Selenium fixer stain problem

[cirwin2010]

I'm getting splotchy stains on some of my prints after selenium toning and I'm trying to figure out where I am going wrong. The stain looks like what happens if you don't properly fix your print before selenium toning, but I think I'm doing everything right? Not sure why this suddenly became an issue.

I'm working with a relatively new bottle of Ilford Rapid Fixer and a new box of Ilford Multigrade Classic FB paper.

My process is as follows:
1. develop in 1L of Liquidol 1+9 for 2.5 minutes with constant agitation
2. agitate in a water bath for 20 seconds
3. fix in 1L of Ilford Rapid Fixer 1+4 for 60 seconds with constant agitation
4. rinse and store in a holding bath (up to several prints in the bath)
5. Selenium tone in Kodak selenium toner 1+9 until desired effect
6. rinse and move to wash bath
7. was for 60 minutes

After getting some staining on a recent print, I went ahead and made some more but this time using a fresh batch of fixer and fixing for 2 minutes. After making another 3 copies a processing as above mentioned (just with a 2 minute fix now) I got the following results:

First Print:
Looks fine.

Second Print:
Looks fine until the my scrutinizing inspection. You can just see some splotches if viewed from the right distance and lighting, or if you shine a bright light through the back of the print.

Third Print:
Visible brown splotches in the highlights.

This seems to be a pattern where later prints are getting stains. I had a similar problem a previous session (again with fresh fixer) after making a few prints. The fixer should be no where near exhaustion as I only made a handful of prints. I don't print enough to justify setting up a two bath fixer setup, so I tend to just make fresh fix for each working session.

Not sure where I am going wrong. I did order some more fixer just in case (and as I am running low).

 

[cirwin2010]

I would like to add that I got these results when working with 11x14 paper. Just happened to be the size I'm working with on the given project. Also the previous batch of paper that showed staining was Bergger Neutral FB paper. So it doesn't seem paper specific.

 

[cirwin2010]

Since I have been sitting here wondering. Could this be an issue with not using an acid stop bath, or inadequate washing prior to toning? Can the fixer itself cause stains when exposed to selenium?

 

[xkaes]

I've never had this problem. I don't think the lack of a stop bath would do it, but I always use one, so I can't say what impact that has on the fixer. My guess would be fixer contamination of the wash water carried over to the toner. I think I read that even a little fixer can mess things up.

 

[koraks]

2. agitate in a water bath for 20 seconds

Replace this with a proper stop bath and see if the problem goes away.

I don't think the lack of a stop bath would do it

I have my doubts; I'd still give it a go since it's easy enough to mix up a tray of citric acid or acetic acid solution.

Can the fixer itself cause stains when exposed to selenium?

My guess would be fixer contamination of the wash water carried over to the toner. I think I read that even a little fixer can mess things up.

Maybe, and that's also worth a try. Note that selenium toner has some thiosulfate (=fixer) in it. However, it doesn't (shouldn't) have silver-thiosulfate complexes in it, which used fixer of course does have. So it's not the fixer as such, but it may be used fixer.

So add a stop bath, and wash more thoroughly between fix and toning.

 

[Nicholas Lindan]

It sounds like your bottle of mostly fresh fixer isn't fresh and only has 1 print's worth of capacity. Am. Thiosulphate fixers can go bad in the bottle.

My general advice. Not telling you anything you don't already know, more pour encourager les autres.

As Koraks said, use a proper acid stop bath. It keeps the fixer from going bad quickly and keeps developer out of the fixer. Developer getting into the fix will also cause stains, especially if you turn the lights on right after the print goes in the fix. This is a real problem if you use an alkaline stop/fix regime.

Use a 2-bath fixing regime - 2 minutes in each bath minimum. After each session save the old second bath for use as a first bath in the next session - the method uses no more fix than using only one bath.

Use HCA and a proper wash.

You don't want any fixer-silver compounds in the print when it goes into the Se.

 

[cirwin2010]

Well it was either the lack of stop bath or not enough washing after the fix.
I just tried again with three prints, but this time use an acid stop bath and washed for about 10 minutes prior to toning. I don't see any stain this time.

 

[snusmumriken]

Back along (quite a few years back), I did pretty much exactly as you describe, except that I always used a stop bath, and got the same stains. I don't get stains any longer. What I have changed:

1. I use a 2-bath fixing system with Ilford Rapid Fix 1+5 [EDIT: sorry, I meant 1+9!], 1 minute in each bath (not 1 min in total, despite what Ilford say). The second bath is always freshly mixed for the session, and becomes the first bath next time.
2. I wash each print in running water while I make the next print. It may then go into a holding bath, but either way it gets washed for a full 15min in running water before toning.
3. After toning, I wash again for 15-20min in running water. I don't want to have to make these prints again!
4. All my trays and their tongs are labelled and reserved for that particular function.

Glad to see you have overcome the problem while I have been typing, but it's my belief that each of these four measures contributes, and together they amount to a kind of chemical hygiene.

Happy printing!

 

[xkaes]

It's a warning/reminder to all of us.

 

[koraks]

Well it was either the lack of stop bath or not enough washing after the fix.
I just tried again with three prints, but this time use an acid stop bath and washed for about 10 minutes prior to toning. I don't see any stain this time.

I'm glad you've been able to so quickly make progress. You could now try to track it down to either the stop bath or the wash-after-fix regime. Or just call it a day and from now on do both the stop bath and the more extensive wash and get it all over with.

 

[cirwin2010]

Actually, sorry, I think I spoke too soon. I just took the prints out of the wash bath and moved them to different lighting. There are still stains, but much better this time. The pattern is similar. One print has no stain at all. Another has maybe the smallest hint of something if you squint and stared at it long enough. And a third that has more visible stain, but only really visible on the borders of the print. :/
Again this was with a new fixer bath. I don't really have room in my sink for a two bath unfortunately. I made my sink a little too small for that.


I'm going to try something. I'll take a unexposed, undeveloped strip of paper, fix it, wash it, and put it in the toner. Then see what happens. In theory nothing should happen, but if something does, then obviously something is off.

 

[Doremus Scudder]

My thoughts after 40+ years of dealing with selenium toner:

First, stains from the toner are caused by two things: 1. insufficient fixing 2. a too-acidic fixer right before the toner. Neither of these may be your problem, see below.

Dealing with the first cause of staining problems is easy; use fresh fix and a two-bath fixing regime and make sure your second fix is not too acidic if you're transferring prints directly from the fix to the toner. Note that if you use an acidic fix, you really need to wash your prints well before toning or staining can result.

There are a couple of strategies for the toning regime. The first is to use whatever fixer you like, acidic or not, and then wash your prints well (think 20 minutes) before toning. The second is to use a near-neutral or alkaline pH fixer immediately before the fix and then transfer the prints directly from the fixer to the toner. I use the second method.

FWIW, I use Ilford Rapid Fixer at the 1+9 dilution and a two-bath fixing regime. I have no problems transferring the prints directly from the second fix to the toner. I use 1.5-2 minutes in each bath.

Enough about fixers and toners. I have a suspicion that neither of those is your problem. I had severe staining problems when using Liquidol. There is something in the developer that gets carried over, even with an acid stop bath and adequate fixing that can stain. I suspect the fact that your fresh solutions result in less staining, which progressively gets worse as you use them, is a result of whatever by-product or component in the developer getting almost completely removed or neutralized at first, but then progressively becoming less so.

Try a different print developer and see if the problem goes away. I ditched Liquidol and have had zero staining problems since.

And, while I'm on my soapbox, do use a two-bath fixing regime if you can, to ensure really good fixation before toning. Also look into reusing and replenishing your toner if you aren't already (I've posted rather extensively on this, so just search here and over on the LF forum if you want more info). I just finished a toning session with 10+ year-old toner; the prints look great.

As far as two-bath fixing and space goes: I divide my workflow into printing and toning sessions. The printing session consists of developer, stop, fix 1 and a 30+ minute wash and then dry. Fix 1 is 2 minutes in Rapid Fixer 1+9. This only needs three of four trays (I use four, since I always have a running-water tray for a holding bath).

I collect prints, culling the non-keepers, and collect enough for a toning session, which is one two three washer-fillings for me (12-36 prints). I then set up for toning: water soak, fix 2 (always fresh), toner, water rinse, wash aid and finally a 30+ minute wash and then dry. This saves me both space and time.

Hope this helps,

Doremus

 

[xkaes]

If you're short on space, you can solve lots of problems by using tubes. They use a lot less chemicals and every print gets fresh chemicals. I'm not short on space, but my tubes give me more space for trays for washing and toning -- which I need frequently.

 

[cirwin2010]

Actually, sorry, I think I spoke too soon. I just took the prints out of the wash bath and moved them to different lighting. There are still stains, but much better this time. The pattern is similar. One print has no stain at all. Another has maybe the smallest hint of something if you squint and stared at it long enough. And a third that has more visible stain, but only really visible on the borders of the print. :/
Again this was with a new fixer bath. I don't really have room in my sink for a two bath unfortunately. I made my sink a little too small for that.


I'm going to try something. I'll take a unexposed, undeveloped strip of paper, fix it, wash it, and put it in the toner. Then see what happens. In theory nothing should happen, but if something does, then obviously something is off.

Well, I think I just discovered for myself that selenium toner only works on metallic silver, not silver halides. I did the following tests.

1. paper straight into the selenium = stains eventually (probably from light exposure printout)
2. fixed paper 1 min -> selenium = no stain
3. stop bath -> fixed paper 1 min -> selenium = no stain
4. developed paper with and without exposure in liquidol -> stop bath -> fixed 1 min -> selenium = STAIN
5. developed paper with and without exposure in liquidol -> stop bath -> fixed 2 min -> selenium = STAIN
6. developed paper with and without exposure in xtol -> stop bath -> fixed 1 min -> selenium = STAIN
7.developed paper with and without exposure in liquidol -> stop bath -> fixed 2 min -> selenium -> washed for 60 minutes = IN PROGRESS

I think I can conclude it isn't the developer in this case per Doremus' post. I'm not really sure what to make of this yet. If there is no stain after fixing undeveloped paper then I would think the silver halides are being adequately removed from the paper. But if I put the paper in developer first (as you normally would) then I get staining. Only variable I think is left is washing the print well prior to toning. I have a test strip washing right now and I'll throw it in the toner in about a hour. Fingers crossed it is just a simple issue of inadequate washing.

To be continued...

 

[Doremus Scudder]

Try diluting your fixer 1+9 and transferring the print directly to the toner, after fixing adequately, of course.

Best,

Doremus

 

[MattKing]

As a film developer, XTol would normally be much less active than Liquidol, so I'm not sure that will tell you a lot.
Try another developer set up for prints.

 

[cirwin2010]

The results are in! The test strip I washed for 60 minutes prior to toning does not have any stain! Assuming this is a wash issue, I'm going to get myself a nice slotted print washer. Shuffling multiple print and keeping print submerged in a trickle tank is not a fun way to spend my time...
I would like to retest, but I don't have the energy to set up all my trays again today.


Also assuming this is a wash issue, I'm not sure I understand the interaction between the developed paper and remaining fixer in the selenium toner.

I'm trying to think through why this might not have been an issue before. Lately I've mostly been sepia selenium split toning my prints. This process requires a thorough wash prior to bleaching and redevelopment so all the fixer would be gone. Two years ago I was only selenium toning my prints, but I think I was using TF-4 which is an alkaline fixer. Maybe that is why I didn't experience this? Or a change in the paper I am using could also be the culprit?

 

[cirwin2010]

Try diluting your fixer 1+9 and transferring the print directly to the toner, after fixing adequately, of course.

Best,

Doremus

Something I will have to try later. I'm out of fresh fixer to mix up, but I have more coming in the mail. I know 1+9 requires at least 2 minutes of fixing for FB papers, but do you think the lower dilution may be easier to wash out?

As a film developer, XTol would normally be much less active than Liquidol, so I'm not sure that will tell you a lot.
Try another developer set up for prints.

It was mostly to rule out some sort weird interaction with liquidol and the selenium toner. The xtol test strip did develop an image, but it was slightly lower contrast than the liquidol. Obviously xtol is not a great choice, I just tried it for the sake of my testing. I'm planning to purchase the ingredients to make Ansco 130 once this batch of liquidol is out.

 

[Nicholas Lindan]

It isn't the fixer per se that causes the problem, but the fixer-silver compounds and silver halides that remain in the paper. Active developer that finds its way into used fixer (and it will be used as soon as the first print hits fresh fixer) will develop the silver in the fixer. Developer that has soaked into the paper will develop the silver in the fixer as the fixer penetrates the paper fiber.

 

[cirwin2010]

I think I have a bad habit of prematurely celebrating? So now that the last test strip is dried I took another look at it. Viewing it normally I don't see any stain. But if I shine a bright light through it I still see stain....

So washing for an hour before toning certainly helped, but either wasn't enough or bad washing is compounding some other issue.

So things to try:
-2 bath fix regime
-different fixer (less acidic?)

 

[Doremus Scudder]

Something I will have to try later. I'm out of fresh fixer to mix up, but I have more coming in the mail. I know 1+9 requires at least 2 minutes of fixing for FB papers, but do you think the lower dilution may be easier to wash out?


It was mostly to rule out some sort weird interaction with liquidol and the selenium toner. The xtol test strip did develop an image, but it was slightly lower contrast than the liquidol. Obviously xtol is not a great choice, I just tried it for the sake of my testing. I'm planning to purchase the ingredients to make Ansco 130 once this batch of liquidol is out.

The lower dilution of fixer will not be quicker to wash out. You'll need a wash aid and a minimum of 20-30 minutes of wash time. The upside is the less-stringent timing requirements and the ability to transfer the print directly to the toner from the fix and not to have to wash for 60 minutes (or whatever).

Short washes happen when the fixing time is very short and doesn't let the fixer soak into the paper fibers. If that happens (more than 60 seconds in the fix) then wash time needs to be extended.

Why not try a standard print developer like Dektol or Bromophen before going to Ansco 130 or whatever to rule out the developer as a possible source of the staining?

Best,

Doremus

 

[cirwin2010]

I got my new bottle of Ilford rapid fixer and I did some more testing

Test 1 (control): developed a test strip, fixed in old fixer for 1 min, short rinse, selenium = stain
Test 2: developed a test strip, fixed in 2 bath fixer for 30 seconds each, short rinse, selenium = stain
Test 3. developed a test strip, fixed in new fixer only for 1 min, short rinse, selenium = stain

fixer dilution 1:4

Going to do some more testing with washing now

 

[snusmumriken]

How long are you giving it in the stop bath? The paper is saturated with developer as it enters the stop bath, and it will take a good minute to neutralise all of it. See @nicholas Lindan’s post #19 above.

Another thought: are you filtering your selenium toner before each use? Paper coffee filters are good for this. Once the bottle is empty I give it a violent shake with clean water to dislodge any further sediment, ready to receive the toner again at the end of session.

 

[cirwin2010]

How long are you giving it in the stop bath? The paper is saturated with developer as it enters the stop bath, and it will take a good minute to neutralise all of it. See @nicholas Lindan’s post #19 above.

Another thought: are you filtering your selenium toner before each use? Paper coffee filters are good for this. Once the bottle is empty I give it a violent shake with clean water to dislodge any further sediment, ready to receive the toner again at the end of session.

I've tested using a water stop, 30 second acid stop, and 60 second acid stop. All yield stains.

Also I'm working with relatively fresh selenium toner. I tend to keep the solution for about a year at a time and just mixed up some new solution last week. I have not filtered it, but I never found the need to.

 

[cirwin2010]

Completed some more tests. So far the issue seems wash dependent.
I made two new test strips. Both using the two fix bath process and toned in selenium 1:9 for 5 minutes.

This time instead of doing a quick rinse I washed one strip for 20 minutes and another for 5 minutes in water, 10 minutes in hypo clear solution, and 5 minutes again in water.

The strip that had the 20 minute water wash stained. But, it was barely visible in the white areas of the paper. The strip that went through the hypo clear shows no stain with perfect whites. I had a third party validate this too because I'm maybe going a bit mad at this point.

As previous commenters pointed out, I'm assuming this means the hypo wash is clearing out the residual silver compounds that is bonding with the selenium.


I ordered myself some Formulary TF-4 fixer like I used to use. I'm pretty sure I was using this stuff back when I was only selenium toning prints and I never had staining issues. I'm going to retest once I have it. I'm hoping that simply switching to a different fixer will help.