SilverGrain Clear Fix

I have to set the historical record straight on at least one paragraph in this raddled compendium.

"As far as I know, all fixer products Kodak offered in the past and present, including fix for color paper and films, are adjusted to acidic pH. The highest pH fixers are the ones for color materials but still below 7."

But you don't know. Kodak has not offered alkaline fixers to the public but started using them in machine processing in the early 1950s, in some cases at pH levels as high as 10.5. An enormous amount of research went into these products; none of it has ever been published.

"In such formulae, triethanolamine offers no useful effect. Also, triethanolamine has no buffering capacity or fixing accelerating effect in such a low pH range. Most other alkanolamines are stronger base than triethanolamine and they would be even more useless in acid fixers. It is obvious Kodak never had any reason to use alkanolamines in fixers."

This statement is nonsense because it is based on the incorrect assumption that Kodak never made alkaline fixers. What is your source for this information? Mine was H.D. Russell, who formulated those fixers.

The foundation of the photographic industry has always been the trade secret. Ryuji, you have always refused to recognize this and have made the flawed assumption that all valuable information has been published either in patents or in the technical literature. In fact, the best information has always been closely held, and the only way to get at it is to gain the trust of those few who are somewhat willing to disclose a little of this information, now that silver-based photography is discernably moving in the direction of commercial irrelevance. Now is not the time for you to play the temperamental grad student. Now is the time to go out there and listen to whoever is still alive and willing to talk about these things. There aren't many and time is running out.

Kodak sold an alkaline fixes for many many years. They used sodium metaborate as buffer and sodium hypo to prevent odor. One version also contained formalin and was used for hardening at the working pH of about 9.5.

Kodak holds some of the few patents on TEA in fixers, but never released a fix using it. The last one is rather recent and still in force IIRC.

My point in mentioning amines is that they don't normally form nitroso compounds but when they do, they are not good. But gelatin, metol and many of the nitrogen containing compounds you mention are not sources of nitroso compounds under conditions we normally encounter in processing or keeping.

PE

To listen, even to hear, is not to know. (L. E. Modesitt jr.)

To not even be willing to listen is worse IMHO.

PE

billtroop said:

"In such formulae, triethanolamine offers no useful effect."

This statement is nonsense ...

Click to expand...

Foul! Ryuji's comment has been taken out of context. Dan

dancqu said:

Foul! Ryuji's comment has been taken out of context. Dan

Click to expand...

Maybe I'm being dense, Dan, but I don't see the problem here. Out of context of what?

Bill, I think Dan's point is that whether Kodak made an alkaline fixer at one time or not, alkanolamines are still poor buffering agents for acidic fixers, and Ryuji's "In such formulae" referred to acid fixers.

billtroop said:

DT: Accelerated age tests were performed on
the products by Ryuji Suzuki.

BT: OK, so what were they and are they verifiable?
Accelerated aging tests have often proved disappointing
when it comes to the archival stability of silver images.

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Not possible to verify I'd say what with their having
"often proved disappointing". Imagine, passing the
500 year test then turning yellow a year later.
Or is that a microfilm test? Well, 100 year.

I've read that the ST-1 test is a centuries test. One
anybody can do at home. Also, although the HT-2 test
does not test AT archival levels, zero stain results will
confirm a paper's residual thiosulfate levels are very
near archival. What else to test for and with tests
which do not disappoint?

Although not so certain, tests which have been
done have only been done with papers acid processed.
Is that true? Should we consider the absence from the
market of any alkaline fixers from Ilford, Kodak, and
a few others an indictment of alkaline fixers?

I think the shift from acid to alkaline has opened
a bigger can of worms than the inclusion of a small
amount of TEA. All that fix chemistry going from ph
5.5 to 7.5 or better. My fix, a little alkaline. Dan

Kodak did sell alkaline fixers for many years as I pointed out above. The fact that they don't now is due to the lack of a rapid fix rate with sodium based alkaline fixers, and the smell with ammonium based alkaline fixers. I could list a rather large compendium of problems, but in the end, Kodak has sold alkaline fixers longer than TF-4 has been on the market.

Kodak decided that the odor and rate were important factors and went with near neutral fixes for the most part with the exception of the KRLF which is rather acidic if the optional hardner is used.

Grant Haist argued strongly in favor of alkaline fixers due to wash rate in which he foresaw the use of water to be a future problem. As it turned out, he was right, but he didn't know at the time that there were other solutions to that problem. Those other avenues were never explored by EK due to the demise of all B&W R&D.

Several involved non-polluting organic silver halide solvents for example. They quickly biodegraded and/or were not very toxic. They could be used in situations where silver was easily recovered as well. They had no effect on image stability.

Now, regarding the ST-1 test and the HT-2 test. Work has been done that showes that photo images that pass both of these tests may still be unstable in ambient conditions and may fade rapidly. Ctein has shown clearly that over washed prints will pass these tests but will fade within just a few years. This has been verified by others.

Other chemicals can interfere with these tests to give the appearance that a photo image has passed, but the interfering chemical has prevented the test from registering a problem.

I am interested in the answer to Kirk Keyes question, namely, what test is used to detect residual TEA in a coating. It appears that the orignal test mentioned was actually not the one used.

PE

Dan, I don't think you're getting the point. Ryuji concludes that Kodak never could have researched alkalonamides in fixers because, he says, they never made alkaline fixers. He's wrong on both counts. It's a good example of sloppy thinking. It shows what happens when your research is inadequate in the first place, and you make further conclusions based on that inadequate research.

In addition, as O'Reilly et al. have long since established (Ron, it is this research on which Ctein's conclusions are based; it is this research which should be cited, not Ctein's secondary reporting, even though it has considerable confirmatory value), the major problem with archival stability has been discovered _not_ to be residual thiosulfate levels. Please have a look at that paper, online, that I referenced earlier. It really does give a good snapshot for where we are now. The major problem is finding a way to protect silver from atmospheric attack. One way of achieving this is by having _some_ residual thiosulfate. But that is another topic. Here we are interested in TEA, and what test, if any, may have been used to detect its residua, it having been established that it was not the test Ryuji said it was. We've heard about 'buried in my notebook somewhere' but isn't that the same thing as 'dog ate my homework' ? ? It's an excuse I have often heard from this quarter . . . . . .

The work by Ctein was and is easily accessable by most APUG members, and to add to that, it is not strictly a small amount of thiosulfate which should remain in the coating. It is actually any sulfur containing compound which can decompose into sulfur during keeping. The presence of a tiny amount of sulfur protects the image.

PE

Jordan said:

Bill, I think Dan's point is that whether Kodak
made an alkaline fixer at one time or not, alkanolamines
are still poor buffering agents for acidic fixers, and
Ryuji's "In such formulae" referred to acid fixers.

Click to expand...

That is correct. The two posts in question are Ryuji's #49
and Troop's #51. Troop's post presents a split paragraph
which occurs approximately mid Ryuji's post. Troop's
"Nonsense" caught my attention so I checked it
out. In context, not at all nonsense. Dan

dancqu said:

That is correct. The two posts in question are Ryuji's #49
and Troop's #51. Troop's post presents a split paragraph
which occurs approximately mid Ryuji's post. Troop's
"Nonsense" caught my attention so I checked it
out. In context, not at all nonsense. Dan

Click to expand...

Dan, you have missed the point, but I think I now understand why, so let me explain.

The sentence that I omitted in the quotation states:

"Also, triethanolamine has no buffering capacity or fixing accelerating effect in such a low pH range."

With this sentence I have no argument. It states that TEA does not have buffering capacity or accelerative effect at low pH range, i.e., the acid range that Ryuji erroneously claims all Kodak fixers are formulated for.

What I argue with are the two parts that I included. Here he states that (a) Kodak never used alkaline fixers and therefore (b) never studied the effects of alkanolamides in alkaline fixers.

Both parts of the this statement are untrue, as I both state and as Ron Mowrey confirms in a later post.

Ryuji's statement that TEA has no useful buffering or accelerative effect at low (i.e. acid) pH range (he should have been more precise) is true, but it is irrelevant to the correction I made. Hence, since it had nothing, whatever, to do with my point, I omitted it.

Please let me know if this is still not clear. I always omit parts of quotes that are irrelevant or confusing ... I am sorry that, in this case, it has added to confusion.

[QUOTES=billtroop;439810]
"The sentence that I omitted in the quotation states:"

""Also, triethanolamine has no buffering capacity or fixing
accelerating effect in such a low pH range."" RS

Correction: Your quote does include that sentence. Post #51

"What I argue with are the two parts that I included.
Here he states that (a) Kodak never used alkaline fixers ..."

Correction: Ryuji: "...all fixer products Kodak offered in the
past and present .... are adjusted to acidic pH." So they never
"Offered" alkaline. Your statement; "Kodak has not offered
alkaline fixers to the public but started using them in
machine processing ..." So what's the beef?

Reminds me of the large regional processing labs of 50
years ago. So 50+ years ago Kodak did Use an alkaline fix.
My guess, no way an 'offering. We were left out.

"...and therefore (b) never studied the effects of
alkanolamides in alkaline fixers."

I don't see anywhere in the paragraph, split in post 51,
any wording by RS stating or implying that Kodak did not
study the effects of alkanolamides. He does say they
"...never had any reason to use ..." them in fixers.
And why? Because they are "... useless in acid
fixers" Kodak's only public offerings. Dan

Dan;

Kodak offered alkaline fixes for many years from the 50s through the 60s for commercial use in some processes and up to about the 90s in X-ray processes using a glutaraldehyde hardener. The commercial color process was offered in a home color kit called P-122. You were not left out, you were probably in diapers then. P-122 lasted a long long time.

Bill knows this and was basing his remark on this.

I have given the known reasons for abandoning these.

The latest Kodak patents on TEA and alkaline fixers date to the mid 90s. This work was never realized and Bill knows this as well. The patent was issued, but the product was never released. I think that is a point to consider here, that Kodak had an ongoing program investigating alkaline fixes to reduce the amount of water needed for washes among other things.

I assure you, and have posted this, that since they sold alkaline fixes, and studied TEA, they had a reason to use them, but chose not to and chose to discontinue those that they did offer.

There were reasons for not using TEA, but I cannot remember them and discussions with Grant Haist have not uncovered the reason. His memory and mine coincide but the reason escapes both of us.

I have been studying image stability for over 30 years on and off, and have had extensive discussions with Henry Wilhelm on this subject. I took the ICIS course in image stability by Jon Kapecki a year ago. There is, unfortunately, no current or existing new work on B&W image stabilty except for the Ctein work and others such as Beveridge of Ilford cited here. It pretty much ceased in the mid 80s. We cannot comment definitively one way or the other on the effects of TEA in a fixer.

Your apparent contention that Kodak and others AAMOF, only offered acid fixers to hobbyists is wrong. Alkaline fixers have been known for years and Grant Haist was merely the conduit for publication of the information in the 70s. I know this clearly, as I helped edit his book at EK at the time.

PE

Photo Engineer said:

Dan; Your apparent contention that Kodak ... PE

Click to expand...

You've got the wrong guy. That is Mr. Troop's contention.
I've only quoted what he has said; post 51. "Kodak has
not offered alkaline fixers to the public ..." Machines
yes, public no.

Of course it's good news if true. It is an endorsement
of the alkaline fix. With emulsion incorporated hardeners
there is less need for acid fixers. Odd they should drop
their offerings of alkaline fixers. Dan

Dan;

Bill also referred to my earlier post that Kodak had offered alkaline fixers for general sale. I wish to correct one thing I said. When P122 converted to the alkaline fix it was marked Ektaprint-C in trade dress. He is aware of what they sold and who they sold it to. He incorporated my comments by reference in his posts.

Bill is also aware that Kodak chose to remove them from the market. Alkaline sodium based fixes were too slow and ammonium fixers had an objectionable odor. They would not use TEA for some 'forgotten' reason even though research continued on TEA until the 90s. Instead, they developed the neutral pH (pH 6.5) series of fixes and used other means to accelerate both fix rate and wash rate. This work started in 1965. I was a member of a team that did the color work and Grant worked in the B&W area. That is how I first met Grant.

Grant explained most of this to Bill when Bill was writing his portion of the A&T book. I know it because I was there for the full term of the research, part as a member and part on the outside observing from other projects. Keith Stephen's office was about 4 doors down from mine. We talked often until his untimely death.

I used to test samples of these novel fixers, and novel fixing agents. I used to do 'homework' here in my own darkroom at night testing fix rate on film strips. I can tell you, among other things, that the original formulas for many of the fixes and blixes looked quite different from the first to the last iteration. This is for safety, cost and method of manufacture. All of those factors and more enter into the selection of a final formula.

PE