Hardening Fixer Doesn't Increase Wash Times ? Show Peer Reviewed Data or Call me Crazy

mshchem · Dec 10, 2022

I know that everyone knows that hardener increases wash times. The Ilford folks, who I have immense respect for say so, all the internet wizards say so. I'm looking for genuine, published data. Does it exist?
These are the kind of things that Kodak's research labs back in their glory days were so good at producing data that was unambiguous, non-empirical, and often peer reviewed.
I can except that hardener is absolutely not needed for almost every application. Exceptions being use of toners or heated dryers.

With modern analytical technology a very elegant experiment could be achieved, probably wouldn't cost more than 2 million USD.

I'm looking for published data, opinions on my sanity are welcome as well.
Best Regards Mike

Anon Ymous · Dec 10, 2022

Get a gram of silver nitrate and some acetic acid and you can make some HT2 test solution. Then you can experiment and make your own data.

Now that I think of it, IIRC, an ex member did this sort of testing, but these posts have been deleted.

mshchem · Dec 10, 2022

Anon Ymous said:
Get a gram of silver nitrate and some acetic acid and you can make some HT2 test solution. Then you can experiment and make your own data.

Now that I think of it, IIRC, an ex member did this sort of testing, but these posts have been deleted.

I've done this to test for residual fixer, there's also a test that uses a visible light ordinary spectrophotometer, low tech, colorimetric test. I know that there's old, published data. I need to do some digging. To bad I don't live near the main library of Rochester Institute of Technology, it would be in the journals there.
CE Kenneth Mees, started Kodak Research labs, held that hardener had no effect on wash times. There's beautiful literature out there. I need to investigate.

Patrick Robert James · Dec 10, 2022

That is a lot of work just to satisfy your curiosity. I'd say take the experts at Kodak and Ilford at their word.

koraks · Dec 10, 2022

mshchem said:
I know that everyone knows that hardener increases wash times.

Yes, common sense dictates as much. Except when the additional hardening makes only a marginal or even insignificant difference in the hardening of the emulsion, and that's not such a far-fetched idea with today's films and perhaps papers as well. There's a point beyond which no additional hardening will actually make much of a difference in the nature and permeability of the gelatin matrix, I think.

aparat · Dec 10, 2022

I was curious about this myself a while back. This is probably close to a scientific account on the effect of washing off hardening and non-hardening fixer. You can use the references at the end to find more papers on the subject. It's old, but most papers on similar topics tend to be rather old:

Diffusion of the thiosulfate ion out of photographic film during washing

The thiosulfate ion does not freely diffuse out of a hardened photographic gelatin emulsion. Salts in the washing water displaces the adsorbed thiosulfate ions and allows them to freely diffuse out of the emulsion. The effect of temperature upon the diffusion of the thiosulfate ion is on the...

scholarworks.rit.edu

MattKing · Dec 10, 2022

Game, set and match to aparat

mshchem · Dec 10, 2022

Patrick Robert James said:
That is a lot of work just to satisfy your curiosity. I'd say take the experts at Kodak and Ilford at their word.

The information from pre 1990ish (ish means I can't remember) Kodak doesn't spell out that hardener effects the diffusion of chemicals in the emulsion. I am a skeptic.

mshchem · Dec 10, 2022

MattKing said:
Game, set and match to aparat

It's not a competition or a match!

mshchem · Dec 10, 2022

aparat said:
I was curious about this myself a while back. This is probably close to a scientific account on the effect of washing off hardening and non-hardening fixer. You can use the references at the end to find more papers on the subject. It's old, but most papers on similar topics tend to be rather old:

Diffusion of the thiosulfate ion out of photographic film during washing

The thiosulfate ion does not freely diffuse out of a hardened photographic gelatin emulsion. Salts in the washing water displaces the adsorbed thiosulfate ions and allows them to freely diffuse out of the emulsion. The effect of temperature upon the diffusion of the thiosulfate ion is on the...

scholarworks.rit.edu

This is a lot of gibberish without others repeating, that's the first thing. Secondly the graduate student seems to be comparing pre-hardening with formaldehyde vs a harde

mshchem · Dec 10, 2022

Formaldehyde vs hardening Fixer and using salt in the wash water.
I've read this paper before, it's not impressive to me. I have no reason to doubt the findings but it's to jumbled too many variables

mshchem · Dec 10, 2022

I may to try and find a old but reliable B&L spec 88, I think we would need several investigators involved.

mshchem · Dec 10, 2022

Arthur: I am, and this is my trusty servant Patsy. We have ridden the length
and breadth of the land in search of knights who will join me in my
court at Camelot. I must speak with your lord and master.
Guard: What, ridden on a horse?
Arthur: Yes.
Guard: You're using coconuts!
Arthur: What?
Guard: You've got two empty 'alves of coconuts and you're bangin' 'em
together!
Arthur: So? We have ridden since the snows of winter covered this land.
Through the kingdom of Mercia, through...
Guard: Where'd you get the coconuts?
Arthur: (somewhat taken aback) We found them.
Guard: Found them? In Mercia? The coconut's tropical!
Arthur: What do you mean?
Guard: This is a temperate zone!
Arthur: The swallow may fly south with the sun, or the house maarten or the
plummer may seek warmer climes in winter, but these are not strangers
to our land!
Guard: Are you suggesting that coconuts migrate?
Arthur: Not at all! They could be carried.
Guard: (indcredulous) What, a swallow, carrying a coconut?
Arthur: It could grip it by the husk!
Guard: It's not a question of where 'e grips it! It's a simple question of
weight ratios! A five-ounce bird could *not* carry a one-pound
coconut!

mshchem · Dec 10, 2022

http://www.mit.edu/afs.new/sipb/user/ayshames/Python/SWALLOW.PYTHON

MIT!

MattKing · Dec 10, 2022

Don't forget that Kodak haven't sold pre-packaged non-hardening fixer for a very long time - if ever!
The fact that their Rapid Fixer was sold in a form that allowed the user to use it without hardener was a non-documented feature .

mshchem · Dec 10, 2022

I will behave. I would love to see a modern peer reviewed study. My question is, especially with MODERN materials, that have pre-hardened at the factory emulsions, why would fixer hardener have any significant impact.

I use hardener with fiber base prints because they will stick to the belt of my dryer. I've been working this way for 30 years (this proves nothing!) without any problems.

MattKing · Dec 10, 2022

The tests and results in that paper are accurately reflected in the synopsis:
"The type and amount of hardening also affects the diffusion of thiosulfate. The diffusion of thiosulfate out of the emulsion is fastest when a non-hardening fixer is used. The use of an alum hardening fixer results in slower diffusion than with formaldehyde prehardening"

mshchem · Dec 10, 2022

MattKing said:
Don't forget that Kodak haven't sold pre-packaged non-hardening fixer for a very long time - if ever!
The fact that their Rapid Fixer was sold in a form that allowed the user to use it without hardener was a non-documented feature .

Powdered F-5 fixer is good old stinky hardening (boric acid and alum? I think) fixer. I doubt many people are still using F-5. Liquid non-hardening rapid fixer is the norm. I'm not looking to argue, I'm just looking for genuine proof of the assertion that hardener slows the removal of fixer from the emulsion. Temperature and agitation would seem to blot out anything that hardener would do
It's good to have this discussion.
I'm neutral on the subject.

mshchem · Dec 10, 2022

MattKing said:
The tests and results in that paper are accurately reflected in the synopsis:
"The type and amount of hardening also affects the diffusion of thiosulfate. The diffusion of thiosulfate out of the emulsion is fastest when a non-hardening fixer is used. The use of an alum hardening fixer results in slower diffusion than with formaldehyde prehardening"

It's a start but it's far from a peer reviewed proper investigation. Cold fusion started this way.

mshchem · Dec 10, 2022

I'm taking a supper break.

Don_ih · Dec 10, 2022

I thought it was the acidity of hardening fixer that required the longer wash time. Use some hypo clear with alkaline fixers and the paper is good after a 15 minute wash. But the acidity of hardening fixers is a separate problem that isn't solved as readily by hypo clear.
Or that's what something led me to believe at some point. Don't ask me what - I have no idea.

aparat · Dec 10, 2022

mshchem said:
This is a lot of gibberish without others repeating, that's the first thing. Secondly the graduate student seems to be comparing pre-hardening with formaldehyde vs a harde

You need to have realistic expectations. I said it was close to a scientific account, not that it is a definitive account. The truth is nobody in the scientific community is interested in these kinds of investigations. What funding agency would be interested in offering a grant to study the subject? What journal would you say would be interested in publishing such a paper? Who in the scientific community would be interested in reading it?

It's similar to audiophiles complaining that there are no "scientific," "peer-reviewed" studies of auditory perception of different alloys used in the design of audio cables or solder. And there are a lot more audiophiles and audiophile companies than film photographers and film companies. Nobody cares enough for such studies to exist.

So you can keep complaining or you can do something about it and design a study and do it yourself. It's not that hard, if you are interested in having a ballpark estimate. You don't need millions. You need some simple equipment (buy used from eBay), have it calibrated, buy some materials, and devote several months of your time. Then, publish on the forum. Problem solved.

wiltw · Dec 10, 2022

This video clearly shows that use of hardener causes a higher level of hypo retention in film, than use of

non-hardening fixer, or
hardening rapid fixer followed by hypo clearning agent

no matter the washing techique used during 2 hours of washing

And [non-hardening fixer] is no different than [hardening rapid fixer + hypo clearing agent] in their ability to achieve archival freedom from residual fixer

MattKing · Dec 10, 2022

Don Heisz said:
I thought it was the acidity of hardening fixer that required the longer wash time. Use some hypo clear with alkaline fixers and the paper is good after a 15 minute wash. But the acidity of hardening fixers is a separate problem that isn't solved as readily by hypo clear.
Or that's what something led me to believe at some point. Don't ask me what - I have no idea.

There is a connection, but no causality.
In order to make a fixer a hardening fixer, it needs to be acidic - hardener won't work in an alkaline environment.
So when the starting point is a need for hardener, the fixer needs to be acidic.
Alkaline fixer also has the disadvantage that, if there is no stop bath in the process, development will continue in the fixer, which outside of the world of monobaths isn't a good thing.

pentaxuser · Dec 10, 2022

mshchem said:
Arthur: I am, and this is my trusty servant Patsy. We have ridden the length
and breadth of the land in search of knights who will join me in my
court at Camelot. I must speak with your lord and master.
Guard: What, ridden on a horse?
Arthur: Yes.
Guard: You're using coconuts!
Arthur: What?
Guard: You've got two empty 'alves of coconuts and you're bangin' 'em
together!
Arthur: So? We have ridden since the snows of winter covered this land.
Through the kingdom of Mercia, through...
Guard: Where'd you get the coconuts?
Arthur: (somewhat taken aback) We found them.
Guard: Found them? In Mercia? The coconut's tropical!
Arthur: What do you mean?
Guard: This is a temperate zone!
Arthur: The swallow may fly south with the sun, or the house maarten or the
plummer may seek warmer climes in winter, but these are not strangers
to our land!
Guard: Are you suggesting that coconuts migrate?
Arthur: Not at all! They could be carried.
Guard: (indcredulous) What, a swallow, carrying a coconut?
Arthur: It could grip it by the husk!
Guard: It's not a question of where 'e grips it! It's a simple question of
weight ratios! A five-ounce bird could *not* carry a one-pound
coconut!

I remember that one well. The best of the Python films I believe

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Hardening Fixer Doesn't Increase Wash Times ? Show Peer Reviewed Data or Call me Crazy

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