Kodak chemicals -- now what??

[Kevin Crisp]

I've been using Rapid Fixer since I developed my first roll of film back around 1970. So I know the product.

This evening I reached for my mixed jug of it. It has been about 11 months and it had finally developed precipitate so I dumped it. This batch had a decent life span; nothing out of the ordinary for me.

Opened a new box of the concentrate. I bought this June 2021 from Freestyle. The bottle was filled with milky yellowish precipitate. I opened my back up box, purchased the same day. Same thing -- useless. I have kept the concentrate new in the box for years before. 3 to 4 years? No problem. Now this. What gives? This stuff isn't cheap.

[domaz]

Might be a good time to switch to TF-5 (https://stores.photoformulary.com/tf-5-archival-fix/), a very nice working "odorless" fixer. I've kept the concentrate around for well over a year and it still seems clear and has no issues. Mix with distilled water and with decent ventilation you won't really smell it.

[paulbarden]

I now use TF-5 exclusively.

[david@bigeleisenlaw.com]

I use TF-4 and Ilford rapid fixer. Both work fine.

David

[jnantz]

you folks don't get that reek with T4 and 5? I tried to join the chuckwagon years ago when I first read everyone's love-posts and that it was "odorless" but it reeked of ammonia so much I had to get rid of it. I use sprint and have pretty exclusively since 1980 ( its local and easy for me to get, now sold through their website ) .. and it doesn't smell at all ...

[interneg]

you folks don't get that reek with T4 and 5? I tried to join the chuckwagon years ago when I first read everyone's love-posts and that it was "odorless" but it reeked of ammonia so much I had to get rid of it. I use sprint and have pretty exclusively since 1980 ( its local and easy for me to get, now sold through their website ) .. and it doesn't smell at all ...

C-41 fix is the best of the lot - essentially odourless (near neutral pH) and ultra efficient.

[Tin Can]

TF4 is NOT TF5

TF5 must use 'pure' Distilled water

I have a one gallon sealed test bottle of TF5, now 7 years old stored in shed that moves from 110 F to -20

Still clear as a bell

I believe in Photo Engineer

RIP

[Michael R]

Alkaline rapid fixers such as TF-4 will have the ammonia smell depending on how alkaline. Neutral pH fixers should have relatively little odour. TF-5 is an example. You’re fine with Sprint. C-41 as mentioned by interneg is also near neutral. Ilford Rapid Fix is mildly acidic so not odourless, but perfectly good.

Generally speaking, an acidic fixer such as the Kodak product mentioned by OP will have a shorter shelf life. The yellowish sludge OP saw is from sulfurization which happens over time.


you folks don't get that reek with T4 and 5? I tried to join the chuckwagon years ago when I first read everyone's love-posts and that it was "odorless" but it reeked of ammonia so much I had to get rid of it. I use sprint and have pretty exclusively since 1980 ( its local and easy for me to get, now sold through their website ) .. and it doesn't smell at all ...

[LabRat]

Sulfurization/precipitation in rapid type fixers tend to happen in stock solutions over time... Mixing & storing at working strength extends them for very extended life...

If stock is new and bad, send it right back...

Steve K

[esearing]

I'm a TF5 convert and my current stock is about 3 years old and near the bottom of the gallon jug. I use it mainly for fixing Pyro-M negatives. - But there is also good ole plain hypo crystals so you can make a fresh batch each session. When I visit the local camera store I always buy a couple liters of Ilford Rapid Fix too which I tend to use for Fiber papers. TF4 has its uses for Alt printing too and can create different color shifts than hypo.

[bob carnie]

I like to mix my own chemicals when possible, I have not been successful being able to mix a rapid fix that is easy and saves me dollars. With the cost of a Gallon of Hypam around $50 I am now again looking at doing this
any one here mixing rapid fix from scratch and willing to discuss the pros and cons.?

[Michael R]

You ideally need a source for bulk ammonium thiosulfate which is typically sold in 60% solution. You’ll then have to do the math and see if it makes financial sense to mix vs buying large volumes of Ilford or Kodak C-41/Flexicolor.

Contact Alphachem in Mississauga. Terrific bulk chem source and ammonium thiosulfate is in their regular catalog.


I like to mix my own chemicals when possible, I have not been successful being able to mix a rapid fix that is easy and saves me dollars. With the cost of a Gallon of Hypam around $50 I am now again looking at doing this
any one here mixing rapid fix from scratch and willing to discuss the pros and cons.?

[Alan9940]

I like to mix my own chemicals when possible, I have not been successful being able to mix a rapid fix that is easy and saves me dollars. With the cost of a Gallon of Hypam around $50 I am now again looking at doing this
any one here mixing rapid fix from scratch and willing to discuss the pros and cons.?

I mixed my own rapid fix for a little while but found that it really wasn't particularly cost-effective vs just buying it pre-made. Perhaps buying the ammonium thiosulfate in larger bulk sizes, as Michael R suggests, would substantially reduce the cost. Anyway, I went back to my long-time standard F-24.

[Kevin Crisp]

Per Kodak (and this is consistent with my experience) the shelf life of the concentrate in the box, undiluted, is "indefinite." So if it goes bad in well under a year in a cool darkroom something is wrong.

[Doremus Scudder]

Kevin,

Contact Freestyle and explain the problem. I've found them more than willing to make things good whenever I had problems with paper/chemicals.

FWIW, I use Ilford Rapid Fixer or Hypam (whichever is cheaper whenever I order) these days (I ditched TF-4 too - haven't tried TF-5).

Stock solutions of rapid fixers do go bad over time. Try not to order so long in advance so you don't have to store the fixer stock for such a long time. Remember, you have to add how long you've had the product on your shelf to how long it was in the supply chain and on the dealer shelf...

Best,

Doremus

[Ironage]

I also mix my own. F-34 rapid fixer has been working well for me. Got the recipe from digital truth app.

[Richard Wasserman]

I have mixed Ryuji Suzuki's Neutral Fix for years.

ammonium thiosulfate 200ml 60% solution
sodium sulfite 15g
sodium metabisulfite 5g
water to make 1.0 liter

[bob carnie]

I have mixed Ryuji Suzuki's Neutral Fix for years.

ammonium thiosulfate 200ml 60% solution
sodium sulfite 15g
sodium metabisulfite 5g
water to make 1.0 liter

Hi Richard - if you use a double fix how long in each is required with this formula?

tks

Bob

[Bernice Loui]

Yes, there is a problem with "Kodak".. Previously noted and verified problems with other Kodak foto chemicals XTOL, Dektol and ?
Time has come to let go of "Kodak" as Kodak is no longer what the brand name Kodak once was.

Kodak foto chemistry and silver paper is produced and brand name owned by Sino Promise, China.
https://www.insideimaging.com.au/2022/exclusive-unpromising-future-for-sino-promise/

Sino Promise appears to be experiencing difficulties in varied ways.

This is an example of the market value of a brand name and brand identify.. Putting blind "faith" and believe into a brand name without verifying the brand name's product content and actual abilities often results in problems minor to very serious.

The behavior of Kodak company heads has not been ideal for their user base and future in many ways..
https://www.psychologytoday.com/us/blog/greening-the-media/201804/the-environmental-ruin-eastman-kodak#:~:text=People%20in%20and%20around%20the,disaster%20of%20the%20late%201970s).


The better long term solution to this problem is to mix your own foto chemicals. It is NOT difficult.
Get a magnetic stirr plate like this:
https://www.amazon.com/Magnetic-stirrer-magnetic-Stirring-Capacity/dp/B072K24X5P/ref=asc_df_B072K24X5P/?tag=hyprod-20&linkCode=df0&hvadid=198074333025&hvpos=&hvnetw=g&hvrand=4211756736299001336&hvpone=&hvptwo=&hvqmt=&hvdev=c&hvdvcmdl=&hvlocint=&hvlocphy=9031909&hvtargid=pla-355194351026&psc=1


Teflon stir bar:
https://www.amazon.com/Noorlee-10pcs-Magnetic-Stirrer-Spinbar/dp/B079JPTDCZ/ref=asc_df_B079JPTDCZ/?tag=hyprod-20&linkCode=df0&hvadid=312158944530&hvpos=&hvnetw=g&hvrand=4852423733657385916&hvpone=&hvptwo=&hvqmt=&hvdev=c&hvdvcmdl=&hvlocint=&hvlocphy=9031909&hvtargid=pla-571944073421&psc=1


Real chemistry glass ware, beakers as a start:
https://www.amazon.com/Karter-Scientific-213A2-Borosilicate-Beaker/dp/B006UKICJA/ref=sr_1_9?crid=387NTQJW7S2JB&keywords=1000ml+beaker&qid=1658684293&s=industrial&sprefix=1000ml+%2Cindustrial%2C136&sr=1-9

Digital gram scale (modern food scale is good enough):
https://www.amazon.com/Etekcity-Multifunction-Stainless-Batteries-Included/dp/B0113UZJE2/ref=sr_1_4?crid=2BAXKMTKWAB0Q&keywords=digital%2Bgram%2Bscale%2B5kg&qid=1658684448&s=industrial&sprefix=digital%2Bgram%2Bscale%2B5kg%2Cindustrial%2C187&sr=1-4&th=1

Then dry chemicals as needed from:
https://stores.photoformulary.com/
and MANY other chemical supplies on line today.

As for fixer, basic Kodak formula F24 has worked for decades, easy to mix up and the chemicals are not pricy.
600 ml Water (125F or 45C)
240 g Sodium Thiosulfate
10 g Sodium Sulfite
25 g Sodium Bisulfite
Top up to one litre water

~Mix in the dry chemicals in the formula order from top to bottom. Add the other dry chemicals once the initially added dry chemicals have completely dissolved into water. Problems happen when the order is not followed or if the dry chemicals have not fully dissolved and the other dry chemicals added.

Plain "Hypo"
https://www.largeformatphotography.info/forum/showthread.php?73713-Making-Hypo

Not convinced "rapid fixer" has much advantage over plain Sodium Thiosulpate based fixers.

Store the mixed chemistry in glass bottles up to the filler cap reducing as much air in the bottle as possible.


Bernice

[Michael R]

Yes Ryuji’s neutral rapid fix is as good as any standard rapid fix and it really doesn’t need to be any more complicated than that. Ammonium thiosulfate is always the active ingredient in rapid fixers.

To answer Bob’s question you can basically use Ilford’s instructions (Rapid/Hypam) at 1+4 dilution for either one or two bath. For example, two bath fixing at 1+4 for FB paper would be 30s in each bath. Etc.

For those interested in or wanting even faster fixing there is also PE’s Superfix I but it contains ammonium thiocyanate and thiourea to complement the ammonium thiosulfate.




I have mixed Ryuji Suzuki's Neutral Fix for years.

ammonium thiosulfate 200ml 60% solution
sodium sulfite 15g
sodium metabisulfite 5g
water to make 1.0 liter

[Richard Wasserman]

Hi Richard - if you use a double fix how long in each is required with this formula?

tks

Bob

Bob,

I do 1 minute or so in each of 2 baths.

[jnantz]

Per Kodak (and this is consistent with my experience) the shelf life of the concentrate in the box, undiluted, is "indefinite." So if it goes bad in well under a year in a cool darkroom something is wrong.

I hope that is still true these days. the last kodak chemicals I used ( not concentrated fixer but dry-print/film developer so obviously much different ) screwed the pooch ... not sure what is up, I think it's owned by Sino-promise now ? if so it's being made and shipped from great distances, and maybe stuck in a container for a long long time before it's circulated, or ... like the Chinese Amidol situation in days of yore, maybe QC isn't what one would expect (especially from something branded KODAK) ...
I've opted out, I've stayed local, and when I can make from scratch ..

good luck!
John

[Michael R]

Fixer will not keep forever. I don’t recall Kodak indicating indefinite shelf life. That would be pretty surprising. As the Kodak product is very similar to the Ilford product we can use Ilford’s instructions as a guideline in the absence of specifics from Kodak. 2 years for unopened bottles with proper storage.


I hope that is still true these days. the last kodak chemicals I used ( not concentrated fixer but dry-print/film developer so obviously much different ) screwed the pooch ... not sure what is up, I think it's owned by Sino-promise now ? if so it's being made and shipped from great distances, and maybe stuck in a container for a long long time before it's circulated, or ... like the Chinese Amidol situation in days of yore, maybe QC isn't what one would expect (especially from something branded KODAK) ...
I've opted out, I've stayed local, and when I can make from scratch ..

good luck!
John

[jnantz]

Fixer will not keep forever. I don’t recall Kodak indicating indefinite shelf life. That would be pretty surprising. As the Kodak product is very similar to the Ilford product we can use Ilford’s instructions as a guideline in the absence of specifics from Kodak. 2 years for unopened bottles with proper storage.



no infinite shelf life, bummer.
2 years?
probably translates this way > from overseas on a slow boat stuck in the Suez Canal and then stuck at sea circling the landing strip, and then stuck in a container at port means use it super fast, it 2 weeks once its in our hands !

[Vaughn]

"indefinite shelf life" ('indefinite' is defined as: lasting for an unknown or unstated length of time) -- that means they do not know the shelf life, correct? It is not that it lasts long on the shelf.

[Doremus Scudder]

no infinite shelf life, bummer.
2 years?
probably translates this way > from overseas on a slow boat stuck in the Suez Canal and then stuck at sea circling the landing strip, and then stuck in a container at port means use it super fast, in 2 weeks once its in our hands !

Is that why they call it "rapid fixer"?

[Michael R]

Cute


"indefinite shelf life" ('indefinite' is defined as: lasting for an unknown or unstated length of time) -- that means they do not know the shelf life, correct? It is not that it lasts long on the shelf.

[Kevin Crisp]

I know from decades of experience that in a sealed stock bottle (and now, box) it will last for many years. Based on this recent experience, where the mixed fixer seems to have lasted longer than the undiluted stock, I'd say there is a problem.

Kodak replied to my email the next day. Said Freestyle will refund and get credit back from Kodak. They also want lot information, which I will send them. And the two boxes that went bad both are labeled Made in the USA.

[Michael R]

Good news that they responded quickly. I assume at this point this was from Sino Promise as they took over the Kodak chemicals business.


I know from decades of experience that in a sealed stock bottle (and now, box) it will last for many years. Based on this recent experience, where the mixed fixer seems to have lasted longer than the undiluted stock, I'd say there is a problem.

Kodak replied to my email the next day. Said Freestyle will refund and get credit back from Kodak. They also want lot information, which I will send them. And the two boxes that went bad both are labeled Made in the USA.

[Kevin Crisp]

Correct.

[Mark Sawyer]

no infinite shelf life, bummer.


Sealed powdered sodium thiosulfate fixer has at least a decades-long shelf life. I was using canned Korean War era military surplus powdered fixer up until I ran out last year.

Just wondering, can the precipitated sulfur in rapid fix be redissolved somehow, perhaps by heating the solution?

[Michael R]

Sequestered unmixed powders are a different story. They can have long shelf lives. Generally only non-rapid (sodium thiosulfate) fixers are supplied this way but rapid fixers are the better processing option.

Once the fix has sulfurized it is done. It’s decomposition of thiosulfate, not a matter of re-dissolving things that have come out of solution.


Sealed powdered sodium thiosulfate fixer has at least a decades-long shelf life. I was using canned Korean War era military surplus powdered fixer up until I ran out last year.

Just wondering, can the precipitated sulfur in rapid fix be redissolved somehow, perhaps by heating the solution?

[interneg]

For those interested in or wanting even faster fixing there is also PE’s Superfix I but it contains ammonium thiocyanate and thiourea to complement the ammonium thiosulfate.

With the warning (that Ron made when disclosing these additives) that they may blister less well hardened emulsions. I'm not sure how much difference there really is between TF-5 and something like Tetenal's Superfix Odourless - or most C-41 fixes - I get the general impression that Ron/ PE's contributions to TF-5 were to that end.

C-41 fix is highly efficient at removing residual dye etc - just in case anyone gets concerned about fix that's purple or luminous pink after use on B&W film...

[Daniel Stone]

With the warning (that Ron made when disclosing these additives) that they may blister less well hardened emulsions. I'm not sure how much difference there really is between TF-5 and something like Tetenal's Superfix Odourless - or most C-41 fixes - I get the general impression that Ron/ PE's contributions to TF-5 were to that end.

C-41 fix is highly efficient at removing residual dye etc - just in case anyone gets concerned about fix that's purple or luminous pink after use on B&W film...

So would the use of C-41 fixer be avoided if one uses staining developers such as procat-hd, 510 pyro, ABC, etc?

[koraks]

So would the use of C-41 fixer be avoided if one uses staining developers such as procat-hd, 510 pyro, ABC, etc?

No, pyro stain is not cleared by c41 fixer.

[interneg]

So would the use of C-41 fixer be avoided if one uses staining developers such as procat-hd, 510 pyro, ABC, etc?

No. This is about excess/ waste sensitising/ trimmer/ antihalation dyes, not whatever imagewise coupler/ 'stain' of questionable archival stability that has been formed via the oxidation of Pyrogallol or one of the Dihydroxybenzenes.

[xkaes]

Perhaps I missed it, but I'm really surprised that no one has suggested that the fixer in question be tested. It may be "old", but it's very easy to simply test it.

[Kevin Crisp]

If you pour the fixer out of the stock sealed bottle, it comes out as a yellowish clouded mush. It will choke a filter funnel in seconds. I don't think there is any question it is bad.

[Kevin Crisp]

My working solution, which lasted longer than these two newer ones in reserve, didn't go toes up in the usual fashion. In the past, when the RF goes it gets lots of small while flakes in it. The working solution this time developed dark gray or black flakes. I got about 10 months out of it, no problem with that. But when a diluted solution outlasts the stock in the bottle, something is wrong at the factory.

Kodak did request information on the mfg lot, which I gave them.

Since I had some film to develop, I used a bottle of F6 I had mixed it up. It cleared the film quickly. It was a test with the Frankenfilm 200, which sure seems to me to be the same as Foma 200. Turned the developer bright green, just like Foma. Same half moon cut out in the corner, same style of packaging without an inner box.

[Kevin Crisp]

Of course I'll take it back if Freestyle tells me to pound sand, but so far the people making it now seem very responsive:

Mr. Crisp,

Thank you for sending photos which clearly provide the lot information needed to investigate this further. This information has been forwarded to the product team for further investigations to be completed.

In the meantime, as we had previously suggested, please work directly with Freestyle on this issue to get your replacement product or credit.

We apologize for the inconvenience this has caused you but are very happy that you have brought it to our attention to look into this further.

Thank you!
-Sino Promise Group Support

[patrickjames]

I've started putting Butane in the stock fix after I open it. Makes it last longer. From what I understand the sulfurization happens with exposure to oxygen, but don't quote me on that. Nothing worse than wasting a gallon of fix. I do the same with paper developers and they last a really long time that way, even partially used.

I think these things are more a problem today because we can't just run down to the local camera store anymore, so we buy in bulk to make sure we have what we need. That means it sits around longer. That is my case anyway.

[Kevin Crisp]

Since I had 3 of them go bad -- unopened -- after a 6/21 purchase I think it is a bad batch.

I noticed today I had a box of RF that was two years older than the ones that went bad. It's fine. I mixed it up and am using it. I'm stopping by Freestyle this week and I'll see what they say about it.

[Kevin Crisp]

The mfg conclusion is that they were cooked at some point. I picked them up at Freestyle, didn't leave them in the car, an stored them in the darkroom.

----------------------------
Hello Mr. Crisp,

After having received your images and continuing the investigation it was concluded that the product is not defective and even looking into the logs, we have not received other trade reactions, complaints, or inquiries about this lot of product.


With the age of the product (almost 2.5 years from manufacturing date) we would have received other complaints if it were related to the manufacturing. After reviewing and investigating this, it can be concluded that somewhere during its life, the product may have been subject to excessive temperature which "cooked" the fixer causing it to lead to sulfurization.

The product contains sulfites which is a common antioxidant. As the product ages the sulfites oxidize to protect the product but there is less and less sulfite remaining. Higher temperatures accelerate the oxidation and cause the remaining sulfites to be used up. Once the fixer itself oxidizes it breaks down into a sulfur precipitate.

Other chemicals which may in fact be older, but have not been subject to high temperatures may perform better - which may be what you described by your third bottle that was older but worked.

For future reference, time, and warm temperature will cause fixer to sulfurize. A good rule of thumb for optimal performance is to use the chemicals within 2 years of manufacturing date, and to not store it in an area with high temperatures.

We hope that this information is helpful to you.

Thank you.

-Sino Promise Group Support

[gypsydog]

These lyrics sum it up!

https://www.youtube.com/watch?v=MFcdBRwtF-M

[Michael R]

The 2-year rule of thumb is good but unfortunately in this day and age that guarantees nothing where photographic chemicals are concerned, especially liquids. Distribution channels aren’t what they used to be, and then retailers often store things under adverse conditions (I’ve seen some ridiculously careless things).

It’s good that they at least responded, although that doesn’t really help you. Sorry this happened. It’s frustrating.


The mfg conclusion is that they were cooked at some point. I picked them up at Freestyle, didn't leave them in the car, an stored them in the darkroom.

----------------------------
Hello Mr. Crisp,

After having received your images and continuing the investigation it was concluded that the product is not defective and even looking into the logs, we have not received other trade reactions, complaints, or inquiries about this lot of product.


With the age of the product (almost 2.5 years from manufacturing date) we would have received other complaints if it were related to the manufacturing. After reviewing and investigating this, it can be concluded that somewhere during its life, the product may have been subject to excessive temperature which "cooked" the fixer causing it to lead to sulfurization.

The product contains sulfites which is a common antioxidant. As the product ages the sulfites oxidize to protect the product but there is less and less sulfite remaining. Higher temperatures accelerate the oxidation and cause the remaining sulfites to be used up. Once the fixer itself oxidizes it breaks down into a sulfur precipitate.

Other chemicals which may in fact be older, but have not been subject to high temperatures may perform better - which may be what you described by your third bottle that was older but worked.

For future reference, time, and warm temperature will cause fixer to sulfurize. A good rule of thumb for optimal performance is to use the chemicals within 2 years of manufacturing date, and to not store it in an area with high temperatures.

We hope that this information is helpful to you.

Thank you.

-Sino Promise Group Support