RC paper, how unarchival is it?

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Note on Ctein

times new roman

Several posters mentioned the experiences of Ctein. His views and tests were very interesting. However, Ctein as of the posting of his book was still producting RC prints for sale. For some images he liked the look. As a point of fact he was working to extend the life of RC prints. His work with Sistan was also interesting. In fact, I started using Sistan. Remember that Ctein mentioned no intention of quitting on RC. We have to be careful about taking work out of context. Ctein was very concerned because he had to replace some prints, however, he worked to retain RC not get rid of it.
I print both FB and RC and I am certain either will last far longer than my ego.
Jerry
 
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I was working for Ilford Limited as a technical writer at the time of the launch of Ilfospeed (graded RC paper) in approx. 1975. I remember about 2 months from launch there was a panic because the prints on accelerated ageing test (in glass cases on the roof of the old Technical Services building in Roden Street Ilford) had deteriorated (the RC base was breaking up although the emulsion itself was OK). I was asked to take any reference to archival permanence out of the literature I was writing, and frantic efforts were made to fix the problem, which was in fact done by the time of launch.

In addition to writing, I did from time to time take pictures for the company and spent quite a bit of time making prints in the Specimen Prints department on Ilfospeed (this department was of course meant to produce prints which showed Ilford materials to best advantage and was therefore equipped to process large quantities of hand-made prints archivally). I still have some of these today (stored in boxes or albums) and they look fine.

I must say today I regard FB and RC as equally good from the point of longevity - RC is hard to retouch and unsuitable, I find, for any toning involving bleaching but with the small darkroom at my disposal at present, it is so much easier when I need to run off dozens of prints of the same neg within a short time (which I do from time to time).
 

Ryuji

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My experience with RC is mostly AGFA MCP, which I have been using for past 11 years. I have many framed work and I also have prints stored in various conditions, and I have run accelerated aging tests including peroxide fuming tests. I also use AGFA MCC (baryta paper) and Forte Fortezo, so I have samples of these papars tested in these conditions as well.

For the AGFA MCP, I have never seen anything that damages the resin layer, paper base, or the gelatin coating in any of the conditions I used. ALL of the problems I could induce to the prints were related to oxidative degradation of the image silver, such as fading, browning, bronzing, and mirroring. The degradation is easily prevented by treating the print in polysulfide toner as a routine part of the processing. The same applies to baryta papers. Untoned metallic silver image is equally susceptible to oxidative degradation just like RC.

The upshot is that, if the permanence is important, tone the print in gold or polysulfide. Fujifilm makes an image stabilizer solution containing 2-(amidinothio)ethanesulfonic acid, which is also shown to be as effective in protecting the image as weak gold toning.

Ctein's results indicated that Sistan was effective in his conditions, but I suspect that Sistan treatment would not be as reliable in conditions where humidity profile goes up and down, because the main ingredient of Sistan, thiocyanate is soluble in water and the window of effective concentration is rather narrow. (The active agent in Fuji Ag Guard is strongly adsorbed on silver surface and the effect will remain even if the treated print is rinsed in water.)

I think the good news about RC is that resin cracking and other early problems are solved in recent products, and my experience can speak about this for AGFA MCP manufactured after 1995. The weakness is in the silver image, which can be solved by sulfur or gold toning.
 
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Can we assume Ag Guard is the image stabilizer solution you're referring to? If so, is there a US source, or should we petition Dirk to add it to the Megaperls catalog?
 

Mark H

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"RC is hard to retouch and unsuitable, I find, for any toning involving bleaching "

David--I'm not sure I understood this correctly, but I have used RC (mainly Ilford) specifically for toning with sepia and thiocarbamide, both of which involve bleaching. Combined sepia and selenium toning give a tone I can't duplicate on FB.
 

Ryuji

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Sal Santamaura said:
Can we assume Ag Guard is the image stabilizer solution you're referring to? If so, is there a US source, or should we petition Dirk to add it to the Megaperls catalog?

Ag Guard is the image stabilizer solution sold by Fujifilm. I have some research results here:

Dead Link Removed

It's definitely worth asking Megaperls to carry this, and they should also send me a bottle so that I can post a translation of the label on my site!
 

Ryuji

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I agree, RC is just as good for bleaching, toning, etc., although I know many darkroom textbooks say that RC is harder, probably because someone started saying that decades ago and the wrong notion got cut and pasted. It's very common phenomenon in photographic textbooks.

Glossy RC surface may be a bit more difficult to retouch with Spotone, etc., but AGFA Semi-matte 312 is very good. (I use glossy baryta and semimatte RC almost interchangeably, except the difference in the base tint.) I think Ilford Pearl is very close in surface as well.
 
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Mark H said:
David--I'm not sure I understood this correctly, but I have used RC (mainly Ilford) specifically for toning with sepia and thiocarbamide, both of which involve bleaching. Combined sepia and selenium toning give a tone I can't duplicate on FB.
I too have successfully toned RC prints using processes that involve bleaching, but the emulsion becomes incredibly soft after bleaching and before toning, and I have accidently wiped parts of the emulsion off the base several times. This is why I prefer FB for anything other than straight prints.

Regards,

David
 

nworth

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dancqu said:
...
RC papers were brought into being to feed the 24 now
1 hour machine processing labs. I'm not going to trust
anything I'd like to last for generations to ANY plastic
coated both sides stiff to work with paper. Dan

Actually, they started in WWII for rapid printing of aerial photographs. I still have some pictures printed on Resisto Rapid N from the 50s that have not significantly deteriorated. The move to the commercial market on the late 50s was an answer to professional photogaphers who needed both more rapid processing and reduced water consumption (which had become a big issue, especially in Europe and the eastern US).

If you read the Ctein article and some of the related material, you will note that the bronzing effect only happened with framed and mounted pictures. The cause was traced, and all the manufacturers applied corrective measures. I'm not sure how good these really were for very long term stability. RC paper has become a very complex system. While testing the permanence of RC paper may not be as straightforward as testing a car door, I do tend to trust those who do it. They follow well established procedures that have been used and improved over many decades and are based on the testing used for papers and pigments used in printing as well as photography. They can be wrong, but they are the best scientific data we can get.
 

Ryuji

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nworth said:
If you read the Ctein article and some of the related material, you will note that the bronzing effect only happened with framed and mounted pictures. The cause was traced, and all the manufacturers applied corrective measures.

Ctein pointed out only ONE aspect of the problems. He found that one cause of the oxidative attack was in the titanium white pigment in the resin layer, and manufacturers might have done something so that titanium related generation of ozone and peroxide are inhibited. However, this is not the end of story. There are many sources of environmental oxidants in residensitial and office environment, and one of the most common source of such thing is nonarchival cardboard and nonarchival adhesives.

I have 10 years old print, dark stored in reasonable temp and humidity condition, bronzing out. The print was taped down (with a nonarchival masking tape) to a nonarchival base board, and it was stored in a portfolio box. This could be easily prevented if I toned this print in polysulfide, or used Fujifilm Ag Guard in place of PhotoFlo.

I'm not sure how good these really were for very long term stability. RC paper has become a very complex system.

Indeed RC paper is somewhat complicated system. But baryta is also not that simple to make. If you grind barium sulfate and mix with gelatin to sub paper, you'll realize that the quality and mechanical integrity of the coating are critically dependent on the size and uniformity of individual barium sulfate grain.
 

Photo Engineer

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It should be noted here that Barium Sulfate and Barium Oxide are both used to make what is commonly called Baryta. Addition of optical brighteners and other chemicals further complicate the picture. European made baryta paper supports are quite different than Kodak baryta paper supports. For proof of this, simply wet a piece of MGIV and Polycontrast IV. One has a strong odor and the other does not, due to the type of additive used during manufacture.

In addition, RC support has used both Rutile and Anatase versions of Titanium Dioxide along with brighteners and antioxidants in both the TiO2 and RC layers. The two forms of TiO2 have a great influence on the final image stability, particularly in color materials where UV is more important. There are numerous patents on the stabilizing agents used by EK and Fuji.

And, photo flo has never been recommended for use with papers. Usually, prints are treated with things like Sistan.

In the final analysis, Ctein has written one of the best summaries of this entire field. He has included tests using Sistan.

I have to add that I'm not familar with the Fuji stabilzer, nor with the chemistry involved, but I am with the effects of Sistan. I would guess that they work by similar methods to what Ctein describes and what I have learned from my own experience, via the use of sulfur to protect the silver image. This method is common in many toning procedures whether it be sulfur or selenium.

PE
 

Ryuji

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Photo Engineer said:
I have to add that I'm not familar with the Fuji stabilzer, nor with the chemistry involved, but I am with the effects of Sistan.

Ron, please explain the details of your testing methods. I've tested Sistan treated prints with 3000ppm peroxide fuming at 90% RH at 24C and the protecting effect was vastly inferior to polysulfide-toned print.

Sistan treatment is also ineffective against standard dichromate test but polysulfide toned print is pretty resistant, as long as the image is sufficiently toned.

Ctein did not perform peroxide test nor dichromate test. He only did sealed frame test to prove his titanium oxide hypothesis, but he didn't intend to study archival issue in general. It's very far from comprehensive study of the whole field, as you said.
 

Photo Engineer

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I agree that the tests done are far from comprehensive. I would like to add that they can probably be somewhat misleading as well.

The tests with Sistan type solutions were done by the B&W division with standard EK methods which don't involve peroxide or ferricyanide. They involve actual light, heat, humidity and oxygen. In fact, I have been told, without verification by myself that the tests you cite are not truly indicative of the true stability of a print. There may be some reference to these tests in Haist, but I cannot remember offhand. I'll check tomorrow.

Mind you, I have not verified the statement regarding peroxide or dichromate being less indicative. I have used the EK method solely which is 4000 or 2000 fch light, 120/40 heat / humidity or 90/10 heat / humidity (wet and dry oven). These can be run with and without forced oxygen. We backed these up with real fading using a northlight window with a sensor to integrate total light vs time. Therefore the accelerated tests could be compared with a real world slow test.

Some of these test ran over several years. Most of the tests in our division were done to test dyes or RC support with the different forms of TiO2 and different chain stoppers with different UV and oxygen barrier layers. We did this baryta support as well.

The B&W division did similar tests with silver images on RC and baryta but tested the silver images.

Both thiocyanate and thiourea were found to stabilze silver images by virtue of forming silver sulfide on the surface of the image. Just as Ctein found, some images benefit from leaving some sulfur compounds in the coating and this is where Sistan comes in.

But, getting back to the main point, it is poorly documented outside of the halls of EK, Fuji and Agfa to name a few. So, your test may be entirely valid, showing the polysulfide to be very effective, but then maybe the peroxide method may be fooling us as to real world events. IDK. I cannot even guess here. I can just go by what was taught me at EK and what I carried out. These tests I used at EK seemed to serve us well as indicators of image stability over a wide range of products from the 40s to the present.

I hope this helps.

PE
 

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Some additions and corrections to the above post.

It should read 4000 hours and 2000 hours at 500 foot candles (multiply hours * intensity to get total fch).

For a general description of this method of image stability testing for color materials, see USP 3. 676. 136. This patent BTW, is a precursor for the newer formalin free stabilization used in E6 and some other processes.

Grant Haist describes image stability in B&W materials in "Modern Photographic Processing", Chapter 14. While he and his associates worked on B&W materials, I was doing work as described in the above patent (among other things - both of us had several projects going at the same time)

PE
 

Gerald Koch

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Sal Santamaura said:
Can we assume Ag Guard is the image stabilizer solution you're referring to? If so, is there a US source, or should we petition Dirk to add it to the Megaperls catalog?
Fuji has announced that they are discontinuing Ag Guard due to the expense of manufacturing the principle ingredient 2-(amidinothio)ethanesulfonic acid. This chemical is another example of a chemical orphan. For awhile Fuji manufactured it itself when there were no other manufacturers but it finally became impractical.
 

Ryuji

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Fuji didn't announce it. They just told me when i asked, so i posted this info to inform current users to stock up. Also, there are at least three manufacturers for this compound, and the synthesis of this compound is not that hard.
 

Ryuji

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Your method may be good enough for testing color material, which is a lot more fragile than properly toned silver image. Silver image is expected to last far longer than color image, and the main mode of degradation is oxidative one. Most sensible accelerated tests aim to investigate the weak point of the material, and in the case of b&w image, oxidative attack is the weak point. It's different from color, and your color testing method is not very good for evaluation of b&w image permanence.

You should refer to ANSI and ISO standards for the standard test methods for b&w images. IPI also issues several technical reports on these issues. There are also several publications from IPI, Konica and Fuji. People like Drago published some aspects on this in refereed journals but IPI documents indicate that Kodak wasn't very active in this area, compared to the IPI itself.
 

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Thiourea treatment is not recommended. Thiourea can decompose to form corrosive acid in presence of oxygen and light on silver surface. Thiourea treatment was used to Daguerreotype silver image in 1950s and it damages most images within 20 years. Bad record.

Thiocyanate is ineffective in low concentration, and it is harmful to silver image (accelerates image degradation) when overdosed. Thiocyanate also loses treatment effect once the print is rinsed in water. Not ideal. Plus, my test indicates that thiocyanate treated image is not as permanent as polysulfide treated prints.

The best method in current knowledge is polysulfide or gold. Next best is selenium. Sistan is less effective than these options.
 
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Ag Guard substitute

Ryuji said:
Fuji didn't announce it. They just told me when i asked, so i posted this info to inform current users to stock up. Also, there are at least three manufacturers for this compound, and the synthesis of this compound is not that hard.
Asking Dirk to add a discontinued item to his catalog doesn't seem appropriate.

Ryuji, if the compound is not that hard to synthesize, may I suggest you work with Photographers' Forumulary to bring an Ag Guard substitute to market?
 

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I am familiar with the work of Drago et al.

I didn't say I agreed with the tests, I said that the tests I report are what were used at EK. EK was very active in the field of dye and silver stability, but did not publish anything and developed their own methodology as I reported.

I cannot agree or disagree, never having used the peroxide and dichromate methods nor have I known of their use at EK (that does not mean that they were not tested or are not in use now). I just know that the conventional position was that the use of peroxide and dichromate to test keeping was not preferred.

PE
 

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Well, I don't recommend thiourea either, I was just making an obsevation that some sulfur preserves silver but too much makes it worse. Also, thiourea is a suspected carcinogen and is prohibited in quite a few places for that reason alone.

As for thiocyanate, since Sistan uses it, and Ctein sees some benefit from it, and I cannot refute the usefulness of Sistan or refute the evidence of Ctein's tests, I would have to say that there must be some benefit and some evidence otherwise Agfa's sale of the product would be rather suspect then. I think that a lot of people have used it and found it useful. I'll go with that evidence.

PE
 

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I have been presenting the chemical mechanisms and also referring to IPI research which confirmed that double strength of Sistan can expedite image deterioration compared to untreated image. All of these sum up to the conclusion that Sistan is not as good as image protecting agent should be.

Your basis to support Sistan is pretty weak: a single report from Ctein (who apparently didn't test anything but the recommended usage of Sistan). What Ctein showed is that Sistan treatment was sufficient to prevent one particular aspect of oxidative degradation at his condition.

The goal of testing for archival processing and image permanence should be to test the material at sufficiently harsh conditions to ensure good survival of the image at all reasonable storage conditions. Ctein's test was specifically designed to make it harsh for RC paper. It is insufficient to conclude general overall efficacy of Sistan treatment, and it is also insufficient in terms of robustness of the treatment efficacy.

How many Sistan users do you think would worry enough to run standard peroxide and bleach test? I've run these tests on Sistan-treated prints as well as prints treated by other means, and I have first hand experience as well as knowledge on the chemistry of these processing. I also follow publications in scientific as well as technical journals and patents on this issue as well as many areas of photography.
 

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Then let's go back to the basic question
what is more destructive to a print?
UV light or environmental pollution?

I went to Ecuador a couple of weeks back and the prints I made in the late 80's early 90's are hanging in my mom's house. The living room gets a lot of sunlight with very high content of UV (right over the Equator at 8000 ft/2400 m). Prints were made in Agfa Brovira/Portriga, Kodak Polycontrast, Forte RC and FB and Ilford RC papers. MOST of the BW prints were not toned. A few were seleniumed and one was tea-stained (brovira).
There were also a few color prints,
The prints were framed with aluminum/wood frames, mat board (passepartout) and glass.

I helped her take the frames apart to clean the glass and change the matt board (passepartout) that had faded badly, specially the one that used to be green.
However, the prints looked fine to me, even the ones in glossy Forte/Ilford RC paper didn't show any signs of yellowing, bronzing or deterioration ( I could compare the borders that were covered to the uncovered portion). Brovira paper looked great as expected, even the one that was tea-stained was not affected.

From the color ones, they showed some discoloration excpet the Cibachromes.

I guess air pollution there is close to nil, her house is surrounded by avocado and citrus trees, and except for bleach used to mop the floors every other while the air should be free of pollutants.

So is it UV or air that kills the prints or both ?
 

Photo Engineer

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I understand with your presenting these mechanisms and keeping up to date with publications.

I merely point out that first, the 'wisdom' accepted at EK when I worked on image stability was that chemical tests were unreliable. Accelerated heat and light tests were reliable.

Also, Ctein's tests were done with natural keeping using light not chemicals. Due to his professional method of testing, and his incentive for solving this problem as best he could, I trust his answer.

I'm not saying one is better than the other, just that our accpted practices at EK at that time correspond roughly to Ctein's tests and that the tests using light and heat rather than chemicals were quite reliable. The accelerated EK tests using light, heat and humidity worked well compared to actual samples kept for 20 or more years. And, these tests were concieved years before there was an external standard that you have cited.

In point of fact, B&W image stability has been well characterized for nearly 100 years and is elaborated on by Haist. It boils down to this, you must retain just a small quantity of sulfur compounds in your print. Too little or too much leads to image degradation, and Ctein's work has indicated the same thing. Image stability of B&W had a resurgance in importance with the introduction of RC, as the stability of the RC support and the images thereon changed due to the fact that the coatings washed more completely changing the levels of retained sulfur compounds and altering image stability. Adding TiO2 and the other chemicals to the equation further complicated issues.

These issues, BTW, applied to some extent to color as well.

In any event, much more was done at EK that was never published than was published, and I'm sure this was so at Agfa during the development of Sistan. I am in no position to suggest that the use of Sistan is useless in the face of evidence that shows otherwise. Used properly it will work, but used improperly it will either not work or harm prints. Our goal is to use every chemical properly. Used improperly, any photographic chemical can ruin otherwise good negatives or prints, therefore I see no problems at all with Sistan provided the instructions are followed. Used outside of those limits, I see no reason to disagree with your asessment either, that it can be harmful.

Hundreds of reports exist internally at EK concerning image stability and hundreds of patents exist on stabilizing both B&W and color images. The internal reports, as noted above, are never released outside of Kodak and the same is true of Fuji and Agfa among others.

Now, Fuji has ceased production of their stabilzer citing the difficulty or expense of manufacture, and yet you say it is rather easy to make. If this is so, as someone asked above, why are they really stopping production? That is a rhetorical question. I really don't care. It is a fact that we cannot change. I'm sure that with proper testing we might find that the Fuji compound also has 'loopholes' in stability.

And that is my final point here. There are compromises and loopholes in all practical applications of chemical solutions to image stability and in testing image stability. I've pointed some of each of them out above. So, knowing theory and running a few tests is quite useful, but not broadly revealing. It is when you have a roomful of people who have run thousands of tests, and you statistically compare results that a picture begins to emerge. That is where the corporate approach has benefit for the average photo artist and hobbyist.

In fact, I have found based on a single image stabilty test that something was worse, but statisticaly it was better, but had a higher variation. So, a single test was useless. I have found that theory predicted one thing, but practice gave a different result over a number of trials, and I had to accept practice over theory. Again, a single test was useless.

Due to this, I find that repeated statistical tests are the most useful, and that if practice overrules theory, the theory may still be correct but I have to accept what results from practice.

PE
 

Ryuji

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Photo Engineer said:
I merely point out that first, the 'wisdom' accepted at EK when I worked on image stability was that chemical tests were unreliable. Accelerated heat and light tests were reliable.

You are swithching the point. Light-accelerated fading test is testing a different mechanism than oxidative attacks, which are the main cause of b&w image deterioration. You can't take one test and argue different mechanism.

The accelerated EK tests using light, heat and humidity worked well compared to actual samples kept for 20 or more years. And, these tests were concieved years before there was an external standard that you have cited.

Yes, the result was that Kodak b&w papers presenting the same fading problems. Indeed, it was Kodak who aggressively marketed microfilm to Library of Congress in 1940s and forward, telling them that silver image is stable for many decades, only to discover untreated microfilm was beginning to degrade in 1950s. Henn proposed gold toner, and Brandt did an excellent early stage research on the mechanism, but greater importance of modern research is due to Image Permanence Institute and Fujifilm for their very detailed and thorough research.
In point of fact, B&W image stability has been well characterized for nearly 100 years and is elaborated on by Haist.

Most old silver images are toned in noble metal or sulfur. Unless the image is stored in absence of pollutants, untoned silver image can go bad much faster than that. Plus, arguments based on survived images are very weak, because such arguments ignore the factors that affected images that didn't survive.


It boils down to this, you must retain just a small quantity of sulfur compounds in your print. Too little or too much leads to image degradation, and Ctein's work has indicated the same thing.

Ctein's work did not indicate it. He only tested one product using one particular kind of sulfur compound.

Now, Fuji has ceased production of their stabilzer citing the difficulty or expense of manufacture, and yet you say it is rather easy to make.

This is incorrect. Fuji still lists Ag Guard in their catalog and there was no announcement of discontinuation of this product.

I'm sure that with proper testing we might find that the Fuji compound also has 'loopholes' in stability.

There are published tests that indicate Ag Guard is as effective as gold toning. I have also tested amidine-thioether compounds as well as other amide-thiol compounds and some of these are clearly superior to thiocyanate or Sistan.

Anyway, just like you criticize everything I write, I have to point out that your arguments are based on:

* your speculation
* one study published by Ctein in non peer-reviewed popular magazine

what kind of Photo Engineer are you? You should be solidly evidence based.
 
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