[pure-silver] Re: acrchival wash in cold water?

  • From: "Richard Knoppow" <dickburk@xxxxxxxxxxxxx>
  • To: <pure-silver@xxxxxxxxxxxxx>
  • Date: Fri, 15 Apr 2011 13:36:05 -0700


----- Original Message ----- From: "Eric Nelson" <emanmb@xxxxxxxxx>
To: <pure-silver@xxxxxxxxxxxxx>
Sent: Friday, April 15, 2011 7:39 AM
Subject: [pure-silver] Re: acrchival wash in cold water?


That's good to know. I washed them for an hour in the archival washer and then left them in there overnight to leach out whatever else was left. I'll give them a little more wash before laying them on screens. There's some definite "B" prints in there so those will be good tests for the toner. Draining the water heater now and about to chase down an installer. The dimensions of the heater will be different than the old one so better to have a "pro" do it who can cut pipe etc where needed. We're also in the midst of a major electrical upgrade so yes, perfect timing! At least Home Depot will give
me 12 months interest free on this purchase!

Since I rent I have no idea where to buy a water heater. Overnight soaks are not a good idea and I intended to add that to my post. Such soaks were suggested by David Vestal and possibly even Ansel Adams in the past. Vestal retracted his advice in his later books. There are a couple of problems with long soaks: they can damage the paper support; while the paper used for photographic paper has very good wet strength it will eventually begin to disintegrate, also, the emulsion and barytal layers can begin to delaminate. Further, since washing is partly a diffusion process and for the paper support, partly a frictional process, the water at the surfaces must be renewed frequently or the hypo will reach a sort of equilibrium and the further diffusion be slowed to a stop. In the emulsion, and in the baryta substrate, the hypo and reaction products wash out mainly by diffusion but, according to Ilford research, the hypo in the paper support is partly held by frictional forces to the fiberous structure. That is the main reason that "fiber" or untreated paper takes so long to wash out. In the emulsion and baryta substrate the hypo and reaction products are held by chemical binding of two varieties, both of which are broken by the use of a buffered sulfite wash aid such as Kodak Hypo Clearing Agent, and the evidently identical Iford product. The two kinds of bonds are: a bond due to the electrical charges in the gelatin of both emulsion and substrate; and, a chemical bond due to the use of white alum hardener. This last is not present when a non-hardening fixing bath is used or when chrome alum is used as the hardener (never for prints because it stains). Both bonds are pH dependant. By increasing the pH to neutral the "mordanting" bond of white alum is eliminated without loosing the hardening effect. Greater pH will also break the bond but will also eliminate the hardening. Since photographic gelatin has an isoelectric pH slightly on the acid side of neutral the internal charges tend to attract ions with even lower pH, this tends to hold the hypo and any reaction products to the gelatin when an acid fixer is used. By increasing the pH to neutral the charges are changed so that the gelatin is slightly more alkaline than the hypo so that the charges repel and facilitate washing. Sodium sulifte, and other sulfites, have a further effect on washing; they act to displace thiosulfate ions through a process known as ion exchange. This active displacement takes place even when a non-hardening or non-acid fixer is used, much accelerating washing and making the wash less sensitive to temperature. When a wash aid such as KHCA is used the wash time for film is reduced to about 1/6th the time needed for film treated in a hardening, acid fixing bath and for fiber paper about the same if you consider one hour a sufficient normal time for double weight paper.
    Overwashing.
About 1961 T.H.James, of Kodak Research Laboratories, discovered that a very small residue of thiosufate in the emulsion would _stabilize_ the image where it was exposed to oxidizing agents such as peroxides in the air. His discovery meant that the sort of very long washes and soakes recommended at the time resulted in _less_ not morestable images. This was such heresy that he was reluctant to publish the results until a researcher from Fuji's laboratory published similar results. The result of this was that Kodak completely revised their recommendations for residual thiosulfate in archival materials and with that their washing recommendations. There are no very definite quantities given for the desired amount of thiosulfate remaining but Kodak's washing recommendations since the 1960's reflect it. The recommendations for washing after using KHCA also take this into consideration. The protection provided by the thiosulfate residue is minimal, it does not take the place of toning but James and others found that even when dilute selenium toner was used the resistance of images to oxidation was greater when the residual thiosulfate was present. Highly diluted (1:19) Kodak Rapid Selenium Toner is no longer recommended as a routine method of protecting iamges because it was discovered about twenty years ago that it no longer seemed to work. This was the result of research by the Image Permanence Institute into why microfilm at a large archive were showing signs of image degradation despite having been processed according to the accepted recommendations for permanence. There was never any definite answer as to why the treatment had stopped working; Kodak stated that neither the formula or method of production of KRST had changed. There was speculation that some raw material used in the original had some impurity that resulted in the superior protection but that remains only speculation, the fact is that KRST, in high dilutions tones different size silver crystals at different rates, the result being that low density areas are not protected. KRST was popular because it was cheap, easy to use, and did not significantly change the density or structure of the silver image, both of which are vital to microfilm use. KRST will provide full protection if used in stronger dilutions, Dr. Douglas Nishimura, the principal researcher at IPI, recommends not less greater than 1:9 and for not less than 3 minutes @ 68F. IPI now recommends a polysulfide toner like Kodak Brown Toner for routine use on microfilm. The old standard Gold toner is still considered the standard but is quite expensive.

--
Richard Knoppow
Los Angeles, CA, USA
dickburk@xxxxxxxxxxxxx
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