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Ken Lee
2-Feb-2015, 13:43
I mix my own fixer, using the classic TF-3 formula (http://www.jackspcs.com/tf3.htm): fast, cheap, alkaline, low odor.

TF-3 has a long life and capacity, but over time it continues to clear the film but even a soak in Sodium Sulfite won't entirely clear the dye out of the film.

When I change over to fresh fixer the magenta dye leaves the film immediately after fixing but the cycle repeats.

One solution is to toss the fixer after use, but that seems unreasonable. Another is to stop using film with magenta dye, but I really like TMY. For the record I do a 3-minute soak in plain water prior to development: this removes a lot of dye, but not enough apparently.

Is this classic formula inappropriate for modern films which contain dyes ?

Can someone kindly explain what is going on here and suggest a remedy ?

Many thanks in advance !

jp
2-Feb-2015, 13:56
Tf4/tf5 the dye clears out by itself between uses. Returns to the jug slightly pink but the fixer is always clear next time I use it.

Ken Lee
2-Feb-2015, 13:58
Sorry - I was confused. I notice the same thing with TF-3: the color of the fixer clears. However, over time the dye won't leave the film: either the fixer loses its ability to clear the dye (if that's what's supposed to happen), or something else is afoot.

Drew Wiley
2-Feb-2015, 15:07
Why reuse fixer? I personally use TF4, always one-shot. The very last of the magenta dye clears during the final wash. It just takes a few minutes in the washer to completely clear. But the antihalation dye of FP4 is a bit more stubborn and seems to need UV light bleaching to clear the last 2 to 5 cc's of magenta.

Doremus Scudder
2-Feb-2015, 15:17
Ken,

You might want to take a look at my thread over on APUG about retained dye in TMY.

I've notified Kodak of my problem, but have not heard back from them yet.

Summary: I had a dense blue/magenta base fog that would not process out in the normal sequence. I found that an alkaline bath cleared the film and removed the dye.

The entire thread is here: http://www.apug.org/forums/forum37/137626-tmy-dense-bluish-base-fog-cause.html

I hadn't had this problem before with TMY, but if it occurs again in the rest of this box of film or with TMY in general, I at least know how to clear the dye; add an extra alkaline rinse after the fix and a wash. FWIW, I didn't try sodium sulfite, but had good results with sodium metaborate, sodium hydroxide and sodium bicarbonate.

Hope this helps,

Doremus

jp
2-Feb-2015, 15:27
My tmy2 gets a long soak in rinse water. The water gets pretty pink after 30 min. I'd dump the fixer if it still won't clear.

NPR
2-Feb-2015, 17:22
I use TMY-2 in 120 and I'm able to clear the film with Ryuji's Neutral rapid fixer (in APUG recipes)

by Ryuji Published on 10-31-06 08:52 PM

ammonium thiosulfate 120g
(or 60% solution 200 ml)
sodium sulfite 15g
sodium metabisulfite 5g
water to make 1.0 liter
target pH 7.0 plus/minus 0.5

This fixer gives rapid fixing and rapid washing, same benefit as what's claimed for alkaline fixers, but with minimum of swelling.

with this fixer, I can get the pink out of TMY-2 but I still cannot get all the purple out of 400TX 120 (although most of it)

Ken Lee
2-Feb-2015, 17:30
I use TMY-2 in 120 and I'm able to clear the film with Ryuji's Neutral rapid fixer (in APUG recipes)...

Actually, that's the classic TF-3 fixer (http://www.jackspcs.com/tf3.htm).

Michael R
2-Feb-2015, 19:03
Actually, that's the classic TF-3 fixer (http://www.jackspcs.com/tf3.htm).

Ken - The formula in post #7 is a buffered neutral fixer, whereas TF-3 is alkaline. The dyes you see coming out of the film are acutance and sensitizing dyes. It is possible the dyes are more quickly soluble in an alkaline fixer, and that with repeated use/storage the pH of TF-3 becomes less alkaline, which means the dyes don't come out as fast. It is also possible that despite being a well pre-hardened emulsion (all Kodak, Ilford and Fuji films are) the alkaline fixer causes at least some minor degree of swell, which may (or may not) increase the diffusion rate of these dyes. In either case my guess is the declining pH is what causes the dyes to come out more slowly. However a longer wash with some standing soaks always seems to work for me (I don't use an alkaline fix).

Richard Wasserman
2-Feb-2015, 19:30
I also use Ryuji's Neutral Fix and my experience agrees with NPR's. I have used it for years for both film and paper with no issues. And it pretty much is odorless,which cannot be said for all fixers.


I use TMY-2 in 120 and I'm able to clear the film with Ryuji's Neutral rapid fixer (in APUG recipes)

by Ryuji Published on 10-31-06 08:52 PM

ammonium thiosulfate 120g
(or 60% solution 200 ml)
sodium sulfite 15g
sodium metabisulfite 5g
water to make 1.0 liter
target pH 7.0 plus/minus 0.5

This fixer gives rapid fixing and rapid washing, same benefit as what's claimed for alkaline fixers, but with minimum of swelling.

with this fixer, I can get the pink out of TMY-2 but I still cannot get all the purple out of 400TX 120 (although most of it)

Ken Lee
2-Feb-2015, 19:41
Ken - The formula in post #7 is a buffered neutral fixer, whereas TF-3 is alkaline.

Perhaps I am missing something, but the formulas seem identical to me. The only difference seems to be that the TF-3 recipe is for stock solution - to be diluted 1:4 - while the Ryuiji amounts are given for making a working solution, IE already diluted.

Richard Wasserman
2-Feb-2015, 19:50
Ken, TF-3 calls for 1.25g/liter of Sodium Metaborate (working strength) while Ryuji's calls for 5g Sodium Metabisulfite. Otherwise they are the same

Michael R
2-Feb-2015, 20:09
Ken, TF-3 calls for 1.25g/liter of Sodium Metaborate (working strength) while Ryuji's calls for 5g Sodium Metabisulfite. Otherwise they are the same

That's an important difference. Sodium metaborate is an alkali. Sodium metabisulfite is acidic (which is what lowers and buffers the pH of the sodium sulfite in the Ryuji formula). Sodium metaborate has some buffering strength depending on concentration and the pH of the solution.

Ken Lee
2-Feb-2015, 20:16
Thank you very much !

If I understand correctly, the TF-3 formula starts out alkaline but becomes more neutral, possibly acidic eventually - and therefore unable to remove the dye.

Why then would the already-more neutral Ryuji formula be more effective in reducing the dye ? Because it is buffered and remains neutral ?

Michael R
2-Feb-2015, 20:39
I doubt the Ryuji formula is more effective at removing the dyes. Difficult to explain the different experiences without knowing more about the rest of each person's workflow and running some tests so I can really only speculate that the higher pH of fresh TF-3 was helping. Even if it is dropping with use/time, it would just be less alkaline. It wouldn't become acidic unless you used an acid stop bath directly before fixing.

The TMax films in particular are interesting when it comes to retained dyes. For me it always comes out over time in the wash. Others report a substantial amount of retained dye even after pre-soaks, extended fixing times and extended wash times. Varying experiences in between.

blueribbontea
2-Feb-2015, 22:23
"The TMax films in particular are interesting when it comes to retained dyes. For me it always comes out over time in the wash. Others report a substantial amount of retained dye even after pre-soaks, extended fixing times and extended wash times. Varying experiences in between."

Perhaps an effect of the difference in tap water from user to user?

Tin Can
2-Feb-2015, 22:58
Off topic, but tonight I developed four TMAX 100 sheets. I use TF5 and fix for 6 minutes, then wash for about 8. As they wash I can see the dye go away. My wash is a slow trickle, not a heavy flow of tap water. I stop the wash after not more than 10 minutes and they are not tinted.

Doremus Scudder
3-Feb-2015, 01:39
I doubt the Ryuji formula is more effective at removing the dyes. Difficult to explain the different experiences without knowing more about the rest of each person's workflow and running some tests so I can really only speculate that the higher pH of fresh TF-3 was helping. Even if it is dropping with use/time, it would just be less alkaline. It wouldn't become acidic unless you used an acid stop bath directly before fixing.

The TMax films in particular are interesting when it comes to retained dyes. For me it always comes out over time in the wash. Others report a substantial amount of retained dye even after pre-soaks, extended fixing times and extended wash times. Varying experiences in between.

Could there be variations in manufacturing? My recent experience certainly points to a change in dye retention by TMY from either age, storage or manufacturing variance. As noted, a soak in an alkaline solution worked for me.

Doremus

Deval
3-Feb-2015, 03:44
+1 for the long wash. Ken have you tried a test strip to come up with a personalized number of sheets/roll for your fixer.

NPR
3-Feb-2015, 05:59
I should add that for film I only use water for a stop bath and that when I am fixing TMY-2, I fix for 5 to 6 min. to make sure that I can get the pink out. I use the modified Ilford method of washing with three to four water rinses, each one with at least 5 min. standing after agitation and because I am often caught doing other things at home, the five min. can go up to 30. When I cannot get the pink out of TMY, I mix up a new batch of fixer (usually after 15 to 20 rolls). I wonder if there is a difference between sheet and roll TMY for fixing?

Michael R
3-Feb-2015, 07:31
Could there be variations in manufacturing? My recent experience certainly points to a change in dye retention by TMY from either age, storage or manufacturing variance. As noted, a soak in an alkaline solution worked for me.

Doremus

Hi Doremus (by the way for reference I'm Michael R 1974 on APUG),

It is possible. I haven't used TMY-2 in several months so I'd have to try it with a new batch. Hopefully Kodak will respond to your recent query. I followed your APUG thread and it does seem odd you had all that dye even after your tests with longer fixing and washes.

Ken Lee
3-Feb-2015, 07:36
I live in a rural area and my water comes from a well. It would be no surprise if that had something to do with it. Is there a cheap way to make distilled water ?

Tin Can
3-Feb-2015, 07:42
I buy distilled water for $1 a gallon and find that cheaper than another gadget that will break .

Michael R
3-Feb-2015, 07:49
"The TMax films in particular are interesting when it comes to retained dyes. For me it always comes out over time in the wash. Others report a substantial amount of retained dye even after pre-soaks, extended fixing times and extended wash times. Varying experiences in between."

Perhaps an effect of the difference in tap water from user to user?

Yes, differences in tap water can have effects on washing times.

In my experience TMX comes clear faster than TMY-2, but again that's only my experience. Everything from the type of developer to water hardness/softness can change things.

Also just a general note about the dye coming out in the wash (and washing in general). Depending on water type, flow and aeration, over time in the wash lots of tiny air bubbles often accumulate on the film. The same thing can happen when washing prints. Make sure to periodically get those bubbles off with agitation etc. Further to this point, some soaks in fresh standing water at the end of the wash sometimes work as well or better than just more time in running water when it comes to removing dyes.

Michael R
3-Feb-2015, 07:54
I live in a rural area and my water comes from a well. It would be no surprise if that had something to do with it. Is there a cheap way to make distilled water ?

Note while distilled water is good for mixing photographic chemicals, and for final rinses/soaks before drying, purified water is actually a relatively poor washing medium, particularly when it comes to washing out fixer. The dissolved salts in tap water are actually beneficial.

Richard Wasserman
3-Feb-2015, 09:17
I too am on a well and recently installed a reverse osmosis system from Lowes—their website, where they have better units than in their stores. I use RO water to mix all chemistry and final rinse. So far all is good.

It
I live in a rural area and my water comes from a well. It would be no surprise if that had something to do with it. Is there a cheap way to make distilled water ?

Ken Lee
3-Feb-2015, 10:08
I too am on a well and recently installed a reverse osmosis system from Lowes—their website, where they have better units than in their stores. I use RO water to mix all chemistry and final rinse. So far all is good.

http://www.kenleegallery.com/images/forum/moonshine_still.jpg

Those units look pretty sophisticated. I had in mind something a little more low-tech :)

Richard Wasserman
3-Feb-2015, 10:12
And this system comes with many other benefits—good choice!



http://www.kenleegallery.com/images/forum/moonshine_still.jpg

Those units look pretty sophisticated. I had in mind something a little more low-tech :)

Ken Lee
3-Feb-2015, 10:52
I doubt the Ryuji formula is more effective at removing the dyes. Difficult to explain the different experiences without knowing more about the rest of each person's workflow and running some tests so I can really only speculate that the higher pH of fresh TF-3 was helping. Even if it is dropping with use/time, it would just be less alkaline. It wouldn't become acidic unless you used an acid stop bath directly before fixing.

If keeping the pH slightly higher is the purpose of the Sodium Metaborate (also known as Balanced Alkali or Kodalk I've since discovered), could we add some over time to act as a sort of replenisher ? If so, how much would be appropriate ? What would be the consequence of using too much ?

Drew Wiley
3-Feb-2015, 11:21
I don't know how "hard" well water will affect this, since our water here is piped in exceptionally good snowmelt. You could simply leave the film a little while in a tray of distilled water either before or after the formal wash cycle, prior to the final photoflo treatment, and most of the dye would probably dispel. Or you could
try your idea of a dilute metaborate soak prior to formal washing. I work with an alkaline fixer to begin with, so TMY clears very fast for me, with zero leftover
stain. I realize you're trying to save some money on fixer; but what is your time and headache coefficient worth? That made me switch to TF4 and stick with it.

Doremus Scudder
3-Feb-2015, 11:58
Hi Doremus (by the way for reference I'm Michael R 1974 on APUG),

It is possible. I haven't used TMY-2 in several months so I'd have to try it with a new batch. Hopefully Kodak will respond to your recent query. I followed your APUG thread and it does seem odd you had all that dye even after your tests with longer fixing and washes.

Hi Michael,

Yeah, my processing workflow, chemicals and water all stayed the same, so I'm thinking some kind of change in the characteristics of the film for some reason. I just received an e-mail from Kodak Alaris regarding the dye retention problem I posted about at APUG. They have forwarded my message with the link to that thread to their QC department. Let's see what comes of that...

In the meantime, I'm just going to add the extra step of an alkaline bath before the wash whenever I have this problem. It worked extremely well last time.

@Ken: you could just use a rounded teaspoon of sodium bicarb (good old Arm & Hammer) in 500ml of water as a down-and-dirty alkaline bath after your fix and a water rinse and before the wash if you still have problems with retained dye.

That said, T-Max films are harder to fix and use up fixer faster than "conventional" films. If your capacity is something like 20 8x10s (or rolls) per liter, even two-bath, before the retention starts to show up, I would simply discard the fix and mix new, even if the clearing times are still good.

Best,

Doremus

Tin Can
3-Feb-2015, 13:42
My TMAX is fresh. Waiting for fresher 11x14 TMAX 400 from Keith Canham.

How about a report from NYC, as they have some of the best water available. Not kidding.

I no longer drink Chicago tap water.

Michael R
5-Feb-2015, 09:46
If keeping the pH slightly higher is the purpose of the Sodium Metaborate (also known as Balanced Alkali or Kodalk I've since discovered), could we add some over time to act as a sort of replenisher ? If so, how much would be appropriate ? What would be the consequence of using too much ?

Ken - apologies I didn't see this earlier.

I wouldn't want to guess at the answer here without testing, first to confirm a pH drop, then to see how is needed to restore to initial pH.

The amount wouldn't be all that critical as it takes relatively large changes in metaborate concentration to materially alter solution pH even in plain water. For example, 1g/l ~pH 10.5, 10g/l ~pH 11. In addition, accuracy to a specified 0.1 pH is not as important as it would be for a developer.

It might be more simple to just replenish/"top up" with fresh stock solution, but in general I wouldn't recommend replenishing used fixer.

In the end, I'd just do some additional soaks in standing water at the end of the wash cycle to clear the dye.

Ken Lee
5-Feb-2015, 10:07
Thank you for your helpful insights.

I already soak the film in standing water (see Dishrack Film Washer (http://www.kenleegallery.com/html/tech/dishrack.php)) - but when the fixer reaches a certain age, soaking (even preceded by a Sodium Sulfite bath and rinsing) never entirely removes the dye: hence this thread.

Up to now, I have been discarding my fixer once several minutes are required to clear the film (viewed under an Infra Red monocular, it's easy to observe).

Going forward I will discard my fixer as soon as the initial post-fixer rise no longer readily clears the film of magenta dye.

AtlantaTerry
5-Feb-2015, 17:13
Why all this bother?

Does any residual dye actually make a difference when enlarging or scanning?



Back in the mid to late 20th century when I used mainly Kodak Tri-X for my 4x5" LF work I never pre-soaked. Now (per advice here) with Shanghai 50 and Arista EDU Ultra 100 film, I do pre-soak. I am astounded how much dye comes out during the pre-soak. Maybe back in the old days I shoulda pre-soaked my Tri-X but never had an issue with it when enlarging.

Tin Can
5-Feb-2015, 17:16
Why all this bother?

Does any residual dye actually make a difference when enlarging or scanning?

Now we need the Density Meter folks...

Peter De Smidt
5-Feb-2015, 17:41
Not much. It's like adding a little magenta filtration. Most enlarging systems have no problem getting very low contrast, which is provided with green light with VC paper. The magenta will block a little green, but unless it's pretty extreme, you should still be able to get grade 0 or softer.

Ken Lee
5-Feb-2015, 17:51
The base of Kodak TMY (when properly cleared of magenta dye) appears to my eyes as more transparent than my recollection of other films like Tri-X, HP5+, etc. Someone with a densitometer can report the facts: I may be wrong.

One reason I returned to the use of a non-staining developer was to avoid overall image stain (which I could never adequately distinguish from magenta dye and which required clearing with Sodium Sulfite to remove).

Whether clearing the magenta stain (or having less fog or overall stain) results in any gain in film speed or other benefit I can't honestly say. I confess this is an entirely subjective judgement, but when I see a nicely exposed and developed negative free of such impediments, it's a bit like using a lens with modern coating: it looks like it was exposed on glass and is simply more... appealing.

Jac@stafford.net
5-Feb-2015, 17:55
Soak your purple/violet/magenta film in Decktol and wash again. It will be gone.
.

Peter De Smidt
5-Feb-2015, 19:22
Any alkaline solution should work. Borax (20 Mule Team from the grocery store) in water is cheap.

Ken Lee
5-Feb-2015, 19:47
What happens to film long-term if we soak it in an alkaline solution: is that like soaking it in bleach ? I presume a long soak in water is required afterwards, no ?

Michael R
5-Feb-2015, 20:38
A wash for a few minutes afterward is fine. A soak in an alkaline solution post-fixation will do nothing to the image as long as it has been fully fixed and no developer remains in the emulsion, and it will have no effect on archival stability. It will wash out and it's gone. At one time Agfa recommended an alkaline bath for prints to decrease washing time.

If you want to remove the dye and an alkaline bath does the job, consider simply adding a home-made hypo clearing agent to your wash cycle (wash, HCA, wash). Some people like to use HCA with film anyway. A fresh 20g/l sodium sulfite solution will initially have a pH between that of borax and metaborate.

Regarding the earlier question about retained dye, unless there is a lot of it, the effects in printing should be trivial (if there is any effect at all).

Peter De Smidt
5-Feb-2015, 21:18
No, it's not like soaking the negative in bleach. :) Developers are alkaline, which is why the suggestion of using Dektol above would also work. As Michael says, hypo clearing agent is mostly sodium sulfite. If you have that on hand, it'll work fine. So will borax, and it's cheaper and very easy to get. You want to use the least alkaline solution that'll work, within reason, and the more alkaline the solution is, the more the gelatin will swell. In other words, don't use sodium hydroxide.

Doremus Scudder
6-Feb-2015, 02:24
Ken,

Michael and Peter are giving you great advice. Try HCA or a sulfite solution if you have that. If, for some reason, it doesn't do the job, move to borax, etc. After the dye has cleared, a normal wash will remove the alkaline.

For the record: The problem I had recently with dye retention in TMY was, in my experience, anomalous. The dye retained in the emulsion was excesseve and gave the neg a dark blue base tinge that was very dense. The dye would not release from the emulsion till I gave the film an alkaline bath. I did not try sodium sulfite simply because I had none on hand. I did use sodium metaborate (Kodalk), sodium bicarbonate and a very weak solution of sodium hydroxide. All three did the job.

I'm including my photos of the situation below. The negative is an unexposed, but developed, stopped, double-fixed and washed TMY 4x5 sheet.

Photo 1 shows the offending neg after double fix and wash on the right (very blue base) compared with a properly processed Tri-X neg.
128954

Photo 2 shows the neg in the alkaline bath (sodium metaborate in this case) and the dye diffusing into the solution.
128955

Photo 3 shows the neg after soaking in the alkaline bath and then washing.
128956

The slight yellow/green base tint is overall stain from the staining developer I use and is minimal.

One more thing. We should distinguish between the anti-halation dye that comes out in the pre-soak or in the developer and which is rarely, if ever, a problem and the pink/magenta sensitizing dye that seems difficult to wash out.

And don't soak your negatives in chlorine bleach; it will strip the emulsion right off! :)

Best,

Doremus

Ken Lee
6-Feb-2015, 03:05
My original post number 1 reads:

"TF-3 has a long life and capacity, but over time it continues to clear the film but even a soak in Sodium Sulfite won't entirely clear the dye out of the film".

I haven't tried Borax. I'll see if that works better.

If not, then I'll toss the fixer sooner... and steer clear of Sodium Hydroxide :rolleyes:

Michael R
6-Feb-2015, 05:46
Forgot you had tried sulfite already. Then I'd suggest sodium metaborate. A fresh (ie made up for immediate use, not stored, used etc.) sodium sulfite solution has a pH higher than borax. If the clearing rate is indeed directly related to pH and sodium sulfite isn't working, metaborate will give you a higher pH.

Ken Lee
6-Feb-2015, 05:48
Thanks - could you suggest the concentration: how many grams per liter please ?

Michael R
6-Feb-2015, 05:57
I'd start with 1g/l. If that doesn't do it, try 5g/l.

I might have to get a new batch of TMY-2 and see what the deal is. I haven't used it in several months but this whole dye clearing issue (including Doremus's recent experiences) seems odd to me.

Joe O'Hara
6-Feb-2015, 07:09
I've occasionally had a little dye retention in TMAX films after washing (~25 minutes at 72F in slightly alkaline tap water), but nothing like the picture that Doremus posted above.
FWIW, I find the remaining dye washes out in the Photo-Flo solution that I rinse the film in before drying.

Our well water is very soft but given where you live, that may not be the case for you and it may be affecting your results. Maybe just running it through a water softener cartridge will do the trick.

Peter De Smidt
6-Feb-2015, 08:06
Personally, I'd buy cheaper fixer, such as Ilford or Kodak rapid fix from BHphoto, and not keep it as long. I use rapid fix one-shot in my Jobo for film.

Doremus Scudder
6-Feb-2015, 08:22
My original post number 1 reads:

"TF-3 has a long life and capacity, but over time it continues to clear the film but even a soak in Sodium Sulfite won't entirely clear the dye out of the film".

I haven't tried Borax. I'll see if that works better.

If not, then I'll toss the fixer sooner... and steer clear of Sodium Hydroxide :rolleyes:

Ken,

I wasn't sure if your sulfite bath was before or after the fixer. If after, then obviously, it isn't working. Try the metaborate next.

FWIW, I did try a weak sodium hydroxide solution, and it did the job just fine with no damage to the negatives. So did sodium bicarbonate, though.

A sulfite solution has a pH of around 9 - 9.7. Hydroxide is in the 11s and bicarbonate is in the mid 8s. Metaborate in the high 10s to 12, depending on concentration.

It could be that my problem and its solution are not related to yours...

Best,

Doremus

Ken Lee
17-Mar-2015, 17:00
I recently discovered that Ilford has a solution to this problem: it's called HP5+ :rolleyes:

I know, it's not the same as Kodak TMY, but it's available in 5x7 and whatever dye there is, comes out in a brief pre-soak.

Michael R
18-Mar-2015, 06:12
Seems like an unfortunate way to have to solve a problem like this, but HP5 is a wonderful film too.