Sodium Citrate developer and Ferric Oxalate sensitizer lifespans (Kallitype)

[BHuij]

I dipped my toes into Kallitypes about a year ago and had some fun. Then put the Kallitype stuff away to focus on silver gelatin printing for a while. Most of the chemicals involved are, I think pretty stable (sodium thiosulfate fixer, clearing bath that's just citric acid and water, etc. etc). But the developer I'm using is 20% sodium citrate in water. Any chance it's still fine or should I plan on tossing what's in the bottle and mixing some up fresh?

Same question for my Ferric Oxalate - I understand that stuff tends to go bad easily which can lead to print fogging? Honestly I can't even remember if I have it in powder form or if I just bought a solution for part B of my sensitizer. It's been stored cool in a glass container out of the light, but for something like 15 months. Heh... now I think about it, do I need to be worried about my silver nitrate?

 

[Andrew O'Neill]

The Sodium Citrate developer should be okay. I used mine after a year of sitting in a cupboard (I mainly use Sodium Acetate), and it was fine. Mixed up Ferric Oxalate will be bad. You'll have to mix up another batch. The longest I've gone without using the Silver Nitrate mixture was a few months, and it was fine... but I've heard that it will go bad.

 

[BHuij]

Good to know, thanks.

I'm going to have to dig through the bin when I get home from the office today, because I can't remember if the ferric oxalate I bought was a pre-mixed 20% solution or a dry powder with which I premixed my own solution. The solution would be bad in either case - and when I find it I assume I should expect to find crystals in there to attest to that fact. But if I did indeed buy powder, will the powder still be good? I'm remembering that it was kind of difficult to track down good quality ferric oxalate, and a fair amount of drama between people who had different religions on how best to synthesize it and whatnot.

 

[Andrew O'Neill]

All the FO in powder form that I have used has lasted for ages... I have a bottle that has been sitting for several years, and it works fine. I usually get FO from Bostick & Sullivan. That stuff is a pleasure to work with as it goes into solution very easily.

 

[BHuij]

Yeah when I first got into it, I bought some powdered ferric oxalate from the formulary. They said they were discontinuing it and this was one of the last ones left on the shelf, and it was old. They couldn't vouch for its quality so they gave me a discount IIRC. When it arrived, it was a greenish rock. I could get powder off of it to mix up, but it took forever go to into solution, and every Kallitype I tried to make with it was fogged. I can't remember if I then got powder or liquid FO from B&S, but whatever I got worked perfectly. I'm hoping it was powder, guess I'll find out when I get home tonight. Seems the method of degradation is that it doesn't want to stay anhydrous. So if I find powder I may try and get it good and sealed up when I'm done mixing up a fresh batch of concentrate.

Same thing with my silver nitrate. I think I got powder, so I can probably mix up a fresh solution if the one I have in the jar isn't good anymore. Probably only one way to find out with that; trying it.

 

[nmp]

Yeah when I first got into it, I bought some powdered ferric oxalate from the formulary. They said they were discontinuing it and this was one of the last ones left on the shelf, and it was old. They couldn't vouch for its quality so they gave me a discount IIRC. When it arrived, it was a greenish rock. I could get powder off of it to mix up, but it took forever go to into solution, and every Kallitype I tried to make with it was fogged. I can't remember if I then got powder or liquid FO from B&S, but whatever I got worked perfectly. I'm hoping it was powder, guess I'll find out when I get home tonight. Seems the method of degradation is that it doesn't want to stay anhydrous. So if I find powder I may try and get it good and sealed up when I'm done mixing up a fresh batch of concentrate.

Same thing with my silver nitrate. I think I got powder, so I can probably mix up a fresh solution if the one I have in the jar isn't good anymore. Probably only one way to find out with that; trying it.

If you bought the kit, you would have received solutions of the two. Silver nitrate solution can last for a long time or forever as long as it is not contaminated or it does not have any additives like citric acid and exposed to light.

:Niranjan.

 

[BHuij]

Yeah I didn't buy the kit, I knew I was going to be doing low-volume, so I would have bought things that I could store long term to the maximum extent possible.

Checking my email for some old receipts tells me I did I get the powdered Ferric Oxalate from Bostick & Sullivan, as well as powdered silver nitrate from Formulary. So I should still have everything I need to get going again.

 

[BHuij]

Would ferric oxalate dissolve in propylene glycol? Or is there some other solvent besides water that I could use to make a 20% solution that might last longer before going bad? Just brainstorming a bit here.

 

[koraks]

But the developer I'm using is 20% sodium citrate in water. Any chance it's still fine or should I plan on tossing what's in the bottle and mixing some up fresh?

In my experience this will tend to grow molds that form large, billowy clusters floating around inside the jar. Just filter them out and it should be fine.

 

[BHuij]

My bottles are opaque, but I'll pour them in the tray and check for molds or other obvious problems. If there's anything wrong... sodium citrate is cheap. I'll probably just rinse out the bottles and start fresh.

 

[Andrew O'Neill]

My bottles are opaque, but I'll pour them in the tray and check for molds or other obvious problems. If there's anything wrong... sodium citrate is cheap. I'll probably just rinse out the bottles and start fresh.

Opaque Sodium Citrate developer? My old stuff has been a darkish green, and not opaque. For fun, I'd run a print through it to see what happens... after filtering it, of course. I always replenish my developer, same way I replenish Xtol-R.

 

[koraks]

Opaque Sodium Citrate developer?

Opaque bottles, I think he meant. Not an opaque fluid inside them.

 

[Andrew O'Neill]

Opaque bottles, I think he meant. Not an opaque fluid inside them.

Of course!

 

[BHuij]

Yep, opaque bottles. I was also using a replenished setup, per (I think) Sandy King's recommendation. So my "working" bottle of developer has always been given 1ml of fresh, unused developer for every square inch of image developed. Neither bottle had any signs of mold, precipitate, or other issues.

I'm glad I kept really good notes on all this stuff when I was doing my initial tinkering. Made it easy to pick right up where I left off.

Last night I cleaned out my bottle of ferric oxalate solution. It was basically water with a giant blueish crystal in there, as expected. Mixed up a new batch from my Bostick & Sullivan powder. Other than taking 3280314 years to go into solution (again, normal IIRC), it seems fine. Not caked up or excessively greenish.

My 10% silver nitrate seemed to have a hair bit of metallic precipitate settled at the bottom, but a good shake and it was coming out of the dropper clear. It has been stored in the dark and out of the heat, so I figured it was probably fine.

Today I ran through and made a quick 4x5 test print and it came out exactly as I would expect. Identical contrast range to the last one I made in late 2021 (which has been hanging up in my darkroom). No apparent fogging. Just still kinda riding the line between having dmin acceptably close to paper base white, and still getting a halfway decent dmax. I guess that's an artifact of using digital negatives. In my last tests, I stopped just short of adding some potassium dichromate to the developer for extra contrast. I might finally cross that line in the coming few weeks. That stuff just makes me really nervous.

In any case, my developer and silver nitrate seem good to go! Thanks all.

 

[BHuij]

Wanted to report back here now that I've made several prints, and iterated through a few different tone curves in Photoshop for converting my files to inkjet negatives on Pictorico. I didn't end up needing to play with dichromates (phew), and I think I'm getting a full range of tones between a fairly decent dmax and paper base white. The trickiest part is achieving a good dmax and a true paper base white at the same time as getting good shadow tone separation. In most of my earlier kallitypes, the shadows get muddy and bleed into each other really fast. Adding a substantial amount of contrast to the shadows and a somewhat lesser amount to the highlights seems to have been the ticket for me.

I also had to re-build a few parts on my DIY contact printing frame. I wasn't getting perfect contact, and it was resulting in noticeably soft/blurry areas on my prints. After tightening some things up, I can no longer detect any spots that look out of focus.

All together, I'm really thrilled with the results I've been getting. Pardon the phone picture of a still very wet print, but I think this is the best kallitype I've made to date, so I wanted to share. Thanks all for your expertise and help.

 

[Andrew O'Neill]

Very nice image but...it's a little pinky on my screen...

 

[BHuij]

Very nice image but...it's a little pinky on my screen...

That’s basically how these look before they dry. I’m gold toning, so when they dry down they get a bit darker and shift to a fairly purple color. While still wet they’re more pinkish brown.

 

[Andrew O'Neill]

That’s basically how these look before they dry. I’m gold toning, so when they dry down they get a bit darker and shift to a fairly purple color. While still wet they’re more pinkish brown.

Are you gold toning before or after fixing? I get a pinky tone if I gold tone after fixing...

 

[BHuij]

Before fixing, after clearing.

Here’s an actual scan of the dry, flattened print that shows its final color.

 

[Andrew O'Neill]

Before fixing, after clearing.

Here’s an actual scan of the dry, flattened print that shows its final color.

Now that I like! Beautiful!

 

[revdoc]

Nice image! It looks like you're getting some spotting or uneven tone in the sky. Which paper are you using?

 

[BHuij]

Nice image! It looks like you're getting some spotting or uneven tone in the sky. Which paper are you using?

I noticed that too. The paper is HPR. I believe that the spots are indicative of either insufficient brushing, or insufficient drying before I exposed the paper. But if you have ideas for what might be causing it, I'm all ears. The spots are not on the negative. I made a second print from a different negative last night too, and gave it more dry time, and did not get spots. All the ones I've made over the past few weeks have also been spot-free.

 

[nmp]

Looks like the contrast came down somewhat after drying, perhaps lower Dmax as well - is it the magic of iPhone or real?

 

[BHuij]

I don't think the dmax or the contrast came down significantly, other than what you would normally expect a wet print vs a dry print to look like.

That said, it's entirely possible that the iPhone pic shows higher contrast than the scan. When I took the iPhone pic, I tried hard to get the color balance and white/black points to look on my screen the same as they did on the real life print as viewed under a daylight balanced bulb. And when I say I "tried hard," I mean I used the sliders for 30 seconds.

Same story for the scan. I held the dry print in front of me and tuned the (very flat) scanned TIFF using a levels adjustment layer until what I saw on the screen felt like a faithful reproduction of what I was seeing in the print in real life. I put more effort into this than I did with the iPhone pic. But I'm sure neither digital representation is a perfect match for what the physical print looks like. If for no other reason than that screens are backlit and prints are not.

I guess what I'm saying in a lot of clumsy words is, the real life print did not lose dmax or contrast when it dried, and when I adjusted the phone pic and the final scan, my goal in both cases was honest reproduction of the physical print when setting black/white points and color balance, rather than artistic interpretation.

 

[nmp]

I don't think the dmax or the contrast came down significantly, other than what you would normally expect a wet print vs a dry print to look like.

That said, it's entirely possible that the iPhone pic shows higher contrast than the scan. When I took the iPhone pic, I tried hard to get the color balance and white/black points to look on my screen the same as they did on the real life print as viewed under a daylight balanced bulb. And when I say I "tried hard," I mean I used the sliders for 30 seconds.

Same story for the scan. I held the dry print in front of me and tuned the (very flat) scanned TIFF using a levels adjustment layer until what I saw on the screen felt like a faithful reproduction of what I was seeing in the print in real life. I put more effort into this than I did with the iPhone pic. But I'm sure neither digital representation is a perfect match for what the physical print looks like. If for no other reason than that screens are backlit and prints are not.

I guess what I'm saying in a lot of clumsy words is, the real life print did not lose dmax or contrast when it dried, and when I adjusted the phone pic and the final scan, my goal in both cases was honest reproduction of the physical print when setting black/white points and color balance, rather than artistic interpretation.

Makes sense. I was just wondering if there was anything in the process that is unique to kallitype that reduces Dmax/contrast on dry-down.

:Niranjan.