Selenium Toning - Overall Stain Due to Fix Acidity

[Rafal Lukawiecki]

Bill, it does seem like rinse duration is an issue in your case, and I'd agree with Michael, that your fixing time seems to be on a longer side, which would require a longer rinse. I do not know the Kodak Rapid Fix formulation, but I believe it has to be quite acidic, if it allows the use of a hardener. Too much acid in the print will cause staining in KRST. If your holding bath has many prints and not much turnover, plus a longish fixing time, you are bound to have this issue, as you are adding more and more acid into it with each print. Some of the people who I know and trust who use Kodak fixers, use 2-bath fixing, with the second bath quite neutral, made of plain sodium thiosulfate (but it does not keep). Prints remain in a holding bath after the first (acidic) fix, but they go straight from the second fix into KRST with no intermediate rinse.

If you would like to shorten the rinses and your overall process time, so that prints have been toned and are dry the next morning, consider a less acidic fixer.

For what it is worth, I use Ilford Rapid Fixer, which is only mildly acidic, hence it cannot be used with a hardener. Sometimes, I use Ryuji's fully neutral rapid fix, but the process is the same as with Ilford Rapid. I use it as per Ilford recommendation, 1+4 (film strength, ie. ca 10-12% ammonium thiosulfate) for about 1 min, single bath, then a quick rinse of 10-20 mins, and then into KRST 1+9. No staining using MGWT or MGIV fibre. Then wash aid (HCA, or 2% sodium sulfite) for 3-4 minutes, then a running rinse of 45-60 min in a slot washer. My prints test excellent for residual thiosulfate and residual silver halide.

By the way, an overconcentrated stop bath can also lead to staining in the Se toner. However, I wonder if yours is too weak, perhaps: I thought the Kodak Indicator Stop was supposed to be diluted 1+63. For 32 fl oz, ca. 1000cc, you would need about 15cc of it, not the 4cc you have mentioned. Considering that you only use 1 l of the stop, assuming a typical print size (8x10 or 11x14), and maybe 10-20 sheets of it in a session, this would mean that you might have another issue of an unneutralised developer carrying over from stop into the fix, causing another unwanted interaction. Having said that, your description (brown or yellow cream colour stain) fits the overly acidic print hypothesis better than this alternative, which could lead to dichroic fog stain.

PS. I was just refreshing my memory from Tim Rudman's "Toning Book". He mentions selenium staining a good few times, notably on p 46. To sum up, it is either underfixing or acid in the print. In addition to what has already been mentioned, he suggests using a bath of a wash aid (HCA etc) prior to toning, as a way to neutralise the acid from the fixer. As an aside, he also mentions that, apparently, this was one of the reasons Ansel Adams recommended diluting KRST with working strength HCA, instead of water, to help prevent staining.

 

[Bill Burk]

Thanks Rafal,

Helpful information, I think you're right.

For me, using Hypo Clearing Agent might be the way I go to avoid staining. Relying on an hour of water running is wasteful and I want to avoid that. Ronald Moravec's 8 cycles in 30 minute wash is an alternative that also fits my style, I make 3-4 11x14 prints in a session so I can pay attention to each print end-to-end.

I was afraid Tim Rudman's book would have a lot of good information in it about Selenium toning... because there are threads about how expensive that book is.

 

[Rafal Lukawiecki]

Michael, I am surprised that the Kodak Rapid Fix is not more acidic. It is interesting that 0.5 pH difference, at that level, makes it hardener-friendly, compared to Ilford Rapid Fix, which isn't. Still, the scale is logarithmic.

Bill, please let me know if introducing the HCA before toning, without a longer rinse, has eliminated the stain. And in any case I'd be cautious about a holding bath that accumulated a lot of fixer, though it largely depends on the bath's volume, I suppose.

 

[Rafal Lukawiecki]

That makes perfect sense, Michael. Thanks for explaining.

 

[NB23]

It is comon knowledge that a print should never be fixed if it contains a hardener since it won't wash well and it particularly won't tone well, with stains all over.

 

[Bill Burk]

Right, just the Rapid Fixer part A... Part B bottles are just accumulating with nothing to do.

 

[MattKing]

The part B hardener is great to have if you sepia tone.

 

[Vaughn]

My work flow led me to make prints over a period of time, and then take a couple copies of each image to tone (KRST) all at once -- perhaps ten or more 16x20 prints. Not knowing exactly when I'd get around to toning, I gave all but the work prints an archival wash and then dried. And then a long soak right before toning.

I used two different papers and worked out a work flow that gave me consistent results, so I could match print color pretty well over time. The Ilford Gallerie changed color only very slightly then stopped, and over-toning was not an issue. The Portriga Rapid was touchy -- I wanted to catch it in the transition color when it when it changed from the original warm-green, but before it went to almost purple-ish. There was a wonderful reddish brown if you could stop it there.

For the record I used Kodak Rapid Fixer, but I used the hardener (part B) at quarter-strength. I tried with no hardener: My prints were usually in the water for a long time as I did a final wash at the end of a 10 to 12 hour printing session. With no hardener, I got an impression of the dry screens on some of the prints (dried face-down) -- so I went back to some Part B, and had no more problems.

 

[Doremus Scudder]

Bill, it does seem like rinse duration is an issue in your case, and I'd agree with Michael, that your fixing time seems to be on a longer side, which would require a longer rinse. I do not know the Kodak Rapid Fix formulation, but I believe it has to be quite acidic, if it allows the use of a hardener. Too much acid in the print will cause staining in KRST. If your holding bath has many prints and not much turnover, plus a longish fixing time, you are bound to have this issue, as you are adding more and more acid into it with each print. Some of the people who I know and trust who use Kodak fixers, use 2-bath fixing, with the second bath quite neutral, made of plain sodium thiosulfate (but it does not keep). Prints remain in a holding bath after the first (acidic) fix, but they go straight from the second fix into KRST with no intermediate rinse.

If you would like to shorten the rinses and your overall process time, so that prints have been toned and are dry the next morning, consider a less acidic fixer.

For what it is worth, I use Ilford Rapid Fixer, which is only mildly acidic, hence it cannot be used with a hardener. Sometimes, I use Ryuji's fully neutral rapid fix, but the process is the same as with Ilford Rapid. I use it as per Ilford recommendation, 1+4 (film strength, ie. ca 10-12% ammonium thiosulfate) for about 1 min, single bath, then a quick rinse of 10-20 mins, and then into KRST 1+9. No staining using MGWT or MGIV fibre. Then wash aid (HCA, or 2% sodium sulfite) for 3-4 minutes, then a running rinse of 45-60 min in a slot washer. My prints test excellent for residual thiosulfate and residual silver halide.

By the way, an overconcentrated stop bath can also lead to staining in the Se toner. However, I wonder if yours is too weak, perhaps: I thought the Kodak Indicator Stop was supposed to be diluted 1+63. For 32 fl oz, ca. 1000cc, you would need about 15cc of it, not the 4cc you have mentioned. Considering that you only use 1 l of the stop, assuming a typical print size (8x10 or 11x14), and maybe 10-20 sheets of it in a session, this would mean that you might have another issue of an unneutralised developer carrying over from stop into the fix, causing another unwanted interaction. Having said that, your description (brown or yellow cream colour stain) fits the overly acidic print hypothesis better than this alternative, which could lead to dichroic fog stain.

PS. I was just refreshing my memory from Tim Rudman's "Toning Book". He mentions selenium staining a good few times, notably on p 46. To sum up, it is either underfixing or acid in the print. In addition to what has already been mentioned, he suggests using a bath of a wash aid (HCA etc) prior to toning, as a way to neutralise the acid from the fixer. As an aside, he also mentions that, apparently, this was one of the reasons Ansel Adams recommended diluting KRST with working strength HCA, instead of water, to help prevent staining.

Bill,

I started a rather long response to you before I read Rafal's post above. I basically said the same thing, so I won't bother to go into more detail and just quote him instead.

FWIW, I use Ilford Rapid Fix or Hypam, two-bath fixation at "paper-strength" and transfer the prints directly from the second fix to the toner. Never any problems with staining. I've used the Kodak (more acidic) products in the past, but didn't like the longer fixing times and the need for a different, less-acidic second fixing bath (I used to mix plain hypo, but now just use the Ilford products for all baths, plus film processing).

Your problem can be traced to either under-fixing or the prints being too acid. A second fixing bath with a less acidic fixer would cure both problems immediately and really give you some peace of mind. And you wouldn't need but one extra step, i.e., fix two. I really encourage you to try a two-bath regime.

Just a couple of other things: A wash-aid is designed to be used just before washing (as an ion exchange), not as a pH changing bath before toning. I differ from Rafal here... Since your toner contains ammonium thiosulfate, using the wash-aid before toning might alter the pH and prevent staining, but it won't help with washing. You would have to use another wash-aid step before washing, thus adding even another step to an already too-long process (fix 2-washaid-toner-washaid-wash...). You can solve the problem much more easily by simply using a more toner-friendly fixer.

If space is your concern, you might consider dividing printing and toning sessions like I do. I develop, stop, give fix 1 and wash and dry my prints in a "printing session." When I've collected enough prints (usually 36-40), then I set up a toning session that consists of a water soak, fix 2, toner, wash-aid and then wash. You don't need any more than four trays at a time.

@Those-who-think-Bill's-fixing-times-are-too-long: Kodak recommends "5-10 minutes for fiberbase papers" in their Rapid Fixer. Bill's 7 minutes is right in the middle of that.

There is another problem with short intermediate wash/rinse times before toning. If the print is not washed well before toning, there are areas in it with more still-undissolved silver compounds than others. Toning such a print can result in uneven toning, since the areas with lots of residual silver compounds may tone differently than the well-washed areas. This is the reason Kodak and others recommend a thorough washing before toning if not transferring directly from fix to toner.

Best and good luck,

Doremus

 

[Bill Burk]

This is the print I've been talking about. It shows the overall stain, which I believe is from the acidity of the fixer due to insufficient washing between fix and toner.

 

[clayne]

Bill, but this is with a single fix bath, isn't it? Try just 2 simple fix baths. Fix, rinse, fix, rinse, tone. You don't need extensive rinsing, maybe 10-20 seconds is all. You won't get staining if the fix is still fixing (which is why that 2nd bath is there). Washing the prints entirely before toning just to wash it all again is a: a lot of time, b: a lot of water.

 

[Bill Burk]

Yes, single bath fixer, but the fixer was fresh and the print had 6 minutes fix with constant agitation. I'm sure that the fixer was working actively enough to completely fix the print. I am also sure other fixer formulations can be used in the sequence you describe. But the Kodak literature recommends an hour wash between fix and toner, a wash aid certainly could reduce the time or need for that wash, but I am pretty sure the directions are there for a reason.

 

[Rafal Lukawiecki]

You won't get staining if the fix is still fixing (which is why that 2nd bath is there).

Clayne, assuming that fixer exhaustion, and therefore residual halide in paper, was the cause of the stain, I'd agree with you. However, there is a second, also common cause of Se staining, much described earlier on this thread, that is the carryover of a stronger acid, usually from a fixer. Some acidic fixer and paper combinations, even with a series of two fresh fix baths, will cause that stain.

 

[Roger Cole]

I believe I have read somewhere I cannot recall, but it was a reputable source... If you selenium tone after washing, it must be a thorough archival-style washing. If you tone after fixing, then go straight from fixer to toner with no rinse whatsoever. Otherwise, staining. Wish I could remember where I saw that, but I do remember it was some book of trustworthy repute.
Side note. Seems almost a pity and a shame to go through an archival wash, just to contaminate the print and have to do it all over again.

I just came up from the darkroom after staining two MCC 110 prints in selenium and searched to find this thread. I never used to get stains, but I used to wash first. Duh. I started going directly to toner from holding bath with MGWT paper into Legacy Pro brown toner, which doesn't seem to mind (in fact, if you use hypo clear, it hardly changes color at ALL, probably the sulfite in the hypo clear, or maybe inadequate wash after it, either way I learned NOT to wash before brown toning.

Problem (probably) solved due to APUG, thanks.

In this case I had some MGWT prints I brown toned and two MCC 110 prints from the same neg I made for comparison (see my recent post on LPD and shelf life. I liked the cooler ones too and set out to selenium tone one and not the other, for comparison. When the first one stained I said WTH and tried the other. At first I thought I escaped the stain but when I looked closely I didn't.

My frustration was that I never used to get this and used to selenium tone MCC 110 all the time (Bill, who started this thread, has such a print of mine.) It escaped me that this was the difference, so...resurrecting and old thread to possibly remind someone else!

 

[Roger Cole]

Quick rinse in water after fix and tone. Learned this from Fred Picker I believe decades ago.

The laborious first method also does work , but since you are getting stains, it is telling you the wash is not removing ALL the fix. First you need several rinses after fix, hypo clear, then wash. Soaking in a tray in insufficient. The best method without a print washer is with two trays, fill first with water and interleave prints while second tray is filling. Transfer prints to second one at a time, interleave two cycles while first tray is being refilled. Repeat through 8 trays of fresh water and it will take around 30 minutes. I have prints 50 years old that are fine.

Since you are getting stains, your method will show as stained prints at some point. I urge you to change method.

This is exactly what gave me stains, quick rinse (holding bath, actually) and then tone. Well - on second reading, no. My holding bath was much longer than a quick rinse, shorter than the wash you describe (well maybe not in time but without the interleaving and fresh changes) so...yeah, I can see that. I'll just use the second method for now.

OTOH I use the Ilford fixing sequence and fix for one minute in fresh film strength Rapid Fix (now, I have TF-5 on order) and that would probably make Fred Picker spin in his grave.

 

[johnnywalker]

I follow Tim Rudman's advice in his "Toning Book - The definitive Guide", which suggests:
1. Develope fully
2. Stop Bath
3. Fix - preferably 2 bath,( I ony use one, but the fix is fresh)
4. First Hypo Clearing Bath - prevents selenium staining (I use 3 minutes)
5. Wash - brief
6. Selenium tone
7. Second Hypo Clearing Bath
8.Final was 30 minutes for fully toned prints, 1 hour for partially toned prints
Resin coasted papers need only a short wash of four or five minutes and no second hypo-clearing bath.

I have never had stains using this regime.

 

[Doremus Scudder]

This is exactly what gave me stains, quick rinse (holding bath, actually) and then tone. Well - on second reading, no. My holding bath was much longer than a quick rinse, shorter than the wash you describe (well maybe not in time but without the interleaving and fresh changes) so...yeah, I can see that. I'll just use the second method for now.

OTOH I use the Ilford fixing sequence and fix for one minute in fresh film strength Rapid Fix (now, I have TF-5 on order) and that would probably make Fred Picker spin in his grave.

(empasis added)

Roger,

There are a couple things in your workflow that might cause staining. One is the less-than-full wash (i.e., water holding bath) that you use. If your stains look more like uneven toning than yellowing of the paper base, this is likely the problem.

The other is acidic carry-over from your fixer. FWIW, I use Ilford Rapid Fix and MC110 all the time and transfer prints directly from the second fix to the toner with no intermediate rinse. The difference is, I use the "paper strength," i.e., 1+9 dilution, which is less acidic.

The third possibility is simply inadequate fixing. To tell the truth, I am suspicious of Ilford's fixing sequence. It is too much "on the edge" for me. Yes, with the right paper, really fresh fixer and precise timing, it is possible to give a quicker fix and keep the fixer from soaking so much into the paper base, thereby reducing wash times.

However, Ilford only tested with Ilford papers... You would have to do tests for residual silver with MC110 (or any other non-Ilford paper) to really confirm that this method works well for it. Plus, you don't really know the capacity of the fix with a particular paper unless you test an entire run and find the point where the fixer no longer does its job in 60 seconds. I prefer the weaker dilutions and two-bath fixing coupled with a wash aid and a longer wash. BTW, I do test for both residual silver and hypo regularly, and have no problems with this workflow. It uses less fixer and works just fine.

The point being: maybe your 60-second fix isn't good enough for MC110... or maybe you've exceeded the capacity of the fix, even if you are still under the Ilford recommendations.

Best,

Doremus

 

[john_s]

.........To tell the truth, I am suspicious of Ilford's fixing sequence. It is too much "on the edge" for me. Yes, with the right paper, really fresh fixer and precise timing, it is possible to give a quicker fix and keep the fixer from soaking so much into the paper base, thereby reducing wash times.

However, Ilford only tested with Ilford papers...

Doremus

I remember reading some time ago (sorry I don't remember where) that the Ilford fixing sequence did not work with Kodak papers (that's how long ago it was!). As Doremus suggests, maybe others as well.

It seems to me that if you have space for a second fixing tray, a simple fixer like sodium thiosulphate plus a dash of sodium sulphite would make a perfect second fixing bath, being cheap and not acidic.

 

[Doremus Scudder]

I remember reading some time ago (sorry I don't remember where) that the Ilford fixing sequence did not work with Kodak papers (that's how long ago it was!). As Doremus suggests, maybe others as well.

It seems to me that if you have space for a second fixing tray, a simple fixer like sodium thiosulphate plus a dash of sodium sulphite would make a perfect second fixing bath, being cheap and not acidic.

Adams and others recommended a plain hypo bath immediately before toning. I would use one too, if needed, but the convenience of being able to use just one fixer for everything trumps that. Plus, plain hypo needs a longer fixing time. As I mentioned, Ilford Rapid Fix diluted 1+9 works just fine.

However, if I were having staining problems, using plain hypo would be one of the first things I did to check the work flow.

Best,

Doremus

 

[Roger Cole]

Thanks Doremus. I did test it, some time ago, and it fixed completely at the time.

But in any case the only reason I was still using Rapid Fix was that Freestyle was out of TF-5 when I had to order fixer because about half of my old big "makes 5 gallons" jug of Legacy Pro RF crystalized in the winter. I now have TF-5 on the way. Hopefully that will also resolve the staining issue. That wasn't the reason for the change - that's mostly the lack of need for a wash aid and the reduced odor.

 

[Andrew Kleinfeld]

selenium toning-staining

I quit using selenium toning years ago because of splotchy (not overall) staining.

But my new (for the last two or three years) protocol seems to prevent this.

When I print, I fix in rapid fixer and don't worry about freshness and thoroughness, and wash a little, but don't worry about archival washing. I don't have an unlimited supply of water from our well.

When I feel like it, maybe weeks or even a couple of months later, I bleach a little if necessary. Then I fix thoroughly in a freshly mixed bath of plain hypo (sodium thiosulfate, which I buy in 10 pounds or 25 pound lots so it's inexpensive), and put the print directly into the selenium toner from the hypo. No washing or wash aid in between. No stain, no blotches, smooth toning.

I think, based on my experience, that the splotchy staining may be caused by inadequate fixing and residual silver rather than the presence of fixer in the paper.

 

[Bill Burk]

Note to self:

5. Wash prints 2 hours.

NOT 20 minutes. While not as extreme a stain as my earlier example, some of my last batch have areas of disconcerting off-white coloration.

p.s. It may help to put a high-lumen light source over the trays while toning. Sure a 60 watt bulb is perfect in the darkroom while printing... But over the toning tray you really need to see if there is staining.

 

[CropDusterMan]

Here in Southern California (and all of CA for that matter), water is at a premium. Washing for two hours
even, is a tough one, especially when you do a lot of printing. I only print fiber, other that contacts, and the
days of washing for several hours are long gone...I've had to scale it back and my Paterson print washer
has helped significantly. I Selenium tone regularly, and have achieved good results.

 

[DREW WILEY]

I haven't read all the preceding threads, so forgive me if I'm merely repeating something already mentioned. I never have a problem. The
sheets are all processed, including my usual TF4 Fixer, then placed in a tray of plain water, soaking while I drain and clean up the other trays, start filling my slot washer, etc. Then I mix or dilute my various toners for that session, possibly including selenium. I use a variety of fiber based papers. To my knowledge, you never get an unwanted stain unless some portion of the print was incompletely fixed. My actual wash cycle is after toning, always. Some toners contain hypo. I never use wash aid - no need with TF4. My normal wash time is one hour, though I've been informed that this is overkill with TF4. We've got an unusually severe drought here, so I'll probably have to alternate between actual active washing and soak cycles in the slot washer. But I normally do most of my black and white darkroom work in winter anyway, when our local reservoirs are full even in bad years. It's our backup reservoirs which rely on Sierra snowpack that are suffering right now, since the Spring snows have been marginal. If I ever ever got an unwanted selenium splotch, it was probably well over thirty years ago, when I was just a beginner at this.

 

[Bill Burk]

Hi Drew,

Your arrangement would always work because TF4 is an alkaline fixer. Kodak Rapid Fixer is acid, so I have to get rid of some of the acidity...

No matter how much experience, when I rush things that need to take time, I usually have to do them over.

I had it down very nicely until I rushed this last bunch...