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ronald lamarsh
12-Mar-2004, 17:58
I have come into possesion of some old negatives of great value to my families history. Some of them though have a darkening around the perimeter of the image and when viewed so that light reflects off the surface this area is very shiny with an almost metallic sheen. Anybody out there seen or know of this and is there a way to restore such negatives. I have already washed them thouroughly and refixed but to no avail.

Jan Nieuwenhuysen
14-Mar-2004, 02:35
As far as I know when a negative or print is improperly fixed and/or washed the image silver can be changed to silversulfite by the sulphur that is present in the residual thiosulfate (fixer) or silver-thiosulfate complexes. (And even sulphorous gasses from the atmosphere I suppose.) The first formation of sulfite can be seen as a metalic sheen on the surface of the image. When more sulfite is formed it will 'bleach' the negatives; they change in color from normal black through purple to brown or even yellowish-brown color. So what I suspect is going on is that sulfite is formed causing the metalic shine and apparent loss of blackness. As far as I know this is irreversible. I am not a chemist so maybe someone with more chemical knowledge can tell you more about damage control.

Ed Workman
15-Mar-2004, 11:37
Try gently rubbing with an "art-gum" eraser by pushing the eraser away from yourself so that the negative does not buckle.

Kathryn Hernandez
5-May-2004, 19:14
I have a similar issue with several 60 year old negatives where the plastic backing has buckled from the silver haloids making the images difficult to scan. Should I soak one in a wash bath to see if it will soften the plastic or will that damage the image further?

Mark_3632
5-May-2004, 19:56
Jan and Kathryn

They might be nitrate negatives. It sounds like it. If you do not know how to test them try this. It is the method we used in the Special Collections Darkroom at NAU. Snip a small sliver off the side of one and put a match to it. If it flames up like a fuse, or lights like a candle it is a Nitrate negative and you should have them copied right away. These things, aside from being combustable and bad to keep around your regular negatives, age really funky. On some, the base shrinks and buckles. The emulsion will also start to crack off if they are buckleing. If you are unsure find a college archive or museum to have them checked.

If the emulsion is starting to come off a soak could remove it entirely. If you are unsure of what to do with it and have a lot of patience I can explain how to float the emulsion and stick it to another base long enough to have a copy neg made. It is a time consuming process, can be expensive, and is definately a last reslt because it is a delicate procedure. You should find some one who knows what they are doing to copy the neg appropriatly. Tell them you want a copy neg made.

Beware the Nitrate Negative. Here are the levels of deterioration. Note Number 2

level 1 No deterioration.

Level 2 The negatives begin to yellow and mirror.

Level 3 The film becomes sticky and emits a strong noxious odor (nitric acid).

Level 4 The film can become an amber color and the image begins to fade.

Level 5 The film is soft and can weld to adjacent negatives, enclosures and photographs.

Level 6 The film can degenerate into a brownish acid powder.

Here is some more reading http://www.nedcc.org/leaflets/nitrate.htm

Michael S. Briggs
6-May-2004, 00:53
Many old negatives deteriorate in ways such that they will be damaged by any water solution. It is best to try any repair method first on unimportant negatives. For important negatives, it would be a good idea to make copy negatives or prints before attempting any treatment.

The 1985 Kodak book "Conservation of Photographs" has some very brief instructions for restoring negatives with the problem you describe. The term for the problem is "dichroic silver". You may be able to find more information using that term.

p. 74 suggests that the cause is reaction with hydrogen sulfide gas.

p. 131 says to use an Ammonium Hypo Reducer prepared by adding 15.0 g of citric acid per liter to Kodak Rapid Fixer with hardnener diluted to 1:3.

p. 132 shows a photo shows of a negative being restored with this solution: the solution is applied using a ball of absorbent cotten with a circular motion. The negative doesn't appear to be immersed, instead a cotton ball, dipped into the reducer, is held in a gloved hand and apparently rubbed over the tarnish.

I have never tried this method.

dvfulwider
21-Sep-2014, 07:41
Ronald, given that this is a VERY old posting, I hope it finds you well.

I too have come into possession of some old negatives of great value to my family... all damaged. I wanted to ask, as a way of starting my research, if you were successful in repairing your negatives to a useful state.

Sincerely, Dave Fulwider// Miami// weeder72@msn.com

Jim Noel
21-Sep-2014, 09:53
I have a similar issue with several 60 year old negatives where the plastic backing has buckled from the silver haloids making the images difficult to scan. Should I soak one in a wash bath to see if it will soften the plastic or will that damage the image further?
Are you sure these are not Nitrate negatives? If they don't say "Safety Film" along the edge they are most likely nitrates. They should be stored in a fireproof container as spontaneous combustion is possible.

Peter Gomena
21-Sep-2014, 10:39
Your best bet is to not attempt to restore them. Make a contact print or projection print from the negative. Deteriorating negatives develop densities impenetrable to typical flatbet scanners but remain quite printable even in a bad state. Some, of course, like early acetate images and many nitrate negatives, already may be beyond salvaging.

Nitrate negatives have a distinct odor that is irritating to eyes, nose and lungs. The "spontaneous combustion" of such negatives occurs only when they are improperly stored. Nitrate sheet film is safe if stored in dry, cool conditions with excellent ventilation. Negatives should be in archival paper envelopes that are open on one end, and should be loosely stored open-end-up in archival cardboard flip-top boxes. Do not store roll film rolled-up. Cut and flatten roll film and store each piece in a separate envelope. Avoid moist, humid, warm conditions. Nitrate negatives do eventually deteriorate to a useless state, and they should be discarded as toxic waste. Early acetate negatives develop "vinegar syndrome" and will delaminate and turn into a warped, bubbled, useless mass. They should be separated and stored separately from other photographic materials. Movie film is a whole other problem because old film often is stored in metal cans, rolled onto reels, which really becomes combustible if improperly stored. Sometimes it just turns to inflammable goo.

blueribbontea
21-Sep-2014, 15:43
When a negative buckles and peels away fro the backing, this is a sign that it is early safety film and what is happening is that the emulsion is shrinking at a different rate than the backing. Thus the first film replacement for nitrate were almost worse than what they replaced. I have tried soaking such negatives to flatten out the image on the backing but the result was the peeling away of the emulsion and its disintegrating in the distilled water.

lenser
21-Sep-2014, 18:33
Consider the aesthetic option in a new approach to thinking. If the "darkening" just occurs along the edges but not intruding into the important subject part of the image, when printed, that will effectively be a vignette and contribute to the aged or antique look of the overall image. It may not be a bad thing at all.