DIY ECN-2, looking for Kodak Anti-Calcium #4 replacement

Rudeofus · Dec 19, 2023

koraks said:
Meh. To be frank, I ditched the pH meters because of persistent calibration problems which caused more trouble than they solved.

Yes, cheap pH meters can be a hassle. Yes, good pH meters are expensive, but in the end I spent vastly more on film and chems than on pH meter and accessories.

As long as you do negatives, you can't really do much wrong (except for underdevelop). Slides are a completely different animal, and small variations in your chems have painful effects.

But let me emphasize this again: accurate pH is only half the game. Temperature control is just as important, rarely discussed and widely underrated.

czygeorge · Dec 20, 2023

I have always been in favor of using H2SO4 or NaOH to adjust the pH value of the color film developer correctly, which will make post-production work much easier：)

I always found that the pH of Kodak's developing (working) solutions is always higher than it should be (including its TMAX developers, RA-4, C-41, and ECN-2), and H2SO4 needs to be used to lower it

For bleaching solutions and fixing solutions, adjusting the pH value with ammonia and acetic acid can also increase their service life ( with rinse step to protect them from contamination)

I have always used calibrated thousandth scales and volumetric flasks to configure ECN-2 (divided into a and b concentrates). I also used Kodak No. 4 anti-calcium and af-2000. In fact, I think the former is what rudeo said atmp na5 (this chemical is very cheap and is also widely used in E-6 reversal). The latter is easy to buy here, but I think the quality of af-2000 produced by Kodak factory China is not very good ( There is precipitate), so I have planned to try using af-4 instead

As we can’t ask the laboratory to do component analysis like the factory do, so we can only try to be as precise as possible during configuration

Rudeofus · Dec 21, 2023

czygeorge said:
I also used Kodak No. 4 anti-calcium and af-2000. In fact, I think the former is what rudeo said atmp na5 (this chemical is very cheap and is also widely used in E-6 reversal). The latter is easy to buy here, but I think the quality of af-2000 produced by Kodak factory China is not very good ( There is precipitate), so I have planned to try using af-4 instead

Please make sure, that you don't mix up Kodak's Anti-Fog (AF) series of chemicals with Kodak's Anti-Calcium (Anti-Cal) series of products. These are very different chemicals and serve very different purposes.

Also, I am not aware of a Kodak Anti-Fog #4 product. There is an article here, which lists some chemical trade names, and the additions made later contain factual errors, e.g. AF-2000 is definitely not related to ATMP.

lamerko · Dec 21, 2023

Both Anti-Calcium #4 and AF-2000 are present in the formula. I assume czygeorge meant the AF-9 for the replacement. Personally, I would not bother at all, but if there is to be a replacement - 0.22 g/l of AF-9 is needed. But according to H2408, omitting AF-2000 will have practically no effect.

BHuij · Dec 21, 2023

Where might I find ATMP Na5? Some quick googling only yielded large industrial suppliers that wanted to generate a quote for some huge quantity rather than selling me a canister with 100g in there

If I were to mix up a capsule of pre-measured dry ingredients to make 250ml of ECN-2 developer:

0.5g sodium sulfite
0.3g sodium bromide
1g CD-3
7.5g sodium carbonate
0.7g sodium bicarbonate

Are there any ingredients there that should not be mixed dry and stored together? In other words, do I need to design a container with multiple separate compartments to store those powders? Assuming they might sit in there for up to several months at a time before being mixed with water.

lamerko · Dec 21, 2023

The problem is that ATMP.Na5 is mainly distributed as a solution, which severely limits the possibilities for fast retail...

koraks · Dec 21, 2023

BHuij said:
Are there any ingredients there that should not be mixed dry and stored together?

At least separate the CD3 from the rest.
The rest may be fine as long as it's kept bone dry. This means you'd have to store under dry conditions and seal hermetically. Sodium bromide and sodium sulfite are hygroscopic; the sulfite will likely degrade (oxidize into sulfate) as it's kept moist / allowed to absorb moisture from the air. I expect the carbonate and bicarbonate to just cake, which may be an issue in terms of getting it out of the 3d printed container when it's time to use it.

It helps that you live in a dry climate.

BHuij · Dec 21, 2023

Yeah luckily I do live in the desert, so in many cases I can get away with not worrying too much about hygroscopic things getting ruined when left out (3D printer filament comes to mind). But it also seems like it wouldn't be that hard to just build an O-ring into the design of the 3D printed container when I make it, and keep the closed containers in a bin with some desiccant.

I'll plan on keeping the CD3 apart from the rest, but otherwise sounds very doable. The few chemicals I didn't already have on hand are on their way, so hopefully I can get out and shoot roll of color negative film in the coming week or so, and test this out.

As always, big thanks to everyone for helping answer all my questions here. I'm always astounded by the wealth of knowledge available from members of this forum. I'll be sure to post results!

czygeorge · Dec 22, 2023

lamerko said:
Both Anti-Calcium #4 and AF-2000 are present in the formula. I assume czygeorge meant the AF-9 for the replacement. Personally, I would not bother at all, but if there is to be a replacement - 0.22 g/l of AF-9 is needed. But according to H2408, omitting AF-2000 will have practically no effect.

Yes thanks lamer 0.22g af-9 is what i meant

I once tried to remove af to test, and there was almost no difference in scan result, since it is already very difficult to achieve the limit value by rotary processing(running control strips)

For anti-cal 4,I believe it's just atmp-Na5(40%),it's a little yellowish and very sticky liquid whose PH is around 11.Also called dequest 2006

I personally feel that this ingredient will protect the life of the concentrate and working solution to a certain extent.

BHuij said:
Yeah luckily I do live in the desert, so in many cases I can get away with not worrying too much about hygroscopic things getting ruined when left out (3D printer filament comes to mind). But it also seems like it wouldn't be that hard to just build an O-ring into the design of the 3D printed container when I make it, and keep the closed containers in a bin with some desiccant.

I'll plan on keeping the CD3 apart from the rest, but otherwise sounds very doable. The few chemicals I didn't already have on hand are on their way, so hopefully I can get out and shoot roll of color negative film in the coming week or so, and test this out.

As always, big thanks to everyone for helping answer all my questions here. I'm always astounded by the wealth of knowledge available from members of this forum. I'll be sure to post results

Yes, it is okay if CD 3 is dissolved as a powder at the end(when you need to use it for processing), but the remaining components are best kept as a concentrate to protect the sodium sulfite and bromide salts

czygeorge · Dec 22, 2023

BHuij said:
Where might I find ATMP Na5? Some quick googling only yielded large industrial suppliers that wanted to generate a quote for some huge quantity rather than selling me a canister with 100g in there

If I were to mix up a capsule of pre-measured dry ingredients to make 250ml of ECN-2 developer:

0.5g sodium sulfite
0.3g sodium bromide
1g CD-3
7.5g sodium carbonate
0.7g sodium bicarbonate

Are there any ingredients there that should not be mixed dry and stored together? In other words, do I need to design a container with multiple separate compartments to store those powders? Assuming they might sit in there for up to several months at a time before being mixed with water.

It will be very laborious (compared to preparing concentrated liquid), and sodium bromide is easy to stick to the weighing paper, makes it will be very difficult to be precise when preparing the powder alone.

lamerko · Dec 22, 2023

czygeorge said:
I personally feel that this ingredient will protect the life of the concentrate and working solution to a certain extent.

At the idea of koraks, I started preparing a concentrate in two parts without CD-3. I add it immediately before use to the already prepared working solution. I prepare the concentrate with deionized water. Therefore, the addition of ATMP-Na5 is not necessary if the chemical is not easily accessible.
As for the pH of this sequestrant - it's really high. Omitting it will lead to the need to adjust the pH of the working solution.
As a matter of fact, I always get a lower pH than the 10.25 indicated, but I've always taken it as normal because I miss ATMP-Na5. At the same time, other people say they get a higher pH. Interesting...

koraks · Dec 22, 2023

lamerko said:
As a matter of fact, I always get a lower pH than the 10.25 indicated, but I've always taken it as normal because I miss ATMP-Na5. At the same time, other people say they get a higher pH. Interesting...

Yes, I actually formulated the concentrate with an amount of NaOH in it to boost the pH of the working strength developer. But I always adjusted pH upon diluting the working strength developer anyway when using this concentrate. I don't recall if it used to be on the high or on the low side.

BHuij · Dec 24, 2023

lamerko said:
As for the pH of this sequestrant - it's really high. Omitting it will lead to the need to adjust the pH of the working solution.
As a matter of fact, I always get a lower pH than the 10.25 indicated, but I've always taken it as normal because I miss ATMP-Na5. At the same time, other people say they get a higher pH. Interesting...

This makes sense. In the interest of establishing a baseline for what kind of results I can expect without going through steps like pH balancing prior to use, I'm probably going to run a first roll of low-stakes film through without trying to adjust it. What kind of signs should I be on the lookout for if my pH is too low or too high? Specific color shifts? Density issues?

Everything is here except the CD-3, which should arrive on Thursday. That's what I get for getting this idea right around Christmas, I guess

koraks · Dec 24, 2023

BHuij said:
What kind of signs should I be on the lookout for if my pH is too low or too high?

Mostly density/gamma. The developer will be (much) less active at a low pH and overactive at a high pH. So you're mostly looking for very similar things as big temperature deviations. There will be color shifts, too, but those are often not as obvious as the contrast issues. If you scan and not print optically, there's a chance you won't notice anything unless you do strict side by side comparisons.

BHuij · Jan 9, 2024

Okay, the first results are in. With my one-shot ECN-2, I have now developed:

A roll of expired Fujicolor 400 (exposed at 200)
A roll of fresh Vision3 250D (box speed)
A roll of expired Kodak Gold 200 (box speed)

The Fujicolor 400 came out looking pretty good, definitely expired-looking fading of the colors, and the density was a bit on the low side.

The Vision3 250D came out looking phenomenal. Colors are dead on, density is perfect, I think I have a new favorite color negative film. I am using kind of odd agitation - it's rotary agitation, but off-axis with a standard Nikor steel tank that holds 2x 35mm reels (or 1x 120). Basically it's constant agitation by inversion at a moderate clip. That agitation scheme seems to have done a pretty decent job getting the remjet off despite me not using a pre-bath for remjet removal. But not perfect. From reading @koraks's blog, I guess the remjet removal bath is basically just a pretty aggressive alkaline, and the remjet is designed to get very soft at high pH, and not harden again even when introduced to acid stop bath. At any rate, my next roll I'll try using a pre-bath as well as taking a more thoughtful approach to the final mechanical removal steps after bleaching and fixing.

The Gold 200 came out looking pretty thin. It seems that CD3 is less active than CD4, and I wonder if that has something to do with why my C-41 films came out thin while my ECN-2 came out great. I think next time I do a C-41 film, especially an expired one (and especially especially an expired one that I didn't downrate by a stop or more), I'll give it extra development time to see if that can build more density. I'm not too worried about building contrast, these films are obviously very flexible in that regard. Might try 4 or 5 minutes instead of 3 next time.

At any rate, it works! As always thanks everyone for your help.

Does anybody know the answers to a few lingering questions I have?

Does ECN-2 need stabilizer? I have some formalin on the way since I've been developing E6 films in HC-110 and this ECN-2 chemistry with good results, but I know for sure that E6 films need a stabilizer for longevity. Wondering if I should be tacking on a quick stabilizer bath to the end of my ECN-2 process after the final wash.
My C-41 films, even the expired ones, are all post-2003. Which means theoretically they don't need stabilizer, but I'm not sure if that's only true when they're developed in proper C-41 chemistry instead of cross processed in ECN-2. Should I be doing a final stabilizer bath for my C-41 films that get run through the ECN-2 process?

lamerko · Jan 9, 2024

There is a lot of information about remjet. In short, it is designed to dissolve in an alkaline solution. Because ECN-2 chemistry is intended for multiple use, the pre-bath contains not just an alkaline solution, but a set of chemicals that only serves to soften the remjet, not separate it and contaminate the chemistry. After processing, the film goes through a decoating procedure - with pressure nozzles and physical cleaning with sleeves. Only then do you move on to the step with the developer.
In case of manual processing, it is necessary to remove the remjet in an alternative way. Many people just use an alkaline solution (for example 2-3 spoons of sodium bicarbonate) as a one-time solution, others do not bother to remove it at all - the developer is highly alkaline, which means that it will soften and eventually the remjet will come off when stirred, but the developer itself it will get dirty. If you're using it as a one-off solution, this probably isn't a problem.
Regarding the activity of CD3 and CD4 - yes, CD4 is almost twice as active.
Do movies need stabilization? The C-41 process films probably don't. For the ECN-2 process, no stabilizer is mentioned anywhere in the documentation. Are these films intended for archival value? In any case, the stabilizer won't hurt...

koraks · Jan 9, 2024

BHuij said:
Does ECN-2 need stabilizer?

I don't know. People at Kodak must know, but I've never heard any conclusive information on it.

As @lamerko says, CD3 is much less active than CD4. This explains why your C41 negatives came out thin.
Developing C41 film in a CD3-based developer is a form of cross-processing and this means all bets are off in terms of dye stability. I'm not sure if a stabilizer will help any in this regard, if there's a problem in the first place, and if there is, how big of a problem it is. Color balance is bound to be affected and you'll have crossover on your C41 film cross-processed this way. If you only scan and you're happy with the results, this may not have to be a problem. I personally don't consider the approach ideal. You might consider getting some CD4 and make a simple C41 developer; it's not very hard to make something that does a decent job.

BHuij · Jan 9, 2024

koraks said:
I don't know. People at Kodak must know, but I've never heard any conclusive information on it.

Glad it wasn't just a failure on my part to find that information, I was baffled that nobody had a straight answer when I was googling. I won't worry about it.

koraks said:
As @lamerko says, CD3 is much less active than CD4. This explains why your C41 negatives came out thin.

Yep, that checks out.

koraks said:
If you only scan and you're happy with the results, this may not have to be a problem. I personally don't consider the approach ideal.

Exactly this. I hoarded some expired Kodak Gold and Fujicolor for shooting family snapshots on my half frame H35. Works great for that. I can settle for overdeveloping a bit with these films and color correcting digitally since I've gotten plenty good enough results to print 4x6s for the photo album. Honestly the imperfect colors rather add to the charm. When the C-41 film runs out, I'm switching to Vision3 250D for this use case, so it becomes a nonissue.

koraks said:
You might consider getting some CD4 and make a simple C41 developer; it's not very hard to make something that does a decent job.

I'm confident this wouldn't be terribly difficult or expensive, but in the interest of simplicity, I think I'm going to stick with ECN-2 developer. One less set of bottles to keep around I may add E6 to the mix at some point too, though I'm getting surprisingly good results just using HC-110, fogging with light, and ECN-2 color developer/bleach/fixer. Formalin arrives later this week so I can stabilize as well.

Thank you!

MattKing · Jan 9, 2024

FWIW, the folks at Eastman Kodak have no data respecting the stability and longevity of any cross-processed materials, don't really have the resources to do the work to obtain and analyze such data, and are telling commercial customers (like labs) that enquire about stability essentially: "we don't know - you are on your own".
They are also concerned about the large amount of ECN film out there where the remjet has been removed chemically prior to sale to the consumer. In particular, concerned about the effect of that film on otherwise in spec C41 lines.

koraks · Jan 10, 2024

MattKing said:
FWIW, the folks at Eastman Kodak have no data respecting the stability and longevity of any cross-processed materials

But do they have data on the longevity of properly processed ECN2 Vision3 film? Evidently they don't bother to test cross-processed materials, but it would help if they would be explicit on the need for a stabilizer for Vision3.

Rudeofus · Jan 10, 2024

From looking at the H2407 sheet provided by Kodak, their ECN-2 process needs no Formalin for unused couplers, but does need a final rinse to prevent germ growth in the gelatin. This puts it in the same league as modern C-41 film stock. It is unlikely, that any of us can legally buy the toxic ingredient of final rinse in pure form, we either have a source for the Kodak product, or we use Formalin. PE explained this in his legendary "final word on final rinses" thread.

koraks · Jan 10, 2024

Thanks for sharing your insight, @Rudeofus!

lamerko · Jan 10, 2024

Rudeofus said:
From looking at the H2407 sheet provided by Kodak, their ECN-2 process needs no Formalin for unused couplers, but does need a final rinse to prevent germ growth in the gelatin. This puts it in the same league as modern C-41 film stock. It is unlikely, that any of us can legally buy the toxic ingredient of final rinse in pure form, we either have a source for the Kodak product, or we use Formalin. PE explained this in his legendary "final word on final rinses" thread.

I do not find such information. It is only mentioned that the solutions of the pre bath and the final wash have the possibility of biological contamination and antibacterial preparations can be added to them. It's about the solutions, not the film. And only if necessary...

koraks · Jan 10, 2024

lamerko said:
I do not find such information.

Page 7-4:

Besides, since a processed color negative emulsion is essentially gelatin with some dyes, it's inherently prone to microbiological damage as there's no protective silver as there is in B&W film. As such, the requirement of a biocide for optimal archival stability is kind of obvious and inherent to a color negative material.

BHuij · Jan 10, 2024

Sounds like the bottom line is, just use a PhotoFlo + formalin final rinse for all my color films, whether they be C-41, E-6, or ECN-2. Easy enough to remember It's easy, and even in cases where it's not strictly necessary, it certainly doesn't hurt. And it doesn't really take any extra time - I was already using PhotoFlo immediately prior to drying. I'm just making the PhotoFlo a bit spicier now.

DIY ECN-2, looking for Kodak Anti-Calcium #4 replacement

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