Photo Forum / Film Photography / Darkroom / June 2004
pure ammonium thiosulfate fixer
|
|
Thread rating:  |
Travis C. Porco - 19 Apr 2004 21:42 GMT Dear Readers--
I have a question: is there anything wrong with the use of pure ammonium thiosulfate as a fixer for pyro-developed film? (I use 35mm Tri-X mostly). I have some of the "60% ammonium thiosulfate" made by Formulary.
Is it possible to use borax instead of sodium metaborate in mixing a fixer? How much? Anchell & Troop list a recipe with sodium metaborate, but not borax.
Thanks kindly.
Jorge Omar - 19 Apr 2004 22:30 GMT AFAIK you can just replace metaborate with borax (same quantity) in a fixer.
Jorge
> Dear Readers-- > [quoted text clipped - 8 lines] > > Thanks kindly. Travis C. Porco - 28 Jun 2004 19:01 GMT Dear readers--a new question:
I got three rolls of old Panatomic X. With film so old (~70s) I expect severe fogging; the film was supposedly stored in a cool closet, but not refrigerated. Any suggestions on how to best process it? The box says shoot at EI of 32, and use 5 minutes in D-76. Should I treat it any differently because it is so old? BTW I'm not shooting anything critical with it; it's just for the fun of it.
--travis
Also, thanks again everyone for the fixer suggestions:
>AFAIK you can just replace metaborate with borax (same quantity) in a >fixer. [quoted text clipped - 13 lines] >> >> Thanks kindly. Ken Nadvornick - 28 Jun 2004 20:11 GMT > I got three rolls of old Panatomic X. With film so old (~70s) I expect > severe fogging; the film was supposedly stored in a cool closet, but not > refrigerated. Any suggestions on how to best process it? The box says > shoot at EI of 32, and use 5 minutes in D-76. Should I treat it any > differently because it is so old? BTW I'm not shooting anything critical > with it; it's just for the fun of it. Hi Travis,
Seems that I also have some old Panatomic-X. It's a nearly complete 100-foot (30.48-meter) bulk roll of 35mm perforated, stamped "Develop before: Sep 1963."
While I fully intend to bulk load a few frames and test it just for fun, I, too, will be interested to read any replies to your inquiry.
Good luck with your rolls.
Ken
Gary Beasley - 28 Jun 2004 21:29 GMT >> I got three rolls of old Panatomic X. With film so old (~70s) I expect >> severe fogging; the film was supposedly stored in a cool closet, but not [quoted text clipped - 13 lines] > >Good luck with your rolls. Slower emulsions are much more durable than the high speed stuff, I'd try a roll at the recommended times just to see. You may have some perfectly good film or need just a little benzotriazole to damp the fogging.
>Ken Mark A - 28 Jun 2004 21:22 GMT > Dear readers--a new question: > [quoted text clipped - 8 lines] > > Also, thanks again everyone for the fixer suggestions: If you have a new question, start a new post, do not reply to an old one.
I recently developed some Panatomic-X that was exposed 20 years ago, and the image lost about 2 stops of exposure. Additional development increases the middle and high values, but does nothing for the shadows. So I would give it some extra exposure.
Richard Knoppow - 29 Jun 2004 01:04 GMT > Dear readers--a new question: > [quoted text clipped - 6 lines] > > --travis I would test a clip of the film. The emulsion is probably pretty stable but heat during storage is the enemy. One of the main causes of fog in old film is a continuation of the processes known as ripening. Modern films (I mean anything made for the last 50 years) have substances added to the emulsion to eliminate or at least substantially reduce the amount of after ripening and thus extend the shelf life of the film. Refrigeration also tends to slow down or stop this process. The other cause of fogging is the accumulation of exposure from cosmic rays. This is speed dependant so does not affect slow films much. Make some bracked test exposures and develop _normally_. Do NOT use an anti-fog agent. If the film is only slightly fogged the effect will be a loss of speed, the images will print well. Benzotriazole is the best anti-fog for old film but the effect is still a loss of speed, the difference is that the shadows will be clear with the anti-fog and have an overall fog without it. There is little or no difference in the resulting printed images providing enough exposure has been given.
You may find the film performs normally with no special treatment.
> Also, thanks again everyone for the fixer suggestions: > [quoted text clipped - 15 lines] > >> > >> Thanks kindly. Neural fixing baths work as well as alkaline baths. A neutral or slightly alkaline bath results when either Sodium or Ammonium thiosufate is used with a small amount of sodium sulfite. The use of sulfite in a fixing bath will insure against overall stain from developer reaction products from carried over developer. For either salt about 5 to 10 grams/liter of working solution is enough.
 Signature --- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com
Jorge Omar - 29 Jun 2004 02:33 GMT I've found that by increasing the sulfite content of an alkali fixer (could it be neutral?) to 30g/liter, the pinkish base of Kodak films is completelly gone. It is carried mostly by first wash (Ilford method).
Jorge
"Richard Knoppow" <dickburk@ix.netcom.com> wrote in news:2kbq0qFirpsU1 @uni-berlin.de:
> Neural fixing baths work as well as alkaline baths. A > neutral or slightly alkaline bath results when either Sodium [quoted text clipped - 3 lines] > carried over developer. For either salt about 5 to 10 > grams/liter of working solution is enough. Dan Quinn - 29 Jun 2004 10:08 GMT RE: Jorge Omar <jorgeomar@ieg.com.br> wrote
> ...the pinkish base of Kodak films is > completelly gone. Kodak's films are not the only ones with a pinkish base. On under fixing Pan F+ I've obtained a pinkish base. Do all under-fixed films exhibit the same when under fixed? Dan
John - 29 Jun 2004 11:58 GMT > Kodak's films are not the only ones with a pinkish base. On >under fixing Pan F+ I've obtained a pinkish base. > Do all under-fixed films exhibit the same when under fixed? Dan Nope. Depends on the dyes used in their manufacture. Films like D3200 use a different sensitizing and AH dyes and usually look gray (like fog) when underfixed.
Regards,
John S. Douglas, Photographer - http://www.darkroompro.com Please remove the "_" when replying via email
Richard Knoppow - 30 Jun 2004 00:41 GMT > > ...the pinkish base of Kodak films is > > completelly gone. > > Kodak's films are not the only ones with a pinkish base. On > under fixing Pan F+ I've obtained a pinkish base. > Do all under-fixed films exhibit the same when under fixed? Dan The pink color in T-Max is from residual sensitizing dyes which are bound to the gelatin. Kodak says its an indication of underfixing but, since thiosulfate and fixer reaction products can also be bound to the gelatin, its possible the fixing is complete. Sufite wash aid tends to free bound ions by two means: it adjusts the pH of the gelatin to above its isoelectric point where the charges in the gelatin tend to repel the bound ions rather than attract them; and it acts as an ion exchanger, displacing them from the gelatin. Since the same forces which bind the thiosulfate and reaction products also bind the dye the dye will be removed. The isoelectric point of most photographic gelatin is slightly on the acid side of neutral. Treating the emulsion in an alkaline or neutral bath will bring the ph to above (more alkaline) the isoelectric point. When an alkaline or neutral fixer is used the emulsion will leave the bath in this condition (pH above the isoelectric point) which is one reason it will wash faster than it will after an acid fixer. However, it is not simply the acidity of an acid fixer which tends to retard washing. Most (but not all) acid fixers contain a hardener composed of Potassium Aluminum Sulfate, AKA white alum or just alum. The alum, over a range of pH, is an efficient binder of ions to the emulsion. It is primarily the alum in hardening fixing baths which retards washing. However, the alum loses its abiility to bind thiosulfate and silver complexes to the gelatin when its pH becomes neutral or alkaline. At neutral pH the hardening action is preserved, at alkaline pH the hardening is lost. The hardness of the gelatin has no effect on wash rate. Fixing baths made with Potassium chromium sulfate (Chrome alum) must be much more acid than those using white alum but the wash rate is no worse than an acid non-hardening bath. The chrome alum does not act as a binding agent as white alum does. Unfortunately, chrome alum fixing baths have short lives and are unsuitable for general use. Gelatin is what is called "amphoretic", that is it does not have a pH of its own, rather it takes on the pH of the last bath its been in. However, there are some pH specific properties, the most important one being the isoelectric point. On the acid side of this point the electrical charges in the emulsion are one way, on the alkaline side they are the other way. Also, the swelling of the emulsion is least when its pH is brouht near its isoelectric point. Low swelling also increases wash rate because it minimises the path ions must follow in diffusing out of the emulsion. There is some evidence that Ammonium thiosulfate fixer washes out faster than sodium thiosulfate fixer but this rate is also dependant on the factors discussed above. So, whatever kind of fixer you use a neutral sulfite bath will increase wash rate and is good practice. Ammonium thiosulfate fixers ("rapid fixers") tend to be less sensitive to accumulated silver and other substances (bromide or iodide) from the emulsion so have greater capicity for completing the fixing process. They are considerably more tollerant of accumulated iodide so they are very suitble for use with fast films. It should be understood that the conversion of the unused silver halide from a non-soluble form to a soluble form is not a simple reaction. Rather it takes place in stages although they are continuous. Since it takes a lot of thiosulfate to make the conversion there must be a lot of free thiosufate ions in the fixer. As more silver is dissolved more of the thiosulfate ions become unavailable. It is the concentration of dissolved silver which is the limiting factor in the ability of a fixing bath to fully convert the unused halide to a form which will wash out. Partly coverted halide is not fully soluble or it may be bound to the image silver or the gelatin. Ammonium fixer will continue complete fixing at silver levels at which sodium fixers no longer fully fix. The use of two successive fixing baths helps insure that the fixing conversion process is completed so that the unused halide is fully washed out. The use of a buffered sulfite wash aid will help to remove some incompletely converted silver complexes by unbinding them from the image silver and gelatin.
 Signature --- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com
Richard Knoppow - 30 Jun 2004 00:17 GMT > I've found that by increasing the sulfite content of an alkali fixer > (could it be neutral?) to 30g/liter, the pinkish base of Kodak films is [quoted text clipped - 13 lines] > > carried over developer. For either salt about 5 to 10 > > grams/liter of working solution is enough. A sulfite after fixing bath will do the same thing. I think you may be getting something like a combination of a fixing bath and wash aid with that much sulfite. I use Kodak Hypo Clearing Agent, the residual dye comes out in the wash aid which turns a sort of lavender color remeniscent of old fashioned ladies underwear.
 Signature --- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com
Donald Qualls - 29 Jun 2004 04:39 GMT > Dear readers--a new question: > [quoted text clipped - 4 lines] > differently because it is so old? BTW I'm not shooting anything critical > with it; it's just for the fun of it. Panatomic-X that's only 30-ish years old probably won't have much fog -- the slower the film, the less fog it will pick up over time from either thermal or cosmic ray sources. You will, however, most likely find it's lost about one stop of speed, so you may wish to expose it at EI 16 or 12 rather than 32 (or 25, which was pretty common).
If you develop in HC-110 instead of D-76, you can further reduce the likelihood of fog problems, with similar grain and sharpness. Generally, Dilution B times are shorter than D-76 times, but not a bunch shorter; with this film, you'd probably gain by going to Dilution H (half strength of Dilution B) or even Dilution G (1:119 from USA syrup concentrate). For Dilution H, I'd give 125% of the D-76 time, and for Dilution G, I'd be tempted to let it stand without agitation (after the first minute of constant agitation) for forty-five minutes to an hour.
I should mention, however, that I've never actually shot Panatomic-X, much less developed it -- however, HC-110 is one of my regular developers and I've used it in the dilutions above for other films, including microfilms with similar characteristics to Tech Pan.
 Signature I may be a scwewy wabbit, but I'm not going to Alcatwaz! -- E. J. Fudd, 1954
Donald Qualls, aka The Silent Observer Lathe Building Pages http://silent1.home.netcom.com/HomebuiltLathe.htm Speedway 7x12 Lathe Pages http://silent1.home.netcom.com/my7x12.htm
Opinions expressed are my own -- take them for what they're worth and don't expect them to be perfect.
Lloyd Erlick - 19 Apr 2004 23:43 GMT >Dear Readers-- > [quoted text clipped - 8 lines] > >Thanks kindly. apr1904 from Lloyd Erlick,
from:
The Negative by Ansel Adams, page 192, isbn 0-8212-1131-5, (this is the hardcover New York Graphic Society edition of the early 1980s.)
"I use the Kodak F-6 formula for all fixing baths. The addition of Kodalk or borax serves to reduce the acidic odor without affecting the peformance of the fixer."
Adams is saying that Kodalk and borax are interchangeable in fixer formulas. They can be considered equivalent weight-wise. In a fixer, there really wouldn't be such a thing as 'too much borax'. There's no point in too much, though, it's a waste.
regards, --le
Richard Knoppow - 22 Apr 2004 20:17 GMT > Dear Readers-- > [quoted text clipped - 8 lines] > > Thanks kindly. I am not a believer in alkaline fixers. As far as effectiveness of fixing the pH does not matter. If you don't want to use acid fixer neutral fixer works just fine and will preserve the stain image as well as an alkaline fixer. Be careful not to confuse the desired stain image with overall staining, which is not desirable. Pyro negatives should be pretty much stain free in the clear areas and have a proportional stain in the image. I think many of those who complain of lack of stain are really looking at overall staining. Fixer needs to have sodium sulfite in it both to protect the thiosulfate from oxidation and to prevent staining from carried over developer which will remain active in neutral or alkaline fixing baths for long enough to cause problems. Sulfite is slightly alkaline anyway. You don't need much, perhaps as little as 5 grams per liter of working solution. Most acid fixers have about 15 grams per liter but need it because the sulfite prevents decomposition of the thiosulfate by the acid. Sodium metaborate is a poor buffer despite Kodak's claims so Borax is actually a better choice if you really want to increase the pH. Tri-X is similar to T-Max in that it needs longer fixing than most other films. Check the clearing time and fix for three times that time. Use a two bath system to insure complete fixing, fix in each bath for half the total time. Ammonium thiosufate is not very stable in powder form so it usually supplied as a 60% liquid concentrat.
 Signature --- Richard Knoppow Los Angeles, CA, USA dickburk@ix.netcom.com
Travis C. Porco - 23 Apr 2004 00:33 GMT Thanks kindly to you and the others who replied; I may try it both without the sulfite and with it and see what happens. Is there a "standard" recipe for ammonium thiosulfate/borax/sodium sulfite?
Also: Anchell & Troop are down on sodium thiosulfate. If you mix up a developer with ammonium thiosulfate, sodium metaborate, and sodium sulfite, it's still got a lot of sodium in it. Is it just good to have less sodium, or is it good to have the ammonium present, or does it just plain not matter?
Final question. I've seen some bottles of Formulary TF-4 with a thick layer of precipitate on the bottom. Does this indicate that the bottle is absolutely no good, or could it be redissolved?
Thanks again!
>> Dear Readers--
>> I have a question: >> is there anything wrong with the use of pure ammonium >thiosulfate as a >> fixer for pyro-developed film? (I use 35mm Tri-X mostly). >I have some of the >> "60% ammonium thiosulfate" made by Formulary.
>> Is it possible to use borax instead of sodium metaborate >in mixing a >> fixer? How much? Anchell & Troop list a recipe with >sodium metaborate, >> but not borax.
>> Thanks kindly.
> I am not a believer in alkaline fixers. As far as >effectiveness of fixing the pH does not matter. If you don't [quoted text clipped - 23 lines] > Ammonium thiosufate is not very stable in powder form so >it usually supplied as a 60% liquid concentrat. Patrick Gainer - 23 Apr 2004 01:25 GMT > Thanks kindly to you and the others who replied; I may try it both without > the sulfite and with it and see what happens. Is there a "standard" recipe [quoted text clipped - 10 lines] > > Thanks again! That's the way it comes. Shake it well if you're only going to mix part of it. When you dilute it 1+3 or more, it clears up.
John - 23 Apr 2004 06:06 GMT >Is there a "standard" recipe >for ammonium thiosulfate/borax/sodium sulfite Just mix F24 and leave out the bisulfite.
Regards,
John S. Douglas, Photographer - http://www.darkroompro.com Please remove the "_" when replying via email
John - 23 Apr 2004 14:34 GMT >>Is there a "standard" recipe >>for ammonium thiosulfate/borax/sodium sulfite > > Just mix F24 and leave out the bisulfite. Kodak's F-24 Fixer Water @ 125F 750ml Sod. Thiosulfate 240g Sod.Sulfite 10g Sod. Bisulfite 25g Water to make 1.0L
Regards,
John S. Douglas, Photographer - http://www.darkroompro.com Please remove the "_" when replying via email
Dan Quinn - 23 Apr 2004 23:11 GMT > Thanks kindly to you and the others who replied; I may try it both > without the sulfite and with it and see what happens. Is there a > "standard" recipe for ammonium thiosulfate/borax/sodium sulfite? The most direct route to what you are after is a one-shot sodium thiosulfate fix mixed at time of use. I don't work with pyro but from my reading the S. Thio. fix is much used. The ph of Photo. Formulary S. Thio has tested 6.8. Try one ounce of the anhydrous in whatever volume of solution needed. The one fluid ounce of A. Thio suggested still stands. The nice thing about S. Thio. is it's keeping qualities. A bottle with tight lid should keep for years. To boost it's or A. Thio's ph to about 10 add a 10th part of S. Sulfite. I've worked with S. Thio. straight and with S. Sulfite and with A. Thio. straight. I use fixer, film or prints, one-shot; always fresh fix. I've determind the amount of S. Thio. needed with Pan F+ to be 15 grams. The one ounce suggested for Tri X should be plenty; so much silver, so much chemistry.
> Also: Anchell & Troop are down on sodium thiosulfate. If you mix up > a developer with ammonium thiosulfate, sodium metaborate, and sodium > sulfite, it's still got a lot of sodium in it. Is it just good to have > less sodium, or is it good to have the ammonium present, or does it > just plain not matter? Sodium in no way will spoil a fix. It makes for a slower fix. Some of A&T must be taken guardedly.
> Final question. I've seen some bottles of Formulary TF-4 with a > thick layer of precipitate on the bottom. Does this indicate that > the bottle is absolutely no good, or could it be redissolved? TF-4 is a B. Troop formulated alkaline RAPID, A. Thio., fix. I'd be very wary of those bottles. I think that must be sulfer on the bottom. With the lid off gently warm and see what happens. Dan
Dan Quinn - 24 Apr 2004 22:57 GMT > > Thanks kindly to you and the others who replied; I may try it both > > without the sulfite and with it and see what happens. Is there a [quoted text clipped - 9 lines] > lid should keep for years. To boost it's or A. Thio's ph to about > 10 add a 10th part of S. Sulfite. Correction to last sentance: I checked my records and found that a 1% S. sulfite plus 3% S. Thio. Penta solution has a ph of 9.6. Dan
> I've worked with S. Thio. straight and with S. Sulfite and with > A. Thio. straight. I use fixer, film or prints, one-shot; always [quoted text clipped - 20 lines] > With the lid off gently warm and see what happens. > Dan Norman Worth - 23 Apr 2004 07:04 GMT If you just want to fix a few films or prints, 180ml of 60% ammonium thiosulfate in water works fine. But mix it just before use, it deteriorates quickly. Sodium sulfite is used as a preservative. I like the Kodak F-34 formula as a non-hardening fixer.
Water 700 ml Ammonium thiosulfate, 58% 185 ml Sodium sulfite, anh. 10 g Sodium bisulfite 8.4 g Water to make 1 l
It was originally intended as the fixer for Eastman 5247 motion picture film, but it works very well for regular film and prints. The pH is only 6.5 - near neutral - so washing should not be a problem. If you must have an alkline fixer, 200 ml of 60% ammonium thiosulfate plus 20 g of sodium sulfite per liter will probably do, but I think a fixer should be slightly acid to make the preservative work properly and to prevent unintended stains.
> Dear Readers-- > [quoted text clipped - 8 lines] > > Thanks kindly.
|
|
|