Alkali Fixers - The Myths & Legends

[Peter Schrager]

smith formula

Dan-that formula is strictly for papers....one pound of thiosulfate; 15 grams of sulfite and 64 oz. water....thank you for the TF2 formula and it is not in the cookbook; at least the older edition
Thanks, Peter

 

[Photo Engineer]

Thiourea, even though it has a long history with toning, is a chemical I try to avoid. It has a Contact Rating: 3 - Severe (Life). It is anticipated to be a carcinogen - in response to that the State of California has declared it to be carcinogenic.

Probably best to avoid the use of it if you can.

I merely mention it, however for CA residents to comply with the regulations there, they must be aware that a lot of their flowering plants must be removed!

Thiourea, as well as urea are metabolic byproducts of a lot of plants and animals.

PE

 

[MurrayMinchin]

What I love about TF-3 is being able to selenium tone test strips and work prints without having to wash after an acid fix, then re-fixing in plain hypo. Toning can sometimes have dramatic effects, especially in clouds, so it's a real time saver being able to go straight from the TF-3 into the selenium toner while trying to nail a print.

Murray

 

[Kirk Keyes]

IThiourea, as well as urea are metabolic byproducts of a lot of plants and animals.

The most reputable source I could find is a report by the World Health Organization, http://www.inchem.org/documents/cicads/cicads/cicad49.htm#4.0,

"Thiourea has been detected but not quantified in laburnum shrubs (Laburnum anagyroides) and is a natural metabolite of the fungi Verticillium alboatrum and Bortrylius cinerea (IARC, 1974)."

I guess I don't have to worry about eating much of those two things.

I just mentioned it as ammonium thiosulfate is pretty safe and very fast acting, either in alkaline, or near neutral/slightly acidic pH ranges.

I understant there are markets or uses where speed is the upmost importance, but for the typical home darkroom worker, it seems a bit overkill to use compounds that are suspected carcinogens in the place of compounds that do not have those properties.

 

[Kirk Keyes]

What I love about TF-3 is being able to selenium tone test strips and work prints without having to wash after an acid fix, then re-fixing in plain hypo.

I do this with Ilford Hypam. Dev, stop, fix, and then into fix with selenium toner, quick water rinse, wash aid, and then wash.

It works fine without an alkaline fix.

 

[CBG]

PE, in the Fixer Articles you have posted:

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.

Is this Super Fix VII or an earlier version?

 

[Photo Engineer]

That is, AFAIK, an earlier version, namely SFI. I did not post it BTW. It was posted by another member who copied it from a very extensive thread on Photo Net. I am up to SFVII which has met the goal of duplicating the results of SFI, but with reduced wash times and better chemistry.

PE

 

[dancqu]

Dan-that formula is strictly for papers....one pound of thiosulfate;
15 grams of sulfite and 64 oz. water....thank you for the TF2
formula and it is not in the cookbook; at least the older
edition Thanks, Peter

"Strictly for papers" Not so. How do you come by that?
A pound. Approximately a double batch of TF-2 minus
the metaborate and half the sulfite.

The formula is in The FILM Developing Cookbook.
Just off hand I can't think of any fixer being either
a paper or film fixer but not both. Dilutions
may vary. Dan

 

[CBG]

That is, AFAIK, an earlier version, namely SFI. I did not post it BTW. It was posted by another member who copied it from a very extensive thread on Photo Net. I am up to SFVII which has met the goal of duplicating the results of SFI, but with reduced wash times and better chemistry.
PE

I figured it was your post. My apologies!

 

[eclarke]

That is, AFAIK, an earlier version, namely SFI. I did not post it BTW. It was posted by another member who copied it from a very extensive thread on Photo Net. I am up to SFVII which has met the goal of duplicating the results of SFI, but with reduced wash times and better chemistry.

PE

By Photo Engineer - 10:23 PM, 02-01-2006 Rating: None
I am now up to Super Fix VII.

Is there a formula for SFVII? If not, is somebody going to sell it?..Evan Clarke

 

[Photo Engineer]

By Photo Engineer - 10:23 PM, 02-01-2006 Rating: None
I am now up to Super Fix VII.

Is there a formula for SFVII? If not, is somebody going to sell it?..Evan Clarke

The formula posting has the ID title:

superfix
unregistered (10-31-06)

The dating of the other posts appear to be in error as they are all dated prior to Sean's update of the articles.

I have never posted any formula but SFI and have only referred to my ongoing work. Several individuals have samples of SFVIII. The formula will not be published.

PE

 

[eclarke]

The formula posting has the ID title:

superfix
unregistered (10-31-06)

The dating of the other posts appear to be in error as they are all dated prior to Sean's update of the articles.

I have never posted any formula but SFI and have only referred to my ongoing work. Several individuals have samples of SFVIII. The formula will not be published.

PE

Too bad, Thanks..Evan Clarke

 

[dancqu]

No published findings that I know of except for the work
by Haist and work I did at EK which is for the main part
unpublished. I can back up most of the assertions on
alkaline and neutral fixes as well from work

I have personally done. As pH goes up, swell goes up
(with bone gelatin) and washing becomes easier. PE

No published findings ... Very few at the most. I find
that odd considering how easy it is to compare washes
at varying fixer ph.

I've done a little testing with respect to comparing
using the HT-1 and HT-2 tests. I like the HT-1 test. It
uses potassium permanganate. A colorimetric titration
is performed upon the wash water. A print or film must
be a part of the test. Any more than a minute trace of
hypo left in the wash water + paper or film will make
colorless the permanganate.

P.K. Turner suggested the use of permanganate when
washing film. The test could be quantified but intuitively
a drop of the PP solution left pink spells extremely low
thiosulfate levels.

Compare. Pit an acid fixer against a alkaline fixer.
Keep notes, then Publish. Testing wash waters, films,
and prints is routine for at least a few APUG members.

I'd run tests myself were it not for the processing
methods I employ; very dilute, minimal volumes,
no stop, etc. A research grant could move me
in that direction. Dan

 

[Photo Engineer]

Dan;

There are many publications. I have probably nearly 200 internal reports at EK, but no public reports. So, sorry, but you will have to rely on the fact that I am trying to reproduce my work here at home as best I can without an army of analytical chemists to back me up.

So far, things are looking good, but I may never prove it to you quantitatively. Sorry. The lack of publications is entirely normal in this field and is why the work "out there" is so patchwork in nature and so subject to potential loss. All I have is what is in my head. All I can do is try to pass it on. If anyone cares to refute or ignore it, then thats ok with me.

PE

 

[Ray Rogers]

All I can do is try to pass it on.
PE

What is that saying about teaching a person to fish?

I am not sure I understand why you don't post your "in house" testing procedure and then share your results.

Perhaps you needn't prove anything...

The one thing we need more than new unpublished formulas with limited testing and a doubtful future is sound training in basic photographic processing research and product development... If you have something to teach... as time passes us by - that will become the more valuable in the long run. (IMHO)

I am sure many may be content to just buy the most recent product inexpensivly, and that IS fine.

However, (I may be wrong!) but I think the most valuable lesson we will ever be able to learn from you is how to think like a Kodak researcher. Strange, but I feel that Kodak research was somehow better than the Kodak products that evolved from it.

Perhaps that doesn't make any sense.

Well, anyway, nice friuts are fine,
but a working knowledge of agriculture is incomparable.

Ray

 

[Photo Engineer]

What is that saying about teaching a person to fish?

I am not sure I understand why you don't post your "in house" testing procedure and then share your results.

Perhaps you needn't prove anything...

The one thing we need more than new unpublished formulas with limited testing and a doubtful future is sound training in basic photographic processing research and product development... If you have something to teach... as time passes us by - that will become the more valuable in the long run. (IMHO)

I am sure many may be content to just buy the most recent product inexpensivly, and that IS fine.

However, (I may be wrong!) but I think the most valuable lesson we will ever be able to learn from you is how to think like a Kodak researcher. Strange, but I feel that Kodak research was somehow better than the Kodak products that evolved from it.

Perhaps that doesn't make any sense.

Well, anyway, nice friuts are fine,
but a working knowledge of agriculture is incomparable.

Ray

Ray;

I have posted both my fixing test procedure and my developer stability and quality test procedure, the latter with results. If you wish, I will re-do this if you really feel it is necessary. Sorry you missed it elsewhere.

As for published works on fixing and washing, I have found quite a bit in Mees and James and Mason. There is quite a bit in Mason, especially on washing which I have quoted elsewhere.

But, basically to summarize, a fixer can be easily tested with 3 solutions.

1. Silver Nitrate in Acetic Acid - Hypo retention test
2. Sodium Sulfide in water - Silver Halide retention test
3. Potassium Iodide in water - Fixer exhaustion test

Instructions are supplied with kits sold by major suppliers of photochemicals. Testing is simply seeing how well a fixer performs in a given sequence of fix time, dilution and wash.

PE

 

[Kirk Keyes]

However, (I may be wrong!) but I think the most valuable lesson we will ever be able to learn from you is how to think like a Kodak researcher.

Ray - the best way to do that is to learn one of the sciences and all the principles, habits, and ways of thinking that go along with that scientific training. The first think to remember is that the men and women doing all that research at Kodak were taught and learned science first, then they worked for Kodak doing research.

I don't want to minimize the way that "Kodak researchers" think, but I'll say that learning how any science researcher thinks will be a benefit.

If that means getting a degree in chemistry or materials science, that that's all the better. If a degree is not possible, it will be that much harder, but the principles can still be learned and used to great benefit. Studing how people have done research can help, but really, practicing science is the best way to learn. There's nothing like using the techniques that one studies about to really let the prinicples sink in.

And I realize that it's quite a big step for most people, but if there is enough determination, understanding of the principles can come, as will learning to think like a researcher.

 

[Ian Grant]

I don't want to minimize the way that "Kodak researchers" think, but I'll say that learning how any science researcher thinks will be a benefit.

The Kodak researchers were taught to do research the British way, by a good mentor.

In the early days Kodak had no specialist Research facilities but George Eastman knew exactly which talented photo-chemist he wanted to head a new one. He took over Wratten & Wainwright in 1912 to gain the companies expertise in Panchromatic emulsions and colour correction filter, as well as securing the skills of CEK Mees.

It's probable that some the Wratten recearch teams moved to Harrow, Mees went to Rochester to found Kodak's Research facilities, he retired in 1955 at the age of 73, heading research at Kodak for 53 years.

Ian

 

[eclarke]

Ray;

I have posted both my fixing test procedure and my developer stability and quality test procedure, the latter with results. If you wish, I will re-do this if you really feel it is necessary. Sorry you missed it elsewhere.

As for published works on fixing and washing, I have found quite a bit in Mees and James and Mason. There is quite a bit in Mason, especially on washing which I have quoted elsewhere.

But, basically to summarize, a fixer can be easily tested with 3 solutions.

1. Silver Nitrate in Acetic Acid - Hypo retention test
2. Sodium Sulfide in water - Silver Halide retention test
3. Potassium Iodide in water - Fixer exhaustion test

Instructions are supplied with kits sold by major suppliers of photochemicals. Testing is simply seeing how well a fixer performs in a given sequence of fix time, dilution and wash.

PE

Well, I have Mees and James and Mason, have to do some better reading..Thanks..EC

 

[Photo Engineer]

Mees was very British.

He would not allow anyone on the elevator with him when he went up to his office, and his office opened directly off the elevator for his convenience. So, when the elevator doors opened for him, everyone then in the elevator was required to step off so that he could ride in lonely splendor to his destination.....

Stories about about Mees. He was a gentleman of a very very old school.

Research at Kodak was really brought into the modern age by the likes of Hanson and Vittum who did a lot of modernization. Others include Leermakers, Stauffer and etc...

PE

 

[Ray Rogers]

Ray;

I have posted both my fixing test procedure and my developer stability and quality test procedure, the latter with results. If you wish, I will re-do this if you really feel it is necessary. Sorry you missed it elsewhere.

True- I have not seen the developer stablty/quality test procedure; I WOULD like to see it. Perhaps someone knows where it is and you won't have to go to all the trouble...

...to summarize, a fixer can be easily tested with 3 solutions.

1. Silver Nitrate in Acetic Acid - Hypo retention test
2. Sodium Sulfide in water - Silver Halide retention test
3. Potassium Iodide in water - Fixer exhaustion test

Instructions are supplied with kits sold by major suppliers of photochemicals. Testing is simply seeing how well a fixer performs in a given sequence of fix time, dilution and wash.

PE

Are these 3 the same that appear in the Kodak darkroom data books?
They all 3 sound very familiar, but are these the tests you used on
SFI -SFVIII?

How do you test for capacity?
Do you controll for silver weight?
Degree of exposure?

I think perhaps I was not clear enough.
What I am interested in learning is your thought process as you worked your way from SFI to SFII...

What promted you to change SFI ?
What were you trying to improve?

When you finally had SFII, what was wrong with it?
Why did you feel the need to change that one and develop SFIII?

Same for SFIV, V, VI and VII...
Why did you find it necessary to keep changing or tweaking?

Is SFVII really any better than SFI?
By how much?

How much improvement has been made between SF VII and SFVIII?
Is the improvement tangible?

If SF VIII is so good, why couldn't you go directly from SFI to SFVIII?
What has enabled you to create now what you could not create earlier?

I don't know if you see what I am asking, but it is the thought process I am interested in and that all too often gets swept under the rug or discussed behind closed doors.

Was SFI buffered?

We are missing a very valuable exercise by not being able to actually follow you through a product's development. You have alluded to it yourself, there is a need to cut corners... to see which corners you cut, how you cut them, and your reasons... could help others who like yourself, are independent researchers, but unlike yourself, do not have the insight that comes from working where you have.

SF series is mentioned here only as an example.

 

[Photo Engineer]

Ray;

I am not permitted to refer to or post these tests, as I am involved in the sale of such products. Anything more than these comments is a clear conflict of interest in the opinion of some APUG members.

As for my thought processes, since they took over 3 years, I have said before that I could teach a 1 year college level course on photo system engineering. This is simply not possible on APUG. Actually, by my notes, it is SFVIII, and it is better ecologically and in terms of features.

Now, the question of going to SFVII or SFVIII from SFI is really similar to saying why didn't mankind go from the dugout canoe to the steamboat directly if steamboats are so much better. That should be obvious to anyone. I didn't know yet exactly what the changes had to be. I had to creep up on them incrementally by using prior experience. This goes directly to what Kirk said in his post.

As for cutting corners. No, I do not. I wish I could, but then I could not face anyone and tell them that the product was good. Sorry.

PE

 

[Ray Rogers]

...the men and women doing all that research at Kodak were taught and learned science first, then they worked for Kodak doing research.

I don't want to minimize the way that "Kodak researchers" think, but I'll say that learning how any science researcher thinks will be a benefit.

Yes.

It is interesting to consider, however, that despite the value of the scientifc method and critical thinking skills, many discoveries might not have been made if scientists never screwed up.

Anyway, a good comparative analysis of research in the American, German, British and Japanese photoindustry would be very interesting, I would think.

Ray

 

[Ray Rogers]

Ray;

I am not permitted to refer to or post these tests, as I am involved in the sale of such products. Anything more than these comments is a clear conflict of interest in the opinion of some APUG members.PE

I am not asking you to plug your own products
Just to discuss how typical products might be improved... and the science behind the improvements.

Now, the question of going to SFVII or SFVIII from SFI is... I didn't know yet exactly what the changes had to be. I had to creep up on them incrementally by using prior experience. PE

That may be true, but the world has had fixers for many many decades...

Suddenly I read someone has a new fixer... three yeras later he has 8!
And I still don't know why we needed the first new one...
much less the other 7.

You hounded Pat repeatedly for data, for proof, but I don't see any for
your own work, probably because its sensitive, it poses a conflict of interest or whatever, in any case, I think, I feel a void.

Frankly, I have been up all night working on a new emulsion formula series.

I don't imagne it will happen anytime soon, but it would be nice to see a real product improvement (such as 2 electron sensitization) discussed from concept through finished product highlighting all the major obstacles and how each was overcome.

Now that would be educational.

As for cutting corners. No, I do not. I wish I could, but then I could not face anyone and tell them that the product was good. Sorry.

PE

By cut corners, I think in post 39 you wrote:
There are many publications. I have probably nearly 200 internal reports at EK, but no public reports. So, sorry, but you will have to rely on the fact that I am trying to reproduce my work here at home as best I can without an army of analytical chemists to back me up.

Without the Kodak Research division back up, I think corners will get cut.
But with your training and Kodak experience, I have no doubt you will pull it off.

 

[Photo Engineer]

Ray;

It does not have 8, it has 1. Only one is satisfactory to me.

As for the rest, these are meaningless arguments. If I said that it relied on swelling agents, Isoelectric point and the relative solubilities of the ingredients related to cations what would be your response?

PE