latter.

Oren Grad · May 25, 2006

Ryuji said:
There is no good published test results using Sistan at ANY condition, as far as I know.

Sorgen's 2003 thesis for the University of Applied Sciences, Cologne, reports a protective effect of Sistan used alone, as directed. Not sure if that should be considered "published"; the peer review was presumably limited to his thesis committee.

Ryuji said:
So, for final bath treatment like Sistan or Ag Guard, I'd much prefer compounds that are not very water soluble but highly argentophilic, being adsorbed on metallic silver surface with forming a barrier of dense assembly of the molecules, rather than a highly soluble compound floating between gelatin or cellulose molecules. Ag Guard is former, Sistan is latter.

If you put it that way, it's hard to argue with motherhood and apple pie. But if you didn't have Ag Guard or selenium at your disposal, would you use Sistan? Or are you arguing that the postulated effects of humidity cycling are both so severe and so likely to occur in typical real-world storage and display conditions that Sistan is worse than nothing?

Ryuji · May 25, 2006

Oren Grad said:
Sorgen's 2003 thesis for the University of Applied Sciences, Cologne, reports a protective effect of Sistan used alone, as directed. Not sure if that should be considered "published"; the peer review was presumably limited to his thesis committee.

I'll check my database to see if anything is published by Sorgen, but do you have it in PDF or other forms? I'd like to read it.

But if you didn't have Ag Guard or selenium at your disposal, would you use Sistan?

In my mind, chemistry is a tool to do what I want. There are some "substitution recommendation experts" out there on APUG, but I'm different. I'll pursue what meets the purpose and use it.

If you have fine art prints in mind, I'd rather stick with tried and true polysulfide. No question about that.

If you are talking about contact prints to be stored in clear file pages, or maybe casual snapshots to be stored in plastic album sheets, I may use Sistan rather than polysulfide. The idea here is that prints are less exposed to environmental oxidants anyway, and it's also somewhat isolated from humidty cycles.

Either way, the real risk is overrating the protective effect of any treatment. In the end, while polysulfide gives more robust protection than Sistan, in poor storage condition, all prints will be degraded to some extent and it is only a matter of degree.

Claire Senft · May 25, 2006

Just a general comment. I think that offering the best protection for print considered to be "fine art" is a very worthwhile goal. I would like to add to that . Any print that one wants to last should be given the best possible treatment for long range stability. Just consider this: A poor quality composition that had decent clarity of the signing of the Magna Carta would be a treasure. 500 years in the future the photograph that you just printed last week of your kids playing in the backyard will be very valuable too.

How archival is a straight print?

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