Tonning silver prints with palladium.

[Jorge]

AFter my discussion with Sandy, I decided to try and tone a silver print with palladium, hoping the print would show a noticieable difference from an untoned print. Sad to say it is not so, the print got a little bit lighter but there was no color change or any noticieable difference that would warrant doing this over selenium.

Ah well, just thought I will let those of you who were curious know.

 

[Donald Miller]

Thanks Jorge...interesting to know.

 

[Annie]

Jorge,
That is unfortunate... what was the formula for you toner... are you going to try a platinum toning? You certainly piqued my interest when you mentioned the possibility of the replacement of a provisional silver image with Pt... So this afternoon I perused sections of The Platinotype by Abney (I am sure this is old hat to everyone but me) ... there are toning processes mentioned in that book and others that certainly concur with your theory of silver replacement..... Perhaps you will have the inclination in the future to try again with different formulas. Thanks for the update.

 

[Jorge]

Annie you are way ahead of me, I just used a plain solution of palladium tetrachloride at about 0.2%. and toned for 5 minutes.

Perhaps the solution was too weak and/or I should have used an "activator" like selenium does, something like ammonium sulfate, but frankly the palladium is too expensive to waste experimenting on this, at least in my case.

 

[sanking]

Jorge,

You probably need an activator. What I used in toning kallitypes with palladium was the following.

5ml of palladium 20% solution
10g citric acid
1000ml of water

BTW, I made the tests today in toning kallitypes with pure platinum, then bleaching. I reported the results on the largeformat forum. Although I used the toner very warm (at about 160 degrees F) as you had suggested the results were not quite as good as with palladium toning at room temperature.

Obviously there is a lot of room here for experimentation and I certianly don't think the two tests I have done to date come close to telling us the whole story about noble metal replacement.

 

[Michael Mutmansky]

Jorge,

As Sandy says, I think you need an activator. I think it should be possible to get it to work using toning formulas similar to those for POP toning, if you have formulas for that.

I'm not going to be able to try this for a few weeks, as I need to stick to pt/pd to get out a handful of images. If you don't get back to it, I'll try it sometime.

---Michael

 

[Jorge]

Yeah I am pretty sure it needs an activator, but I really dont feel like fooling around with this. I now remember why I started printing in pt, there is just something about silver prints that does not satisfy me any more. Trying to make a hybrid really is not something I feel deserves the effort and expense.

Michael, go for it, I am going to stay with pd and pt/pd and try to keep perfecting my technique. If you do get something unusual let us know.

 

[Ole]

Palladium is not a good candidate for showing a significant tonal change from silver. Rhodium or Iridium seem to me to be better candidates, although I have no idea if these will be archival.
Another way could be to go via FSA toning, to get much smaller silver graing before toning. I think this could significantly change the results.

For pure tonal change iron and copper are well known; add titanium, vanadium and cobalt and you should have enough to play with.

 

[Annie]

Don't give up! There are lots of wonderful old formulas out there that were abandoned or not adequately researched. I would certainly do the experiments however, I do not have the knowledge and experience with chemistry. I wanted to try Stieglitz's platinum toning formula but I thought 'nitric' sounded much too close to 'nitro'.... Well if anyone achieves some success with Pt toning please let us know. Hmmmmmm........ Plazo.........

 

[Michael Mutmansky]

Frankly Jorge, I would rather spend the time messing with more gum bichromate printing right now...

I have a friend who makes some Koshyk-style prints, and I'll try to get him to do it the next time he is messing with silver paper. I don't even have a box of FB silver paper in the darkroom. I have some RC for proofs, but that's about it.

Annie, PlAzo... that's a good one! I do have some of that lying around. maybe I'll try it, except I would probably be doing a PdAzo print. Maybe it should be called PtAzo.

---Michael

 

[Ole]

I'll probably be testing a lot of weird toners on a lot of weird papers anyway - results will be posted in "Tales from the Experimental Darkroom".

Now if I could find a way to make a cobalt toner - and a good source for iridium or rhodium...

 

[Jorge]

I am not giving up Annie, but I think this is going to be something that will require some testing and fiddling which I rather not do at the moment.

I am sure later I will get back to it, as it sounds to be an interesting experiment.

Ole, I think on E bay US there is a guy selling rhodium. If not, contact chrristian Nzè he is using rhodium and Iridium to experiment in making coatings a la pt/pd. I will tery to get you his e mail address.

BTW Annie, if you want to try an experiment and are unsure, post it here! I will be glad to help you and I am sure others will also.

 

[Annie]

Soooo... I have decided it will probably not be me that changes the course of photographic history, however, I do print in silver as well as hand coating Pt and I would like to try the standard modern Platinum toning process (this seem more prudent than running off to France to try and dig up de Caranza's 1856 formula). Before I order up a big bottle of Potassium Chloroplatinite I have a few questions....

The standard modern formula that seems to be popular (I believe this is from Peter Marshall):

350ml H20
1g Sodium Chloride
3g Citric Acid
0.5ml Platinum Stock

Platinum Stock
1g Potassium Chloroplatinite
5ml H20

My questions:

1. Many of my images are of the ocean and I am intrigued by the idea of using sea water as the medium for the citric acid & platinum stock any obvious problems with this?

2. What is the difference between the platinum stock of the toning formula and the sodium chloroplatinate solution that we use for coating, is a substitution possible, if so would in be in the same porportions? (the solution as listed on the B&S site is 'Potassium ChloroplatinITE'but the label for my bottle reads 'Potassium ChloroplatinATE'... Did I end up with something different or is this a typo?)

3. Just how difficult and dangerous would it be to mix the Platinum Stock solution... Is this done with ingredients at room temperature?

My primary concerns are.... Explosions, invisible deadly gases, solutions that eat the flesh to the bone in a matter of seconds. Any insights or superior formulas are greatly appreciated!

 

[Ole]

I'll adress the questions I know something about:

1. Many of my images are of the ocean and I am intrigued by the idea of using sea water as the medium for the citric acid & platinum stock any obvious problems with this?

Not a good idea, I think. Sea water doesn't only contain sodium chloride, it also contains sulfate, carbonate, and lots of other stuff in small amounts. It is quite possible (probable) that some of these will form insoluble compounds with the platinum. You're welcome to try, but I wouldn't risk platinum in seawater myself.

3. Just how difficult and dangerous would it be to mix the Platinum Stock solution... Is this done with ingredients at room temperature?

My primary concerns are.... Explosions, invisible deadly gases, solutions that eat the flesh to the bone in a matter of seconds. Any insights or superior formulas are greatly appreciated!

''

It won't explode. It won't give off dangerous gases. It won't eat flesh. But it seems very, very concentrated to me - are you sure it's 5 ml water? It will probably dissolve at room temperature if it dissolves at all.

 

[Annie]

I just checked the numbers and that is what it reads... mind you this is from the web and not the printed page. To complete toning it says to wash and treat in bath of sodium chloride and sodium carbonate (salt & soda). Perhaps that is the step when I can use the sea water. Thanks.

 

[Jorge]

I agree with Ole Annie, dont risk using salt water. Besides, when experiemnting change one variable at the time...not many. If the tonning does not work you wold not know if it was because of the salt water or not.

Mixing pt ot Pd is very simple, it is not dangerous other than the posibility of breathing the stuff. If you do it in a well ventilated place you should not have problems, after all you have to do is mix water, pt ot pd and salt...

The one thing that has helped me get the pt ot pd in solution is heating the water to about 100 ºF.

 

[Annie]

Thanks Jorge... you guys are right it would be a shame if the whole thing was ruined because of a little 'fish pee'.... I will try it at some point though just to satisfy my curiosity... (the sea water that is, not the fish pee)

 

[sanking]

3. Just how difficult and dangerous would it be to mix the Platinum Stock solution... Is this done with ingredients at room temperature?

Mixing the platinum stock is pretty easy and is not hazaradous, but for very small amounts you will save virtually nothing by mixing it over buying the solution already mixed. What you want for the platinum stock is sold by B%S as Platinum Solution #3 (or for palladium toning there is Palladium Solution #3). Both are 20% solutions, i.e. 1g of metal salt in 5ml of water.

A standard toner for toning kallitypes and vandykes consists of 10g oif citric acid and 5ml of either the Platinum Solution #3 or Palladium Solutin #3 in 1000ml of water. This may also work for regular silver gelatin papers, or you can use the Marshall formula which is in fact very similar. It is best to use the solution one-shot, using the minimum amount needed to tone a print. For a kallitype this amounts to about 200ml for a 12X20 print. You really need a flat bottom tray to tone with this small amount of solution.

 

[Annie]

Thanks... that means I have everything I need already.... I am shooting at the beach today so I will do a comparison of the 'sea toning' with the standard Pt toning this evening just for fun.

 

[Annie]

Just in case anyone is curious I made some 'tests' with the pt & pd toning and the results are such that at some point I will continue trying this process. I am no chemist and it is entirely possible that I am no photographer either, however....

My greatest success was with a combination of 8 drops pd and 2 drops pt in 175ml seawater with 15ml acetic solution. I used this amount of toner on a 8x10 for 10 minutes. I seawater developed as usual then soaked for 60 seconds in pure seawater and then to the toning bath and then fixed as usual in seawater rapid fix. At first I thought the image had actually popped at least a ½ grade in contrast from the untoned image but I think this is because of the deeper blacks. On looking at the image further something is happening in the midtones, the only way I can describe it is that there seem to be more of them, I know this does not make sense, I will do some step tablets for a less subjective answer.The colour of the image also shifted next to a selenium toned print it has a subtle hint of olive green but still cool and neutral... (But not that sick green of Ilford Warmtone).

So there you have it now there is only one thing left to decide... (nomenclature has been such an issue lately) what do I call my prints? Hmmmmmmm.... Pacific Silver Palladiums.......

Cheers Annie.

 

[sanking]

J
The colour of the image also shifted next to a selenium toned print it has a subtle hint of olive green but still cool and neutral... (But not that sick green of Ilford Warmtone).

This makes me believe that your toning experiment was a definite success. One of the color changes I have observed in toning kallitypes with a combination of pt/pd has been a slight shift toward green, to a final color I would call olive brown.

 

[Jorge]

Good job Annie!

 

[Annie]

Some further ponderings about Pt/Pd toning......

Subsequently, I have found an older formula that is actually listed as 'Silver Substitution' using precious metal salts. In the listed formula they are using Cobalt Chloride and the text states that the other metal salts are not employed do to reasons of cost. In this formula there is a simultaneous mixing of 2 separate solutions at the time of toning right after development. The first solution is basically Cobalt Chloride & Sodium Citrate the second solution contains Potassium Ferricyanide. Does anyone foresee any obvious problems with substituting Potassium Chloroplatinite for the Cobalt Chloride? My usual concerns..... Explosions, invisible deadly gases, solutions that eat the flesh to the bone in a matter of seconds.

Oh ....and just curious why we were trying to do this substitution thing in the first place?

Thanks.

 

[sanking]

Some further ponderings about Pt/Pd toning......


Oh ....and just curious why we were trying to do this substitution thing in the first place?


Annie,

My interest in the substitution was to obtain greater permanence of kallitype prints. By replacing silver metal, whcih oxidizes readily, with gold, platinum or palladium you should in theory have a print that will be almost as permanent as straight pt/pd prints. Some of my bleaching tests seem to confirm that this is indeed the case.

I think most people would agree that all silver prints, be they salted paper, albumen, kallitypes or contemporary silver gelatin, should be toned for greatest permanence.

 

[Annie]

How would the testing be done to determine if in fact the silver had been replaced with platinum in toning process? If this is in fact occurring do you think would it be more perminant than something like selenium?