Fixer sinking to the bottom (in the factory bottle)?

[grain elevator]

Hello all,
This is the second time I've had problems with a freshly opened bottle of fixer (different fixers, in date, smell and look ok). Namely underfixed film. Weirdly even though the clearing test was a somewhat reasonable time for TMY-2, 3 minutes. I fixed for twice that, at around 19°C and with plenty of agitation.
My new hypothesis is that the ammonium thiosulfate may have sunk to the bottom of the bottle and I mixed a very weak working solution. I'm pretty certain separation can happen with working solution, and very certain I mixed it well this time. But is it conceivable that it happens to concentrate? I thought it was such a concentrated solution that such a thing were not possible, short of something falling out of solution. But it's the only explanation I have. Opinions, alternative explanations, suggestions?

 

[Michel Hardy-Vallée]

Fixer doesn't sink to the bottom: once it's in solution, it stays there. How did you determine under-fixing? Using a test?

Other things to consider: is the fixer expired (check the date)? are you using the correct dilution? Ilford's can be used both at 1+4 or 1+9, but you have to adjust time.

Is your water quality something to consider? Is your thermometer reliable? I know it happened to me once, and what I thought was 20C was in fact 16C. Check it against another thermometer—the odds that both would be equally broken are pretty low.

 

[Lachlan Young]

This sounds like you mixed to the wrong dilution. Fresh, film strength rapid fix should clear film in about 60 seconds - even T-Max.

 

[grain elevator]

Thanks for the quick replies!
Underfixing was obvious when the film was dry, and I then tried re-fixing a (should be-) clear piece of the leader, which confirmed it. I wasn't at my brightest though and tried the re-fixing in the same working solution. Here it gets even weirder. It re-fixed fairly quickly. Then I proceeded to re-fix all the films I had processed the day before (in the same fixer, smart me), and in parallel used another piece of leader to monitor the progress. And that time it was muuuch slower again. The second piece may have been exposed to more light in the meantime, perhaps that would explain that part. Or it may have been from one of the films which was a bit fogged (evenly, probably that roll was on several flights with me), I can't be certain now.
The fixer is in date. Bottle was sealed until a few minutes before fixing. Dilution 1+4 should be hard to mess up, and I didn't, it was among my first thoughts and I visually checked how much was missing from the bottle.
These films were pretty free of the dreaded pink dye, just the faintest hint, I don't think it visually obscured my observations in this case, although it may have made the initial clearing time (the test with unprocessed film) seem longer.
Just compared thermometers again. The one I used reads higher than my other one, but not that much. About one °C. If it was actually 18°C, that difference wouldn't explain the issue it I think.
Water quality is ok for drinking, fairly hard though.
The mystery remains...

 

[pentaxuser]

From what you are saying none of this should have happened. What was the make of the fixer?

pentaxuser

 

[MattKing]

How are you agitating the film when it is in the fixer?
When I fix film, I do a clip test every time. With the film and fixed in the regularly agitated tank, I have a clip of film beside it in a small graduate with some of the same fixer, which is also regularly agitated. I time how long it takes the clip to clear, and then continue the film fixing for at least that length of time again.
I use continuous rotary agitation for the tank, but regular inversion agitation works fine.
I re-use my working strength 1 + 3 Kodak Rapid fixer several times - less than the 32 rolls per litre capacity recommended by Kodak, but still several times.
I use T-Max film for the clips, because they take as long or longer to fix than any film I photograph with.

 

[grain elevator]

The fixer is Kodak Tmax, made in Germany, I assume by Tetenal. I assumed it to be a rapid fixer, as the name suggests it works with the Tmax films, although the words "rapid" or "ammonium" are no-where to be found on the bottle.
I agitated as per Ilford instructions, Paterson twirly stick at first, then inversions, about 10 sec per minute, erring on the side of more agitation. Otherwise I pretty much do what you do, MattKing. Won't be re-using this liter of working solution though.

 

[Michel Hardy-Vallée]

Based on the MSDS, it's a rapid fix: https://parallaxphotographic.coop/wp-content/uploads/2016/09/T-Max-Fixer.pdf

I'm thinking maybe your agitation isn't vigorous enough. With developer, I'm careful and try to be consistent, but for stop and fix, I go instead for max energy. My shake is a combined twist and throw, so that all the liquid sloshes against the walls of the tank. I do 30s continuous initially, then 5s every 30s.

 

[MattKing]

Kodak Alaris doesn't sell T-Max fixer on this side of the Atlantic. With respect to liquid fixers, there is reference in some materials to Polymax T fixer, and more regular access to Kodafix liquid fixer and Kodak Rapid Fixer. Polymax T fixer and Kodafix liquid fixer have hardener included, whereas hardener is optional with Kodak Rapid fixer.
The instructions I see recommend 1 + 3 dilution for films, not 1 + 4, but that may not apply to your fixer, and shouldn't make a large difference anyways.

 

[pentaxuser]

Thanks for the reply. It would seem that unless you have used the wrong dilution then there has to be something else going wrong. Getting the wrong dilution is of course possible for all of us but I get the impression that you are experienced in processing which suggests that wrong dilution is less likely

Even if you got the dilution wrong, none of what you have done explains the sign that fixer has sunk to the bottom. Clearly you have seen something at the bottom which as far as I know, should not be there in new fixer

We suspect Tetenal who make chemicals for Kodak are having problems and this just adds to my concern about problems that Kodak may be experiencing with Tetenal and about when this might stop

pentaxuser

 

[MattKing]

Even if you got the dilution wrong, none of what you have done explains the sign that fixer has sunk to the bottom. Clearly you have seen something at the bottom which as far as I know, should not be there in new fixer

I don't think that the OP actually saw this. I think grain elevator (the OP) was wondering if that might have been what happened, and as others have posted, it really can't happen that way.
A question to the OP - are there any signs of damage to the bottle?

 

[grain elevator]

I don't think that the OP actually saw this. I think grain elevator (the OP) was wondering if that might have been what happened, and as others have posted, it really can't happen that way.
A question to the OP - are there any signs of damage to the bottle?

You're right, the unmixing and sinking idea was just a hypothesis to explain what I experienced. I'm dismissing it.
No signs of damage. The concentrate smells mostly of acetic acid, not sulfur-y like oxidized fixer, and is clear, not yellowed.
The stuff is indeed called Tmax fixer, and 1+4 is the recommended dilution.
I will agitate even more next time, but that the clearing test went ok without much agitation at all leads me to believe that's not it.
I don't suppose we can solve this. I might do some experiments with saved TMY-2 leaders.

 

[MattKing]

Developer contamination can also affect fixer - but it takes a lot!

 

[grain elevator]

Developer contamination is probably not it, the fixer working solution was fresh, and I filled the tank twice with water in place of a stop bath.
I just did some clearing tests, the results are not entirely conclusive. Freshly mixed fixer is a bit faster, no surprise there. Takes a bit longer than a minute for sure. I find it very hard to see when TMY is cleared, because the pink dye also starts washing out with the drops of fixer I put on first, but at a slower rate than fixing, so that a difference between the drops and surrounding area remains for many minutes. When exactly it is only dye and no more silver isn't entirely obvious to me.

 

[Doremus Scudder]

Grain elevator,

You still haven't mentioned how you determine that your film is underfixed. If you are seeing unfixed opaque areas in just a few places or overall cloudiness or whatever would be my question.

And, you should know that fixing film a bit longer than 2x the clearing time won't hurt it at all. I use 3x +10% or so for all my film. There's no absorbent base under the film's emulsion for fixer to leach into and get trapped. So, if needed, extend your fixing time to allow complete fixation.

Back to the first point: if your film just has areas of underfixing, the film is touching something somewhere and not letting the fixer in. If there's overall opaque fog, then either fixing times are too short, the fixer is exhausted or it has degraded through oxidation/sulfurization to the point where it is no longer active enough.

That said, if you get a decent clearing time and you agitate properly and the film isn't touching itself or anything else, it should fix properly.

I might question the three-minute clearing time for TMY. I don't know T-Max fixer at all, but all my rapid fixers clear TMY in under one minute. That might be an indication that the fixer is old and has lost activity.

Best,

Doremus

 

[grain elevator]

Doremus,
The films were evenly underfixed. I've mentioned above that I confirmed underfixing with a (nearly) clear piece of the film. I immersed it partly in fixer and the immersed part cleared further.
The accuracy of the three minutes clearing time is subject to the limitations I've found using the method with TMY, as I wrote in the post above. But it's definitely at least a minute at ~19°C. TMY does take much longer to clear than other films IME.

 

[MarkS]

Rapid fixer concentrate will go bad if unused (although it takes years). The sulfur will precipitate out of the ammonium thiosulfate and leave pale yellow sludge in the bottom of the bottle. There's no mistaking it- and no bringing it back.
Is this your situation? If so, throw the dead fixer out, buy fresh fixer, and re-fix your negatives.

 

[RalphLambrecht]

Hello all,
This is the second time I've had problems with a freshly opened bottle of fixer (different fixers, in date, smell and look ok). Namely underfixed film. Weirdly even though the clearing test was a somewhat reasonable time for TMY-2, 3 minutes. I fixed for twice that, at around 19°C and with plenty of agitation.
My new hypothesis is that the ammonium thiosulfate may have sunk to the bottom of the bottle and I mixed a very weak working solution. I'm pretty certain separation can happen with working solution, and very certain I mixed it well this time. But is it conceivable that it happens to concentrate? I thought it was such a concentrated solution that such a thing were not possible, short of something falling out of solution. But it's the only explanation I have. Opinions, alternative explanations, suggestions?

when I see sulfur particles have fallen out of the fixer solution, I just filter the fixer concentrate through a coffee filter and use as normal; works for me but, I also use the two-fixer processing since I had a few underfixed negatives a few years back and it never happened again.

 

[bunip]

I also have experienced precipitates in some Tetenal's fixer but this happened once after some months from bottle's disclosure and once with an one year old (from purchase date) unopened bottle. I used it anyway and had to conclude it wasn't working properly even if times were adjusted according to the film clearing test times. Everything turned right with a fresh bottle. It is strange as at the same time I used a 9 years old and opened Agefix that worked better.

 

[DeletedAcct1]

when I see sulfur particles have fallen out of the fixer solution, I just filter the fixer concentrate through a coffee filter and use as normal

That way you will not filter colloidal sulfur, which remains in suspension and it will ruin your film.

 

[Michel Hardy-Vallée]

Meanwhile, I suggest, for the sake of experiment, to use a different brand of fixer with the exact same procedure.

Ilford Hypam is pretty much the same as their Rapid Fixer and costs a little less. Both works exceedingly fine.

 

[foc]

These films were pretty free of the dreaded pink dye, just the faintest hint

The pink usually means exhausted fix.
Here is a note from Kodak processing notes.
IMPORTANT: With KODAK PROFESSIONAL T-MAX Films, fixer will be exhausted more rapidly than with other films. If negatives show a magenta (pink) stain after fixing, fixer may be near exhaustion, or fixing time is too short. If the stain is pronounced and irregular, refix the film in fresh fixer.

 

[Doremus Scudder]

Doremus,
The films were evenly underfixed. I've mentioned above that I confirmed underfixing with a (nearly) clear piece of the film. I immersed it partly in fixer and the immersed part cleared further.
The accuracy of the three minutes clearing time is subject to the limitations I've found using the method with TMY, as I wrote in the post above. But it's definitely at least a minute at ~19°C. TMY does take much longer to clear than other films IME.

Then, (assuming you diluted the fixer correctly) either your fixing times are too short or your fixer has lost activity (through use or age). There are really no other explanations. Laws of physics and all that...

Easy to fix either. (Pun intended)

Doremus

 

[pentaxuser]

Then, (assuming you diluted the fixer correctly) either your fixing times are too short or your fixer has lost activity (through use or age). There are really no other explanations. Laws of physics and all that...

Easy to fix either. (Pun intended)

Doremus

The Op quotes the fixer as being freshly opened and in date so only leaves his mistake on dilution. Not impossible but everything he says indicates a faulty fixer. He say it is Kodak TMax fixer made in Germany so he presumes Tetenal which does seem likely. In the event that this is a faulty fixer and one made by Tetenal I'd say it is worth the OP's time to alert his stockist and find out if it is definitely Tetenal and take it from there

pentaxuser

 

[removedacct1]

I’m curious how the OP defines “clearing time”: does he mean he’s watching for the unreduced silver to clear, or does he mean the time it takes to remove all of the pink dye? That pink dye is notoriously difficult to remove from TMY by fixing - I find that at least half of it washes out in the final washing.
Which is to say, that if you are judging the efficacy of your fixer by how completely it removes the pink dye in TMY, then you’re looking at the data wrong. That said, if there is still significant pink dye left in the film after a proper washing (20 minutes without wash aid), then that indicates insufficient fixing.

Lastly, I suggest finding out how much mineral content there is in the water used to mix fixer, and if it’s really high (op suggested he has very hard water) then acquire distilled water (or equivalent) to make fix with. If it takes three minutes to actually clear TMY (the unreduced silver) with freshly made rapid fixer, somethings not right, and I would suspect water quality may be interfering with fixer performance.