Super Fix

rowland_mowrey · October 2, 2004

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Moderator's note: Before handling the individual

components, mixing or using them you should, for your own safety and that

of anyone nearby, completely familiarize yourself with the minimal safety

and health precautions outlined in the MSDS (Material Safety Data Sheet)

which should be readily available from the manufacturer or supplier.

In my opinion, if you're unwilling to take this minimal first step, don't

even bother with the rest. As a former OSHA safety and health inspector

the most commonly heard phrase from supervisors and employers after a serious

work-related injury or fatality was "Well, we'd been doing it that way for

20 years and nothing had ever happened before!"

Most of all, beware experts and experienced people. They tend to have

forgotten what it was like not to have known a thing. Take responsibility

for your own safety and health.

Lex Jenkins

Here is the exact formula and other details of the super fix that I

outlined in the thread on stop vs wash.

Formula:

Ammonium Hypo solution 200 ml/l

Sodium Sulfite (anh) 10 g/l

Ammonium Thiocyanate 10 g/l

Thiourea

10 g/l

As mixed the pH was 7.8 at 22.3 deg C. I adjusted it to 6.6 at 22.6

deg C with about 12 ml of 28% acetic acid. As mixed, it has a faint

ammonia odor, but after the pH is adjusted, it has no odor of

ammonia. The pH range of this fix should be about 6.3 - 6.7.

Test:

I compared it to F5 using Ilford HP5 plus film. At 22.6 deg C, the

film is cleared by the F5 in 5 mins and appeared fully fixed in 10

mins. The super fix cleared the film in 25 seconds, and fully fixed

it in 50 seconds. (it appeared completely fixed in the first 30

seconds but I let it go for the full 50 seconds)

After washing, the super fixed film appeared to be clearer with less

retained reddish dye, but since the film had not been developed, this

may be an artifact of the test.

Notes and precautions:

With proper washing, the archival properties of the film should be

normal. Toxicity and other factors should be similar to photographic

fix baths plus that of other baths which contain thiocyanates and

thiourea. Fixes of this type are used in stabilization processes and

rapid access processes, and image degradation can result, but that is

probably due to the fact that neither of these processes supply

adequate washing.

Excessive immersion time in this fix may bleach out lighter tones in

the film, as reported in the literature for other fix baths.

I have not tested this specific formula for paper, but I intend to

and report results at a future time. I expect that the fix will have

to be diluted by about 1:10 for papers.

I have not tested this with current color films or papers.

Therefore, until I do I cannot recommend it as there may be some

effect on the current dye set.

Ammonia, Thiocyanates, and Thioureas are powerful fogging agents

(well, so is any Thiosulfate for that matter), so be sure not to get

any of this solution into your developer and clean up well.

Observe all precautions for these chemicals as given by such experts

as Susan D. Shaw et al.

Ron Mowrey

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silent1 · October 2, 2004

Ron, can we presume an additional line for "Water to make 1 liter?"

I like this -- your film will be fixed by the time you finish the first inversion cycle! Have you tested for capacity, or on T-grain film? Any idea of shelf life?

rowland_mowrey · October 2, 2004

Don;

All ingredients are in g/l or ml/l as noted above, so you need no additional line in the formula.

Just start with a convenient amount of water and make sure that the final volume is exactly 1 liter when everything is added.

Keeping should equal any conventional fix. There is nothing exceptional in this mixture. Fix solutions like this have been known for a long time. They do contain more hazardous chemicals as you see, and are more expensive.

I would suggest for uniformity sake that you give more than one agitation cycle, with higher agitation.

I have just run tests with paper, and found that the paper is so colorless that I could not judge fixation times at all well. Based on what I saw, I would hesitate to post a time value.

I also placed strips cut from prints on Ilford Multigrade IV paper in the F5 and super fix over dinner, so they went for almost 1 hour. I saw no visible effects of bleaching of low, mid, or high densities after this treatment. I did not dilute these two solutions, so they were at the original 'film' strength for the paper tests.

I'll keep testing and give more data later.

Ron Mowrey

edward_zimmermann · October 2, 2004

"<cite>Here is the exact formula and other details of the super fix</cite>"

Your super fix looks clever.. The main interesting question might be "washing time" but that's easiest enough to test for..

"<cite>that I outlined in the thread on stop vs wash.</cite>"

Gosh, I missed that thread.. from the archives it looks like it was a load of fun..

rowland_mowrey · October 2, 2004

Gentle beings;

I've been thinking of adding something to this thread, and decided to go ahead.

Here is are some factoids never mentiond (AFAIK) in any other generally available photographic publication. Maybe in the SPSE Journal or patents ~grin, but not in books that you can just go into the store and buy. Like, well, any good book containing formulas.

Fixing agents such as thiourea, thiocyanate, thioethers, and hypo are not additive, they are synergistic. This means that if you add two of them together in solution, the activities do not add, they multiply! Add 3 and they cube, or something like that.

This is the key to designing a superadditive or hyper active fix or blix.

Putting more than one fixing agent into a fix makes the solution go into hyperdrive and this is what is taking place in this solution.

Another thing not generally known is that thiocyanates and thiourea are much more stable than hypo. Therefore it is theoretically possible to design a fix that does not decompose if you just leave out hypo and use thiourea and a thiocyanate. Wow, a fix that does not sulfurize.

In addition, many thiol and thioethers are fixing agents or accelerators and are often proprietary. If you don't believe me, look on the bottles of concentrates for E6 pre-bleach, bleach, and fix for examples. (I really don't know where they put the darned stuff now days)

Another fact that is really weird, is that KI (potassium iodide) and KF (potassium fluoride) accelerate fixing. Now, this is counter intuitive, but it does indeed work. Halides should slow down fixing, but they don't and the mechanisms of all of this are not really understood. Being counter intuitive makes this patentable. But then, I know that.

There is a price to pay, literally and figuratively. The chemicals are much more expensive, and more toxic, and dangerous to use. If you don't believe me, read the MSDS as Lex suggests. But if you NEED the SPEED, then I assure you that these work. And, some of them are in use today in E6 and C41 for examples. (again read the bottles)

I caution you about this chemistry. Lex has a good point in his forward to this thread. I thank him for it.

Anyhow, I thought I would bring some less well known facts to the fore to show that there is lots of R&D lurking out there still to be utilized. Much of it cannot be commercialized due to cost or toxicity. OTOH, progress is being made in fixing chemistry.

I want to stress that I don't advocate the use of toxic chemistry. Stay within the limits suggested by the MSDS and you should be safe.

BTW, the thols and thioethers are harder to get but some are much less toxic. I know of one that is totally harmless. Its only problem? It is 100% non-biodegradable. Pity, but it fixes silver faster than anything you ever saw. If we used it, fixes would be very stable, very fast, and the compound would begin to build up in the environment.

R&D on Fixing and Blixing goes on, but is often not published. It is either not known or ignored by the current writers or publishers.

Ron Mowrey

lex_jenkins · October 2, 2004

BTW, only a little *informed* paranoia is necessary.

I recall that as a kid the first time I heard of cyanide was in one of Ian Fleming's "James Bond" novels, which I was allowed to read at far too impressionable an age (when I should have been reading the Hardy Boys or, at worst, Huck Finn). I think it was "Thunderball" - in which one of the baddies does in his fellow crewmembers with cyanide (and is then, in turn, done in by a double-crossing fellow baddie - shiv into the brainpan from under the chin; be careful with whom you shake hands).

For the next several years I was paranoid of any word containing "cyan" including the knob labeled "cyan" on the television. I don't care how badly the teevee got out of adjustment, no way was I touching *that* knob. Even if touching the knob wasn't poisonous, adjusting it might spread deadly "cyan waves" throughout the room. I mean, when you're standing outside the room or house, looking in on people watching teevee, they're all... blue... and they look hypnotized, like they've been drugged by... too much cyan.

As a teenager training for the upcoming Fort Worth Regional Golden Gloves bouts I wouldn't even jog in the Trinity River bottom behind the gym on Jacksboro Highway because the long-abandoned American Cyanamid plant was down there. I didn't know what an "American Cyanamid" was or what they made or did and I wasn't taking any chances. I waited 'til I got home and jogged in the choking dust along my rural backroads, risking being hit by dumbasses in pickups who thought it was funny to drive within a breath of missing joggers and bikers.

Yup, that was *much* safer than that "cyan" stuff.

reuben_c · October 3, 2004

Yup, that was *much* safer than that "cyan" stuff.

So in other words, you said "cyanara" to it all? (heh heh heh)

Ron; speaking of patentable things and proprietary trade secrets, I read somewhere that there are some chemicals that are added to developers for the sole purpose of hampering reverse engineering. These chemicals are supposed to make it difficult to do analysis of the developer to find out what active chemicals went into it.

Can you share anything about that practice, and the kind of chemicals that are used? I find the idea of that kind of skulduggery to be fascinating.

andre_noble4 · October 3, 2004

One minute vs. five minutes on the fix time is not a big deal for me. Unless this F1x fixer is commercially available pre-mixed I'll pass. I'm too lazy to measure and mix that out.

edward_zimmermann · October 3, 2004

The main issues with Ammonium Thiocyanate are that under extreme heat, strong oxidants or acid it can release cynanide through decomposition. This, however, is hardly different from Potassium Hexacyanoferrate(III) [Ferricyanide] which we, without much hawing or insecurity use in many of our bleaches (including Farmer's Reducer). Even the (II), yellow salt, is a mainstay of home chemistry for the Prussian blue..

Realize it or not.. But Ammonium Thiocyanate is probably ALREADY in many of our darkrooms... It's, for example, the main active substance in Agfa's "<cite>Sistan</cite>" stabilization product and I've yet to hear a single cry of panic and worry worry about its use... The old rapid stabilization process too used Ammonium Thiocyanate to stabilize the image-- which was not really (and was not intended to be) archival fixed.

rowland_mowrey · October 3, 2004

Reuben;

AFAIK, the prepackaged formulas are just about equal to those developed by R&D teams with modifications for convenience in packaging. I believe that Lowell Huff mentioned some that his company uses during the milling of ingredients in another thread.

EK adds sequestering agents and drying agents such as calgon and sodium silicate to prevent precipitation in hard water and to help preserve the packaged dry stuff from moisture. The liquid kits are designed to be 'self-preserving' due to their makeup.

All ingredients are packaged under a dry inert atmosphere to prevent aerial oxidation.

Thats about all I can add.

Other notes;

I forgot to mention that NaCl (table salt) and Sodium Sulfite are good fixing agents but only at very high concentrations. In fact D76 is a monobath for chloride papers. If you place an exposed sheet of chloride paper into D76 you get a weak image and the paper is just about completely fixed out. (this, of course will vary from paper to paper so you may get different results than I did)

The KI, KBr and KF listed above are fix accelerators only under certain conditions.

A problem with such synergistic fixes (just as with mixed developing agents in developers) is that you can exhaust one ingredient before another, thereby drastically affecting the activity of such a fix (or developer (metol-hq for example)). If you increase concentration of the auxiliary fixing agents, you have to be careful or the activity of the fix can decrease, not increase. This is also counter intuitive.

These are just some additional facts that those of you interested in the chemistry of fixation might appreciate. BTW, there is an entire group at KRL working on bleaches and fixes. This has resulted in a new generation of E6, RA and C41 bleaches and fixes such as the type III bleach for C41. There was a blip in R&D a few years back due to the death of one of EKs great experts in bleaching and fixing. But, I hasten to assure you that his death was not due to the chemistry. It was natural causes.

Ron Mowrey

edward_zimmermann · October 3, 2004

In addition to speed--- or perhaps nearly more important--- of interest is capacity. Could be not tweak things with some of the accelerators-- or is your super brew already what you consider the "balance"--- to get a predictable and reasonable capacity and speed. Tricks like 2-stage fixing etc. are just "double protection" to try to keep mistakes at arm's length given that an insufficiently fixed print, just as a poorly washed one (and I would suspect that here faster fixing leads to faster washing or, de-facto, a reduction in insufficient washing) leads to poor image stability.. on the other hand.. having some rest thiosulfate it seems (see Sistan) seems to protect the silver..

On the topic of fixing.. I spoke with Agfa about RA (Rapid Access) fixers and they felt that there was no problem (beyond the high cost) of using them with other chemistries, including B&W. These fixers have been designed to act faster and reduce the fixing of C-41 films to under halftime. I have a few boxes of the stuff and have been planning on doing some tests with paper..

rowland_mowrey · October 3, 2004

Edward;

Wash times are NOT reduced! Please follow guidelines for washing and test your prints for silver and residual thiosulfate. The outward diffusion of dissolved salts is still limited and requres a definite time with a definite flow of water as you will find in all processing instructions.

This formula is not an optimum, but just an economical starting point to supply you all with a glimpse into what can be done with fixing chemistry.

Some have claimed to be experts at fixing, or to have the ultimate knowledge about it. Well, no one does, not me, not them. At EK, that team mentioned above has one of the best claims to such knowledge. I'm just publishing something I dabbled with here about 20 years ago and just got around to doing again.

Others at EK can do far better, I would guess. But then, that is their story, not mine to tell if it even ever gets told.

Ron Mowrey

edward_zimmermann · October 3, 2004

"<cite>Wash times are NOT reduced!"</cite>

Why not? I don't quite understand.. With standard fixers, including rapid fixers, the shorter the time needed to fix an image the less time is needed to wash the print. This have been empirically proven time and again and is the basis for the Ilford method of fixing papers using "film strength" fix. With a turbo-fast fix, if the Ilford studies are correct, I would expect that little of the salts would be absorbed into the fibres and this would allow for a very very fast wash.

"<cite>Please follow guidelines for washing</cite>"

What guidelines... ?

"<cite> and test your prints for silver and residual thiosulfate. </cite>"

Of course!

rowland_mowrey · October 3, 2004

Edward;

The current minimum wash times reflect the time necessary for chemistry to diffuse out of a coating. Using a more rapid fix still requires diffusion outward of the fix ingredients and silver complexes. This value has a minimum which was already achieved with the current rapid fixers. Using a more rapid fix still requires that the chemistry be removed by a wash which simply cannot be shortened any more than it is except by raising temperature which increases swell and softness regardless of the process.

This is my opinion based on my current knowledge of wash rates and diffusion.

If the thiourea or thiocyanate complexes of silver are larger, less soluable or diffuse more slowly, a fact I don't posess, then wash may actually be longer.

Hope that helps.

Ron Mowrey

georg_kern · October 3, 2004

To end the confusion: Edward is talking about paper, and Rowland about film (mainly).

rowland_mowrey · October 3, 2004

Georg;

Thus far, I have mainly experimented with film as noted above. However; I believe that wash times will still remain the same for film and paper as they are for the current rapid fixes, due to the limit in the rate of outward diffusion of the chemistry.

Only appropriate tests will tell the user what is suitable.

Ron Mowrey

lowell_huff1 · October 4, 2004

Why would anyone want to mix their own rapid fixer from raw materials?

Why thiourea and thiocyanate?

We manufacturers know the safest, most efficient, most effective formulas. Our fixers clear film in twenty second or less, work equally in machines and hand tanks and have extended shelf lifes which are ready to use at dilution. Please tell me why?

garrylewis747 · October 4, 2004

>We manufacturers know the safest, most efficient, most effective >formulas.

Speaking personnally- NO YOU DON'T!

rowland_mowrey · October 4, 2004

Lowell;

Actually, you have a very good point.

OTOH, if you believe in it, why does your company and many others offer individual chemicals to the hobbyist so that they can scratch mix chemicals?

The reason is summed up as follows: in spite of the logic in your statement, there are experimenters out there; you don't offer the exact formulas that each user wants; and also Gary Lewis has a point as well.

The bottom line, I guess, is that there has always been such a market and it seems that there always will be as long as conventional photography endures, regardless of what you may think.

I love to tinker with both B&W and color processing solutions. How can I criticize someone for doing what I like to do myself?

But, again, I understand the logic in your point as well.

And, I have formulas for even faster fixes, but I'm not prepared to publish them. Really, who needs something that keeps forever and fixes in 15 - 20 seconds? Right?

Ron Mowrey

rowland_mowrey · October 4, 2004

Hmmm, Garry, I owe you an 'r' so here it is.

Sorry.

Ron Mowrey

edward_zimmermann · October 4, 2004

"<cite> And, I have formulas for even faster fixes, but I'm not prepared to publish them. Really, who needs something that keeps forever and fixes in 15 - 20 seconds? Right? </cite>"

I do!!

rowland_mowrey · October 4, 2004

Edward;

I understand your feeling, but you have to realize two things. Uniformity can be an issue at such short times, and I am not ready to publish the formulas. In any event, I think that the practical limit is going to be around 1 minute total fix time.

Ron Mowrey

lex_jenkins · October 4, 2004

I tend to agree with Lowell here. Even if you *could* make something cheaper *and* make it better* than the commercial version, can you also avoid the safety hazards entailed in making the stuff?

For example, for years I've reloaded my own centerfire ammunition. In some cases it's cheaper than commercial loads, especially when I load pistol rounds in bulk for plinking.

In other cases I can tailor a rifle round for far better accuracy than any commercial load.

And I can load up my own cap and ball black powder revolver. There's no other way to shoot the thing.

But make my own gunpowder or primers from scratch?

You gotta be kidding me.

So despite my DIY tendencies I'd have to be awfully motivated to homebrew my own darkroom chemistry when perfectly good stuff is readily available very affordably. And the manufacturer has already undertaken most of the risk. Brewing up RodinX (Rodinal and Xtol) is about as far as I'm likely to go.

Now, if commercially made photochemistry disappears, yeh, I might consider the scratch-brew route.

Or I might just take up painting again.

rowland_mowrey · October 4, 2004

Lex;

Interesting comparison, however your analogy is more akin to suggesting that someone synthesize his / her own hypo, thiourea, and thiocyanate as an example, or making hydroquinone or metol.

There is a similarity between making gunpowder and chemical synthesis as there is a similarity between handloading and scratch mixing a photographic solution.

Buying factory loads and factory mixed developers is another analogy.

I hand load my own shells too, and I know how to make both regular and smokeless powder as well as the fulminates and picrates for the caps, but I would never attempt to make the chemicals from scratch.

Ron Mowrey

kirk_keyes · October 5, 2004

I made mercury fulminate once. I was too chicken to dry it and play with it though... As a photo related note, I believe I used thiosulfate in fixer to neutralize the fulminate before disposal.

It's amazing what you can learn from WWII era chemistry books!

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