Permanganate Reversal and Fixer Tip

[jpo3136b]

<p>One of the things I forgot to mention about a year ago was that I did have one set of negatives processed with permanganate reversal that I got to work. I was using the instructions provided by Ilford; but, I noticed that they seemed to be formulated for "thicker", older emulsion films. When I ran them with Pan F+, I noticed narrow tolerances. Alessandro had mentioned a couple of years ago that I needed to halve the permanganate in that recipe. I did. </p>

<p>But, there was one key point that I had not seen written down elsewhere: the fixer cuts the emulsion off of the film. When doing your tests to get permanganate reversal to work, expose the film to fixer sparingly. Because you can use a cold water rinse in the process, the "fixer" stage can be done (if I remember right) under white light. I only got it right after carefully dunking the emulsion in fixer briefly. By briefly, I mean a dip or two a few seconds at a time. </p>

<p>During this fixing, I remember seeing the emulsion and its image being eaten away. You have to know when to stop. The action I witnessed was very similar to what Ansel Adams described with learning to user Farmer's Reducer. </p>

<p>I mention this because until I violated the directions and skimped on the fixing, I never saw the process work right. If you follow those permanganate reversal directions to the letter, then often you will get nothing but a stripped acetate backing. The emulsion will be eaten right off of the film in the fixer stage. </p>

<p>Hypothetically, if the film were developed and stopped and dried; then it might stand to reason that the fixing could be done later, if the emulsion were re-soaked with cold water first. </p>

<p>If you had trouble getting permanganate reversal to work, too, you have my sympathies. I think those directions we often found from Ilford were leftovers semi-adapted to the newer, thinner films. I bet if you ran those directions on a fat thick piece of sheet film you'd have more than enough tolerance to never have to worry about eating off the entire image. </p>

<p>I don't have a scan of those scrap negatives, but I thought I'd share a description of getting this to work because I found permanganate reversal so frustrating to get right or working even once. Thanks. If any of you got it to work lately, please let us know. J.</p>

[larrydressler]

<p>Could you refer us to the original thread. I have a few Alchemist friends who would love to know some of this.</p>

[jpo3136b]

<p>Larry, I don't remember the thread. I corresponded a couple of times about it. Below, though, are the URLs to the directions from Ilford I was talking about. It's the same set of Ilford permanganate reversal directions that come up everywhere.</p>

<p>References:<br /> http://www.ilfordphoto.com/applications/page.asp?n=90<br /> has this PDF of directions on it:<br /> www.ilfordphoto.com/Webfiles/20061291034093.pdf<br /> Those are the Ilford Reversal directions I was referring to. If you look on page three, there is a step in there on second development and fixing: that's the fixer to watch. If you look at the time chart on page four, Ilford says to fix for five minutes. Don't. Observe as you fix. If you fix for those five minutes, you will sit there in white light and watch that emulsion melt right off of the film base.</p>

<p><strong>Fix for about 15 seconds.</strong></p>

<p>A minute might be too long. And when this emulsion melts off, of course: that's it. Image trashed.</p>

<p>I was using regular Kodak fixer or plain hypo for my trials; it didn't matter which; that fixer will eat it right off. Later I realized that this was a logical consequence of reversing; but, I cannot grasp a good explanation now. I remember that as soon as I realized I needed to skimp on fixer that I then supposed that fix could be almost completely eliminated from reversal developing; I had a hypothesis that this would make permanganate reversal one of the cheapest forms of development because a young kid with access to computers could use it without ever having to need an enlarger. Well, something happened and then I temporarily lost interest before running enough trials to prove it. I do know, though, that it was that fixer stage whose directions were flat out wrong.</p>

<p>Also, I remember now that one of the ideas that came up was that all of this was showing balance: the proportions of the times were important; that was why I suppose that the five minutes were too long; it's like a five minute time would have been good for a sheet film, but obviously not good for the thin roll film. Not only could I cut that fixer time, but I think I had a trial in there where the development times could also be cut.</p>

<p>Five minutes of fixing will rip that emulsion right off. I want to say a realistic time was like fifteen seconds of fix. Just enough of a splash to evenly coat the image. Then cold water rinse. Or dip and inspect and rinse; like a roll film or test strip version of a sheet film develop by inspection; but, with the materials you have and fixer.</p>

<p>In one roll, it came out really dark brown; another got me closer; it was as though this line of reasoning in the directions was telling us to max out development; then they hit you with this five minute fix. Really, I think that it's develop times have to be normal or over (never under); and then fix with care, if needed at all. Unproven, though. Only a couple iterations of this working.</p>

<p>Sorry. I only remembered this because I was laying around recovering from a minor ailment. I do not have good notes on hand. I know, though, that I have one strip of Pan F+ that I got to work to normal exposure levels. Watch that fixer. It will destroy all gains if used as the directions say.</p>

[jpo3136b]

<p>Their plan on development was to make the photographer develop the image to the max and then cut off the emulsion not needed with fixer. Except that the published time is way too long. As I read and re-read those directions, it occurred to me, somehow from the language, that this seemed like an old set of directions incompletely updated for the new product of the Pan F+.</p>

<p>So, I think develop as needed with whatever developer you want to use; but it is imperative that you be extra careful with that fixer. It will cut that thickness off right before your very eyes. If you run a test strip, you'll see. Run one test strip and stall it out in cold water right after the development stages. Run another into the fixer. You will see.</p>

<p>The whole process looks like the ugliest slime of fog when its wet. It doesn't look like a real, stable image until it dries out. When it hardens by air drying, it doesn't fade because of the touch of fixer (I think). The image is much more stable than an incompletely fixed regular positive image.</p>

<p>Alessandro Serrao had a tip in there for using something in water instead of one of the strong alkalines; there is another substitution possible; but I don't think it had any bearing on this fixer bit. Watch the fixer. I can't stress that enough. I was just shocked when I realized that it was as simple as defying the directions and not letting the fixer eat off the image. Test those fixer times. 15 seconds, max. Give that a spin.</p>

<p>I know I typed too much about this, but I want to emphasize this other point about the fixer: it might not be needed if you were good at guessing your development times. I thought that was a big deal. Fixer is pretty much a required ingredient for silver, as far as I know. So, I remembered that because it defied what I had been taught about sodium or ammonium thiosulfate; I had previously thought it was a necessary, required material to make a photo in silver film. If you could reverse and not need to cut the emulsion for exposure, then you could hypothetically make a picture without that critical material. </p>

<p>This led to some guessing on my part about if such a process was used in instant films; but, I am not a physical chemist of any kind at all; so, I could only suppose that kind of idea was outside of my pay grade.</p>

<p>Cut that fixer. Use sparingly. Defy the manufacturers directions. Everything else was close to right for test stripping.</p>

[jpo3136b]

<p>One more:</p>

<p>All this back then led to some guessing on my part about if such a process was used in instant films; but, I am not a physical chemist of any kind at all; so, I could only suppose that kind of idea was outside of my pay grade. I was sitting there, looking at those images and thinking about how thin all this was and how it seemed like it was close to those times from those 1960s films my grandma had left over one time from a Land Camera; and, well, I thought that somehow it looked like it might be close to what Land had thought up. The thinness of the emulsions against the times; and then there was that old tendency for those Polaroid films to have the super-fast (3000 ASA) film speeds; I really thought that something like this reversal might be close to a black and white instant picture if you put it in a plastic bag or on a fiber sheet of paper. Not today's fiber papers with the resin coating; that acrylic botches up all the old ways; but a homemade old-style Polaroid. I looked at that and wondered over it. I think there's something to it.</p>

<p>Part of the reason why was because all of the materials I was using would have been in vogue in the late 40s, early 50s. I was using that homebrew Q developer; I didn't need any Metol or Phenols for MQ or PQ. Those potassium ingredients are cheap; they'd be good choices commercially if you needed to make a mountain of the stuff. The hydroquinone was cheap; if you didn't need hypo, then you wouldn't have to worry about an imbalanced monobath in the instant film packet. So, I speculate. When I saw a trial I did one time with monobath developers, I thought, that's it; but, my monobaths flunked miserably when the water was just a touch too cold; those old Polaroids worked in a wider range of temperatures; almost to freezing. </p>

<p>Well, if an instant film was just a well-measured packet of shock-developed permanganate reversal in a plastic packet against a fiber-paper positive print: that'd be it, I think. All of those technologies would have been available at the time black and white instant films were invented. If I remember the story right, they were discovered in part by accident.</p>

<p>So that was my daydream about it. Permanganate reversals not only work, but if they were measured out right they could probably pop off a picture pretty quick under contained conditions. The reason why, again, was that the balance of times against materials was an important part of what this looked like to me. If you only need to develop and light fog to exhaustion, I bet a good physical photo chemist could calculate that. I'm not that skilled; but that was my guess about instant black and white films from playing around with permanganate reversals.</p>

<p>In my brown trials, if I remember right, I was using that potassium ferrocyanide (same as cyanotyping) for the oxygen. Oh, well, I will develop a roll soon so that I can send you some lab notes with times.</p>

<p>Cut that fixer. Use sparingly. Defy the manufacturers directions. Everything else was close to right for test stripping.</p>

[larrydressler]

<p>Oh sorry we have that I was wanting more personal results....</p>

[jpo3136b]

<p>Alessandro Serrao had the best pack of reversals that I'd seen here. He also had a tip for me about that substitution for the alkali.</p>

<p>I have found that old strip of film, Larry. It was done in HP5. I will recharge these batteries and pop a DSLR pic off of the laptop monitor in a couple hours or in the morning. The photos are just pictures of traffic, but you can see that the process was working.</p>

[larrydressler]

<p>I know him... Thanks.</p>

[peterbcarter]

<p>The thread seems to be here http://www.apug.org/forums/forum228/38437-b-w-slide-tried-true-process.html</p>

<p>He is using TMAX, which is a really 'tough' emulsion. PanF+ is the other extreme. If you are getting the results you say, go 1/4 strength and increase the time of the Bleach *and* clearing bath. I don't use TMAX because what makes it a great negative film does not enhance anything to do with reversals ; money not well spent.</p>

<p>The final fixing bath should never be a problem and I use Kodak's (with hardener) and my own based on Hypo. Your emulsion falling off is signs of things gone bad elsewhere.</p>

 

[peterbcarter]

<p>John, may I ask why you picked PanF+ for reversals? Although I have not used it, it may not be so reversal friendly.</p>

<p>I have had great success with Foma100, PX, UN54, Neopan 400. The Foma100 is about the best as it doesn't require any hypo in the dev (I use Dektol 1:1 on that). UN54 (only available in bulk) is a tie with PX (unavailable).</p>

<p>Here are some done with PX and Neopan 400 (my last roll of 120 is in there) http://www.flickr.com/photos/peterbcarter/sets/72157627520501875/ It is a mixture of 6x9 (120) and 35mm.</p>

<p> </p>

[jpo3136b]

<p>I had picked Pan F+ because I use it a lot and it was repeatedly mentioned in the web references I found. I think the basic idea was to use a slow, thick film to give yourself lots to work with.</p>

<p>Here's the photo. I can see why I quit messing with this now. I could get an image, but not a good enough image. If you look closely, its covered with specs. Also, I had some kind of drainage or flow problem around those rebate sprocket holes. "It'll work," but I was not skilled enough to get it to work well.</p><div></div>

[jpo3136b]

<p>One more. Interstate traffic from an overpass. It's an image. The pictures were DSLR of the film held up against a white curtain at the window. I want to say those specs are from the clinging of the permanganate dust; but, I don't know that for sure.</p><div></div>

[peterbcarter]

<p>I will explain the same problem with Dichromate (which I use). It uses chromium for the exchange and I just forget what the permanganate uses. The have the same reasons and cures.</p>

<p>Here are some reasons for the spots.</p>

<p>1) Not enough rinse between steps bleach and clear....carry over.</p>

<p>You will prematurely exhaust the clear. The clear is responsible to carry away all the chromium bits left over, which reside in the 'clear' sections of your image.</p>

<p>2) Not enough sulphuric acid, or spent bleach.</p>

<p>The acid is not just to provide a ph shift, it has to provide food for the reaction. You cannot use just any acid. It has to allow the dichromate or permanganate work unhindered and provide the other bits for a HO3 exchange.</p>

<p>3) not enough rinse before the second developer.</p>

<p>If the clear and other junk is not completely rinsed away, chrome gets left behind and baked in, on the clear spots of your image.</p>

<p>4) Dichromate bleach can use Sodium MetaBiSulphate or Sodium Sulphite, but permanganate can only use potassium metabisulphite. When using permanganate, the wrong one can give your results.</p>

<p>What is likely happening is you are getting busted on several counts. If I wasn't clear - rinse,rinse,rinse......</p>

<p>Use the weakest bleach you can use. It's not a good thing to watch your silver wash down the drain. You use enough when your 35mm leader (the end that the film is loaded on) is clear. There is not benefit to bleach any longer.</p>

<p>If you find that your images are too low in contrast, dev longer and / or stronger. Use a paper developer and don't waste time on the usual developers. Thus is a process that needs to turn most of the silver.</p>

<p>If you are not getting enough blacks, make sure you are using a strong paper developer for the second stage. You need to develop the remaining silver to completion.</p>

<p>You need to fix. A fix with a hardener is better. There are always dead halides that don't develop. Just like your negs, the film will become darker over time if not properly fixed.</p>

<p>You are getting something so you are on the right track.</p>

<p>Today I am doing about 10 rolls, but usually about 2 a week. All I do now is reversals and my xtol is getting lonely.</p>

[Mike Howard]

<p>John, I've done both FP4+ and Pan F+ from Ilford, with Ilford's instruction sheet, and have never had the problems you are describing with fixing. I always did the full 5 minutes in Hypam, even though the Ilford instructions state "optional". There is something else causing your issue, perhaps the sulfuric is at too high a concentration or your clearing bath is wrong?</p>

[alex_xaralampidis]

<p>Hello, I processed some plus x super8 7276 film in a recipe that I have tried a lot of times with different films, even with 7276. I used permanganate bleach and Agfa Neutol as first and second developer. Usualy I have Neutol WA (warm color) but that time I had Neutol NE (neutral color). Well, the process went fine until the re-exposure. The film looked as expected. Then I used the same developer for the 2nd time but after 6 minutes the developer came out black and the film was striped from all its emulsion. I was left with clear base!<br>

I have read somewhere that I should not wash after clearing but I don't undestand why. Have you any idea about what have happened?</p>

 

[peterbcarter]

<p>It looks like your bleach didn't work. The second developer is supposed to work to completion, as it did. The bleach is supposed to etch away at the developed silver, which gives you the image.</p>

<p>After you bleach, you can look at the film in daylight. You should see images on your film. If it still comes out too dark, adjust your developer strength and/or solvent.</p>

<p>Try doing some strip tests before wasting large amounts of film.</p>

[alex_xaralampidis]

<p>I made another test yesterday using Neutol WA as first and second developer, permanganate bleach (3gr/litre) and potassium metabisulphate clearing (20gr/litre) in other words my usual recipe. The only difference (which I overlooked the first time) is that it is summer (I made my previous succesful processes during the winter) and the temperature of my chemicals was around 24C.<br>

Well, the emulsion had melt and washed away during the final wash. <br>

My question is, does 4 degrees celsius can make such a difference? I will try again but at 18C and I will report.</p>

[alex_xaralampidis]

<p>I made another test yesterday using Neutol WA as first and second developer, permanganate bleach (3gr/litre) and potassium metabisulphate clearing (20gr/litre) in other words my usual recipe. The only difference (which I overlooked the first time) is that it is summer (I made my previous succesful processes during the winter) and the temperature of my chemicals was around 24C.<br>

Well, the emulsion had melt and washed away during the final wash. <br>

My question is, does 4 degrees celsius can make such a difference? I will try again but at 18C and I will report.</p>

[larrydressler]

<p>I may have an answer for this. PolypanF is a very thin emulsion film on a polyester base.</p>

[peterbcarter]

<p>The temp probably did make a difference. Not in activity, but to make the gel in the film softer. I use dichromate which is gentler, and reduce the strength by 1/4 to cut down the amount of acid. I would rather wait longer than see all the silver go down the drain.</p>

[alessandro serrao]

<p>Hi folks, long time no see!<br>

It's been quite a while since I last reversed a b&w emulsion. I almost forgot everything. You guys re-ignited my interest again in trying once more.<br>

I've found by trials and errors that 18°C works best with a permanganate bleach though probably it's because other parameters and the 18°C finding was a mere coincidence. Who knows? I'm not a chemist at all, I like to play with various chemicals, though I'm a little worried experimenting with dichromate and thiocyanate, the latter because of the potential cyanide gas release (thiocyanate + acid).<br>

So I opted for hypo as the silver halide solvent.<br>

@John: I didn't know that was actually the fixer to cause emulsion shrinkage and peeling off. I always pinpointed this problem to the huge pH shift from a very alkaline first developer to the very acidic bleach. <br>

I'd like to shorten as much as possible the process because more than 10 steps are a bit akward to do in my basement :-))<br>

I had the same problems John reported with PanF+. Emulsion very fragile.</p>