Van Dyke/Argyrotype - Archival Properties 101

Mac064 · May 29, 2010

I am sure that this has come up before in various threads but I want to try and pull this together in a 101 format for my small brain.

I have done some Van Dyke and Argyrotype prints in the past as one off experiments, more than anything. I have, however, a specific project that I want to use one (or maybe both) processes in. I have all the material to mix either solutions and think that I have the right paper (I realise that Argyrotype is far more 'paper sensitive' than VDB but I have Fabriano 5 and Hahnehmule paper which I have used before which seems to work).

Here is the thing. I would really appreciate someone explaining about the archival qualities of both processes. All the books say that VDB (and Kallitypes generally) are less archival than the Argyrotype and that Kallitypes generally are not as archival and regular silver gelatin prints. Although the literature stetes this, it doesn't expand on what that in practical terms means. I have the following questions that I would really appreciate some assistance with:

a. I take it at face value that that the iron salt is susceptibile to attack but what does that exactly mean and what affects this attack?

b. How long is a VDB/argyrotype image likely to last generally? How do I ensure that my prints last as long as possible.

c. If I sell my work do I run a risk of the image deteriorating quickly?

d. What effect does toning have? I have read that selenium and gold toning can bleach the image if it is left too long. Can sepia toning work (accepting that all Kallitypes are brown and a further sepia tone may have no effect at all)?

e. I use a lot of mixed media in my photography including waxing/encaustic waxing my prints, what effect, if any, would coating a VDB/argyrotype print in wax have (in particular would this protect the image from attack or make it worse)?

I know this is a lot and any help would be greatly appreciated but I really would like to get to the bottom of this, if I can. The last thing I would wish for is to sell some work only to find in a period of time it deteriorates.

Thanks for taking time to read the thred.

sanking · May 29, 2010

My answers to your questions below. They apply to argyrotype, vandyke and kallitpe

a. I take it at face value that that the iron salt is susceptibile to attack but what does that exactly mean and what affects this attack?

My answer -- All of these processes have images made up of small silver particles. Small silver particles are much more susceptible to attack from the atmospher than large grain silver particle. Also, there is no protection for these particles because they are on the surface of the paper, or just in the fibers of the paper, not in a gelatin binder.

b. How long is a VDB/argyrotype image likely to last generally? How do I ensure that my prints last as long as possible?

If well processed they should last quite a long time, at least a couple of decades if kept in good conditions. If you want them to last as long as possible you must tone them, either with one of the noble metals or sulfite or selenium. An untoned argyroptype is probably more archival than an untoned kallitype or vandyke, but for maximum permanence all three should be toned, and when toned the three processes should have about the same permanence.

c. If I sell my work do I run a risk of the image deteriorating quickly?

Yes, if you do not tone it.

d. What effect does toning have? I have read that selenium and gold toning can bleach the image if it is left too long. Can sepia toning work (accepting that all Kallitypes are brown and a further sepia tone may have no effect at all)?

The best way to tone IMO is with gold, platinum or palladium before fixing. Selenium toning may be done after fixing and washing but I am not positive that it offers as much stability as toning with the noble metals, which in esssence replace a large percentage of the silver metal with either gold, platinum or palladium.

e. I use a lot of mixed media in my photography including waxing/encaustic waxing my prints, what effect, if any, would coating a VDB/argyrotype print in wax have (in particular would this protect the image from attack or make it worse)?

I think waxing with a good product, Renaissance wax for example, is ok and offers some protection. Also, it can be removed later if necessary.

Those are my answers/opinions. Others may differ.

Sandy King

smieglitz · May 30, 2010

Kodak selenium toner is in large part ammonium thiosulfate (aka rapid fixer) and will bleach a VDB (and I suspect the other kallitype flavors) before significant toning and protection is reached unless the stuff is so dilute (1+500 or more) to be questionable in terms of protection, IMO.

I use Clerc's gold toner with VDB which shifts the color to a cooler purple-brown. I've made VDBs for years and have some that go back maybe 16 years without any noticeable change. I did a toner comparison once between gold, sepia, and selenium toner on VDB and also varied the sequence of toning before or after fixing. I've recently changed ISPs, but perhaps the file is still online:

VDB & toners

I think the kallitype variants got a bad rap due to poor processing in the past. Replacing the silver with gold or platinum via toners improves the color and the archival properties IMO. Getting all the iron out is also important so you may want to use an initial 2% citric acid bath for the first rinse. I've also read that part of the reason there is a lack of early kallitypes is because platinum toning replaced the silver making the prints indistinguishable from platinotypes.

Mac064 · May 30, 2010

Thanks guys for the clear and quick responses, I really appreciate it. I do like the ease (at least with VDB) of the processes but want to try and make sure I know what the process will do over time, especially if I sell them.

Smieglitz - In terms of Gold toner, what would be your preferred dilution? I have some Tetenal toner which I will use.

Once again, thanks for your help.

Marco B · May 30, 2010

You may find this part of a document by James M. Reilly of some use, as it gives a clearer view of the kind of (silver-) particles formed in different process, and why one maybe more vulnerable to attack than others.

Marco

Loris Medici · May 30, 2010

There's no stability difference between well processed Vandyke and Argyrotype prints (see Dead Link Removed) and I definitely agree with the toning advice.

Best regards,
Loris.

smieglitz · May 30, 2010

Mac064 said:
Smieglitz - In terms of Gold toner, what would be your preferred dilution? I have some Tetenal toner which I will use...

I am unfamiliar with the Tetenal product so won't suggest a dilution. I use Clerc's thiourea-gold toner as described in Wynn White's excellent VDB article on the unblinkingeye.com website.

sanking · May 30, 2010

smieglitz said:
I am unfamiliar with the Tetenal product so won't suggest a dilution. I use Clerc's thiourea-gold toner as described in Wynn White's excellent VDB article on the unblinkingeye.com website.

I also use the thiourea-gold toner and it is my favorite toner for vandyke. The blue black tone is lovely, much more interesting than the brown tones you get with palladium and platinum toners. Also, I get really great Dmax with the gold toner and some papers. I am attaching a print that is a direct scan in RGB of a gold toned Vandyke. The Dmax (shadow density) of this print is log 1.55, which is about as good as you can get with any of the iron processes. This print is on Lanaquarelle.

Sandy King

Marek Warunkiewicz · May 30, 2010

@sanking

Hey, Sandy!

Great shot, really makes me want to see the original.

Marek

sanking · May 30, 2010

Marek Warunkiewicz said:
Hey, Sandy!

Great shot, really makes me want to see the original.

Marek

Hi Marek,

Thanks for the comment. That is the kind of tree some photographers could fall in love with!!

I am attaching another vandyke image, this one shows the blue tone that you get with gold toning a bit better. This image is on the Weston parchment paper.

Sandy

Marek Warunkiewicz · May 30, 2010

@sanking

Hi again!

Another great shot. The tones seem so lush. I just purchased 5 grams of gold chloride and am hoping to make some gold toner next week.

Thanks for the inspiration.

Marek

Loris Medici · May 31, 2010

Great images/prints Sandy. They've made me (almost!) want to return to iron-silver printing...

Loris Medici · May 31, 2010

Weston paper is great for vandykes and trad. cyanotypes BTW; it has just right amnt. of absorption, therefore gives no bleeding and very good Dmax...

Mac064 · May 31, 2010

Sandy,

Thanks for the great advice. I have been concentrating on selenium toning for much of my previous work but have a litre of Tetenal gold toner which for some reason I have never got round to using. I will use it for the VDB prints I am doing. I also made up some argyrotype solution last night so will give that a crack too. Trying to get to the bottom of what's in Tetenal toner actually contains is not easy. There is nothing on the container to say what the gold content is but it does say that it contains thiourea which is good as I too like the darker blue-black effect rather than the sepia. Unfortunately, unlike other toners it does not come with an instructions sheet.

One of the issues I have is that some of the literature on gold toning VDB prints say it is best to have a weak toning solution (especially when using selenium). I don't know if I should use the Tetanal as it is or dilute it further. I guess I just have to experiment. As an aside, not having used gold toner before how do you know when it's exhausted? Is it just a case of noting when there is no longer a colour shift. Sorry for the less than technical questions, I need to keep things really simple for my small brain!

Again though, thanks for the kind support.

Loris Medici · May 31, 2010

Two strategies there:
1. Use fresh toner single shot - in a flat tray just larger than your print, with very little toner; say... err ... something like 25ml per 8x10" print.
2. Re-use the toner until toning time becomes impractical; >15 minutes, for instance.

I'd go for #1 - best way for consistency. Gold-thiourea toner isn't that much expensive when you compound it yourself.

Regards,
Loris.

Mac064 · May 31, 2010

Thanks Loris,

Good advice. I actually would like to mix my own but I am struggling to find a place in UK where I can purchase gold-chloride. Don't know if anyone else has had that problem.

sanking · May 31, 2010

Mac064 said:
\
One of the issues I have is that some of the literature on gold toning VDB prints say it is best to have a weak toning solution (especially when using selenium). I don't know if I should use the Tetanal as it is or dilute it further. I guess I just have to experiment. As an aside, not having used gold toner before how do you know when it's exhausted? Is it just a case of noting when there is no longer a colour shift.

The recommendation to use a weak toning solution is based on the fact that most people want to use Rapid Selenium and in strong concentration it will bleach the image. Unfortunately in weak concentrations it won't tone enough to protect the print so my advice is to forget selenium.

My guess is that the Tetenal gold toner will work more or less like the Clerc's Thiourea Gold Toner. I would recommend using it one shot at full strength one shot and discard. If you use a flat bottom tray you will only need 20ml-30ml per 8X10 sheet, which makes it fairly economical.

In the future you will find it more economical to buy the gold chloride, thiourea, tartaric acid and sodium chloride (table salt without iodide) and mix your own gold toner.

Vandyke is not as paper sensitive as argyrotype but even so you will get much better results with some papers than with others. As with pt/pd printing some papers give much better Dmax if you soak them in a weak acid solution, say 1% citric acid.

Argyrotype, kallitype and vandyke need very little fixing as the silver salts that are not used to form the image wash away easily. Two or three minutes in a plain 3% sodium thiosulfate solution is plenty.

A print toned with one of the metal salts will have a large percentage of the silver replaced by the toning metal, but not all of it, and if you fix too long you will reduce the remaining silver metal in the print, which will weaken it. Fixing will not reduce the noble metal of course.

Sandy King

nze · May 31, 2010

Double toning may convert all the silver in other metal. A Palladium or platinum toning convert about 90% of the silver in noble metal. If you make a second toning you have a great archival print.

Marco B · May 31, 2010

sanking said:
My guess is that the Tetenal gold toner will work more or less like the Clerc's Thiourea Gold Toner.

nze said:
Double toning may convert all the silver in other metal. A Palladium or platinum toning convert about 90% of the silver in noble metal. If you make a second toning you have a great archival print.

If the Tetenal toner indeed contains thiourea next to gold chloride, it is probably already a very effective and archival double toner. Thiourea will convert the non-gold replaced silver to very stable silversulfide (Ag2S).

sanking · May 31, 2010

Marco B said:
If the Tetenal toner indeed contains thiourea next to gold chloride, it is probably already a very effective and archival double toner. Thiourea will convert the non-gold replaced silver to very stable silversulfide (Ag2S).

Marco,

Would you direct me to a source in the literature that discusses conversion of the non-gold replaced silver to silversulfide with gold thiorea toners? I am very interested in reading more.

Sandy

Marco B · May 31, 2010

sanking said:
Marco,

Would you direct me to a source in the literature that discusses conversion of the non-gold replaced silver to silversulfide with gold thiorea toners? I am very interested in reading more.

Sandy

Sandy, I don't have such literature, but thiourea is also (at least weakly), a direct toner, as I know of my own experience. Normally, it is used as an indirect two bath bleach / redevelop sepia toner with ferrocyanide as the bleaching step.

Now I am not a chemist, and know little about gold toning, but if it weren't for the toning effect, why would thiourea be added to a gold/thiourea toner at all??? What other function would it have?

It just seems logical that it is added for its toning effect. But I might be missing some other chemical function of it in gold toner...

Loris Medici · May 31, 2010

I'm not a chemist and/or know the chemistry behind, BUT, I presume gold chloride + thiourea is forming a relatively stable gold thiocarbamide complex. ??? Mind gold thiocyanate toner; the working solution is not very stable and has to be mixed right before using whereas gold thiourea toner working/stock solution is very stable (relatively!), it has a very good shelf life... It's very practical compared to gold thiocyanate. Maybe that's the reason of using thiourea with gold chloride. ???

As for toning effect of thiourea (if free thiourea exist in the compounded toner, that is), I think that's highly pH dependent; remember that you have to add alkali activator to the toner stock solution. What's the pH of the gold-thiourea toner?

Anyway, this is pure speculation; just some food for thought... The only thing I know is that gold-thiourea toner is great and it was my only choice for iron-silver prints.

Regards,
Loris.

Marco B · May 31, 2010

My suggestion was also pure speculation... unless someone turns up a document showing the chemical processes going on in gold/thiourea toning, I don't know for sure.

Nice document by the way I just hit upon on an UNESCO website:

The Preservation and restoration of photographic materials - PDF document

And a bizar method for the ultimate negative intensification if you screwed up and severly underdeveloped your negative (Warning, radioactivity here!!!)

http://www.freepatentsonline.com/4323641.html

Marco

Marco B · May 31, 2010

And of course there is Mike Ware. He developed the Chrysotype alternative process utilizing gold, if anyone could answer these questions it is him...

http://www.goldbulletin.org/assets/file/goldbulletin/downloads/ware_3_39.pdf

Loris, you might consider contacting Mike. Looking at some of the chemistry in this document by the way, your remark about the stabilizing effect of the thiourea might be right, but I am not sure. Mike mentions some other chemicals (ligands) to stabilize a gold solution.

Mac064 · May 31, 2010

I didn't expect the post to generate such an interesting debate, thanks all it is great stuff. I just wish I had paid attention in my chemistry classes instead of daydreaming about being in the Clash. I may get in touch with Mike Ware to see where one can get gold chloride in the UK. Mind you reading his article it would make me sound a complete philistine if that was all I asked him so maybe I better not!

Van Dyke/Argyrotype - Archival Properties 101

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