Anyone tried a "tartaric acid print"?

NedL · Jun 29, 2018

Has anyone ever tried this?

From Wilson's Cylclopedic Photography, 1894

That would be about a 17.5% solution of tartaric acid and about an 11% solution of silver nitrate with some acetic acid added to it ( typically in the 2 to 6% range ). I guess it might form silver tartrate. It's making me think about experimenting with tartaric acid instead of citric acid in salt printing.

Peter Schrager · Jun 29, 2018

Pursue it please and report back...
I don't have time to try every process
Always intrested though
Just learned how to make ziatypes properly and I feel it's way less complicated than regular plat/palladium...and you can get different color variations too which you can with standard practice but more effort...
Salt prints are tough

NedL · Jun 29, 2018

Hi Peter, I will try it!

It's easy to get a picture with salt printing ( and that, all by itself, is pretty wonderful ) but you're right they are finicky, especially if you want no stains and perfect whites. A few months ago I discovered that gelatin was the source of some minor problems I've been having. I've been fussing around with different starches for more than a year -- with various problems -- and that finally really got me trying harder with starch. Just in the past week I think I've finally figured it out. So now I'm going to print the rest of the calotypes I made with the camera you sold me ( I really love that camera! ) I'd been waiting to print them until I got these last troubles solved...

pdeeh · Jun 30, 2018

i shall try this today (while abandoning everything else I am doing :

pdeeh · Jun 30, 2018

waaaaait a minute ... this aceto-nitrate stuff ... i'm not going to end up making some sort of highly unstable explosive mixture like the last time you gave me a recipe am i?

pdeeh · Jun 30, 2018

NedL said:
an 11% solution of silver nitrate with some acetic acid added to it ( typically in the 2 to 6% range )

So is that 11% AgNO3 plus a bit of 2-6% Acetic acid or 11% AgNO3 of which 2-6% is Acetic acid?

pdeeh · Jun 30, 2018

From https://www.scientificamerican.com/article/photographic-landscapes-on-paper/

J.Stewart said:
Solution of aceto-nitrate of silver in the following proportions ; 15 parts of nitrate of silver ; 20 of glacial acetic acid ; 150 of distilled water.

(Mr. Stewart is " brother-in-law of Herschel, the astronomer")

pdeeh · Jun 30, 2018

OK ... 17 minutes in on an exposure in direct sun, at the brightest part of the day and all the forecasts saying Very High UV ... Just starting to see a low-contrast image forming.

I'm struggling to understand how this works chemically tbh.

Maybe it's silver tartrate, but then again we know you can get an image off just about anything by coating with Silver nitrate.

Of course,we also have to reckon with my remedial-grade arithmetic when I was working out my dilutions and whatnot, so there's potentially huge holes for errors at my address.

Peter Schrager · Jun 30, 2018

NedL said:
Hi Peter, I will try it!

It's easy to get a picture with salt printing ( and that, all by itself, is pretty wonderful ) but you're right they are finicky, especially if you want no stains and perfect whites. A few months ago I discovered that gelatin was the source of some minor problems I've been having. I've been fussing around with different starches for more than a year -- with various problems -- and that finally really got me trying harder with starch. Just in the past week I think I've finally figured it out. So now I'm going to print the rest of the calotypes I made with the camera you sold me ( I really love that camera! ) I'd been waiting to print them until I got these last troubles solved...

You go need! I love your spirit!!

NedL · Jun 30, 2018

pdeeh said:
OK ... 17 minutes in on an exposure in direct sun, at the brightest part of the day and all the forecasts saying Very High UV ... Just starting to see a low-contrast image forming.

I'm struggling to understand how this works chemically tbh.

Maybe it's silver tartrate, but then again we know you can get an image off just about anything by coating with Silver nitrate.

Wow... all this happened while I was over here lazily sleeping away!

I'm really not sure at all... I suspect silver tartrate is light sensitive, but I didn't look it up. If the tartaric acid had been a weaker solution, I would have dismissed it as a version of Niranjan's "saltless salt prints", just as you say -- and maybe it still is. But the strong solution of tartaric acid made me think it might be that strong for some reason that contributes to the printing.

That was a total guess about the amount of acetic acid... the amount in that letter from Stewart is about normal for using in developing calotypes, but I was thinking less acetic acid because it acts like a restrainer. I meant 2 to 6% acetic acid in total, ie. in each 100 ml water, 2 ml acetic acid and 11g AgNO3.

Are you using a paper negative or a clear negative? 17m for a faint image w/ a paper neg is slow but still reasonable.... for a clear negative it does not sound encouraging!

NedL · Jun 30, 2018

pdeeh said:
waaaaait a minute ... this aceto-nitrate stuff ... i'm not going to end up making some sort of highly unstable explosive mixture like the last time you gave me a recipe am i?

pdeeh · Jun 30, 2018

Well.
It was quite a nice film negative from which I've made some attractive cyanos, quite contrasty.
Tbh I was doing this quickly before I went out (I'm writing this half way up a chalk down in the heart of the countryside) & wasn't paying too much attention to what I was up to.
The exposure ended up being nearly 40 mins which was clearly too much as it just looks a bit foggy .
it's as bad in a confined space as ammonio-nitrate by the way. Headache inducing!
I'll look again at my arithmetic for the acetic. I may have buggered it up ...

NedL · Jun 30, 2018

oh gosh yes, I agree. You need to be careful.

If I try this, I'll probably combine a few drops of 24% silver nitrate with a few drops of household distilled vinegar ( ~5% ) and paint it onto the paper... if it looks promising but fogs I'll break out the glacial acetic acid and make a little stronger solution for mixing with.

The sensitizer I use for calotypes is only 6% acetic acid... hardly stronger than salad vinegar, but after making a few of them I noticed that I felt something in my throat the next day and yes the beginning of a headache when using it. Now I use an "acid gas respirator" which lists acetic acid as one of the things it is meant for, and I can't even smell it.

NedL · Jun 30, 2018

A little while ago, I took 1g of tartaric acid, and added 5.5 ml of room temperature DH2O. After stirring for a few minutes, it did not all dissolve.
I just looked up solubility of tartaric acid and it shouldn't have been a problem... I probably should have let it sit... oh well. Anyway, I painted it generously onto some paper and it's drying. When it's done I'll paint some silver nitrate onto it, let it dry, and then just carry it outside into the sun and see what happens.

Edit: 3 hours later. I mixed 3 drops of 24% silver nitrate with 3 drops of white distilled vinegar. When I painted it on the tartaric acid paper, it reduced quickly and make a brown streak. A little later, drying in the dark, it was dark brown and when I took it into the sun it didn't change... all the silver that was going to come out already had I'll try later w/ stronger acetic acid.

pdeeh · Jul 1, 2018

NedL said:
all this happened while I was over here lazily sleeping away!

well gotta allow for the TZ Ned ... but on the other hand I did get up at about 0510BST that day (not something I make a habit of but the weather's a bit warm right now for sleepings)

Ah so that's interesting about the almost instant reduction!

I'll have another play tomorrow morning (today - gasp! - is quite cloudy, after 10 days of uninterrupted really hot (well 25-30 is really hot in the UK) dry cloudless weather).

nmp · Jul 1, 2018

pdeeh said:
waaaaait a minute ... this aceto-nitrate stuff ... i'm not going to end up making some sort of highly unstable explosive mixture like the last time you gave me a recipe am i?

Are you sure about aceto-nitrate being hazardous? May be you mean amonio-nitrate of silver...

pdeeh · Jul 1, 2018

nmp said:
Are you sure about aceto-nitrate being hazardous? May be you mean amonio-nitrate of silver...

I think the point has sailed over your head with quite a lot of clearance there, Niranjan

pdeeh · Jul 2, 2018

ok, so, bear with me here.
I was looking in the cupboard under the sink and I found a bottle with some stuff in it, so I sniffed it.
Hmm well that smells of thymol, so it's probably something with ferric ammonium citrate in it.
ooh there's something floating on the top, definitely ferric ammonium citratey then.
what happens if I shake it?
ahhh, full of precipitatey stuff.
conclusion - old Namias' solution. Very old in fact, probably, um, 18 months or more ...
OK let's filter out the crap and see what's left in the filter paper (I say 'filter paper' like I've got an analytical laboratory here, but what I've actually got is a pack of Melitta coffee filter papers)
Well, what's left is a pale greeny solution and a quarter of a teaspoon (maybe less) of brown/grey powder and flakes of what looks like silver metal. Maybe the brown/grey stuff is silver citrate or somesuch. Or maybe just silver metal too? Or some iron thing beginning with f?
anyhoo, whatever, there's definitely less silver nitrate left in that solution than was in it originally. I wonder how well it works?
(forgets about it for a couple of days)
today: lovely sunny day, sweltering hot again, thin thin cloud, I guess I could make a print. Maybe I'll try another aceto-nitrate print.
Ah, no I won't, I seem to have somehow thrown away my carefully measured 19% solution of Acetic acid. How did that happen? The bathroom stinks tho. Hmm. Maybe I brushed my teeth with it.
I know, I'll try that old Namiasy stuff on the scrap of Tartaric-ed paper I have left over.
4 minutes (or was it 7 minutes? Must try to keep notes! (hahahahah like that'll happen [insert emoji for rolling eyes])) in full sunshine, 1500BST. Not much of an image there, but lets wash it and see ... ooh wow kablooey yes that's worked.

Moral: Making prints without any idea of how to repeat the results because reasons, is fun.

('phone camera renders it a bit too rich and reddish/aubergine according to my eye, so imagine it a bit less rich and reddish/aubergine; and a tad less contrasty)

Mainecoonmaniac · Jul 2, 2018

I the tartaric acid the haliding agent for the sliver? If it is, is it better than salt?

pdeeh · Jul 2, 2018

first indications suggest that it's not better than table salt, which is an actual halide (or rather contains one) and thus possesses excellent sensitivity.
Tartaric acid is just ... Tartaric acid.
It's not a halide, doesn't contain one of any kind. It's not at all clear what's going on, except Ned's suggestion that it forms Silver tartrate in combination with Silver nitrate.

Silver nitrate will form a light sensitive compound with all sorts of things (your skin being one ) but the critical thing is that needs to be fast enough to make exposures manageable, can achieve a decent DMAX and is fixable.

It'll take a PE or a Gerald Koch (or someone like Rudeofus) to give a proper steer about the photochemistry that's actually going on.

Mainecoonmaniac · Jul 2, 2018

pdeeh said:
first indications suggest that it's not better than table salt, which is an actual halide (or rather contains one) and thus possesses excellent sensitivity.
Tartaric acid is just ... Tartaric acid.
It's not a halide, doesn't contain one of any kind. It's not at all clear what's going on, except Ned's suggestion that it forms Silver tartrate in combination with Silver nitrate.

Silver nitrate will form a light sensitive compound with all sorts of things (your skin being one ) but the critical thing is that needs to be fast enough to make exposures manageable, can achieve a decent DMAX and is fixable.

It'll take a PE or a Gerald Koch (or someone like Rudeofus) to give a proper steer about the photochemistry that's actually going on.

It's probably salt in our sweat that the halation agent. To be specific, the chorine in the salt

nmp · Jul 2, 2018

Mainecoonmaniac said:
I the tartaric acid the haliding agent for the sliver? If it is, is it better than salt?

Most likely the tartaric acid forms calcium tartrate first in the paper assuming you are using buffered paper. Silver nitrate will react with calcium tartrate to form silver tartrate which should reduce photo-chemically like other salts. I have experimented with citric acid and oxalic acid in the same way, i.e. floating/brushing the acid solution first on the paper, dry and then coat silver nitrate solution. No salt (NaCl) added. The resulting paper showed an improvement in staining tendency (dark reduction) in both cases and slightly better contrast than straight silver nitrate. I suspect tartaric acid should behave the same way. For pdeeh's Namias print, the tartaric acid simply acted to acidify the paper which is fortuitous for the all iron-based processes.

:Niranjan

pdeeh · Jul 2, 2018

nmp said:
For pdeeh's Namias print, the tartaric acid simply acted to acidify the paper which is fortuitous for the all iron-based processes.

Forgive me for saying so, nmp, but you speak with such certainty without having considered what else may be going on.

You have not considered, for instance, that in my case it may have produced something akin to a Van Dyke brown - the formula for which includes Tartaric acid, Silver nitrate and Ferric Ammonium citrate.

In the case of a VDB, the Tartaric acid is clearly not simply functioning as an acidifier.

And with a relatively high concentration of Tartaric acid in the paper as in my case, the chances are that something more is going on.

nmp · Jul 2, 2018

pdeeh said:
Forgive me for saying so, nmp, but you speak with such certainty without having considered what else may be going on.

You have not considered, for instance, that in my case it may have produced something akin to a Van Dyke brown - the formula for which includes Tartaric acid, Silver nitrate and Ferric Ammonium citrate.

In the case of a VDB, the Tartaric acid is clearly not simply functioning as an acidifier.

And with a relatively high concentration of Tartaric acid in the paper as in my case, the chances are that something more is going on.

My explanation did not preclude what you are saying. Whether you add the acid in the sensitizer or the paper, the effect can be the same. If you have buffered paper, it will have a greater propensity to stain in presence of silver nitrate on the one hand and hydrolyze ferrous/ferric salts to form ferrous hydroxide which is another source of brown stains, on the other hand. All I was saying that the presence of tartaric acid, far from being detrimental, was good - whether by becoming VDB-like or not. I have not delved in to the history of why the tartaric or citric acids were used in VDB or Namias respectively, but I can see it would help in the same way pre-acidification helps in cyanotypes or Pt-Pd.

(Just because I say something, it does not mean I haven't overlooked something else. Just the opposite. I thought I had ample use of "should," "most likely," 'suspect" etc to project that.)

Disclaimer: I am not sure of any of the above.

NedL · Jul 2, 2018

you got a nice print out of whatever happened!

I have a vague memory of reading somewhere that one function of the tartaric acid in VDB ( and presumably the citric acid in Namias' ) is to keep the silver from reducing right away when mixed with AFC. In fact, I think I might remember one version of VDB adding the tartaric acid last, little by little until the precipitated silver compound is redissolved.

I still have some "tartaric acid paper" but haven't tried anything else with it yet. But it seems to me there must be more to this than just pH .... I haven't tried Niranjan's ( no salt ) test with oxalic acid but I have tried it with citric acid and vinegar and both behaved as he described ( up to a point.. if you use very strong CA it will eventually inhibit reduction and reduce contrast that way ). But in my test the strong tartaric acid paper reduced the silver nitrate immediately.

Anyone tried a "tartaric acid print"?

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