Is very acidic Ferric Oxalate a problem - Clearing Kallitypes

[davido]

Oh man, I'm practically pulling my hair out trying to produce a Kallitype with nice clean whites.

Here's my process:
Mixing 10 drops of each FO & SN into a solution and brushing on Cott paper - taking about 10 seconds of brushing with a Richeson 'Magic Brush'.
Leaving the paper to dry flat for 5 minutes and then 30 minutes hanging to dry.
Exposing in a Nuarc 26-1K
Developing in Sodium Citrate with potassium dichromate 2ml/litre.- citric acid added to bring up acidity - 8 minutes
Cleared in Citric Acid Baths - X2 total of 8 minutes
washed
Toned in Gold Thiourea - 4 minutes
washed
Fixed in Sodium Thio. - 2 minutes.
washed - 30 minutes.

The FO solution was made less than a week ago, from FO from B&S. It was made without hot water (magnetic stirrers are awesome!) and has been stored in the fridge.
The prints are not 'almost completely clearing of stain" coming out of the developer (as Sandy K. says they should). When dry, the test prints have a slight yellow in the highlights.

I have also tried Ammonium Citrate/Sodium Acetate developer which is recommended in Christopher James' book for solving the problem of buff coloured highlights.

Possible culprits:
- The developer appears to be around PH5, slightly more acidic than it should be (PH6). How would I make it more alkaline?
- The FO solution has a PH of 1.5? This seem extra-specially acid? This may because my distilled water is about PH 4.5!
- The SN solution is fairly old (2007) but I don't think that would cause staining? My Silver Nitrate crystals were given to me by a friends and are most likely fairly old.
- I have the Nuarc surrounded by black-out material, so it does get hot in there. Could heat be a problem?
- Perhaps I need to try another brand of distilled water?

Thanks for your help. I hope to solve this problem before I pull out all of my hair!

david

 

[Andrew O'Neill]

Have you tried a different paper?

 

[davido]

I have used other papers.

Thanks Andrew.
Yes, I have used other papers. I was originally using Platine but it was not clearing. I've also recently tried Buxton and Herschel which seemed to be clearing fairly well but not upon close inspection. Also, the texture of the papers wasn't working with my current project. I do quite like the Cott paper, as it's a brighter white with a smooth texture.
Though it's close, the Cott is not completely clearing; the whites are buff. This shows when the test print is scanned.
It's close thought, really close. So I'll keep working on it.
I'm concerned about the acidity of my FO solution though? Is that normal?

david

 

[Erik L]

Perhaps try some EDTA after the initial citric acid clearing baths. Tablespoon/liter should do. I've never had a problem with cot 320, but you might give a minute or two soak in a 3% oxallic acid solution prior to coating and see if that helps. Your process looks fine to me, sometimes the stars don't align and cause havoc for some reason,

 

[Klainmeister]

Perhaps try some EDTA after the initial citric acid clearing baths. Tablespoon/liter should do. I've never had a problem with cot 320, but you might give a minute or two soak in a 3% oxallic acid solution prior to coating and see if that helps. Your process looks fine to me, sometimes the stars don't align and cause havoc for some reason,

This^^^

 

[cliveh]

Have you tried developing without the potassium dichromate?

 

[davido]

Have you tried developing without the potassium dichromate?

Clive,
Looking back at my notes, I did try developing half the print with potassium dichromate and the other without, but that was with ammonium citrate/sodium acetate dev.
The one without had much worse stain. Even the one with, had noticeable stain.
I will try this with sodium citrate developer, doing the same type of test.

 

[davido]

Perhaps try some EDTA after the initial citric acid clearing baths. Tablespoon/liter should do. I've never had a problem with cot 320, but you might give a minute or two soak in a 3% oxallic acid solution prior to coating and see if that helps. Your process looks fine to me, sometimes the stars don't align and cause havoc for some reason,

I have used EDTA disodium and it does help. Sandy King suggests that the print should have most of the stain removed by the developer. So I'm focusing on that. Perhaps I will try the oxallic acid soak on the paper. Though it seems that the oxalic acid is primarily helpful in creating deeper blacks. Though the Cott is supposed to be a very neutral ph paper, perhaps my Cottt has been compromised? and needs to be acidified?

 

[Klainmeister]

What color is your SN solution? I'm having a very similar issue with the Athentype and realized that I have way more precipitant than I recall in the past. EDTA helped quite a bit with mine, but somewhat in the same boat as you. I'll escalate this discussion to Dick Sullivan Thursday night and see what he has to say.

 

[davido]

What color is your SN solution? I'm having a very similar issue with the Athentype and realized that I have way more precipitant than I recall in the past. EDTA helped quite a bit with mine, but somewhat in the same boat as you. I'll escalate this discussion to Dick Sullivan Thursday night and see what he has to say.

My Silver Nitrate solution appears pretty much clear. It was made in 2006 and is in a small brown bottle which has been kept in the dark.

I'm curious about this Athenatype process. Could someone please tell me it's benefits over the kallitype/vandyke/argyrotype processes. Does it clear better and have better dmax? How does that work chemically?
Most of which I found has to do with the fumed silica aspect and not the actual process.
Thanks.

 

[Klainmeister]

That's because it's a very, very beta process. In fact, it's so low in terms of development and research that I took 200ml of the essential solutions home and am slowly working my way through the process in hopes of delivering more information. Effectively, it's a silver/iron process that when paired with selenium toning (pure, not KRST style with thiosulfate involved) it has the appearance and DMAX of a good PT/PD print, except very cheap by comparison. Beta is the keyword here. Sullivan focused his attention to the Oil Print, AKA Rawlings Print which we're almost %90 dialed. More on that at APIS, but it's very exciting. In a sense, he gets very focused and hands off projects for the rest of us.

Here's the best break-down of our Athenatype postings: Dead Link Removed

Sorry, wish I was a better chemist and could provide more information.

EDIT:

The reason why you find a lot with fumed silica is that the discovery of the two coincided chronologically, so it got mixed in with the other projects at the SkunkWorks. At the moment, we have about 5-6 experiments going on all the time. It's hard to keep things straight with a bunch of creative types.

 

[Jim Noel]

From time to time I have had trouble with kallitypes, and other iron based processes not clearing completely on various papers. I have now switched to a series of clearing baths each of which contains 1 TBS citric acid, 1 TBS EDTA and 1 TBS sodium sulfite. This may be overkill, but so far I have not found a paper or iron based process which does not clear beautifully.

 

[Andrew O'Neill]

Klanmeister, are you toning with selenium metal or salt? Thank you.

 

[Klainmeister]

All you need to know about the process and toner is towards the bottom of the procedure: Dead Link Removed

B&S started mixing a more pure version of selenium toner because of the nasty effects it had on certain processes. I can ask Dana and find out his exact take on things (I just used the stuff, didn't mix it), but I believe it some sort of selenium metal base rather than salt.

 

[jorj]

What a tease! I've tried several times to find a source of guanidine carbonate just to try that athenotype process. I got close once, and then it was mysteriously not available. I assumed everyone had given up on them due to the difficulty of getting that stuff.

Where do you get yours?