Alkaline Fixer

A

Anthony

Guest
I saw the archival washing post. Some of you may be interested in this.

I've used alkaline fixer for films and papers for the last 20 plus years or so with excellent results. Prints show no stain from HT-2 after 10 minutes washing in trays; about 10-12 changes of water. In fact, a test print showed no stain after 6 minutes but I wash for 10 anyway, 6 for film. Pretty frugal for a Yank, eh?

Because it's not an acid solution, the paper fibers don't compress and trap the fixer. Nothing has to leach out over many hours. That's an outdated notion. Film and paper has been pre-hardened for quite a few years now.

The same principle applies to laundry detergent. It's why acid-based clothing stains that are so tough to wash out - tomato sauce, wine . . . Laundry detergent is alkaline - it "opens" the fibers so that dirt and stains can wash out.

If you have even moderately careful darkroom habits, you won't damage film and prints. Sometimes edges of print emulsion may dislodge - at least with Foma paper - but the black border from a film holder is plenty of allowance. And this effect is minimized if the wash water is 22 C (70 F) or below. I've never found it to be a problem. If you mix your own hypo clear, add some sodium bisulfate and you'll be fine. Now that I think back on it, I don't remember Multigrade doing this . . . in any event the effect is very marginal.

You do need to treat film and prints in hypo clear - 2 minutes. For a large stack of prints, about 4 times through the pile. You'll almost feel when the print is washed properly - you can feel the "tooth" of the paper.

Alkaline fixer is also completely odorless. It's pleasant to use - not harsh like acid fixers. You also can't overfix with alkaline fixers. If you're interested I can post the formula here, give times, and answer questions if you have any.

I know, I know . . . I didn't believe it would work either. In my old darkroom I tested this over and over and got the same result. I retested in the new one and got the same wash times. Twenty plus year-old prints are fine - no yellowing, no fading.

Best thing about it - It does just as good a job, and saves a lot of time and bother. I'm a big fan of eliminating drudgery, eh?
 
Don't know about alkaline fixers in general, but the Photo Formulary's TF-4 just has too much ammonia smell for me to use in open trays; especially over the longer darkroom times when printing. FWIW, I have prints in my portfolio and several framed prints on my walls that are nearly 40 years old and they don't appear to have changed at all. I'm sure my process to achieve these results took more time than what you've stated above, but as I type this I'm thinking of something my photo mentor used to say about the use of "regular" fixer vs rapid fixer: "What's the rush?" :)
 
No rush of course, but if I can take 10 minutes to wash prints rather than hours, I'd rather do that. Save time for all the creative decisions during printing.

The formulary stuff is rapid fix, what I use isn't. I agree about the smell. The alkaline fix I use is just pleasant to use. I'd use it for that reason alone.
 
I guess the time it takes to wash prints doesn't bother me. I usually run the washer for about 1/2 hour, then let it sit for maybe another 1/2 hour, then run it one last time for 20 - 30 mins. Back in the day, I used to leave the prints in the washer overnight, but I think that's overkill.

Can you post the formula for your alkaline fix?

Thanks!
 
Sure thing - here it is.

Alkaline Fixer, 4 Liters
Water - 2800 ml
Sodium Thiosulfate (crys)* - 1000 grams
Sodium Sulfite - 60 grams
Sodium Metaborate** - 40 grams
Water to make - 4000 Ml (4 liters)

I start with water temp about 40 C or higher (100 F). Hypo cools the water as it dissolves.
*not anhydrous
**Balanced Alkali

Fix twice the time it takes to clear the film. I fix prints for 3-1/2 - 4 minutes. For 2 bath fixing, about 2-1/2 - 3 minutes in each (you can't overfix in this stuff).


I'll also include a formula for Hypo Clearing Agent. This is based on an old Kodak Research formula (Hence the KR). It works the same as their regular hypo clearing agent.

KR Hypo Clearing Agent
Water - 3 Liters
Sodium Sulfite - 160 grams
Sodium Bisulfate - 16 grams
Water to make - 4 Liters

Dilute 1:1 for use. After fixing, rinse with water, then agitate for 2 minutes or so.

If you use alkaline fixer, wash 6 minutes for prints, 10 minutes for prints. One complete change of water per minute will do it. I agitate through the pile, dump the water, and refill.

Capacity is about 25 8x10 prints per liter of working solution.

Enjoy.
 
Thank you, Anthony.

A couple of questions:

1. Do you use only a water stop for both film and prints?

2. Regarding washing... Did you mean "wash 6 minutes for film, 10 minutes for prints"?
 
Alan - I'm sorry, yes you're correct. Six minutes for film washing (6 changes of water) and 10 minutes for prints (10 changes); temperature at 22C or slightly below.

And I omitted clarification about the stop bath. I haven't used an acid fix or stop bath in so many years I didn't think of it.

Use plain water for an alkaline fix stop bath. For an 8x10 print in a 10 x 12 half full tray, 30 second stop bath in plain water. For up to 4 prints, agitate through the pile and change the water once. For more 2-3 prints at a time, I always change the water.

When the fixer clearing time is nearing twice the original, the fixer is exhausted. Capacity is about 100 8x10 prints per 4 liters.

Good?

I'll provide my toning setup in a bit here . . .
 
I've always used a water stop for any alkaline fixer, but I just wanted to clarify that point to be sure. Thanks!

Always interested in how other photographers work...looking forward to your toning technique.
 
Selenium Toning

For final prints, I always tone them. Prints acquire a cool purplish color, and toning increases permanence (not that I really care about that - if the prints outlast me, that's fine.)

I fix prints in alkaline fixer for 3 minutes. I have 4 containers mixed - A, B, C, and D. Each holds 2 liters. I use one container, let's say A for general use - film, proofs, and a 1st fixing bath for final prints. So for example I'm using A. After fixing, prints go in a holding bath until I'm done printing. If A isn't exhausted, I place it back in its container until next time. When I'm ready to tone, I'll use a fresh fixing bath - B.

The trays are set up left to right - water, fix B, toning bath, hypo clearing agent, water. Fix B is always used for the second toning bath. When A exhausts, then B becomes the general use fixer, and fix C becomes the second toning bath and so on, yeah?

The toning bath starts out as 2 liters of water, to which I add about 1/2 teaspoon of Sodium Metaborite (Balanced Alkali). To this I add 40 ml of Kodak selenium toner. The toning bath must be alkaline or the prints will stain. Selenium is poisonous, so wear gloves; You don't need a respirator for relatively short time periods - toner gives off a little ammonia, as do lots of household cleaners.

You'll see it recommended to mix the toning bath in hypo clearing agent. That does no harm, but since there's hypo in the toner, it doesn't make much sense. Prints wash faster if you use the HCA after the toner.

I take about 8 prints and fix them, agitating for 3 minutes, then transfer the entire pile to the toner. Eight to 10 prints are about the limit that I can efficiently agitate in 30 seconds. Agitate the prints in the toner and note the color change. In this dilute toner solution, Foma VC paper (fiber of course) seems to tone quickly. If I recall correctly, Ilford Multigrade tones a little slower. When the color cools, and the blacks are deep and rich - about 3-4 minutes - I transfer the pile to the hypo clearing agent. Agitate for 2 minutes. If you use the KR HCA, make sure it's at 22C or a little less. Same with the wash water.

After the HCA, I put the fixer back in the B bottle, dump the toner solution and rinse the tray. Off with the gloves. I fill the tray about half full with water, put the prints in it and agitate through them. Dump the tray, fill by half and repeat. I fill the trays half full initially to carry away heavy concentrations of fixer quickly. After doing this twice, then you can fill the tray completely - this is for 5x7 prints in an 8x10 tray; for 8x10 prints in a 10 x 12 tray, filling the try may be overkill. Half or 3/4 full is fine because the fixer doesn't imbed itself into the fibers, it only acts on the unexposed silver. Agitating the prints frees the fixer into solution.

For 16 to 20 5x7 prints, agitating prints through 10 changes of water in an 8x10 tray or for about 10 minutes gives an archival wash - no HT-2 stain visible. 8x10 prints are about the same. For a greater quantity of larger prints, you may need to wash a little longer, but not much. Test with HT-2 to be sure. You can feel the tooth of the paper fiber when the print is washed well.

I always dump the tray rather than let water run in and out. It's more efficient. Get the fixer out of there completely, although with alkaline fixer, washing is fast either way. I never bother with massive archival washers anymore - by the time I load the prints in there, I could be halfway through washing them in a tray.

If you've done a good job fixing your prints, they'll be clear and brilliant. If not, they'll be stained. So toning is a good test of how well you're fixing your prints, comrades.

Sound like fun? Carry on.

(Why didn't Kodak ever offer an alkaline fixer if it's so much better? Because that noxious powdered stuff sold by the bushel - "the old standby." It's the reason that eventually sunk them. Greed.)
 
There's some very mixed up assumptions here.

Firstly most modern fixers are Rapid and based on Ammonium Thiosulphate, ironically although Rapid they aren't as efficient as you re-use them and silver levels build up, which is why two bath fixing is recommended.

These days even Rapid (acid) fixers are close to neutral pH5.4, black coffee is pH5, a typical acid stop bath pH2, so called Alkali fixers are onl just past neutral typically pH6.5

The issue with Ammonium Thiosulphate fixers is Ammonium is itself a Silver solvent forming weaker silver complexes that those formed with the Thiosulpate these permeate the fibre base and form cellulose-silver complexes. These are all equilibrium reactions and with fresh fixer in a two bath regime. I did some reasearh into all the intermediary complexes formed for work 30+ years ago.

pH also affects emulsion swellimg although most films and papers are well hardened, this affects the rate at which silver-thiosuphite complexes will was out of the emulsion. If a slightly acidic fixer like Hypam or Kodak & Ilford Rapid fixer then a wash aid is benificial with Fibre based paper, firstly they are mildly alkali but more importantly they are Dodium based predominantly Sodium Sulphite, although Agfa used Sodium Carbonate, and Sodium Chloride will work as well. What's happening here is the Ammonium ion in the Ammonium/Silver complexex is replaced by the Sodium ion and the resulting complexes bind less well with cellulose and can wash out.

There's mention of "Sodium Bisulfate", no way shouls a Sodium Sulphate be in a wash aid as it's a gelatin hardening agent and will inhibit washing, it's probably a type.

With RC papers and films a wash aid has little to no benefit.

Ian
 
The man asked me about toning procedure and I posted it. I didn't think I was testifying before the US Senate.

This isn't an Ammonium Thiosulphate fixer, it's sodium thiosulfate. I use it because it's cheaper and milder, and fixes the prints just as well. I'm aware of the Ilford rapid fix philosophy - the fixing is so quick that the chemical doesn't soak in. I'm aware of that. It's great information. Ilford's a great company.

I know pH affects emulsion characteristics. That's why until films and papers were pre-hardened, alkaline fixers weren't practical. And that's also why wash water shouldn't be too warm. I also know most fixers are neutral pH without an acid hardener. So what?

Hypo clearing agent is just highly refined salt water. The US Navy in WWII discovered that prints washed faster in salt water than in fresh water. HCA was marketed after the war. The bisulfate keeps the emulsion from softening excessively in the HCA, that's why it's there.

Of course for waterproof papers you need none of this. I'm not discussing waterproof papers. But this alkaline fixer is mild, so I use it for those papers also. I don't use rapid fixers because they're harsh and unpleasant to use - for me.

Some very bright people recommended these methods to me many years ago. I followed the recommendations and testing bears out the practicality of using them. I don't know why they work. I couldn't care less either. I just work them.

Look man, use whatever you want to. I use this stuff, it makes darkroom work easier and faster and saves me money. For years I've tested it over and over. I have very old prints processed using these methods and they're in fine shape. If you want to use rapid fixer, use it. If you want to use premixed wash aids, use those. I'm happy about it, whatever you use. This is what I use and it works.

Gracious . . .
 
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I had realised you posted a Sodium Thiosulphate based fixer.

You need to check that frmula uses Bisulphate because Kodak Hypo Clear is predominatly Sodium Sulphite and Sodium Metabisulhite with a small amout of EDTA and Sodium Citrate.

In fact Sodium Bisulphate would inhibit effective washing very significantly as it's very acidic, it's used in some reversal bleach formulae in place of Sulphuric acid.

Ian
 
Obviously you're very knowledgeable and an expert in photographic chemistry. I appreciate your comments.
 
Barry Thornton improved TF-3 fix for Dixactol to retain pyro stain. Reducing the Sod. Sulphite and increasing the Sod. Metaborate is implemented to retain the stain on the negatives.
Ammonium Sulphite (anhy). 57-60% solution 800ml
Sod. Sulphite (anhy). 20g
Sod. Metaborate 15g
Water up to 1 ltr.
 
Anthony said:
Obviously you're very knowledgeable and an expert in photographic chemistry. I appreciate your comments.
Click to expand...

Spent over a decade as an emulsion & photo chemist :D


Camerashy said:
Barry Thornton improved TF-3 fix for Dixactol to retain pyro stain. Reducing the Sod. Sulphite and increasing the Sod. Metaborate is implemented to retain the stain on the negatives.
Ammonium Sulphite (anhy). 57-60% solution 800ml
Sod. Sulphite (anhy). 20g
Sod. Metaborate 15g
Water up to 1 ltr.
Click to expand...

That should be Ammonium thiosuphate.

Actually SAndy King and others found that Hypam. or Ilford & Kodak Rapid fixer have no detrimental affect on staining. I use an Ilford Olive Brown toner IT-8 this uses a simle Pyrocatechin redeveloer, but I found Pyrocat HD at 1 + 1 to 10 works just as well. Experimenting with test strips I found once formed the stain is very stable near impossible to reduce.

When PMK was introduced by Gordon Huching it was recommended that you keep the used developer and after fixing and a brief rinse immerse the film in the used developer as it increases the staining. It does but unevenly and as a base fog, essentially the oxidised developer acts as a weak dye. Tht recommendation was quickly droped as it decreased negative quality.

Ian
 
Yes Ammonium thiosulphate, I agree Hypam rapid fix has no detrimental effect on pyro stain, it is acid in the stop bath that may slightly reduce the stain. I use 3 rinses of water as a stop bath.The stain occurs during development. Alkaline fix maybe beneficial with regard to reducing wash times with fb papers. Alkaline fix has a long shelf life due to it not having any acid in it. Ilfords new heavy weight RC Portfolio paper looks like a good alternative to fb paper, has anyone tried it yet?
 
I read somewhere recently that Gordon Hutchings recommends using Kodak F-24 fixer (an acid fixer) for PMK negs. I've used it with Pyrocat-HD negs for years and if it reduces stain I never noticed it. I know a couple of photographers using good 'ole Kodak Fixer with staining developers and I've never heard them complain about stripping the stain. IIRC, even Sandy King said at some point that "regular" fixers were acceptable with Pyrocat use. Personally, I remain unconvinced that any fixer is of any concern with a stained negative so I'll continue on with F-24.

@Camerashy, I've been watching for a dealer here in the USA to get stock, but nothing, yet. I'm not a fan of RC papers, but I'll certainly give it a go when it's available here.
 
Hi, if you do a search for Steve O'nions on YouTube he has a short video about Ilford new papers.
 
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