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Don Wallace
23-Oct-2003, 08:20
I want to explore a number of different Victorian printing processes over the next few years, with an eye toward platinum/palladium as my goal. Pt/Pd looks pretty expensive so I thought that other methods, such as salt and Van Dyke printing would be good practise in learning how to coat paper, etc. My question is, would the contrast range of the negatives be the same for these different processes? I have an interesting book on printing (Secrets of Salts) but none of how to process negatives for these types of prints. Any suggestions as to a good starter book? I will shooting 5x7 and 8x10.

William Marderness
23-Oct-2003, 11:36
Coating paper for pt/pd is not difficult. I got great results with my first print. Don't start with salted paper. It is difficult to coat. I tried coating salted paper with no success. The negatives needed for the processes you mention are similar to pt/pd negatives.

sanking
23-Oct-2003, 13:23
The process most similar to pt/pd is kallitype, but traditional kallitype that uses ferric oxalate, not Vandyke. The coating method and final tonal range of pt/pd and kallitype based on ferric oxalate is almost identical, and they both require negatives of very similar density range.

Salted paper is quite different. The coating method is more complicated and you need a negative with a longer DR. Also, salted paper is a printing our process, in comparison to pt/pd and kallitype which are developing out processes.

Michael Mutmansky
23-Oct-2003, 14:46
Don,

Sandy has it right, I think kallitype is the closest in a number of ways. I would add that if you are going to do pt/pd, don't mess around with another process, because as you get better you will really be getting better at the other process, not pt/pt.

What I mean is that there are a handful of steps in kallitype that are basically identical to pt/pd, but the fine details could end up being completely different. A paper that may be suitable for one, may not work for the other. Pretreatment with oxalic acid will help with one, but may not the other. Double coating helps with some papers, but may not in the other process. As you learn to overcome these finer details, the experience can be applied to pt/pd, but the factual results cannot. That will have to be learned a second time through when you actually do pt/pd.

The skills you need to start are quite easy really, and an afternoon with an experienced pt/pd printer will get you very far down the path to competant printing. Then, you can spend the rest of your life mastering what I consider to be an easy process to learn, but a very difficult process to master.

Besides, pd prices are near a 7 year low right now, so there is no better time than the present to get started with the process. Ultimately, the only real cost difference between these processes is the metal salts, and while they are intimidating at first, a little goes a long way. You might actually find that the paper you print on is actually the most expensive part of the process.

I encourage you to jump right in to pt/pd, as it is very rewarding, and the results obtained even from the first session (with an experienced guide) will be quite satisfying.

---Michael

Jorge Gasteazoro
23-Oct-2003, 17:25
Since MIchael already said it, I will add my vote to his opinion. I tried Kallitypes and I was not happy. THat is not to say that is not a good medium, it only showed my ignorance of the process, but I have found pt/pd much easier and decided to just dedicate myself to pt/pd instead of wandering all over with other methods.

If expense is your worry, just get the Richeson 9010 brush, it is expensive but the savings you get in coating will pay for itself in a few printing sessions.

The rest of the materials are about the same price, papers, Ferric Oxalate, etc....so if you can make significant savings by using the Richeson brush I think both processes would be about the same price.

Good luck and lets know how you get along.

Michael J. Kravit
23-Oct-2003, 19:56
Michael and Jorge,

Ya know, we have been raving about the Richeson brush for the past few years, but I recently tried a Simmons Skywash brush and found it to work better for me. The Simmons has more bristles and seems to coat smoother.

The price is similar and I find that I do not have to use anymore emulsion. The Simmons just feels right in my hand. Karma I suppose. ;-)

Anyway, As Michael and Jorge suggested, buy some chemicals, paper and jump right in. Palladium is not all that expensive these days. Start with 4x5 negatives until you become a master, then jump to bigger prints.

Michael

Michael Mutmansky
23-Oct-2003, 20:27
Michael,

I haven't tried the Simmons, but I have heard good things. The next time I get a brush or so, I'll add one to the order.

Don,

By all means if you want to do brush coating, spend the extra cash on a Richeson, and don't waste your money on the inexpensive Hake brushes. Here's why:

The Hake burshes work decently, but they must be bone dry befor you use them. So, you have to have multiples around for multiple prints. The Richeson brush, while much more expensive, is used wetted with distilled water, so you can continue to use the same single brush over and over, with just a rinse and dip in distilled water in between.

The Richeson also does a substantially better job of coating in my hands, so I find it to be a much better brush all the way around. As Jorge states, you use less chemical with the Richeson, so it actually ends up being less expensive in the long (and even shor, when you consider the number of Hake brushes you save) run.

I used to do rod coating, because I was unhappy with the quality of the coat with brush methods. That has been replaced entirely with the Richeson brush, as it is even better than rod coating for me.

---Michael

Don Bryant
24-Oct-2003, 13:15
So where are folks purchasing their palladium and platinum these days to get these low prices?

Thanks,

Michael Mutmansky
24-Oct-2003, 14:53
DOn,

Low is a relative thing. Compare pd to pt, and it'll seem low. Compare it to silver nitrate, and it'll seem high. Palladium chloride prices is basically driven by the metals markets, and the current prices for palladium are historically quite low. About a year and a half ago, the palladium prices were actually higher than platinum, and it resulted in much higher costs for us printers.

Look here for some pricing history:

http://www.kitco.com/charts/livepalladium.html

Anyway, you can get palladium chloride from Bostick Sullivan (highly recommended), Artcraft (also recommended), Photo Formulary, and a few other places, including Freestyle and I think even B&H now.

B+S has palladium chloride solution, 250ml for $300 or so, 100ml for $150, and 25ml for $62.50. It typically takes about 3/4 to 1 ml of solution for an 8x10, so your costs per print can be as low as about $1.25 per print for the palladium. I don't know if B+S has the best prices, but I do think they are the most knowledgeable, and they are very willing to help out a beginner with information and guidance.

---Michael

sanking
24-Oct-2003, 15:18
Michael wrote:

"I would add that if you are going to do pt/pd, don't mess around with another process, because as you get better you will really be getting better at the other process, not pt/pt. "

I would agree that one would learn very little about pt/pd printing by becoming an expert in salt printing. However, I fundamentally disagree if the issue is kallitype and palladium, and I think my own experience clearly support the difference in opinion. I learned kallitype printing about three years ago primarily as a proofing system for carbon printing and it has proven very useful in this way. At the same time, however, I have come to see it as an end in itself and have made some really nice kallitype prints, easily equal in quality to the best work I have seen in pt/pd.

Until about five months ago I had never really done any serious work with pt/pd. However, in May or June I had an opportunity to go in on a group order and buy a fairly large amount of palladium chloride. So I decided that I would make some palladium prints. For my first print I used the same negative (7X17") and paper that were used to make a palladium-toned kallitype. It took me two test prints to calibrate the speed and contrast of the two processes, but the third palladium one was a perfect match of the kallitype. And I emphasize *a perfect match," in terms of richness, contrast, image color, and tonal values.

So I would strongly suggest that even if your ultimate goal is to make palladium prints you could learn a tremendous amount with kallitype that can be directly applied to palladium. It is true that the devil is in the details, but the actual fact is that between a palladium toned kallitype and a *true* palladium there are very few details that are different, even little ones.

So from my perspective it makes a lot of sense form an economic point of view to start with kallitype, even if your eventual goal is to make palladium prints. You will certainly save a little money in the process, and in the end you may find that since the actual final product is the same in terms of appearance and permanence you might never both with palladium.

Don Bryant
24-Oct-2003, 15:21
Michael,

> B+S has palladium chloride solution, 250ml for $300 or so, 100ml for $150, and 25ml for $62.50. It typically takes about 3/4 to 1 ml of solution for an 8x10, so your costs per print can be as low as about $1.25 per print for the palladium. I don't know if B+S has the best prices, but I do think they are the most knowledgeable, and they are very willing to help out a beginner with information and guidance. >

B&S prices have been pretty much the same for the past few years, the prices don't reflect the market trend for the past 12 months. But that is understandable since they are selling palladium in solution and is targeted to small quantity users. Besides B&S has always had the best service and I've never been dissatisfied with my purchases.

But at the same time I want to make more and larger prints so I was thinking about purchasing the metal and making my own solutions to save some $$$.

Thanks,

Michael Mutmansky
24-Oct-2003, 17:01
Don,

There are other places out there that sell palladium chloride. Artcraft in particular sells the powder, and their prices may be based on market prices.

If you want a very large amount of palladium chloride, you can find a precious metals supplier, I suppose, but that involves a very large investment, since those guys are not normally used to selling in small quantities.

I bet a bit of time on Google will yield a reasonable number of sources to persue.

---Michael

sanking
25-Oct-2003, 10:29
Just a few more thoughts that might be of interest to anyone currently working either kallitype or palladium who might be interested in trying the other process.

1. In my experience all papers that work well for palladium also work well for kallitype. The opposite is not true because kallitype is much less paper sensitive than palladium.

2. For coating a given area you need slightly less of the palladium sensitizer than kallitype sensitizer. An 8X10 print, for example, might need 2.5ml of solution of kallitype sensitizer but only 2.0ml of palladium sensitizer.

3. Exposure times for kallitype are about 1/2 stop faster than palladium.

4. Kallitypes clear much faster than palladiums.

Because of the fact that exposure times are shorter, and because kallitypes clear faster than palladiums, in my experience total processing time is less with kallitype than with palladium.

I am aware of the fact that the price of palladium chloride is fairly low at this time but if you make large prints there is still going to be a significant difference between making a palladium toned kallitype and a straight palladium print. Now quite frankly cost would not be a consideration for me if the straight palladium offered me anything that the palladium toned kallitype did not, either in ease of operation, richness, tonal range or permanence. But for me there is just no difference. In fact, I see the two processes as simply different ways of arriving at the same finished product, a palladium print, because that for all practical purposes is what you have with a well-processed palladium tone kallitype.

On anothe forum a couple of pt/pd printers have expressed the opinion that kallitype is a lot more trouble than palladium. Quite frankly I just don't get the point because in my own work flow I just don't find any significant difference in ease of operation between the two processes. But people are gong to believe what they want to believe so that is that.

But in case you might want to know a bit more about making permanent palladiumd prints with the silver iron process see my my article on kallitype at http://unblinkingeye.com/Articles/Kallitype/kallitype.html

And by the way if you do wind up making palladium or platinum toned kallitypes and don't know what to call them just label them platinum or palladium prints, because that is what they are.

Jorge Gasteazoro
25-Oct-2003, 11:23
And by the way if you do wind up making palladium or platinum toned kallitypes and don't know what to call them just label them platinum or palladium prints, because that is what they are.



Well, I never thought I would disagree with anything Sandy said, but there is always a first time for everything. :-)



I think if it is a palladium print it should be called palladium print, not pt/pd. The same goes for a pd toned kallitype, it should be called a palladium toned Kallitype. If we object to the usage of terms like "digital platinum glicŤe" on the basis that there is actually no platinum in these ink jet prints, then I think we should strive to be as accurate as possible in the naming of our own processes or prints.



I think from a collectors point of view a person would be dissapointed and perhaps even mad if they found out that what they thought was a palladium or pt/pd print is nothing more than a toned kallitype....

sanking
25-Oct-2003, 11:57
Jorge,

Two different persons who know a lot about alternative processes and the chemisty of processes made this suggestion to me. And the reason is that there is in essence no difference between a palladium toned kallitype and a straight palladium. Both consist of a image made up of palladium metal on a paper surface. The only differnce is in the process by which this palladium metal winds up on the paper surface. And my understanding is that there is no test, destructive or other, capable of indicating any physical difference between the two. If there were some kind of test that could show a difference I would certainly have another opinion on the subject.

Frankly I am much more interested in exhibiting and selling carbon prints than kallitypes or palladium, but unless someone could prove to me that there is any real difference in the final print between a palladium toned kallitype and a straight palladium print I personally see no ethical problem in the label.

BTW, you probalbly know that Dick Sullivan of B&S has expressed the opinion that in all probability many vintage prints that are being sold and exhibited as platinum prints are in reality platinum toned kallitypes.

Jorge Gasteazoro
25-Oct-2003, 16:56
Hmmm, perhaps you misunderstood their explanation Sandy, I am a chemist and I can tell you with 100% certainty that a palladium tone Kallitype is not a palladium print. IOW the palladium tonning has not replaced silver as the image forming material, it has simply bound to the silver layer to produce a silver/palladium complex, much like selenium does not replace silver when you tone a silver print. As a matter of fact one of my "just for grins" experiments was toning a kallitype with selenium. Not surprisingly you get a similar effect when you tone a kallitype with selenium as you do when you tone a silver print.



On the matter of testing, if I recall correctly there was a talk in the last APIS where a lady talked about a recent non destructive testing procedure which can differentiate between a kallitype and other metals based prints. I dont konw about this test so I am unable to provide you with more info. My guess is that it is some kind of spectrometric/exitation state method, perhaps you can ask about it in the B&S web site. But I do know about destructive test that can easily and readily differentiate between a kallitype, a pd toned kallitype and a straight pd print. To name a few there is chromatography, x ray diffraction and mass spectrometry. So I would not rely on the "there is no test to tell them apart." Perhaps to the naked eye they look identically, but I assure you, chemically there are plenty of ways to tell.



Since toning with palladium can form an outer layer in the silver of the kallitype print, if one uses a loose definition of a palladium print this could be true, but then, we dont call silver prints toned in selenium, selenium prints do we?



I dont know Sandy, but I doubt any chemist worth his/her salt will tell you that a Kallitype has becomed a palladium or platinum print just because you toned it in the respective toner. And if they did, I can tell you with a 100% certainty that they are wrong and will be glad to prove it to them.

sanking
25-Oct-2003, 22:10
Jorge wrote, "Since toning with palladium can form an outer layer in the silver of the kallitype print, if one uses a loose definition of a palladium print this could be true, but then, we dont call silver prints toned in selenium, selenium prints do we?"

Jorge,

I am not a chemist so I have to rely on what published information I can find on the subject of toning, and on the information provided by chemists with whom I have discussed the subject. My review of the literature suggests that the subject is rather complex. Putting aside for the moment your question about selenium toning, my understanding is that the process of toning a silver metal image with either gold, platinum or palladium does not involve merely the formation of an outer plating of the silver metal, but a *replacement* of the silver metal with metallic gold, palladium or platinum, plus silver ions. I can not find any details of this chemical reacion with palladium or platinum but Grant Haist provides the following information relative to gold.

3 Ag + Au3+ gives Au + 3Ag+

metallic silver + auric gold gives metallic gold + silver ions

or

Ag + Au+ gives Au + Ag+

metallic silver + aurous gold gives metallic gold + silver ion

Depending on various conditions the degree of replacment could be partial or total.

Thanks for your comments, and for any additonal technical insights you may be able to provide on this subject.

Jorge Gasteazoro
26-Oct-2003, 11:23
Hey Sandy, I understand, I am certainly not accusing you to purposely try to mislead people. In my book you are one of the good guys and I certainly dont want to cause you any embarrasement, nor am I accusing you of being dishonest. My personal dealings with you have shown me that your honesty is unquestionable, coupled with your willigness to share your knowledge without any reservations I think makes you one of the most valuable persons in photgraphy today. So please, I want to make clear it is not my intention to offend you or ridicule you, as I said I understand you are not a chemist, but I also know many of us come to you for guidance and questions and I know you would not want to provide misleading info if you can help it. That is the only reason for this discussion.



Lets examine the equation you were given, on the surface this might appear to be a reasonable outcome. What this equation is telling us is that 3 atoms of silver donate an electron each to an atom of gold. When this happens silver becomes ionic, thus it becomes soluble and gold falls into it's base state, also known as metallic state. I suppose whoever gave you this equation is theorizing that as silver becomes ionic and more soluble, gold in its metal state replaces those sites where silver has solubilized.



But, there are a few problems with this equation as presented. One, Silver in its metal state will be more stable than gold in its ionic state. IOW silver will not want to donate an electron that readily, unless there is another agent present that forces it to do so, what we know as oxidizers. Now, my understanding is that gold toner is a solution of gold chloride. Now one might say, hey chlorine is present and it is a terrific oxidizer! And this is true, the only problem is that chlorine in this solution is already in its reduced state, IOW it has already "robbed" an electron (from gold) to attain its more stable configuration. Chemistry is not an absolute process, it is not an either/or process, things are in transition all the time, so there is certainly the possibility that a chlorine atom might be "caught" in an electronic state where it needs an electron and it "takes" it from a silver atom rather than a gold one, and this can be the beguinning of the process you mention. But it will not be a process that goes to completion, nor will it be a predominat process IMO.



Let me give my attention now to the balance of the equation, IOW the quantities involved to acheive this process. As the equation states you need 3 atoms of silver to donate an electron which then become soluble and the gold atom "deposits" in the place that silver occupied. Can you see the problem now?
Unless the optical density of gold is much greater than that of silver (which I doubt, but I admit I dont know and perhaps it is so), you would run out of silver way before you have deposited enough gold in those sites to give the same tone. The result of course would be a much lighter print if this was the way it happened. Remember, at this time you have a finite amount of silver, and once it is all gone that is it, the process cannot continue. Where is the extra silver necessary to acheive the same optical density comming from?



There are other objections I have for this theory, but I dont want to bore the rest of the group with a technical disccusion.



I am a water chemist, metals chemisry is not my area of expertize. So I am fully aware that I could be wrong and there is a mechanism here which I dont know that does produce the results you mention. But from a simple chemisty examination I find some things that just dont make sense. My guess is that the process is somewhat in between, some gold replaces the silve completly, some forms a silver/gold/some other thing complex, and some if not most of the silver is left untouched. Perhaps the persons who gave you these explanations can give me their sources or e mail me and explain to me the basis of their theory. I will be more than glad to come back to this forum and admit I was mistaken, after all the pourpose of this forums is to learn and offer accurate information.

Michael Mutmansky
26-Oct-2003, 12:52
Sandy and Jorge,

If the resultant toning with palladium or platinum results in a true, pure palladium or platinum metal, and there is not remaining silver left after the toning process, then I will accept a toned kallitype as a palladium print.

My reasoning is that if I could be assured tha the two printing processes actually result in an identical image, with identical characteristics and identical archival properties, then I guess there is no functional difference between the two, and they are simply two paths to the same end.

However, I am doubtful that the silver is completely removed from the kallitype, and so the resultant image is actually a combination of silver and palladium particles. If this is the case, then I don't think it is 'right' to be labelling a palladium toned kallitype as simply a palladium print.

As you state, Dick does mention the fact that there are many masqueraders out there in museum archives, and I think his point is that it is very important that the actual process be identified correctly, at the very least for the sake of researchers and archivists of the future.

---Michael

Jorge Gasteazoro
26-Oct-2003, 13:42
I agree completely Michael and it is exactly my point. If the process occured as it was explained to Sandy then why hassle with making a pure platinum print, it would be a lot easier and much cheaper to make a kallitype and then just tone it in a platinum solution. Nothing to it, and then you would get a "platinum" print.

Certainly it would be to our advanatge to be able to market "gold" prints, no?

I dont know, something about this theory does not sit right with me, and unless someone can unequivocally prove to me that this is in fact what is happening, I think I would preffer to to call a pd toned kallitype just that...

sanking
26-Oct-2003, 13:55
Jorge,

There is no reason to be concerned about questioning my statement that a palladium toned kallitype is physically the same as a straight palladium. I would assume that somebody would question a statement of this type and if I were wrong I would want to know so the discussion is really very useful. However, I still believe I am right in that there is no essential physical difference between these two types of images. However, your comments about completion raise some questions as to whether the replacement of silver by gold, palladium or platinum can b e 100%. But the fact that a palladium toned platinum is visually identical to a straight palladium suggests to me that the percentage of replacement is extremely high, and if it is indeed very high it seems reasonable to believe there is the possibility that it might go to completion.

For what it is worth I agree with both you and Michael that if the replacement is not 100% we should not label a palladium toned kallitype as a palladium.

The formula given in the earlier message is from Grant Haistís Modern Photographic Processing, Vol. 2, p. 122. Grant Haist was a senior research scientist at Eastman Kodak in Rochester for many years and this book is in my opinion the most authoritative work ever published on photographic processing.

I think you have a good point when you write, "Unless the optical density of gold is much greater than that of silver . . . you would run out of silver way before you have deposited enough gold in those sites to give the same tone" Haist himself mentions that the difference between the amount of gold deposited when gold is in its aurous state, which is about three times as much as deposited in the aurici state, is a result of the two oxidation states of gold. In practice you will indeed find that when a kallitype print is toned to completion with gold the final image is significantly lighter than before toning. With palladium and platinum toning, however, there is no loss of density. To the contrary, there is a slight gain in density.

Platinum and palladium toning of silver gelatin prints was very rarely done in the 20th century and Haist does not indicate how the process of metal replacement takes place. Perhaps someone with experience in metal chemistry can provide guidance on this issue.

sanking
26-Oct-2003, 14:13
Just a thought. How would one test for the presence of silver metal in a print? It strikes me that a test of this test could conclusively answer the question regarding whether or not palladium or platinum can completely replace the silver.

Michael Mutmansky
26-Oct-2003, 15:29
Sandy,

I'm sure there are several destructinve ways to do this, including mass spectroscopy and also possible re-dissolving the metals with an appropriate acid solution (agua regia?) and then a re-reduction of the metals into precipitates or other derivitaves.

I'm nowhere near a chemist, so I wouldn't know how any of this could be done, but Howard or Dick may have some suggestions as to how a procedure may be determined.

I'm sure the people at the Getty have a procedure that will test for silver in a print. I think all we really care about is that there isn't any residual silver left, which may compromise the image longevity.

---Michael

Jorge Gasteazoro
26-Oct-2003, 16:32
Good enough Sandy, I just wanted to make clear there is no "ax to grind" here, only a good natured discussion.

So, a couple of observations.One, if as you say toning a kallitype with pd increases reflection density, then that suggests to me there is some kind of aggregate mechanism where the combined densities of pd and silver are greater than that of a pd or Kallitype print untoned. This suggest that there is some silver left in the toned kallitype print. I guess that if you make a pd print and a toned kallitype from the same negative and took reflection desnsities this could be verified and we can take a step in the right direction. I might even try it myself, I think I still have the chemicals for kallitypes.

Two, a visual comparison is not "proof" that this is in fact what happened, coupled with the increase of density theory, this would actually suggest that there is more of a "plating" mechanism than one of replacement taking place.

Michael made a good guess, if it was me I would not use aqua regia, I would simply use a strong enough solution of nitric acid and then titrate for silver. Why nitric acid? Because silver is less stable than pd, the nitrate ion should be able to oxidize the silver present (if any) bring it into solution and leave the pd in the paper. If the right concentration of nitric acid is choosen, then even before titration there should be an indication of the presence of silver in the print by the appereance of the print. If at the time you soak the print in the nitric acid solution it becomes lighter, then this would suggest some silver has been dissolved resulting in a lower density. Of course further titration would confirm this, as it could be possible to dissolve some of the pd as well.

If I guessed correctly I beleive you work at a university, perhaps the chemistry department is willing to give you a hand on this, it would make an interesting study case for the undergrad students.

sanking
26-Oct-2003, 18:25
Jorge,

Sounds like a soak in nitric acid might be an easy and interesting procedure to check for silver bleaching. What percent solution would you recommend and how long to you think I should soak the print.

BTW, need to correct something I said earlier. The palladium toning results in more contrast, not greater density. This seems to result from a slight clearing of the highlights that takes place during toning.

Jorge Gasteazoro
26-Oct-2003, 22:36
I would say a 5% solution of Nitric acid should do the job. you dont need to soak it for more than 30 to 45 sec, the action should be pretty fast. But you do need to agitate to aid the reaction.

Let me know what you find out...

Pete Caluori
27-Oct-2003, 17:48
Interesting discussion guys. This past APIS, Dr. Dusan Stulnik (I sure hope I spelled his name correctly) gave an interesting presentation on the non-destructive identification process that the Getty Institute has developed. If I recall correctly, it's some type of spectroscopy and it will identify all substances in the print.

Much the same as Dick Sullivan, I suspect that quite a few historical Kallis and even Van Dykes are masquerading as palladium, or platinum/palladium prints. I asked Dr. Stulnik for his thoughts on this and he too suspects this may be the case, but there is no evidence at this point. An insufficient number of prints have been tested to prove this one way, or the other.

The chemical bonds and reactions are well beyond me, but from my work with Van Dykes, I can say that a palladium toned Van Dyke will virtually not bleach in the fixer, whereas a untoned print will "fade" before your eyes. To me that means the silver has either been converted to a new compound that is not affected by thiosulfate, or it's been replaced. Regardsless, I'm a firm believer in being exact in labeling all processes. I don't know how many folks I've talked to that call their prints platinum, when in fact they have 80% palladium and 20% platinum in their prints.

I sure hope we don't get so hung up on platinum and palladium so as to lose sight of the other processes. Kallis, salt prints, albumen, etc. as all are capable of producing beautiful prints, just different and therein lies our goal - beautiful prints.

Regards, Pete

sanking
30-Oct-2003, 10:30
This message was first posted on the alt-photo-process list but I am also putting it here since it is a continuation of this thread.

I ran a silver bleaching test of some palladium toned kallitype with the ferri+bromide Kodak R-14 formula, diluted One Part A + 15 Parts B + 150 Parts Water for one-shot bleaching of four 4X5 test prints.

The four tests themselves were toned for 10 minutes each with different strength toners, ranging from 2.5ml to 10ml of a 20% palladium solution per liter of toner. All of the prints were toned with 10ml of the working toning solution. As you can see, the print with the strongest toner used about 0.1ml of the 20% palladium. By contrast I need about 0.5ml of the 20% solution to make a straight palladium print.

All of the prints were bleached for 10 minutes each, after I determined that this was the time needed to completely bleach out the image of an untoned kallitype. The amount of density lost in bleaching ranged from a lot for the one toned in the weakest toning solution to very little for the one toned in the strongest solution.

Regarding the print that was toned in the strongest toning solution (10ml of a 20% palladium solution per liter of toner), the measured reflective density before bleaching was 1.42, and after bleaching it was 1.36. This means that the palladium in the print, whatever its form, was contributing about 96% of the total density of the print before bleaching, with 4% coming from the silver. This is actually quite a bit higher than I anticipated after hearing of the results of Etienne with other processes. I believe from my data that it would be possible to reach an even higher percentage of total density from palladium by the use of stronger toners and longer toning times, but it does not seem likely to me that a figure of 100% replacement or conversion could be reached.

What I gather from this test is that a palladium-toned kallitype should have great permanence since virtually all of the silver has been either replaced or coated with palladium. However, since a very small percentage of the silver remains in a palladium toned kallitype I would personally not consider it appropriate to call it a palladium, even though for all practical purposes they are *almost* that.

Jorge Gasteazoro
31-Oct-2003, 17:41
I dont konw Sandy, first I have to say I was wrong and there seems to be a pd replacement process that I was not aware of. Of course I researched this after I opened my big mouth so I am having to eat crow now..:-)

I think that the remaining unreplaced silver is due more to a mechanical problem than a chemical one. IOW I think some of the silver is too deep in the paper and the pd cannot reach it to complete the process. I imagine that with some more agitation, or perhaps heating the tonning solution you could get a 100% replacement.

So in the stricktest sense of the word if the toning is not done to completion then perhaps it would be inaccurate to call it a pd print, but I dont know that it would be misleading if the person took care to tone a Kallitype to completion to call it a palladium print.

Mainly I wanted to say you were right, I was wrong and I learned something new.

Michael Mutmansky
31-Oct-2003, 18:28
Jorge,

Don't let him off the hook that easily! I want to know how much of the silver is plated with platinum or palladium. That is really what you were arguing anyway, and the speculation on the alt-photo group was that the plating could be a substantial factor in the resultant image.

At this point the test Sandy has done only confirms that there are some un-plated and un-replaced silver particles in the print that comprises at least a few percentage of the total visible reflectivity.

The next step is to run the same batch with a palladium 'control' so that the actual results can be compared to one that is known to have no silver. Then the bleached tests can have the further tests done that will confirm the presence of plated silver. Since that control should have none, the difference between the two should be readily apparent if plating is occurring.

Sandy, I'm only busting your chops for the sake of the potentially very useful knowledge that you have begun to collect, as I think we are both on the same page about this issue anyway. It's good to see that you have already advanced the level of understanding on this issue, as it appears that there is little data out there regarding what is actually happening in the toning process. Keep up the good work.

---Michael

Jorge Gasteazoro
1-Nov-2003, 09:43
Michael, I thought about when I wrote the message, but without a lab or spending some money it is impossible to accuratelly tell how much of it is replaced. A "visual" check with a densitometer is actually a very accurate indication of the degree of removal.

We can think there are two possible scenarios. One the pd completly "coats" the silver thus inhibiting bleaching, and the other one is that pd replaces the silver. Occam razor tell us that if we hear hoves we should think horses not zebras...or KISS. I think that if you heated the pd toning soultion, the reaction would be 100% or so close to it that for all practical purposes it makes a pd print.

I wish I had access to a lab, since the implications this experiment has can be very interesting. Making a pure pt print is a PITA, but if this reaction behaves the same way with pt then making pure pt prints would be no longer so difficult and much, much cheaper...

Michael S. Briggs
1-Nov-2003, 12:03
Re how much silver is replaced by palladium when a kallitype is toned with palladium: as already stated, there are two main hypotheses. Hypothosis 1 is the coating hypothesis, which has two sub-variants: 1A is that the palladium coats the silver grains and 1B is that the palladium replaces a surface layer on the grains. Hypothesis 2 is that the palladium replaces essentially all of the silver, essentially all meaning something like 95%.





The tone, bleach and measure density experiment that Sandy conducted answers the most important question: it shows that fully-palladium-toned kallitypes resist chemical attack more like palladium prints than like kallitypes. This is important because it shows that fully-palladium-toned kallitypes will probably last almost as long as a palladium print. I agree with Sandy's statement "What I gather from this test is that a palladium-toned kallitype should have great permanence since virtually all of the silver has been either replaced or coated with palladium."





However, my opinion is that Sandy's experiment is of very little use deciding
between the hypotheses of "replace or coated with palladium". Under both hypotheses a fully-palladium-toned kallitype could be highly resistant to bleaching. Obviously, if the silver is fully replaced the print will resist bleaching as if it were made only with palladium. But under the Hypothesis 1, if the silver grains are essentially fully coated with palladium (either by an added layer or by a replaced layer), then the print will also be highly resistant to bleaching because the bleach won't be able to reach the silver.





My knowledge of chemistry isn't deep, so take the next two statements with a caveat. I doubt that a simple chemistry experiment that can be done with equipment typically used by even advanced darkroom workers will be able to distinguish between the two hypotheses. I also guess that the more likely toning action is the first hypothesis, coating, rather than the near total replacement of the second hypothesis.





If the first hypothesis of coating is correct, the fraction of silver in the toned print will vary with grain size because large grains have a smaller ratio of surface area divided by volume.





Unless someone convincingly demonstrates the second hypothesis of near total replacement, I think it would be highly misleading to call a palladium-toned kallitype print a palladium print. I am surprised that this idea was suggested, considering the strum-und-drang on another recent thread (http://www.largeformatphotography.info/lfforum/thread.php?topic=496940) about calling ink jet prints carbon prints. If essentially total replacement is demonstrated, then the issue about whether using the term palladium print is appropriate for a fully-palladium-toned kallitype would be whether the difference in the actual steps taken to reach the final print were too different. Based on the long usage history of platinum/palladium and kallitype, my opinion is that pladium-toned kalliptypes should not be called palladium prints even if the silver is fully replaced.

sanking
1-Nov-2003, 15:30
I am responding to several messages so I hope that all points are covered.

1. I think my experiment demonstrates that Jorge was more right than me. I had thought that a toning bath of 10-15 minutes with a toning solution rich in palladium would entirely replace the silver. This did not happen and it is therefore my belief that it would not be appropriate to call a palladium toned kallitype a palladium.

2. Since the silver was not entirely eliminated, either through replacement or plating, the issue of replacement versus plating was rendered mute. Had there been no loss in density, which would have demonstrated 100% plating or replacement of the silver with palladium, further testing would have been warranted to determine exactly what the reaction was.

3. Further investigation shows that there is no good scientific literature on toning with platinum and palladium, and in fact the exact nature of the reactions are not well understood even by experienced scientists. As far as I am able to determine no one has ever done any testing to show whether toning results in replacement of plating, or if both, the relative percentages of each. But, there are apparently tests, both destructive and with instruments, that can show this.

Even though the tests did not demonstrate what I expected, they were nevertheless useful in showing that toning a kallitype print with palladium provides great protection against oxidative reactions, and thus gives great permanence. 100% protection against oxidative reactions would probably be accomplished by further toning the remaining silver metal with a polysulfide toner. I plan to continue testing along these lines as soon as I acquire the necessary chemicals.

Michael Mutmansky
1-Nov-2003, 17:49
Sandy,

I had one other question regarding the visual compatability of a pd toned kallitype and a traditional palladium print.

When you printed the kallitype and the pd print, what developers were you using for both, and what temeratures? I ask this because, as I'm sure you know, the color of the tone can vary substantially based on the chosen developer and the temperature.

With pd, if you print with sodium citrate you will get a fairly cool print, relative to a potassium oxalate developed print. The difference is much more substantial if you heat the potassium oxalate to 120 degrees (or even higher). Some peoiple develop at as high as 180 degrees for a very warm (almost sepia) print.

Is it possible to print the kallitype and achieve a warm print, and then pd tone it to keep the warm tones? I used to print 50/50 pt/pd, but I switched to pure pd and hot developer because I prefer the warmer tones that it produces.

So the question is how much flexibility is there to tune the image tone as there is in the traditional pd process?

---Michael

sanking
1-Nov-2003, 17:58
Michael Briggs wrote:

"Unless someone convincingly demonstrates the second hypothesis of near total replacement, I think it would be highly misleading to call a palladium-toned kallitype print a palladium print. I am surprised that this idea was suggested, considering the strum-und-drang on another recent thread about calling ink jet prints carbon prints. If essentially total replacement is demonstrated, then the issue about whether using the term palladium print is appropriate for a fully-palladium-toned kallitype would be whether the difference in the actual steps taken to reach the final print were too different. Based on the long usage history of platinum/palladium and kallitype, my opinion is that pladium(sic)-toned kalliptypes should not be called palladium prints even if the silver is fully replaced."

The issue raised by me on the other thread, i.e. real carbon versus inkjet carbon, was primarily one of a hand-made process versus a machine process. Any comparison of the issues raised in that thread to the issues of this thread is simply too silly to merit a serious response. I am really quite surprised that you would have even considered such a comparison appropriate.

You may or not be aware of the fact, but in pt/pd printing there is a long history of adding metals other than platinum and palladium (gold, silver and mercury) to the sensitizer, and the result is a final image that comprises a significant percentage of a metal other than pt/pd. What would you call an image that consists of 90% pt/pd and 10% gold? Or one that comprises 90% pt/pd and 10% silver? Or 90% pt/pd and 10% mercury. I know people who are using additives in this way on a regular basis. Sure, many of the folks working in this way carefully note on the print the actual metals used in the sensitizer but it would never cross their mind that the final image should not be called a real pt/pd print, even though the final image comprises a high percentage of a metal other than platinum or palladium

Finally, we know from destructive tests conducted by the French chemist Etiennne that actual silver replacement of up to 80% has been achieved in gold toning of albumen and salted paper prints, so in theory actual replacement, and not just plating, is possible in toning kallitypes with more noble metals.

sanking
1-Nov-2003, 18:30
"So the question is how much flexibility is there to tune the image tone as there is in the traditional pd process?"

Michael,

I use only sodium citrate for developing kallitypes. The resulting image is a very warm brown tone, much warmer than you get when developing pt/pd in warm potassium oxalate.

Subsequent toning of the kallitype image will give a very neutral black image if toning is done with only platinum, and a much warmer brown if toning is done with only palladium. However, the very warm brown that you get from toning with pure palladium is not quite as warm as the color that you get from developing straight palladium in a warm potassium oxalate solution.

I have not done any testing to see if it is possible to get even warmer brown tones with toning.

Donal Taylor
1-Nov-2003, 18:53
Michael Briggs wrote:

"Unless someone convincingly demonstrates the second hypothesis of near total replacement, I think it would be highly misleading to call a palladium-toned kallitype print a palladium print. I am surprised that this idea was suggested, considering the strum-und-drang on another recent thread about calling ink jet prints carbon prints. If essentially total replacement is demonstrated, then the issue about whether using the term palladium print is appropriate for a fully-palladium-toned kallitype would be whether the difference in the actual steps taken to reach the final print were too different. Based on the long usage history of platinum/palladium and kallitype, my opinion is that pladium(sic)-toned kalliptypes should not be called palladium prints even if the silver is fully replaced."

The issue raised by me on the other thread, i.e. real carbon versus inkjet carbon, was primarily one of a hand-made process versus a machine process. Any comparison of the issues raised in that thread to the issues of this thread is simply too silly to merit a serious response. I am really quite surprised that you would have even considered such a comparison appropriate."

I've always editioned my prints whether silver gelatin or Pd. Do others edition theirs or not? I'm starting to think perhaps not?

sanking
1-Nov-2003, 19:21
"I've always editioned my prints whether silver gelatin or Pd. Do others edition theirs or not? I'm starting to think perhaps not?"

I am curious as to what you have found in this thread that has anything at all to do with editioning? Editioning was about the last thing on my mind.

Donal Taylor
1-Nov-2003, 20:39
""I've always editioned my prints whether silver gelatin or Pd. Do others edition theirs or not? I'm starting to think perhaps not?"

I am curious as to what you have found in this thread that has anything at all to do with editioning? Editioning was about the last thing on my mind."

What you said below, as quoted:

"The issue raised by me on the other thread, i.e. real carbon versus inkjet carbon, was primarily one of a hand-made process versus a machine process."

I had never considered my printing process that way, as hand made versus machine made. If I want to consider my prints as hand-made, why edition them, apart from convention? It would make more sense just to sell each one as an individual print, especially the platinum prints.

Years ago when I first started platinum printing I didn't number them, mainly because I made very few and sold even fewer. It was only when I started selling through a gallery that they asked for editions and I went along with it and have done so ever since.

Michael S. Briggs
1-Nov-2003, 21:48
The issue raised by me on the other thread, i.e. real carbon versus inkjet carbon, was primarily one of a hand-made process versus a machine process. Any comparison of the issues raised in that thread to the issues of this thread is simply too silly to merit a serious response. I am really quite surprised that you would have even considered such a comparison appropriate.





It seems to me that part of the issue in the Anybody else getting heartburn with the new 'Carbon Print' ? (http://www.largeformatphotography.info/lfforum/thread.php?topic=496940) is whether it is proper to use a term with a long established meaning for a new process, e.g., will this mislead buyers about what they are getting? Some makers of some types of inkjet prints want to call them "carbon prints" on the basis that the pigments used contain carbon, while some others object that this term already has a meaning and object to assigning a new meaning to the term. In comparison, palladium-toned kallitypes probably contain a lot of palladium and the photographic literature hasn't called these prints palladium prints, so would it be misleading to start using the term "palladium print" for palladium-toned kallitypes? It is true that the differences in process between carbon print and inkjet print is much greater than the difference between palladium-toned kallitype and palladium print.

Jorge Gasteazoro
2-Nov-2003, 03:17
so would it be misleading to start using the term "palladium print" for palladium-toned kallitypes?



If the issue of percent replacement can be verified and it is proved that it is 100% then it would not be misleading to name a pd toned kallitype a palladium or platinum print. How you arrive at the final result, IMO is unimportant. You can take the stair or an elevator, but you eventually end where you a re going.



THis is an entirely different matter than the ink jet vs carbon printing, that thread has to do with misappropriating a process name, this thread has to do with naming a process as accurately as possible. It is why I disagreed with Sandy at first, but I am now convinced that the actual process involves replacement rather than "plating".

sanking
2-Nov-2003, 07:03
"The next step is to run the same batch with a palladium 'control' so that the actual results can be compared to one that is known to have no silver. Then the bleached tests can have the further tests done that will confirm the presence of plated silver. Since that control should have none, the difference between the two should be readily apparent if plating is occurring. "

Michael,

The first time I read your message I missed the suggestion about running the same batch with a palladium control. In fact I did make this test by bleaching a straight palladium print at the same time I did the other tests. My assumption was that there would be no loss of density during bleaching with the straight palladium, and this was indeed the case. Since the test confirmed my assumpion I just figured there was no need to report the results.

sanking
2-Nov-2003, 08:05
"Some makers of some types of inkjet prints want to call them "carbon prints" on the basis that the pigments used contain carbon, while some others object that this term already has a meaning and object to assigning a new meaning to the term. In comparison, palladium-toned kallitypes probably contain a lot of palladium and the photographic literature hasn't called these prints palladium prints, so would it be misleading to start using the term "palladium print" for palladium-toned kallitypes?"

But the two cases are very different.

Assuming that it is possible to replace 100% of the silver in a kallitype with palladium, the final print would be physically identical to a straight palladium. And we are dealing in both cases with hand made prints that use a processing method that is virtually identical. In both cases the light sensitive element is ferric iron and the final result is an image on paper that consists of palladium metal.

Pigment inkjet versus real carbon is an entirely different matter. A finished real carbon print comprises some type of pigment that is embedded in a layer of gelatin that has been hardened by UV light. It is not just the pigment that provides permanency but the hardened gelatin as well. We know from historical record that hardened gelatin has great archival properties so the layer of hardened gelatin is important in providing permanence for the print, and at the same time the gelatin gives a soft sheen to the print that is quite different from what you see with an inkjet print. A pigment print made with an inkjet printer has some type of protective coating sprayed over the pigment. I donít know anything about the physical properties of this coating but I know by its operating properties that it could not be gelatin because you could not spray cool gelatin through the nozzle of an inkjet printer.

There is also the question of exclusivity. Making palladium toned kallitypes and straight palladium prints requires an equal amount of skill and time. What comparison is there in the skill and time required to make an inkjet print and that needed to make a real carbon. A carbon print is for all practical purposes a unique print because closely matched auditioning is very difficult with the process. With my inkjet printer I could easily make 200-300 identical pigment prints of 11X17" or 13X19" in size per day. If I were able to make even two or three t identical real carbon prints of that size in a day it would be a very good day indeed. And I have a *lot* of experience at making carbon prints.

However, back to the issue of names. What my research and tests on toning kallitypes with palladium is that it might be possible to combine very long toning times with heated solutions and get 100% replacement of the silver. But is that a practical and efficient way to work? I don't think so. Might as well make straight palladiums. It makes more sense for me to follow the palladium toning with a toning in selenium or polysulfde to convert the remaining silver in the print to other substances that will also resist oxidation.

Michael Mutmansky
2-Nov-2003, 08:33
Sandy,

Your test with the palladium control is intresting, as I expected _some_ loss of density in the pd print due to the loss of residual FO and possibly mild bleaching of the pd and even bleaching of the paper. So this test is really an excellent indication of the effect that the silver has on the final toned print, and as your results indicate, the difference is not too great.

I was wondering if the temperature of the toning bath will affect the tone of the final print? If you heated that pd toning bath to 140 or 160 degrees, and then let it cool down as the print toned for 10 minutes or so, whether it would result in a warmer tone as is the case when developing a straight pd print.

Next time I order from B-S, I'll get the needed chemicals to try a few kallitypes, and see what this process looks like for myself.

---Michael

N Dhananjay
2-Nov-2003, 08:59
Thanks for a very interesting discussion and some fascinating data. However, while it might settle the issue of what to call it, the plating versus replacement still seems up in the air and has me wondering. I was hoping Jorge would throw some more light on why he is convinced that it is more likely to be replacement. I wonder if the following test would help. Its been suggested (e.g., Tim Rudman) that selenium operates by replacement i.e., by converting the silver to silver selenide whereas gold is supposed to operate by plating. When doing combined toning (i.e., tone the print partially in each toner), it is generally advised that one do the selenium toning first. The reason for this is that if the gold toning is done first, the selenium apparently can get under the 'plating' and change the silver to silver selenide, thereby changing the color of the print. To that end. if selenium changes the color of a palldium toned print, it would pretty much prove that this was a plating process. Of course, if it doesn't, it leaves us where we are since the null result is pretty inconclusive (i.e., it would indicate either that it was replacement or that is plating but a plating that was impervious to selenium, unlike gold plating). Just a thought. Thanks again, folks. Cheers, DJ

Jorge Gasteazoro
2-Nov-2003, 14:58
DJ, I did a half assed experiment which seemed to indicate that replacement is the mechanism that is occuring here. I made a Kallitype, toned it in a pd solution at room temperature for 3 minutes and collected the toning solution after the toning was completed. The toning was done after washing the print in 3 different water baths to remove any residual silver not bound to the paper.

To the "spent" toning solution I added a 3% solution of sodium chloride, in a attempt to precipitate silver chloride. My thinking was that since the the active pd solution is palladium tetrachloride the pd should not precitpitate but the silver should. I then filtered the "spent" solution and I got a precipitant that is more likely silver chloride as there is not other possible combination in the solution. IMO this demonstrates that silver which was not initially present in the pd solution, after toning it is present as a soluble compound which can then be removed. I know from the "chemistry" point of view there are many things wrong with this experiment, but I think the theory is solid and all that it lacked was some controls. Given the appropriate lab equipment and a correctly designed procedure I think it is feasible to prove that indeed replacement is the mechanism happening in the toning procedure.

Initially I thought as you did , that the toning procedure was forming a silver palladite compound (if such thing exists) much like a silver selenite compound that forms when we tone in selenium. But if that was the case then there should not have been any silver in solution or it should have been a minimal amount.

Let me know what yout think.

sanking
2-Nov-2003, 15:25
Jorge,

OK, I am going to run some tests this week with pure platinum toned kallitypes. But instead of toning at room temperature as I normally do I will use a very warm solution in an effort to see if there is a higher percentage of replacement/plating of the silver metal. What temperature would you suggest?

Your point is well taken about platinum. Since it is so much more expensive than palladium there might well be a good case made for getting there with a toned iron-silver process rather than straight platinum. This could result in an actual cost saving of 70-85% over the use of pure platinum, and this would really be a significant amount of money if we are talking about a large print.

Jorge Gasteazoro
2-Nov-2003, 19:20
Sandy, since you are trying to verify replacement, why dont you use the solution hot enough so that the reaction is assured, I would say 160 to 180 ļF should be good enough without harming the print or paper.

Let me know what you find out.

N Dhananjay
2-Nov-2003, 22:59
Jorge, Thanks for sharing that. Interesting experiment - I'd agree with your conclusions. Cheers, DJ

sanking
7-Nov-2003, 18:49
Jorge et al,

I ran the same bleach tests of platinum toned kallitypes that I previosly ran and reported on with palladium. Here are the particulars.

The silver bleaching test of pure platinum toned kallitypes was made with the ferri+bromide Kodak R-14 formula, diluted One Part A + 15 Parts B + 150 Parts Water for one-shot bleaching of four 4X5 test prints.

I made two tests, using 5ml of a 20% platinum solution per liter of toner for one test, and 10ml of a 20% platinum solution per liter for the other. I used the toner at about 160 degrees F.

The two prints were bleached for 10 minutes. The amount of density lost in bleaching was slightly more than in my tets of palladium toned kallitype.

Both test prints had an initial Dmax of 1.40. After bleaching the Dmax of both prints was about 1.30 for both. This is slighly more density loss than I experienced when toning with pure palladium.

I did another test in which I followed the pure platinum toning with toning in a 1:100 solution of Rapid Selenium *after fixing*.. Dmax before bleaching was 1.40, after bleaching it was 1.34, indicating that platinum toning plus selenium toning provided slightly more protection to oxidation than platinum by itself.

Jorge Gasteazoro
7-Nov-2003, 22:07
Hmm, this really is surprising. I would have thought that at least pt was as effective as pd. Perhpas it has to do with the size of the atom, pt being much larger than pd and perhaps being able to occupy less spaces than pd, but to tell you the truth I am stumped. Perhpas Howard or DJ and shed some light.

N Dhananjay
9-Nov-2003, 13:53
Hmm, I dunno. Although the difference is small enough to make me wonder about just statistical error i.e., both of them have about the same level of replacement but there is some error associated with any particular test (time in solution, minor random fluctuations asociated with agitation patterns, phases of the moon and such). Cheers, DJ