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Photo Forum / Film Photography / Darkroom / March 2006Intensifying underdeveloped negatives?
It's been a LONG time since I've been in the darkroom; but a friend had a question - is there a way to salvage underdeveloped negatives? She developed in the wrong dilution of HC-110 and got a very thin roll of negs. I vaguely remember reading of a post treatment to improve the situation somewhat, but can't remember any details. Anyone? The easiest and safest way would be to try scanning negatives since scanners work better with "thin" negs. And what looks thin to human eye is sometimes fine especially if you are using Tmax. If you want to go the wet route, make fresh rapid fixer, fresh Kodak Rapid Selenium Toner 1+4 using Fresh Kodak HCA instead of plain water and another bath of fresh HCA without toner. Wash the film, refix, go straight from the fixer into the toner and tone to completion (probably 10 minutes) then rinse, treat with HCA and rewash and finish as normal. This was mentioned by Ansel Adams in one of his later books. Need I add that you should test all these procedures before committing irreplaceable images to an untried process. It has the advantage that it is a permanent intensification where most Mercury intensifiers (can you say TOXIC?) are not permanent.  Signaturedarkroommike > It's been a LONG time since I've been in the darkroom; but a friend had > a question - is there a way to salvage underdeveloped negatives? She [quoted text clipped - 3 lines] > I vaguely remember reading of a post treatment to improve the situation > somewhat, but can't remember any details. Anyone? > The easiest and safest way would be to try scanning > negatives since scanners [quoted text clipped - 23 lines] > say TOXIC?) are not > permanent. I don't know why Adams would have suggested the procedure above, the use of the fixing baths is unnecessary. KRST is an effective intensifier, it must be used at a strong dilution, 1:4 is fine. It is a relatively mild intensifier but a reliable one and it can not damage the negatives. Also, the intensified image is permanent, which is not true of all intensifiers. The negatives should be washed according to the toner instructions. Unless the negatives are very thin it should be possible to get decent prints by using higher contrast paper. The disadvantage of this is that it will also increase the visibility of any blemishes on the negatives. Intensifiers work by adding to the image already on the negative. If there is no image no itensifier can bring one out. Where film is underdeveloped an intensifer will often work to increase contrast. Where the film is underexposed an intensifer may not improve things because there is simply no image in the shadows to intensify. Signature--- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com It's been my experience with selenium toning (of paper) that selenium toners work best in either a fixer free environment (hard to achieve) or in a fixer saturated environment. Since the second is much easier to achieve I think that was at least part of the rationale for this procedure. Additionally, refixing in fresh fixer gets rid of a lot of fixer by-products which can affect the eveness of toning. Much more mission critical when toning for intensification of a negative. The process may not actually be much different from the old uranium intensifiers since selenium and uranium have similar chemical propensities in some ways. And since I really didn't appreciate having to wash all the fixer out of prints before toning and then having to wash again after toning it wash always my practice to go straight from the second fixing bath into the toner. Since selenium toning baths already have thiosulfite in them this does not contaminate the toner and it sure sped things up. OP suggested that the "thin" negatives in question were underdeveloped rather that under exposed. -- darkroommike > > The easiest and safest way would be to try scanning > > negatives since scanners [quoted text clipped - 42 lines] > intensifer may not improve things because there is simply no > image in the shadows to intensify. > It's been my experience with selenium toning (of paper) that selenium toners > work best in either a fixer free environment (hard to achieve) or in a fixer [quoted text clipped - 14 lines] > OP suggested that the "thin" negatives in question were underdeveloped > rather that under exposed. If you are using an alkaline fixer, you _might_ get away with this procedure, though people have complained of staining using even that precaution. In an acid environment, thiosulfate reduces selenite and selenide to red selenium metal that is responsible for staining. If one adds a drop of KRST to an acid fixer, it is quickly reduced to metal. KRST is stable in a dilute Kodalk or borax solution that keeps the pH high enough to prevent reduction by fixer carryover, and it's far more stable than KRST in EKC hypoclearing agent. Also, toning is accelerated without staining. The warning concerning reduction by hypo appears in the Merck Index. I've posted the results of short term and long term KRST stability tests and toning effectiveness years ago. With respect to intensification, after removing all traces of fixer, the negatives may be bleached in ferricyanide/bromide, and redeveloped in pyro or another staining developer. The negatives never are refixed, but may be washed, bleached and redeveloped to increase the stain image. After redevelopment, they may be toned in KRST diluted 1+3, rinsed in 1% borax to restore maximum stain intensity, and washed. refixed, Yes, the staining you refer to occurs when you have a partially cleared print, if the print is either completely fixer free or fixer saturated (both are even distributions of fixer) differential staining (AKA uneven toning) cannot occur. Signaturedarkroommike > > > It's been my experience with selenium toning (of paper) that selenium toners [quoted text clipped - 40 lines] > intensity, and washed. > refixed, > Yes, the staining you refer to occurs when you have a partially cleared > print, if the print is either completely fixer free or fixer saturated (both > are even distributions of fixer) differential staining (AKA uneven toning) > cannot occur. That isn't what I wrote. A "saturated" acid fixer solution will reduce KRST to metal very quickly. It has nothing to do with partial fixing, and the effect is well known. One old workaround advocated the use of alkaline plain hypo as a second bath, in which case rapid reduction doesn't occur. Add a drop of KRST to a teaspoon of acid fixer, and watch what happens. >> If you are using an alkaline fixer, you _might_ get away with >> this procedure, though people have complained of staining using [quoted text clipped - 19 lines] >> in KRST diluted 1+3, rinsed in 1% borax to restore maximum stain >> intensity, and washed. refixed, > Add a drop of KRST to a teaspoon >of acid fixer, and watch what happens. Yuck ! I forget the details but I has something like this happen in the darkroom once and the results was something that looked a lot like dirty engine oil. Also there was a little gas released and it made Polytoner look good ! I'm coming in on the tail of this one. Are you saying that residual complexes are not to blame for the staining some of us have run into ? Or is that a parallel difficulty ? == John - Photographer & Webmaster www.puresilver.org - www.xs750.net >>Add a drop of KRST to a teaspoon >>of acid fixer, and watch what happens. [quoted text clipped - 3 lines] > dirty engine oil. Also there was a little gas released and it made > Polytoner look good ! It's likely that the gas was sulfur dioxide which is formed when sulfite is acidified. It certainly is not selenium as some people have rumored in the past. If the fixer is used, you may get silver precipitating with the selenium. > I'm coming in on the tail of this one. Are you saying that residual > complexes are not to blame for the staining some of us have run into ? > Or is that a parallel difficulty ? There's more than one way to make a mess. When some individuals used careful archival two bath fixing followed by selenium toner diluted in hypoclearing agents or water, red or pink stains occurred on the paper. After the second fixer, there's essentially no silver halide in the paper, and very little in the second fixer. To avoid that problem, prior to toning fixer may be removed with a hypoclearing agent and/or washing, an alkaline second fixer may be used or the toner may be buffered with borax/Kodalk. I preferred 2% Kodalk since KRST was stable for 6+ months when diluted in it even with fixer added. It wasn't stable in water or hypoclearing agent, especially if traces of fixer were present. As you know, Reticulation Master, I only use acid stop baths and acid hardening fixers (two bath) with film and paper to avoid other problems that frequently show up on the net. After hypoclear treatment, wash times are short. for film and paper to On Sun, 12 Mar 2006 19:00:21 GMT, Michael Gudzinowicz <m_gudzinowicz@verizon.net> wrote: >One old workaround advocated >the use of alkaline plain hypo as a second bath March 13, 2006, from Lloyd Erlick, Hey, who's old?! I'm working on it, though, as well as fat. I can't seem to add rich to that list... Well, "alkaline plain hypo" has been working for me in every bath, first and second, film and paper (but not bubble...). Maybe the term 'plain fixer' should mean a solution of thiosulfate and sulfite, and 'plain hypo', thiosulfate alone. In any case, the 'workaround' works fine. regards, --le Signature________________________________ Lloyd Erlick Portraits, Toronto. voice: 416-686-0326 email: portrait@heylloyd.com net: www.heylloyd.com ________________________________ > Maybe the term 'plain fixer' should mean a > solution of thiosulfate and sulfite, and [quoted text clipped - 6 lines] > email: portrait@heylloyd.com > net: www.heylloyd.com Workaround? There is no workaround with plain fixer or plain hypo. Preservatives, ph modifiers, and calgon or, are the workarounds: Preservatives for day after day, week after week, out of the bottle, into the bottle. Ph modifiers for retaining the emulsions integrity and allow for further improvement in integrity with added hardeners. Calgon or for cleaning up dirty water. All that's really needed is that thiosulfate ion. Likely It's attached only to sodium or ammonia because they are soluble in any usable portion and the two are compatable with any other chemistries which may be present. I use the stuff, S. or A, unadulterated; ph 6.8 and 7.6. The very dilute fix is used so voluminously as to cause archival results with a single one-shot fix. I've done the arithmetic. Dan >> Maybe the term 'plain fixer' should mean a >> solution of thiosulfate and sulfite, and [quoted text clipped - 23 lines] >The very dilute fix is used so voluminously as to cause archival >results with a single one-shot fix. I've done the arithmetic. Dan March 14, 2006, from Lloyd Erlick, Yes, I'm with you all the way. The workaround I was referring to came from a remark by Michael Gudzinowicz: "One old workaround advocated the use of alkaline plain hypo as a second bath". I was only remarking that I've been using this workaround for a long time. I don't really see how it's ...'around'... it seems easy and direct to me, not to mention cheap. regards, --le Signature________________________________ Lloyd Erlick Portraits, Toronto. voice: 416-686-0326 email: portrait@heylloyd.com net: www.heylloyd.com ________________________________ Perhaps I should used a different word. Using plain fixer as a second fixer works, however, that option like borax or other treatments requires one to use solutions and procedures that are _NOT_ mentioned in manufacturer's recommendations/instructions. Since adherence to product instructions may lead to problems, I consider alternatives that are not mentioned but get around the problems to be "workarounds" regardless of semantic nuances. The "problems" aren't new as a google groups search for "hypo selenium stain" will reveal. Kodak knew about inadequate fixing and acidic hypo reduction of selenium at the time when KRST dilution in acidic hypo clearing agent was recommended as the next step after acid fixing. >>>Maybe the term 'plain fixer' should mean a >>>solution of thiosulfate and sulfite, and [quoted text clipped - 47 lines] > net: www.heylloyd.com > ________________________________ >if the print is either completely fixer free or fixer saturated (both >are even distributions of fixer) differential staining (AKA uneven toning) >cannot occur. March 13, 2006, from Lloyd Erlick, In addition to uneven toning there is the problem of bright yellow stains appearing on prints. Michael Gudzinowicz has explained the cause. Very small deposits of stain appear yellow -- surprisingly bright yellow, at that. If more stain material (I didn't realize it was metallic selenium) is present it appears orange or red. I haven't seen any of this since I removed acid from my stop and fix. regards, --le Signature________________________________ Lloyd Erlick Portraits, Toronto. voice: 416-686-0326 email: portrait@heylloyd.com net: www.heylloyd.com ________________________________ On Fri, 10 Mar 2006 12:49:37 GMT, Michael Gudzinowicz <m_gudzinowicz@verizon.net> wrote: >If you are using an alkaline fixer, you _might_ get away with >this procedure, though people have complained of staining using >even that precaution. March 13, 2006, from Lloyd Erlick, I've been getting away with it for years. I eliminated acid from my darkroom years ago, and have never had a moment's problem. Zero stains on my prints. I would never claim perfection for any procedure, and no doubt there are workers who have had stains, but my long-term experience is that non-acid fixer permits selenium toning, without rinsing or any treatment of the print, immediately after the fixer. It is indeed a time saver. I think it's in "The Print" that Adams remarks that using 'plain fixer' as the second fixer in a two bath setup is a good way to avoid stains if the print is moved from fix to selenium toner with no rinse or treatment. I've simply changed to plain fixer for all fixing, film and prints. Adams publishes the formula for plain fixer in the Appendix of "The Print". I find it suitable for all my needs, and it is cheap and very quick to prepare. Plain fix: one liter distilled water (if you must, use tap water or whatever you like...), 160 grams sodium thiosulfate anhydrous or 250 grams crystalline, and 15-30 grams sodium sulfite anhydrous. (A tablespoon holds about 20-25 grams of sodium sulfite anhydrous.) It's not really plain, I suppose, but the sulfite allows a service life equal to any other fixer. I prefer sodium thiosulfate fixer because it has a lower capacity than ammonium thiosulfate based fix. My throughput is not huge, and I prefer to be able to use up a fixer and get rid of it rather than keeping it around until its huge capacity is exhausted by my few rolls. regards, --le Signature________________________________ Lloyd Erlick Portraits, Toronto. voice: 416-686-0326 email: portrait@heylloyd.com net: www.heylloyd.com ________________________________ very convincing. W. Krug and H-G Weide in Wissenschaftliche Photographie in der Anwendung (Leipzig 1972) suggest chromogenic development to form yellow image, which is very efficient in blue sensitive papers. Unlike other intensifiers, that method does NOT increase grain. The process can be repeated until satisfactory results are obtained. The authors believe that even single treatment will increase speed 2-2.5 times. Done twice will increase speed over 3 times. wash your film well, bleach in ferricyanide/bromide bath 1-3 min wash very well - 5 min develop in 20°C 5-10 min TSS, CD1 or CD2 or CD4 1.1 g sodium sulfite anh 1.0 g potassium bromide 1.0 g potassium carbonate anh 50 g calgon 2.0 g water to 1 l prepare fresh just before use add 0.75 g of benzoylacetaldehyde in 20 mL of dioxane. wash 10 min the image is formed by metallic silver and yellow dye. If you prefer less contrast, the silver part of an image can be fixed out. #The easiest and safest way would be to try scanning negatives since scanners #work better with "thin" negs. And what looks thin to human eye is sometimes #fine especially if you are using Tmax. # #If you want to go the wet route, make fresh rapid fixer, fresh Kodak Rapid #Selenium Toner 1+4 using Fresh Kodak HCA instead of plain water and another #bath of fresh HCA without toner. # #Wash the film, refix, go straight from the fixer into the toner and tone to #completion (probably 10 minutes) then rinse, treat with HCA and rewash and #finish as normal. # #This was mentioned by Ansel Adams in one of his later books. Need I add #that you should test all these procedures before committing irreplaceable #images to an untried process. It has the advantage that it is a permanent #intensification where most Mercury intensifiers (can you say TOXIC?) are not #permanent. Thanks for the input, all. I'll just have her try a shot of selenium, which she already knows how to handle. It appears I was thinking of the old mercury-based techniques, as I recall the effect was not permanent. I thought it was a commercial product, which would of course be long gone now; my memory was from the early 70's. Worst case, the photos CAN be re-shot. > Thanks for the input, all. I'll just have her try a shot > of selenium, [quoted text clipped - 7 lines] > > Worst case, the photos CAN be re-shot. There were a couple of variations of Mercury intensifiers,mostly in the redeveloper. Probably the one which was most widely used in general photography was Victor intensifier, a packaged product which was available for decades. Mercury intensifiers are exceedingly poisonous. There is no real need for them, other intensifiers are equally effective without the extreme toxicity and leave more permanent images so Mercury should be avoided and considered of academic intrest only. Monckhoven's Intensifier, a type of Mercury intensifier, is particularly hazardous because it contains both Mercuric chloride and Potassium cyanide. It has the peculiar property of simultaneously intensifying and reducing. The Cyanide redeveloper is also a very strong silver solvent so it tends to reduce the density of the lowest densities and intensify the higher densities. It was used mostly to sharpen up the dots in the old wet plate half-tone process. I can't think of any valid reason to have either Mecuric chloride or Cyanide in a modern photogaphic darkroom and lots of reasons not to have them. Signature--- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com If you have some sepia toner, you can use it i the same way that the bleach/redevelop in staining developer was recommended. This technique increases contrast far more than toning in selenium will. Jay >If you have some sepia toner, you can use it i the same way that the >bleach/redevelop in staining developer was recommended. This technique >increases contrast far more than toning in selenium will. I used Polytoner which is combination of selenium and sulfide and the increase in contrast was dramatic. So was the increase in apparent granularity. I don't recommend it for small format negatives. == John - Photographer & Webmaster www.puresilver.org - www.xs750.net > I used Polytoner which is combination of selenium > and sulfide and the increase in contrast was dramatic. > > John - Photographer & Webmaster > www.puresilver.org - www.xs750.net No bleach? I seem to recall having read some where that sulfide will in itself increase contrast. Selenium and Sulfur are very similar elements. Perhaps the KRST way is no more than a matter of convenience way? Dan >> I used Polytoner which is combination of selenium >> and sulfide and the increase in contrast was dramatic. [quoted text clipped - 6 lines] >Sulfur are very similar elements. Perhaps the KRST way >is no more than a matter of convenience way? Dan KRST works and can add a level of protection to the image but I'm sure that sulfide is a good deal more reactive. Also the brown tone of the image worked as a stain as well. Not exactly like a stain generated from the tanning action of a developer. Much more coarse. Reminds me of the time I used PMK to push APX25 to EI80. Boy was that a mistake ! == John - Photographer & Webmaster www.puresilver.org - www.xs750.net Well that and the smell, Dan! I can handle the ammonia odor much better than sulfide and since I tone in my darkroom I don't care for the fogging potential of sulfides in the air. Signaturedarkroommike > > I used Polytoner which is combination of selenium > > and sulfide and the increase in contrast was dramatic. [quoted text clipped - 6 lines] > Sulfur are very similar elements. Perhaps the KRST way > is no more than a matter of convenience way? Dan >Well that and the smell, Dan! I can handle the ammonia odor much better >than sulfide and since I tone in my darkroom I don't care for the fogging >potential of sulfides in the air. Ya know I've read all about this potential for fog but never have I seen a valid example. Has anyone run into this ? == John - Photographer & Webmaster www.puresilver.org - www.xs750.net > Well that and the smell, Dan! I can handle the ammonia > odor much better than sulfide and since I tone in my > darkroom I don't care for the fogging > potential of sulfides in the air. > > darkroommike I've made up the sodium sulfide solution used for the ST-1 test; the test for residual silver. I've not yet detected any oder; no oder at all. That smell I think must be caused by ph and preservative components added to off-the-shelf poly or plain sulfide toners. Kodak's Sepia Toner has sodium sulfide as the toner B part. No precautions with regard to oder, fumes, or fog. A little sodium sulfide goes a long way. The IPI suggests a 1:9999 dilution as a completely effective archival treatment of micro film. Given micro film's and B&W print paper's similarity I'd think it a good treatment for prints as well. How would one go about making S. Sulfide Smell. Were I to experiment I would want to be prepared. Dan > > > I used Polytoner which is combination of selenium > > > and sulfide and the increase in contrast was dramatic. [quoted text clipped - 4 lines] > > Sulfur are very similar elements. Perhaps the KRST way > > is no more than a matter of convenience way? Dan >very convincing. > [quoted text clipped - 29 lines] > > One may also redevelop in an alkaline solution of hydroquinone. Development is to completion so there is no requirement of accuracy in mixing this second developer. Sulfite will kill the stain, so don't use any. Just a teaspoon of carbonate and a teaspoon of hydroquinone in a pint of water should do the job. Hydroquinone is a staining developer in the catechol class. The two in fact have the same empirical molecular formula. It will add the stain to the originally developed silver. Graded paper or VC paper with blue or magenta filtering will print with increased contrast. Needless to say, this redeveloper is not to be reused. >#The easiest and safest way would be to try scanning negatives since >scanners [quoted text clipped - 24 lines] >#permanent. > |
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