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

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BHuij

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The recipe I'm using calls for 2ml in a liter of the developer, and another 2ml in a liter of fixer.

Unfortunately it looks like sources of non-bulk quantities of this stuff have dried up, and I'm not ready to drop $200 on it a B&H.

Does anyone have a good substitute? Or has anyone managed to get good results and avoid hard water stains by just using only distilled water to mix up any of the chemicals?
 

lamerko

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You can replace it with the sodium salt of EDTA or simply omit it if you are using deionized water.
 

koraks

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I just leave it out and get perfectly fine results.
I guess hexametaphosphate might work, too, but since I've never seen the need for it, I never tried it.

I use tap water btw. The developer gets a little cloudy, but it doesn't affect the negatives in any way. I use my developer one shot; if I would let it stand, the turbidity would settle to the bottom of the jar/bottle in a day, so it could even be decanted or siphoned off. Demineralized water would also help, and using a high purity grade of sodium carbonate.

Note that the drying marks are virtually never caused by the developer. They're caused by calcium carbonate in the
wash water.
 
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Okay. Test 1 will be just leaving it out entirely. If I get acceptable results then that's that. I do actually have some tetrasodium EDTA (ironically I use it as a chelating agent for my E-72 paper developer to avoid cloudiness), so if I feel like I'm having issues with the process, I can try with that. It kinda sounds like the exact amount of this particular additive might not be critical? Just kind of "enough to get the job done"?
 

koraks

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Do you have a link? I can find evidence of such a product on sites like Adorama and B&H, but it's expensive and out of stock. Formulary website itself doesn't seem to have any product called "anti calcium" by any brand.

It's in their catalog, at least the one available for download on their website, I think it's dated 2018 or so. But it's not in their actual web shop. I wonder if they still carry it. It's also kind of conspicuous that they list it as a package size of e.g. 130g, while as I understand, this material is generally sold as a watery solution of 60% or so. Makes me wonder if it's really the same thing. I couldn't find an SDS for the stuff, either, making it hard to verify what it is.
 

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It's in their catalog, at least the one available for download on their website, I think it's dated 2018 or so. But it's not in their actual web shop. I wonder if they still carry it. It's also kind of conspicuous that they list it as a package size of e.g. 130g, while as I understand, this material is generally sold as a watery solution of 60% or so. Makes me wonder if it's really the same thing. I couldn't find an SDS for the stuff, either, making it hard to verify what it is.

If you look at their catalog, you will see several "anti-calcium" compounds:

1702837722751.png


Their "Anti-Calcium" product seems to be Sodium Hexametaphosphate, which is one of the worst sequestering agents for our purpose: like EDTA it doesn't impede the Fenton reaction, and unlike EDTA it also hydrolyses in alkaline solution. Use it only, if you mix fresh, and if you have issues with water hardness turning your developers milky.

I did not find anything about their "Anti-Calcium #4" product, but Kodak has a sequestering agent with the exact same name, and it's ATMP-Na5, which would be excellent for our work. It may be worthwhile asking the people at Formulary, whether this compound is still available and whether it is indeed what I suspect it is.
 
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BHuij

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The original article I used to source my recipes and procedures for DIY ECN-2 states only that the original writer had issues with hard water stains (despite final rinsing in distilled water and using PhotoFlo) until they began using the Kodak Anti-Calcium #4. It seems everyone here is saying the only reason you'd need it is if your developer isn't transparent and that's bothering you.

I'm inclined to try just mixing all my chemistry in distilled water (which was the plan anyway since it's just best practice), and not worry about anti-calcium in the developer or fixer unless I find a need for it.

The good news is, the reason I'm going the DIY route isn't so much for saving money this time (the FPP ECN-2 kit will do 12 rolls for $20, and I have had excellent results from it thus far). It's more about being able to mix up on-shot sized portions of chemistry so I don't have to sit around for months, collecting exposed rolls of color negative film, before I can develop them and see the results. By my math so far, I can still develop 1-2 rolls at a time for a cost of about $3, so the costs aren't hugely higher than the kit anyway. The reason I bring this up is because if I do end up needing to experiment with sodium hexametaphosphate or Calgon or ATMP-NA5 or EDTA or anything else to help control calcium buildup on the negatives, it shouldn't really matter if I'm not preventing the Fenton reaction, since the developer only needs to remain good for about an hour after mixing to stabilize at the right temp and be used a single time.
 

koraks

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I can relate; those were also my motives; being able to mix fresh every time, so I could enjoy good consistency as well as low costs. It works fine for me and I've never added a chelating agent to my ECN2 developer.
 

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I also skip the chelating agent, but because of the poor water quality and questionable impurities in it, I use deionized water. I don't know the Fenton reaction is typical of this developer - a working solution after six months in a tightly closed bottle works well. Of course, the recipe is designed to be used with a replenisher for an unknown (to me) long period. Perhaps in this case the accumulation of chemicals, oxidation and the long period of use require chelating agents.
 
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BHuij

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I can relate; those were also my motives; being able to mix fresh every time, so I could enjoy good consistency as well as low costs. It works fine for me and I've never added a chelating agent to my ECN2 developer.

I have read that it's possible the developer does better if allowed to sit and "season" for a day or so after mixing. Not only does that kind of interfere with the whole "mix and use one-shot as needed" approach I'm hoping to take, but if I'm cutting corners on ingredients that can help prevent developer degradation, I'm worried letting it sit for 2 days might have a noticeable effect on my final image quality. Do you just mix and use right away? If so, mind sharing your recipe? I'd be interested to see how well it matches mine. The hope for me is to mix up 250ml of developer at a time and use one-shot for 1-2 rolls in my steel Nikor tank with constant agitation. There's probably no reason to mix up stop bath, bleach, or fixer one-shot for this process since they'll all keep just fine for a long time, so I've given my recipe for those in 1L quantities.

I am skipping the remjet removal bath, since I rarely shoot actual ECN-2 films anyway, I mostly just use this for C-41 films, and occasionally for E6(-) development.

Developer (250ml for 1-2 rolls of 35mm or 1 roll of 120):
200ml distilled water
0.5g sodium sulfite
0.3g sodium bromide
1g CD-3
7.5g sodium carbonate
0.7g sodium bicarbonate
Balance distilled water to 250ml after thorough mixing

Stop bath (1L):
990.6ml distilled water
9.4ml Kodak Indicator Stop Bath
(if Kodak Indicator Stop Bath is 80% acetic acid to 20% water as my research indicates, then this should match the concentration of the "250ml 3% vinegar to 750ml water" recipe I found published

Bleach (1L):
900ml distilled water
40g potassium ferricyanide
25g sodium bromide
1.5g borax
Balance distilled water to 1L after thorough mixing

Fixer (1L):
700ml distilled water
181.3ml ammonium thiosulfate (60%)
10g sodium sulfite
8.4g sodium metabisulfite
Balance distilled water to 1L after thorough mixing
 

koraks

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I have read that it's possible the developer does better if allowed to sit and "season" for a day or so after mixing.

That sounds sketchy to me. Where did you read this?

Do you just mix and use right away? If so, mind sharing your recipe?

Yes, mix and use immediately. On occasion I've kept it around for a second (test) roll a day after and never noticed anything odd; seemed to work exactly the same way. But I didn't do any densitometry to verify this.
https://tinker.koraks.nl/photograph...lor-developer-formulas-including-c41-and-ra4/ About halfway down that page you'll see a section on ECN2, which starts with the official Kodak formula, and then proceeds to give a simplified version for home use. That's the version I make.

For the stop bath, @Photo Engineer used to be quite adamant that it had to be sulfuric acid. He contended that if acetic would have been OK, Kodak would undoubtedly have specified it. I admit I always use acetic acid and never noticed a problem.

For the bleach I use regular C41 bleach, which seems to do the job just fine. The same for fix. I'm not a fan of the ferricyanide bleach, but have used it for many rolls when I started with ECN2 and it worked OK, is fast and has good capacity. I still have that bottle and I don't doubt it still works!
 
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BHuij

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The "sit and season" advice is something I read in passing somewhere. Sounds like it's safe to ignore.

The original article where I got my formulas also talked quite a bit about how the sulfuric acid really is imperative - even used that exact line of reasoning, if Kodak could have gotten away without using it, they would have, and that a Kodak engineer said as much. I assume this person was referring to the very same comments from Photo Engineer. At any rate, I will probably discontinue the project and go back to the FPP kits if I can't get good results with acetic acid. I have no interest in trying to source or work with sulfuric acid haha.

What is it you don't like about the ferricyanide bleach? Is it mostly the risk of cyanide gas from sulfuric acid stop carryover?

Edit: After reading through your enlightening article, it appears my developer recipe is virtually identical to yours, other than using monohydrate sodium carbonate and sodium bromide instead of potassium. If you're happy with the results you're getting then I'm very excited to try it out. My color negative film only ever gets scanned; I don't have much interest in RA4 at this time, so I'm hoping I will be able to get good results quickly!
 
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koraks

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Sulfuric acid is easy to get. Battery acid, for sale in any auto parts store, is 37% sulfuric acid. It's not any more obnoxious or dangerous than acetic acid at the same concentration - less so, since the smell is a lot less bad. But rest assured - acetic acid will work just fine.

What is it you don't like about the ferricyanide bleach?

Let me preface that there's nothing inherently problematic here; it works. It's mostly a matter of preference.

Firstly, mixed with a strong mineral acid, ferricyanide produces cyanide gas, which is deadly. While this is something that won't happen easily in a normal development process, I prefer to just not invite disaster if it's not really necessary. Secondly, and more importantly, pot. ferricyanide instantly oxidizes any developer carried over into it. This fogs the film, since oxidized developer links up with the dye couplers in the emulsion, so it creates (colored) density. I guess this will mostly happen at the film surface, so it'll be a yellow dye fog (blue in positive). It's easily prevented by using a stop bath. Which of course takes us back to #1 with the strong acid/cyanide, but if you do a water rinse after stop, that's also eliminated. Some suggest a sulfite rinse after the stop bath to get rid of any remains of developer before the ferricyanide kicks in.

If, on the other hand, you use C41 bleach, you can go from developer right to bleach and there won't be a problem. You decide to use a stop bath and a little carries over, again, no problem. Want to develop some C41 film and don't want to worry about ferricyanide somehow affecting long-term stability of the negatives, again, no problem.

So it's a 'why bother' thing for me. Ferricyanide of course is cheap. It has that going for it.
 
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Makes sense. If I was doing C-41 chemistry anyway I'd probably just use that bleach and use a water stop instead of acetic acid. It seems there are many ways to skin this cat.

But the main reasons I'd rather do ECN-2 than C-41 is because a) for whatever reason, I always just got better results from the FPP ECN-2 kit than I ever did from the C-41 kit with Blix, even with C-41 films, and b) I am toying with the idea of getting into DIY E6 as well, so having CD3 on hand already is a good position to start from.

Your article mentions some concentrates - measuring out a couple of liquids and adding CD3 does sound much easier than measuring out individual doses of everything. How long do your concentrates last if stored in glass with inert gas topping?
 

koraks

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use a water stop instead of acetic acid

No, no water stop with color. You'll just create a very weak developer. I doubt it will be a big problem, but still...

Your article mentions some concentrates - measuring out a couple of liquids and adding CD3 does sound much easier than measuring out individual doses of everything. How long do your concentrates last if stored in glass with inert gas topping?

I don't know, and to be frank, these days I just mix fresh from powder and skip the concentrates. It's only four ingredients.
In terms of longevity, the problem is mainly with the sulfite, which will oxidize. I don't think there's much you can do about it to prevent this.
When I used the concentrates, I think the longest I kept them around was a few months. Never noted any problems, but, you guessed it...no densitometry. So no guarantees.
 
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BHuij

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Okay.

Back when I was first getting into DIY chemistry with E-72 paper developer and Mytol (you probably remember long, rambly threads with astonishing numbers of questions...), I ended up designing and 3D printing custom "capsules" to hold the right volume of each ingredient and keep alkali separate from everything else. They've been working great all year, when I need to mix up Mytol to develop a roll or E-72 for a print session, I can just unscrew the lid, dump in water, and stir/shake to dissolve. Once every couple of months or as needed, I sit down with my scale and jars of white powder, and re-fill all my empty capsules so they're ready to go again.

I imagine I could do the same thing with ECN-2 capsules for 250ml of developer.
 

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I can just unscrew the lid, dump in water, and stir/shake to dissolve. Once every couple of months or as needed, I sit down with my scale and jars of white powder, and re-fill all my empty capsules so they're ready to go again.

I imagine I could do the same thing with ECN-2 capsules for 250ml of developer.

The most important parameters for color development are IMHO not the precise composition or freshness of your ingredients, but solution pH and their exact temperature. Even if your "just weigh the ingredients" formulas work perfectly right now, switch to a new source for some ingredient and pH will be all over the place. If you mix separate concentrates for color developer and alkali, the first one will give you colorful indication of its decay, whereas the latter will quietly pick up aerial Carbon Dioxide, lose alkalinity and appear exactly the same as on the day you mixed it.

Use a calibrated pH meter, make sure, that calibration liquids are not way out of whack, especially the pH 10 liquid, use a decent thermometer, maybe do some measurements of tank interior at different water jacket temperatures, and your results will be great. Avoid this effort, and enjoy countless hours of happy post processing the awful scans you'll inevitably get. Been there, done that :-(
 

koraks

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Avoid this effort, and enjoy countless hours of happy post processing the awful scans you'll inevitably get.

Meh. To be frank, I ditched the pH meters because of persistent calibration problems which caused more trouble than they solved. The quality of my negatives hasn't deteriorated. As long as I use (reasonably) fresh film and expose properly, printing is predictable and sufficiently consistent. Scanned negatives are so malleable that it's not worth fussing much over processing parameters to begin with; see my recent Harman Phoenix scans for an illustration of how systematically crossed over, gamma-out-of-whack negatives yield presentable images while straight darkroom prints from the same negatives are impossible.

There are two archetypical ways of doing color processing: the strict way, which involves fresh chemistry, proper replenishment or one shot use, strict process control, fresh film from a major manufacturer (i.e. Kodak), etc. etc. Then there's the happy-go-lucky way that reuses chemistry of the kitchen sink variety until it's more colorful than the photos are supposed to be, Lomo film that has aged in a hot truck for a couple of years, temperature control consisting of sticking a finger in the air and mumbling "yah, good enough" and timed development by counting the drops from the leaking tap over the sink. I think the main trick is to figure out which variant between these extremes suits each individual photographer best. This should be a function of the requirements on the final image, and in practice it's just as much a matter of temperament. As time goes by and I become increasingly aware of the intricacies of film-based color photography and the myriad ways in which it can go wrong, I'm increasingly hesitant to push whatever standards onto someone while warning them for the fire and brimstone they'll risk if they don't mark my words.

Finally: this is not a popular thing to say on here, and I'm not saying it to be argumentative, but to instill a sense of realism on this rant: if as perfect a match between original scene colors and final output is desired, the sensible thing is really to shoot digital and to calibrate the workflow. In the digital domain, this is far more effective and efficient than in a film-based workflow.

PS: this is not to say you're wrong with the pH and temperature control. Of course that's the 'right' way to do it. And especially pH is critical (temperature a little less so in my experience). This is also one reason why I abandoned the ECN2 developer concentrates and mix fresh from powder; it replaces the need for pH adjustment of the developer upon mixing with a consistent pH point which may (fat chance) or may not be (more likely) exactly on spec. While it may not be perfect, it'll at least be consistent. And yes, it'll be so until chemistry changes, but it takes me a couple of years to run out of it, and I'm perfectly happy settling on a new equilibrium when I purchase some new carbonate, CD3 etc.
 
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BHuij

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Yeah, I mean I'm very much in the "dive in and try it" camp. I already have temperature control sorted with an immersion circulator, and I've been getting excellent results (including good color balance that did not cause any headaches in post processing after the scan) with C-41, ECN-2, and E6 kits for a several years.

The other piece of context here is this: I don't really do "art" on color negative film. The color negative film I do shoot, 99% of the time, is in my Kodak half frame point & shoot, where every photo is at fixed hyperfocal distance with a plastic meniscus lens, and 1/100th of a second at f/9.5. The only control I have is whether the flash is on or not. These are family snapshots. They are shot, developed, scanned, briefly corrected in LR, and then printed at 4x6 to put in a photo album. So if the colors are a little wacky because my pH wasn't perfect in the developer... I'd consider it a complete nonissue.

When I want to do "art" in color, I shoot slide film or digital.

E6 is a challenge to be tackled another day. Again, I've had success with kits, and I suspect I'll be able to build a good workflow for achieving similar success with DIY E6 chemistry. And if that process involves some pH validation steps before committing expensive 4x5 sheets of Ektachrome, that's fine with me :D
 
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