Using exhausted fixer remover(?)

Hi all,

I’ve been using the fixer remover provided by my school, only to realize that it’s expired (12 month shelf life). It’s the Sprint Fixer Remover, which is a aqua marine blue when fresh (exhausted when yellow/green). In the past, I’ve washed my film with water for 1 minute with agitation after fixing, and 15 minutes after the fixer remover. With the most recent rolls I’ve developed, I’ve used the Ilford washing method (5 inversions of fresh water, empty, 10 inversions, empty, and then 20 inversions, empty), and I do that right after fixing, as well as after using fixer remover. My question is, should I check all the negatives that I’ve processed for residual fixer, and re wash them in trays, or is it fine because of washing? Does the color indicator in the Sprint fixer remover dictate completely it’s effectiveness? I’ve been fastidious about my washing, so I would imagine that would midicate any residual fixer?

Thank you

I've never used anything to remove fix. I just wash with water, more or less following the Ilford method.

Search PhoTrio for "hypo clearing agent" for more information than you will ever need.

You can use a simple solution of S. Sulfite; commercial HCA adds a pH buffer and a sequestrant for dealing with hard water.

IIRC a working solution is 1 tablespoon in a quart of water. Use and discard, the same bath can be used for a work day but the stuff doesn't keep in the open.

I find the value of HCA is that it removes the last of the purple from TMax films.

S. Sulfite in buckets is available in the swimming pool aisle of Walmart. Also from Artcraft Chemical.

Washaids improve the efficiency of washing, and permit you to reduce the washing time and water volume required. When combined with a water minimizing washing system like you are using - which might otherwise be "just enough" washing - they increase the safety factor. Your using the regime twice, so that increases the safety factor too.
As you can effectively wash the film without a washaid, so it isn't necessarily disastrous that your washaid may have lost effectiveness.
But it never hurts to have an effective one instead.

xX_M@m!yaL0v3r_UXx said:

It’s the Sprint Fixer Remover

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This is a bit of an oddball mix, really. Its MSDS gives the following constituents:
Sodium metabisulfite
DTPA potassium salt
Ethylene glycol
Glutaraldehyde
Formaldehyde

The latter two are hardening agents. Modern film doesn't require these. Formaldehyde tends to evaporate and is a health concern, but the quantity present in this product is so low I wouldn't bother about it. Some people find the quasi-sweet smell obnoxious; I personally don't really mind.

Why the glycol is there, I don't know. I can sort of see its use if this product is primarily intended for use with paper (particularly fiber based) instead of film, which I assume is in fact the case. Wash aids, after all, serve very little real purpose with film. When used on FB paper, the glycol may help the paper to dry flat as it'll remain a little more supple, since glycol is a humectant. What the archival implications of such a treatment are, I don't know. Again, it's not really necessary, like the hardener, even on paper.

The DTPA is a sequestering agent and I assume it's meant to remove remaining silver, although proper fixing would achieve the same. It would also capture stuff like iron, manganese and maybe calcium from the wash water. But this would only be useful if this product is used as the final wet bath the paper (or film) goes through, and I doubt I'd recommend that.

The metabisulfite looks to me the main ingredient in terms of actual fixer removal as it makes washing more effective. A simple solution of plain sulfite or even (sodium) carbonate will achieve the same, with varying degrees of speed/effectiveness.

None of this is required for film, and is essentially superfluous. The usefulness of some of that mixture for paper is equally debatable. For RC/PE paper it's as unnecessary as for film, and for FB paper the hardener is usually not necessary either - there are exceptions, but in those cases, a separate hardening step will usually make more sense as it can be done at the right moment in the cycle and not in necessarily combination with the after-fix wash (e.g. after toning).

Overall this looks like a product in the "because we can" category, to be frank. Feel free to use it; in my own darkroom it would probably end up at the back of a cupboard, forgotten and collecting dust.

Glutaraldehyde, like formaldehyde, is a strong biocide. It is used in very small quantities for selective cleaning in aquariums. The latter two seem to have almost identical properties and perhaps complement each other. The fact that it has glycol makes me think that this is actually a final rinse/stabilizer.

xX_M@m!yaL0v3r_UXx said:

... Does the color indicator in the Sprint fixer remover dictate completely it’s effectiveness? I’ve been fastidious about my washing, so I would imagine that would midicate any residual fixer?

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A few years ago I took a medium format photography class at my local university, and at that time the school was using the Sprint Fixer Remover. After the semester was over, I continued to use it for a while at home. More recently, I was asking the instructor about some photography chemicals and she said the school no longer uses the Sprint Fixer Remover. One reason they dropped it was because she thinks the color indicator is not reliable. I have noticed it is sometimes hard to decide if the solution is still blue, or if it is getting a little bit green(?) Also, every bottle of the Sprint Fixer Remover I've used soon had big chunks of crystalized precipitate in it, which did not improve my confidence in the product, so I switched to other products.

The university lab now uses Heico Perma Wash. I have not yet had a chance to try the Heico wash aid, myself.

In the university darkroom we were making prints on fiberbased paper, and for FB prints, a wash aid is probably a good idea, especially if water is a scarce resource where you live. As others have mentioned, it may be less of a benefit for film. Ilford's Information Leaflet for "hobbyists, students and schools" titled, <PROCESSING YOUR FIRST BLACK & WHITE FILM> does not mention using any kind of wash aid when processing film using Ilford's Rapid Fixer.

xX_M@m!yaL0v3r_UXx said:

Hi all,

I’ve been using the fixer remover provided by my school, only to realize that it’s expired (12 month shelf life). It’s the Sprint Fixer Remover, which is a aqua marine blue when fresh (exhausted when yellow/green). In the past, I’ve washed my film with water for 1 minute with agitation after fixing, and 15 minutes after the fixer remover. With the most recent rolls I’ve developed, I’ve used the Ilford washing method (5 inversions of fresh water, empty, 10 inversions, empty, and then 20 inversions, empty), and I do that right after fixing, as well as after using fixer remover. My question is, should I check all the negatives that I’ve processed for residual fixer, and re wash them in trays, or is it fine because of washing? Does the color indicator in the Sprint fixer remover dictate completely it’s effectiveness? I’ve been fastidious about my washing, so I would imagine that would midicate any residual fixer?

Thank you

Click to expand...

Welcome to Photrio!!

When I started using the Jobo processor, I stopped using Hypo Clearing Agent and instead use 8 500ml rinses. That has worked well for me.

@Rudeofus reached out to me with some additional comments that I'd like to share here. I hope he doesn't mind. This is stuff I didn't know or realize when I posted earlier, so all credits go to him for this additional info, but I take responsibility for any mistakes in relaying it.

The formaldehyde, due to its antibacterial properties, would more logically be part of a product aimed at color materials (i.e. a final wash, conditioner or stabilizer). Indeed, we see formaldehyde and precursors in such stabilizer products (at least in the past) and also as part of the prebleach bath in professional E6 chemistry.

The glycol might be present to prevent the indicator from dropping out of solution. I don't know what indicator dye is used, but I'm going to guess it's thymol blue, which will start to flip over from blue to yellow as pH drops below 8 or so. Thymol blue is insoluble in water, but I suppose it would dissolve in ethylene glycol alright.

The DTPA potassium salts will serve to deal with water hardness, but also capture iron ions and this might come in handy in putting a step on Fenton reaction. The DTPA may also serve as a buffer to keep the solution at >pH8 so that the indicator actually works as intended - and I suppose the high pH also helps to wash the emulsion as it'll help the gelatin to swell. When fixer is added to a final wash of this sort, the low pH of the fixer (which are mostly acidic, and the sulfite in fixer will oxidize into acidic sulfate anyway) will throw the high pH of the Fixer Remover product down, which will be evidenced by the indicator turning towards green and ultimately yellow.

Nicholas Lindan said:

commercial HCA adds a pH buffer and a sequestrant for dealing with hard water.

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So this is indeed what seems to be the case here.

All of the above is to give some additional insight; what it doesn't change is that there's no really good reason to use a product like this to treat film with, in particular B&W. I can sort of see the benefit in using it on home-processed E6 film where no formaldehyde precursor was present in a bleach prebath or on very old C41 emulsions (pre 1990s) that required a stabilizer for long-term dye stability. But in those instances, a final bath consisting of water with a few drops of formalin would be equally effective.

With @Rudeofus' additional information in mind, I suspect that the intent behind this product was to make a kind of 'silver bullet' wash aid that would do something useful regardless of what kind of material you used it on. At the same time, this also means that regardless of the material, you'd also be using stuff on it that isn't really necessary - although this mostly wouldn't hurt, I'm sure.

If we look back a couple of decades: film was unhardened and needed (always acidic) hardening fixers, which were notoriously difficult to wash out. These were the times, when HCA was needed for film. I could imagine some dinosaurs still using HCA from back then, and some other dinosaurs teaching younger ones to use HCA for film. This is how HCA continues to be a product offered and actually sold to us.

We have it on record from PE somewhere, that HCA is no longer necessary for film fixed with modern rapid fixers (pH from 5 up). It's a waste of money and material for all practical purposes, but it also doesn't hurt the film, so people who want to continue to use it can do so without detriment.

Wash aids really only have a place now in processing fiber-base papers. There, they still prove useful for ensuring complete washing.

Doremus

Until recently, Kodafix was probably the largest selling Kodak fixer for small volume users. It was a hardening fixer.
HCA still speeds up washing, and adds extra safety margin for those who might be trying to minimize water use.

MattKing said:

Until recently, Kodafix was probably the largest selling Kodak fixer for small volume users. It was a hardening fixer.
HCA still speeds up washing, and adds extra safety margin for those who might be trying to minimize water use.

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Matt, do you mean for FB paper only, or other materials?

john_s said:

Matt, do you mean for FB paper only, or other materials?

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For film too.
Not for RC paper.

Kodafix is already one of the "newer" hardening fixers with borates, which could operate at pH 4.8 instead of 4.5. This was AFAIK the first generation of fixers, which could be washed out without HCA.

Rudeofus said:

Kodafix is already one of the "newer" hardening fixers with borates, which could operate at pH 4.8 instead of 4.5. This was AFAIK the first generation of fixers, which could be washed out without HCA.

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Are borates in fixer to improve hardening?

I vaguely remember reading something about the benefit of borate in fixer many years ago, but I couldn't find the article again. I think it was in the rec.photo.darkroom site that was really good a long time ago but went to pot more recently.

john_s said:

Are borates in fixer to improve hardening?

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If you raise pH of a hardening fixer, it's hardening component, which is typical some form of Aluminum Sulfate, tends to form an Aluminum Hydroxide precipitate (sludge). This seems to happen at pH 4.5 or above and forced hardening fixers to be formulated as very acidic. H. D: Russel at Kodak discovered, that the addition of borate ions to such a fixer would raise that pH limit to 4.8. At this pH fixer would wash out much easier than at pH 4.5.

@Rudeofus what is the ideal pH if the speed of washing out would be the only criteria?

miha said:

@Rudeofus what is the ideal pH if the speed of washing out would be the only criteria?

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According to Bill Troop (who talked to countless Kodak researchers in their haydays) it's "the higher the merrier". However, rapid fixers have this pungent Ammonia smell at pH > 7, and according to PE a pH above 6.5 doesn't offer enough benefit to justify that smell. That's why the most modern fixers (read: fixers for color processes) all run at pH 6.5, where they act fast, wash out fast and are mostly odorless. This, of course, implies that no hardener is needed.

I use the simple fixative formula from the ECN-2 process - ammonium thiosulfate and some sulfite and metabisulfite. Neutral, with pH 6.5 - maybe not the fastest, but 2:00 min suits me perfectly.

Rudeofus said:

According to Bill Troop (who talked to countless Kodak researchers in their haydays) it's "the higher the merrier". However, rapid fixers have this pungent Ammonia smell at pH > 7, and according to PE a pH above 6.5 doesn't offer enough benefit to justify that smell. That's why the most modern fixers (read: fixers for color processes) all run at pH 6.5, where the are fast, wash out fast and are mostly odorless. This, of course, implies that no hardener is needed.

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Thanks.

Rudeofus said:

If you raise pH of a hardening fixer, it's hardening component, which is typical some form of Aluminum Sulfate, tends to form an Aluminum Hydroxide precipitate (sludge). This seems to happen at pH 4.5 or above and forced hardening fixers to be formulated as very acidic. H. D: Russel at Kodak discovered, that the addition of borate ions to such a fixer would raise that pH limit to 4.8. At this pH fixer would wash out much easier than at pH 4.5.

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Most of us now are using rapid fixers without hardener, such as Ilford Hypam for film and paper. It does contain boric acid as well as acetic acid. I was wondering what the function of the boric acid is, given that there is already acetic acid there, as well as bisulphite, so three acidic components. I would guess that acetic acid would be cheaper than boric acid, so there must be a reason. Maybe it has a hardening function, in addition to its pH?

john_s said:

Most of us now are using rapid fixers without hardener, such as Ilford Hypam for film and paper. It does contain boric acid as well as acetic acid. I was wondering what the function of the boric acid is, given that there is already acetic acid there, as well as bisulphite, so three acidic components. I would guess that acetic acid would be cheaper than boric acid, so there must be a reason. Maybe it has a hardening function, in addition to its pH?

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I did notice, that neutral fixers (see all the official published color chemistry formulas) seem to have no need for borates. The only explanation I have for borates in non-hardening fixers are their specific buffering behavior at pH 5-5.5. You could probably get the same with more Acetic Acid, but it would smell.

I am not aware of any hardening property of borates.