Film Photography Project (not Podcast) archival wash vs Kodak Hypoclear vs Sodium Sulfite

[BHuij]

Decided it was time to get serious about washing my fiber prints properly and went down the rabbit hole today.

I've narrowed it down to 3 options:

1. Kodak HypoClear. Easy to find locally and kind of an "industry standard" but shelf life of mixed solution is measured in hours, and it would be the only part of my printing chemistry that didn't keep at least reasonably well between printing sessions. I frequently go into the darkroom for an hour and make a single print, so mixing this up every time isn't especially economical.

2. Sodium Sulfite. Cheap, apparently just as effective as HypoClear, basically all the benefits of HypoClear, near as I can tell. Same issue with needing to mix up a batch every time I print though.

3. The FPP's own "archival permanent wash." The claims they make of needing only a 5 minute wash are dubious, but the 3 month shelf life of mixed solution is very compelling. Anyone using this for selenium toned fiber prints with good results? Anyone have any idea what's in it and if it can be safely/feasibly made from raw ingredients?

 

[MattKing]

I expect that you are referring to the Film Photography Project, rather than the Film Photography Podcast, so I'm going to go out on a limb and change the thread title.
I also expect you are referring to Kodak Hypo Clearing Agent. I think Hypo Clear is a name used by Photographer's Formulary on their competing product.
In any event, thankyou for not referring to it as "Hypo"!
Kodak Hypo Clearing Agent is mostly Sodium Sulfite. The remaining agreements are there mostly to deal with water quality variations and to ensure that the solution is within the right pH range. It may be that your tap water will work sufficiently well with the Sodium Sulfite to ensure that the extra ingredients are unnecessary.
Personally, I would prefer to at least see an MSDS for the Film Photography Project product before deciding to replace the Kodak product with it. I am comfortable with other competing products like Ilford Washaid and Heico Permawash.
Personally, I just use a teaspoon of the Kodak product per litre per session. It is the only powdered chemical that I'm comfortable with doing that.

 

[BHuij]

Correct and correct, thank you for updating that and clarifying my nomenclature on the Kodak product.

I keep aquariums, so I happen to know that my tap water comes out at about PH 8.0 or 8.1, and is quite hard water. For once this seems to maybe be a pro instead of a con.

B&H has the Kodak stuff cheap. About $7 for enough powder to mix up 5 gallons of working solution, If the powder in an opened bag doesn't go bad and I can just chuck a teaspoon per liter in and mix it up at the beginning of a print session, that's probably good enough for me. Thank you for a helpful reply.

 

[MattKing]

For clarity, I transfer the bag to a glass jar, and then "spoon" from there.
The MSDS for the Kodak product shows this:

The EDTA is the part that deals mostly with your hard water.
As I understand it, the relative proportions of the four listed ingredients aren't as critical with HCA than they are with most photo-chemicals. That is why just keeping the powder shaken up before each spoonful is removed gives acceptable results.

 

[lantau]

How about a strong, neutral fixer, short fixing time of 60s, an intense rinse of 2-3 minutes and 20 minutes of immediate and effective washing. No hypo clear, no keeping prints in a water tray for hours before washing, etc. Short wet time may also help with flat drying.

At the end a bath of Adostab II.

People used to use Na-thiosulphate. This shouldn't even be considered a fixer in 2021. Proper fixing with that makes washing near impossible. With the above method 20 min wash time equals 12h with ancient acid hypo. And yet the old prints survive. So the whole discussion about archival prints is probably a myth anyway.

 

[BHuij]

How about a strong, neutral fixer, short fixing time of 60s, an intense rinse of 2-3 minutes and 20 minutes of immediate and effective washing. No hypo clear, no keeping prints in a water tray for hours before washing, etc. Short wet time may also help with flat drying.

At the end a bath of Adostab II.

People used to use Na-thiosulphate. This shouldn't even be considered a fixer in 2021. Proper fixing with that makes washing near impossible. With the above method 20 min wash time equals 12h with ancient acid hypo. And yet the old prints survive. So the whole discussion about archival prints is probably a myth anyway.

I’m still using sodium thiosulfate based fixer.

 

[removed account4]

you might also look at sprint fixer remover and perma wash...
some of these formulas are tired and true and others work better than the rest..

How about a strong, neutral fixer, short fixing time of 60s, an intense rinse of 2-3 minutes and 20 minutes of immediate and effective washing. No hypo clear, no keeping prints in a water tray for hours before washing, etc. Short wet time may also help with flat drying.

At the end a bath of Adostab II.

People used to use Na-thiosulphate. This shouldn't even be considered a fixer in 2021. Proper fixing with that makes washing near impossible. With the above method 20 min wash time equals 12h with ancient acid hypo. And yet the old prints survive. So the whole discussion about archival prints is probably a myth anyway.

there shouldn't be a problem with archival processing with sodium thiosulfate. ( olde school hypo )
its just a matter of removing what might be lingering ( what fixer remover does ) and diffusing washing.
archival printing is not really a myth, its just science ...

any event, thankyou for not referring to it as "Hypo"!.

no reason to get upset for calling fixer hypo ... that is what it was called, and it's not some sort of slur
https://www.getty.edu/art/collectio...frederick-william-herschel-british-1792-1871/

 

[Sirius Glass]

I expect that you are referring to the Film Photography Project, rather than the Film Photography Podcast, so I'm going to go out on a limb and change the thread title.
I also expect you are referring to Kodak Hypo Clearing Agent. I think Hypo Clear is a name used by Photographer's Formulary on their competing product.
In any event, thankyou for not referring to it as "Hypo"!
Kodak Hypo Clearing Agent is mostly Sodium Sulfite. The remaining agreements are there mostly to deal with water quality variations and to ensure that the solution is within the right pH range. It may be that your tap water will work sufficiently well with the Sodium Sulfite to ensure that the extra ingredients are unnecessary.
Personally, I would prefer to at least see an MSDS for the Film Photography Project product before deciding to replace the Kodak product with it. I am comfortable with other competing products like Ilford Washaid and Heico Permawash.
Personally, I just use a teaspoon of the Kodak product per litre per session. It is the only powdered chemical that I'm comfortable with doing that.

Calling Hypo Clearing Agent "Hypo" is one of many pet peeves. Everyone should have a pet peeve to feed and tend to.

 

[lantau]

you might also look at sprint fixer remover and perma wash...
some of these formulas are tired and true and others work better than the rest..

there shouldn't be a problem with archival processing with sodium thiosulfate. ( olde school hypo )
its just a matter of removing what might be lingering ( what fixer remover does ) and diffusing washing.
archival printing is not really a myth, its just science ...

Of course it is science, but the common wisdom floating around might have become stuck at some point, ignoring new scientific insights.

What I tried to express is that even less than perfectly finished prints might last for a long time, as it is likely that many old prints weren't processed all that well. OTOH hand some people seem to go to ridiculous lengths in terms of wash time in the hope of archival prints, but still use long fixing times (and acidid fixer, which can work fine, but there is no reason for it). Or worse sodium thiosulfate based fixers.

When I began darkroom work a few years ago I found this old german language article from December 2000. The title translates to: 'Long washing won't help - short fixing does!' It cites two articles. One in an old German magazin (Foto Hobbylabor 5/88) and the other on f32.com (can be found on archive.org: https://web.archive.org/web/20000529034401/http://f32.com/Articles/art021.htm).

They probably compared Sodium Hypo to acidic rapid fixers in the 80s (!). A long fixed print took two days of washing to get to thiosulfate levels of a short fixed print after 12 Minutes of washing. The findings resulted in Ilfords washing recommendation.

Today we have neutral fixers. Together with a very short stop in a buffered stop bath (TS-7, read the film developing cookbook) with high capacity it keeps the pH changes and ranges, the emulsion is exposed to, to a minimum. Less swelling and contraction of the emulsion along the process and efficient washing even without washaid.

Later I found that amazing article at fadu: Mysteries Of The Vortex (http://www.film-and-darkroom-user.org.uk/forum/showthread.php?t=296).

One interesting point is that fixer isn't stuck in the paper. More likely adsorbed onto the bariumsulfate (baryta) layer, possibly from the emulsion side. Anecdotally I had a single confirmation, due to an accident:

I wanted to use test solution on a fibre print, which was only rinsed. I wanted to tear the print into test sections and instead tore along the paper 'layers'. I.e. I got a paper wedge, exposing the inside of the paper. The inside tested negative for present fixer, while the emulsion gave a strong stain. I haven't repeated that so far. I have a feeling that, trying on purpose, it will be difficult to tear the paper exactly like that.

The suspician I get from that article of fado is that the quickness of RC paper washing might be down to the titanium oxide layer underneath the emulsion not retaining thiosulfate, while barium sulfate possibly does.

I've learned a lot on forums, especially on Apug/Photrio. But as it is often the case, there will be the occasional old wisdom that should have gone the way of Kodachrome. And looking at the information out there I think the fixing and washing of FB paper is one of those cases.

I rinse my FB prints by washing 2-3 minutes in my slot processors wash slot (essentially what is a full wash for my RC prints), and then do a diffusion wash for 15-20 minutes in a Paterson Major.

 

[jvo]

Calling Hypo Clearing Agent "Hypo" is one of many pet peeves. Everyone should have a pet peeve to feed and tend to.

curmudgeons - makes the world go 'round

 

[removed account4]

Of course it is science, but the common wisdom floating around might have become stuck at some point, ignoring new scientific insights.

What I tried to express is that even less than perfectly finished prints might last for a long time, as it is likely that many old prints weren't processed all that well. OTOH hand some people seem to go to ridiculous lengths in terms of wash time in the hope of archival prints, but still use long fixing times (and acidid fixer, which can work fine, but there is no reason for it). Or worse sodium thiosulfate based fixers.

When I began darkroom work a few years ago I found this old german language article from December 2000. The title translates to: 'Long washing won't help - short fixing does!' It cites two articles. One in an old German magazin (Foto Hobbylabor 5/88) and the other on f32.com (can be found on archive.org: https://web.archive.org/web/20000529034401/http://f32.com/Articles/art021.htm).

They probably compared Sodium Hypo to acidic rapid fixers in the 80s (!). A long fixed print took two days of washing to get to thiosulfate levels of a short fixed print after 12 Minutes of washing. The findings resulted in Ilfords washing recommendation.

Today we have neutral fixers. Together with a very short stop in a buffered stop bath (TS-7, read the film developing cookbook) with high capacity it keeps the pH changes and ranges, the emulsion is exposed to, to a minimum. Less swelling and contraction of the emulsion along the process and efficient washing even without washaid.

Later I found that amazing article at fadu: Mysteries Of The Vortex (http://www.film-and-darkroom-user.org.uk/forum/showthread.php?t=296).

One interesting point is that fixer isn't stuck in the paper. More likely adsorbed onto the bariumsulfate (baryta) layer, possibly from the emulsion side. Anecdotally I had a single confirmation, due to an accident:

I wanted to use test solution on a fibre print, which was only rinsed. I wanted to tear the print into test sections and instead tore along the paper 'layers'. I.e. I got a paper wedge, exposing the inside of the paper. The inside tested negative for present fixer, while the emulsion gave a strong stain. I haven't repeated that so far. I have a feeling that, trying on purpose, it will be difficult to tear the paper exactly like that.

The suspician I get from that article of fado is that the quickness of RC paper washing might be down to the titanium oxide layer underneath the emulsion not retaining thiosulfate, while barium sulfate possibly does.

I've learned a lot on forums, especially on Apug/Photrio. But as it is often the case, there will be the occasional old wisdom that should have gone the way of Kodachrome. And looking at the information out there I think the fixing and washing of FB paper is one of those cases.

I rinse my FB prints by washing 2-3 minutes in my slot processors wash slot (essentially what is a full wash for my RC prints), and then do a diffusion wash for 15-20 minutes in a Paterson Major.

huh
that's all news to me about using plain old sodium thiosulfate as a fixer. I've done that off and on for 30 years and never had problems with retention of fixer in my prints.
maybe im just lucky ?

 

[Doremus Scudder]

The F32 "Comparison of Fixing Methods" article by Heinz Richter linked to above seems rather incomplete and questionable to me. Not only does he not really cite the sources he's drawing from, but he doesn't mention the testing methods he used for determining adequate fixing/washing. Nor is the article very complete, not to mention that the graphic is missing...


Martin Reed's article "The Mysteries of the Vortex" is worth reading. Part 1 is the most important and explains the variables in print washing and the options. I recommend reading at least that part. It is worth noting however, that in Part 2 of the article he states: "Using hypo clearing agent of some sort is the single most important step in washing fibre based papers, and this is true regardless of your aims, whether minimum tolerable standards are sought for the briefest possible wash, or the highest standards of archival permanence are desired. Careful workers are advised to never skip this step."

Advocating omitting this step with fiber-base papers as Iantau does is likely not the best advice.

=====================

In the interest of preventing confusion:
Hypo = sodium hyposulfate = sodium thiosulfate = conventional fixer. This slang name for fixer comes from the older chemical name. Just don't use it anymore and avoid any ambiguity.

Hypo Clearing Agent = Wash Aid = Hypo Clear = "fixer remover" in some cases. This is a sulfite-based solution to increase the efficiency of fixer removal when washing. Don't call it "Hypo" please.

Hypo Eliminator is an ammonia/hydrogen peroxide formula that is no longer recommended. It is not a wash aid of any kind; Hypo Clearing Agent is a wash aid.

=====================

Ammonium-thiosulfate-based fixers are the so-called "rapid" fixers and work faster than sodium-thiosulfate fixers. There is also evidence that sodium-thiosulfate-based fixers work less well with silver iodide, an ingredient in many modern films, so rapid fixers should be used with those. However, for papers, which contain mostly silver chloride and silver bromide, sodium-thiosulfate fixers should work just fine, albeit more slowly, thus requiring a longer wash time.

The entire "film-strength-rapid-fixer-short-wash" sequence is dependent on keeping the fixing time under or at 60 seconds, which prevents fixer from soaking the entire paper base and baryta layer. Fixing longer with any fixer means longer wash times and certainly the use of a wash aid if adequate washing is desired. Note that Ilford's Optimum-permanence Sequence relies heavily on a long (10-minute) treatment in wash aid. There are practical downsides to this method and some of us choose not to use it (me included).

I like two-bath fixing in "paper-strength" rapid fixer followed by a thorough rinse, a long treatment in wash aid and a long (60-minute minimum) wash time. I test with HT-2 to make sure I've washed well too.

@OP

I'm suspect of both Heico Permawash and the "Archival Permanent Wash" you link to above. The fact that the MSDS isn't on the website is a bit suspicious too; it seems they don't want you to know the ingredients. Sodium-sulfite-based wash aids are tried and true. These include the Kodak and Ilford products as well as a number of formulas for mixing it yourself. My favorite is: 1 Tbsp sodium sulfite and a pinch of sodium metabisulfite per liter.

The active ingredient in these oxidizes after a few hours, so it should only be mixed one-session.

Using the Kodak Hypo Clearing Agent one-shot as Matt suggests is likely efficient and easy. The other alternative, which you don't mention, is to make a concentrated stock solution of Hypo Clearing Agent and then dilute that for use as needed - one-shot.

Here's Kodak's instructions for so doing with the standard small packet:
To Prepare a CONCENTRATED STOCK SOLUTION:
1. Start with 1 U.S. gallon • 3.8 litres of water at about 80•F • 26.5"C.
2. Add all contents of this packet to the water.
3. Stir until the chemicals are dissolved and the solution is completely mixed.
For Use, dilute one part concentrated stock solution with 4 parts water.
Storage Life: Mixed Working Solution In a tray-24 hours, stock solution In a tightly-stoppered bottle - 3 months.


Best,

Doremus

 

[Paul Howell]

You can use Photographers Formulary T4 or 5, I've used Heico PermaWash for decades, although Heico claims archival results in as little as 15mintues I usually follow up a 30 minute wash, and I've tested the back of test strips to make sure the prints are clear. As there is chance that due to the ongoing drought my water bill will increase next year or the next I may cut back my wash to 20 minutes.

 

[john_s]

and the Kodak type HCA Stock solution can be made double strength so it's diluted 1+9. This might improve storage life.

 

[lantau]

The F32 "Comparison of Fixing Methods" article by Heinz Richter linked to above seems rather incomplete and questionable to me. Not only does he not really cite the sources he's drawing from, but he doesn't mention the testing methods he used for determining adequate fixing/washing. Nor is the article very complete, not to mention that the graphic is missing...


Martin Reed's article "The Mysteries of the Vortex" is worth reading. Part 1 is the most important and explains the variables in print washing and the options. I recommend reading at least that part. It is worth noting however, that in Part 2 of the article he states: "Using hypo clearing agent of some sort is the single most important step in washing fibre based papers, and this is true regardless of your aims, whether minimum tolerable standards are sought for the briefest possible wash, or the highest standards of archival permanence are desired. Careful workers are advised to never skip this step."

Advocating omitting this step with fiber-base papers as Iantau does is likely not the best advice.

To make it clear, anyone using acidic fixer, please use a wash aid. And it will never harm to use it, anyway. It will require the extra washing time, before applying wash aid.

When using neutral fixer, especially when not using wash aid and reasonably short wash times it might help to also use a well buffered stop bath. The salt load and short stopping time due to higher possible AcOH concentration (keeping the period of low pH as short as possible) help minimise contraction . Otherwise it would counter act the use of a neutral fixer. I also briefly rinse prints after the stop bath to put less stress on the buffer of the fixer.

Not only do I not fancy wasting time and water on excessive washing, I also see the trade off between pushing down levels of residual thiosulfate on the one hand and stressing the paper with long wet times.

I also don't like the idea of collecting prints in a water filled tray before washing them at the end of the day. From the 'Vortex' article I suspect that thiosulfate will entrench itself and be harder to wash out. There is something going on with the baryta. Or maybe the baryta-gelatin-interface. The observation in the article that it isn't the paper bulk and the idea that short fixing times help lead to that suspicion. There could be an adsorption/absorption with a fairly long time constant.

Finally, I do like Adostab II (Sistan). I'm aware of that one user, who ruined his collection by doing what no one could have foreseen (treating existing, old prints). But Adox is selling it and aparently there are no hordes of customers after Mirkos head. And I like the idea of chemically immobilising any residual thiosulfate much better than raping paper with endless washing.

If you are selling prints and truly master the old way, of course, never touch a running system. I simply feel there are pitfalls (such als collecting prints for later washing and/or fixing very long) that can negate that process and for most amateurs the short fix method, especially combined with Adostab, is not worse.

Just my opinion based on my own literature review.

 

[Sirius Glass]

curmudgeons - makes the world go 'round

Using the proper word or terminology is not curmudgeonly, it shows good education and a great mind.

 

[Jay Schrotenboer]

Using the proper word or terminology is not curmudgeonly, it shows good education and a great mind.

Didn’t you know that in these modern times education is a sign of curmudeonry. Only old timers care about education and critical thinking!

 

[Patrick Robert James]

I just throw some sulfite in a tray. Keeps it simple.

 

[AgX]

The suspician I get from that article of fado is that the quickness of RC paper washing might be down to the titanium oxide layer underneath the emulsion not retaining thiosulfate, while barium sulfate possibly does.

Your suspicion is based on the misconception that there is a "titanium oxide layer underneath the emulsion", which there is not. The TiO is a pigment embedded within the PE foil of RC to whiten this.

 

[AgX]

Finally, I do like Adostab II (Sistan). I'm aware of that one user, who ruined his collection by doing what no one could have foreseen (treating existing, old prints). But Adox is selling it and aparently there are no hordes of customers after Mirkos head. And I like the idea of chemically immobilising any residual thiosulfate much better than raping paper with endless washing.

I am not aware of a problem using Sistan on old paper, because of them being old papers. Can you link to such case report?
What is well known though is wrong application of Sistan, forming residual droplets at drying, leading to higher concentrations of Sistan in the dried paper at these spots by magnitudes.

Sistan does not immobilise thiosulfate at all.

 

[lantau]

Your suspicion is based on the misconception that there is a "titanium oxide layer underneath the emulsion", which there is not. The TiO is a pigment embedded within the PE foil of RC to whiten this.

Fair enough, but my argument still stands because the baryta layer may be causing an interesting effect here. RC paper doesn't have it.

I am not aware of a problem using Sistan on old paper, because of them being old papers. Can you link to such case report?
What is well known though is wrong application of Sistan, forming residual droplets at drying, leading to higher concentrations of Sistan in the dried paper at these spots by magnitudes.

Sistan does not immobilise thiosulfate at all.

Not old paper, old prints. There was a case were someone took prints, which had been finished for at least six months, and treated them with Sistan. That did cause problems apparently.

Now that you are saying it (and as usual no more), I think I remember. It isn't Thiosulfate that is immobilised. It is Ag-thiosulfate complexes which get, kind of, immobilised. The problem with thiosulfate is that it can form a complex with Image Silver, and that complex can diffuse. Later the complex can dissociate and deposit the silver. Then the print looks washed out.

With thiocyanate from Sistan being around it will have a higher complexation coefficient and thiosulfate can't do its thing. Not form a complex in the presence of Sistan, or, if it does, it'll hit a thiocyanate very soon and be replaced. That keeps the silver where it is.

Thiocyanate would also bring up the topic of better fixers than thiosulfate based ones. And easier to wash, without a need for wash aid, to get back on topic.

Sorry to the OP, I'm merely suggesting this pathway. But if you are happy with your existing fixer, sure go ahead. As the others noted, self made wash aid will be just as fine. I did do this for a brief period of time. But due to space and time constraints it doesn't fit my dark room process.

 

[AgX]

Yes, I meant to write old prints. I shall try to find out about that case. So far it makes no sense to me. But who knows, there are strange effects in photography.

Sistan scavenges free silver-ions, by this covering even decay not related to bad washing.

 

[BHuij]

I came here and posted this after reading parts 1 and 2 of the excellent Mysteries of the Vortex article. While the argument in favor of a short, strong fix and a subsequent shorter required washing time is strong, I have several years worth of Kodak powder fixer squirreled away, and since it seems it's absolutely possible to make fiber prints that will outlive me even with this outdated chemistry, I think I'll work my way through that before worrying about overhauling my entire approach to fixing.

At any rate, I have ordered and received some Kodak Hypo Clearing Agent. It seem it can be mixed one shot per printing session and discarded without racking up a lot of expense. So that's the right solution for me. Thanks all.

 

[Doremus Scudder]

BHuij,

The fixing regime for optimum permanence with your Kodak powder and fiber-base prints should include two-bath fixation (5 minutes in each bath - don't exceed capacity), a running-water rinse of two minutes or so followed by the treatment in HCA and then a thorough wash. Kodak recommends at least 30 minutes; I like 60.

That will get you prints that last for centuries.

Best,

Doremus

 

[gorbas]

It was APUG member Polyglot who had problems with Sistan. After that I stopped using Sistan on my prints. It was absolutely impossible to keep print face free of ocasional droplets or univeness of liquid Sistan layer. Maybe it works well just in machine processing where print is squeezed by two rubber rollers?