Long term stability of Pt/Pd prints on paper

Hi all,

Now I have no doubt that almost any Pt/Pd print will easily outlast any untoned silver gelatine print, but one thing kept nagging me...

It is a not much discussed topic here on APUG, almost seems to be avoided, but I already knew Platinum (and probably Palladium as well), is a rather strong and effective catalyst, speeding up and enabling chemical reactions. One of the reasons it is used in car's exhausts.

Now I had already seen and partly read James M. Reilly's

“Care and Identification of 19th Century Photographic Prints”

document showing a Pt/Pd print been in contact with another paper, leaving a visible "mirror" image on the other paper by it's catalytic activity. See the attached image in this post. This is not just a "harmless" discolouring of the paper though... as I now recently read an article by Mike Ware about his Gold based Chrysotype process, referring to "embrittlement" of the paper base of Pt/Pd prints. While the highly noble and stable metals themselves will last indefinitely, the paper base and photographic image itself might be lost at some point...

Chrysotype: Photography in Nanoparticle Gold

Mike Ware literally writes in this document:

"It has already been stated that chrysotype resembles the better-known, and at one time widely acclaimed, platinotype process (38). New chrysotypes are extremely light-fast and resistant to chemical attack; they therefore enjoy an archival permanence at least equalling, and perhaps surpassing, that of the platinotype. The conservatorial problem which has beset all historic platinotypes arises from the high catalytic activity of platinum black, which can bring about the aerial oxidation of SO2 to SO3, thus causing serious acid embrittlement of the paper base by sulphuric acid formed in situ. In contrast to platinum, nanoparticle gold has a very low catalytic activity in this respect (39), so this problem should be absent from chrysotypes. The longevity of the paper substrate will also be enhanced by the alkaline conditions of the wet processing, in contrast to the hydrochloric acid clearing baths sometimes used to process platinotypes."

Both James M. Reilly and Mike Ware are highly authoritative and credible sources, and in addition the example image shows that we are not only talking of a "theoretical" option, but a real thread to the very long term survival of the Pt/Pd print.

As the process described by Mike is depended on the presence of sulphurdioxide gas, the generally good recommendation for photos of proper framing behind glass, especially in the polluted environment of an urban city, seems a necessity. It will probably be very effective as a conservation method, as it simply blocks air circulation at the surface of the print, keeping SO2 load to an absolute minimum. In addition, but all Pt/Pd printers are undoubtedly already doing this, only the highest quality 100% cotton rag cellulose papers seems recommendable, to give the paper the maximum chance of long term survival.

What are your thoughts and comments on this issue?

Marco

Thanks for the insight.

As for the remedy:
a. Print chrysotypes! (It's a beautiful process and not too many appreciate it...)
b. (For the conservatives AND conservationists) An alkali buffering bath each 100 years? (Along with keeping the print in good condition/environment - as you stated above...)

Regards,
Loris.

everyone I know uses highest quality cotton for pt/pd.

dpurdy said:

everyone I know uses highest quality cotton for pt/pd.

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Yes, but that by itself is not enough, cotton is just a purer form of cellulose that is less susceptible to self destruction like the cheap high lignin content wood pulp papers like newspaper. Hence the framing recommendation remains.

BTW, (a completely different issue but wanted to mention anyway) if etchings/photogravures (which are made using inks with "oil" binder - oil is big BIG enemy to the paper) are keeping well, why wouldn't pt/pd exhibit similar performance?

Loris Medici said:

BTW, (a completely different issue but wanted to mention anyway) if etchings/photogravures (which are made using inks with "oil" binder - oil is big BIG enemy to the paper) are keeping well, why wouldn't pt/pd exhibit similar performance?

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What is your remark that "oil is a big enemy to paper" based on? Can you give some more info or literature references?

Oils in those etching inks are mostly likely natural drying oils like linseed oil used in oil painting. "Drying" is actually a VERY BAD description of the process, as it suggests a solvent (like water, turpentine) is evaporating, while in reality "drying oils" like linseed, actually do not need a solvent to be fluid and harden by reacting with Oxygen (O2) in the atmosphere in a kind of polymerization process.

I know this polymerization process releases small amounts of potentially harmful peroxides (if I remember well), but this process stops as soon as all oil has "hardened / dried", it is a finite process, contrary to the continuing acidification if the platinotype is exposed freely to air...

Hi Marco, what about a little googling? (Search for: Oil on paper and longevity etc., for instance.) Linen is way stronger than cotton (they were wrapping mummies with linen ribbons remember?) and unprimed (see: gesso) linen canvas will rot if you put oil paint on it. Same for paper... I repeat: if etchings / photogravures are OK, then why pt/pd prints are not?

The Frederick Evans prints at the Getty looked pretty good to me...how long do you want your prints to last anyway?

Loris Medici said:

Hi Marco, what about a little googling? (Search for: Oil on paper and longevity etc., for instance.) Linen is way stronger than cotton (they were wrapping mummies with linen ribbons remember?) and unprimed (see: gesso) linen canvas will rot if you put oil paint on it. Same for paper... I repeat: if etchings / photogravures are OK, then why pt/pd prints are not?

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Loris, I don't actually completely understand your point. Your remark is equivalent to "My grandfather lived 120 years, so why should a Pt/Pd print not survive as long?"...

You're comparing apples and pears... I just made remarks about Pt/Pd longevity and possible issues with the paper base based on a couple of good references.

And about linen and cotton: I am not even sure if cotton was a "base material" for clothing 3 millenia ago. OK, found a reference: cotton, although produced, was not a very common material in Egypt for clothing. And from what I know of the history of clothing in Europe it wasn't either (mainly wool, linen, leather):

http://www.historyforkids.org/learn/clothing/cotton.htm

And don't forget that the mummies wrappings seem also to be glued together with resin, probably further protecting the linen.

http://library.thinkquest.org/C0116982/HTML page folder/hwrapping.htm

"More linen strips are wrapped around the body. At every layer, the bandages are painted with liquid resin that helps to glue the bandages together."

Loris Medici said:

and unprimed (see: gesso) linen canvas will rot if you put oil paint on it. Same for paper... I repeat: if etchings / photogravures are OK, then why pt/pd prints are not?

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Loris,

I have a Dutch book on painting (Het Kunstschildersboek by Kraaijpoel & Herenius) by some Dutch paint experts, and they actually discuss your "rotting canvas" myth, but argue against it: Exactly for the reason you give yourself: Etchings DON'T rot, linen is for the most part similar cellulose as the paper, so why would linen rot??? In addition, they point out, besides having run an unprimed linen oilpaint test for 20 years without issues turning up, that other high cellulose materials (like wood itself), overpainted with oil paints, don't rot / oxidize either... or does your painted wooden living room table fall apart :confused:

According to this book, any small damage (as per the suggested process of drying I described above) would occur in the beginning, stopping when the oils of the paint had dried.

I think the rotting linen myth is more likely originated from old paintings hanging in wet cold European climates against damp walls and getting attacked by mould... a completely different issue.

I repeat: any oil based damage (if it at all occurs in minute amounts) is a FINITE process, while the catalytic acidification of platinotypes is a continued process as long as sulphurdioxide can reach the print.

Marco

Marco, aren't etchings and gravures made on paper? (Just as pt/pd prints...???)

Obviously, linseed oil will do (does - if you like) much more harm (directly that is, not indirectly - as suggested for elementary pt/pd nanoparticles) to paper. So, if people (museums, collectors, conservationists etc.) are confident (or don't bother) about etchings and/or photogravures, then what's the point of questioning the longevity of pt/pd prints? (Let me mind you that we have an abundant legacy of - very old - etchings in the museums and collections...) Seems like an exercise of futility (in practical sense), OR a subject of academic research - which actually may prove very useful, maybe not necessarily in the intended area; sometimes you can't know exactly where a scientific research may lead you...

Hope my point's clear now? Relax and print, make your art...

Regards,
Loris.

P.S. See this:
"...Linen fabric is one of the preferred traditional supports for oil painting. In the United States cotton is popularly used instead as linen is many times more expensive there, restricting its use to professional painters. In Europe however, linen is usually the only fabric support available in art shops. Linen is preferred to cotton for its strength, durability and archival integrity...."

Marco, etchings / photogravures discolor considerably (more the latter) especially in the darkest part of the image (where most ink was deposited). Have you inspected the back of an old photogravure?

Repeating: Relax and print, make your art...

Regards,
Loris.

About the "myth": Your explanation puts all of old masters in a pretty dumb position. Do you know how much trouble is priming canvas with traditional gesso? They were taking all that pain for nothing, poor dumb people... And what about today's acrylic primers? Useless (in terms of longevity) apparently... :rolleyes:

A last point about linen vs cotton: Linen fibers are much longer than cotton fibers, that's why it's better in terms of strength / archival integrity...

Loris Medici said:

Obviously, linseed oil will do (does - if you like) much more harm (directly that is, not indirectly - as suggested for elementary pt/pd nanoparticles) to paper.

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Loris, I am getting slightly irritated here (as you obviously also are for an unknown reason to me).

The only reason I started this thread is:

A) to inform people of not much known but potentially interesting stuff backed up by some observations of well respected authors in the field
B) to start a healthy, open and honest discussion on a subject, where I hoped people would point out other literature and scientific weblinks so as to help further d/refine or discuss the topic

So please, give some good reference that shows to me that oil paint is much more harmful to cellulose art works (whether linen or paper), than is Pt/Pd. Simply saying: etchings last, so must Pt/Pd is from a scientific point of view nonsense, as you know as well.

I have shown, based on the posted image of James M. Reilly's document and Mike Ware's remark, that it is likely that some non-framed Pt/Pd prints might(!) develop issues with the paper base within a timespan of 1-1.5 century, due to the catalytic nature of the used metals. It is very unlikely, and the authors of the painting book I have dispute it, that oil paint would be a similar thread. Oil paint dries, and than becomes more or less non-reactive, as the polymerization stopped.

Loris Medici said:

So, if people (museums, collectors, conservationists etc.) are confident (or don't bother) about etchings and/or photogravures, then what's the point of questioning the longevity of pt/pd prints?

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Loris, again, this point is mute... Etchings and oil are something completely different. You can't compare them to Pt/Pd metals on paper. Please note, If you do have some literature and scientific links that show issues with oil-on-paper, I am highly interested to read them, so post the links here.

Loris Medici said:

About the "myth": Your explanation puts all of old masters in a pretty dumb position. Do you know how much trouble is priming canvas with traditional gesso? They were taking all that pain for nothing, poor dumb people... And what about today's acrylic primers? Useless (in terms of longevity) apparently... :rolleyes:

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Loris, besides this all being pretty much off-topic:

No, they weren't dumb, but I can assure that the authors of the book on painting I have aren't either...

Priming is not only done for "protective" reasons, but also for two other major reasons (and yes, I have studied oil painting quite extensively, and painted a bit myself with classical oil paint, have a look at my website):

- To cover up an absorbent surface, like the linen. Painting directly with oil paint on linen is undoubtedly going to be a pain, as the linen will absorb the oil from the paint, leaving a to dry mass of paint pigment on the canvas, with possible negative consequences for the strength and elasticity of the paint layer as well

- To provide a smooth surface for classical glazing technique and super detailed paintings. The gesso layer was traditionally ground down to create a perfect flat surface, without the structure of the linen.

Marco

And one last point to all, before we end up with endless useless discussion about this:

I have no doubt a properly framed and processed Pt/Pd print, printed on the highest quality paper, will easily last half a millennium or more

It is the unframed versions that might develop issues in a more "humanly" timespan... and are the topic of this thread, together with any further (scientific) insights on the processes underlying the possible degradation of paper caused by the catalytic nature of Platinum or Palladium.

Marco

I've made my points very clearly. Relax and print / do your art Marco, don't be so anal, OK? You look odd by requesting a scientific reference for every claim - I simply asked a logical question: What's the significance of this phenomenon? Is it worth to worry about it? (In short: So what?) Chill out, that's something easy to do in The Netherlands (with some help?), I presume...

BTW see few links about oils on paper here:
http://www.utrechtart.com/ask-the-experts/FAQ_OIL.cfm#Q8 (It's a paint manufacturer's site...)
http://www.winsornewton.com/main.aspx?PageID=344 (Another paint manufacturer...)
http://www.sewanee.edu/chem/chem&art/Detail_Pages/Projects_1998/Binders.htm (See section "Watercolor papers" and the reference right at the end of the section...)
... and thousands more. All sources say either (a.) Don't do it, it's not archival (dismissive) or (b.) Seal the surface with gesso / acrylic binder and such, affix to a rigid support (the latter suggestion occasionally). If not, paper will get harmed...

Do you have a single example / case of pt/pd that was disintegrated due catalytic reaction of pt/pd nanoparticles? (In scientific literature please!) IIRC, the only effect observed was discoloration (proportional to the image) in the facing sheet. (BTW, what do we know about the storage conditions of the print in question?) Do you have a single example / case where the back of a pt/pd print was discolored / weakened (and what not) proportional to the image density in scientific literature? Photogravures do...


P.S. BTW, what you have brought into discussion is well known to serious practitioners of the medium and was discussed (maybe not here - but internet does not consist solely of apug.org, right?) at least once if not more... (I had seen that mirror image at least twice before.) Nothing new in other words. But thanks for good intention anyway...

So let's see if a beginner in Pd-Pt printing understands the content of this dialogue. There's reason to believe that the metallic platinum in Pd-Pt prints catalyzes SO2 to SO3 and hence to sulphuric acid. The process doesn't work with buffered paper, it has to be acidified first. Hydrochloric acid or the oxalate developers do that. At the end, you wash it thoroughly and get it neutral. Couldn't one buffer it again? With what?

Loris Medici said:

I've made my points very clearly. Relax and print / do your art Marco, don't be so anal, OK? You look odd by requesting a scientific reference for every claim - I simply asked a logical question: What's the significance of this phenomenon? Is it worth to worry about it? (In short: So what?) Chill out, that's something easy to do in The Netherlands (with some help?), I presume...

Click to expand...

Loris,

This is the thing I absolutely don't get in your attitude: as soon as the longevity of silver gelatine comes up on APUG, everyone jumps on it, start a healthy discussion with tips about toning etc, and alternative process printers like Pt/Pd or Carbon are saying you "should start print Pt/Pd or Carbon" because "the longevity of silver prints suck" and "why use a material that will self-destruct like silver?" or something similar.

So, if people feel the need to discuss and argue the longevity of silver gelatine prints, why on earth not discuss or argue the possible issues with other print types like Pt/Pd??? :confused:

I just don't get it... I also have the slight feeling that Pt/Pd printers, simply "don't want to hear it"... they invested time and money to get the longest longevity prints, and now someone is telling them there might (!) be issues in some cases they had not foreseen...

Loris Medici said:

BTW see few links about oils on paper here:
http://www.utrechtart.com/ask-the-experts/FAQ_OIL.cfm#Q8 (It's a paint manufacturer's site...)
http://www.winsornewton.com/main.aspx?PageID=344 (Another paint manufacturer...)
http://www.sewanee.edu/chem/chem&art/Detail_Pages/Projects_1998/Binders.htm (See section "Watercolor papers" and the reference right at the end of the section...)
... and thousands more. All sources say either (a.) Don't do it, it's not archival (dismissive) or (b.) Seal the surface with gesso / acrylic binder and such, affix to a rigid support (the latter suggestion occasionally). If not, paper will get harmed...

Click to expand...

Thanks for the links. I appreciate it, will have a look at them.

Loris Medici said:

Do you have a single example / case of pt/pd that was disintegrated due catalytic reaction of pt/pd nanoparticles? (In scientific literature please!) IIRC, the only effect observed was discoloration (proportional to the image) in the facing sheet.

Click to expand...

Loris,

No, I don't have an example YET. That is exactly the reason I started this thread, that people might be able to confirm Mike Ware's remark about issues with platinotypes, preferably posting links to documents describing it and showing real-world examples. But than again, I doubt Mike Ware would make such a significant remark if he hadn't actually seen or been in contact with some good museum conservators who told him about it first hand.

Mike Ware is "not just everybody", he seems quite well respected, and undoubtedly has made some significant contributions to the alternative process community. Why would he risk his reputation telling nonsense about Pt/Pd? So if he says there have been documented cases of issues with Pt/Pd due to acidification, I do think this is something to listen to and possibly learn from.

I repeat Mike Ware's statement here:

"It has already been stated that chrysotype resembles the better-known, and at one time widely acclaimed, platinotype process (38). New chrysotypes are extremely light-fast and resistant to chemical attack; they therefore enjoy an archival permanence at least equalling, and perhaps surpassing, that of the platinotype. The conservatorial problem which has beset all historic platinotypes arises from the high catalytic activity of platinum black, which can bring about the aerial oxidation of SO2 to SO3, thus causing serious acid embrittlement of the paper base by sulphuric acid formed in situ. In contrast to platinum, nanoparticle gold has a very low catalytic activity in this respect (39), so this problem should be absent from chrysotypes. The longevity of the paper substrate will also be enhanced by the alkaline conditions of the wet processing, in contrast to the hydrochloric acid clearing baths sometimes used to process platinotypes."

Now do you really think this is just an arbitrary or non-significant remark that can be simply dismissed without any second thought?? I find his remark strong, and something to think about...

Loris Medici said:

(BTW, what do we know about the storage conditions of the print in question?)

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Completely fair remark. You are right the storage conditions play a significant role, but than again, I already stated properly framed and processed prints are highly likely to keep almost "indefinitely"

Actually: another important thing here is that we may actually be lucky with the current times. After the big "acid-rain" row in the seventies and especially eighties, many western companies invested hundreds of millions to significantly reduce sulphurdioxide emmisions. Our air (even the urban one) is definitely much cleaner in terms of sulphurdioxide than it probably was in the beginning of the industrial age (say 1850-1900 London), where most of the possibly affected Pt/Pd might date from. In addition, the switch to gas instead of coal for heating homes and cooking, has made a significant positive impact as well.

Still, we are not down to really clean air. During my biology study in 1995, I went to Poland. We did a small research project there under the guidance of a Polish professor, mapping out lichens on trees around a small village. This town still used coal for all its heating and cooking. Lichens are very susceptible to SO2, and the Polish professor had made a "measurement scale" that allowed one to determine the level of SO2 in the air based on the lichens present on trees. Worked like a charm, you could see the SO2 load diminish going from the town into the forest by mapping out the susceptible and less susceptible species of lichen...

Loris Medici said:

Do you have a single example / case where the back of a pt/pd print was discolored / weakened (and what not) proportional to the image density in scientific literature? Photogravures do...

Click to expand...

Again, I was starting this discussion in the hope of some healthy contributions of others, possibly confirming Mike Ware's significant remark by showing an actual example.

phaedrus said:

So let's see if a beginner in Pd-Pt printing understands the content of this dialogue. There's reason to believe that the metallic platinum in Pd-Pt prints catalyzes SO2 to SO3 and hence to sulphuric acid. The process doesn't work with buffered paper, it has to be acidified first. Hydrochloric acid or the oxalate developers do that. At the end, you wash it thoroughly and get it neutral. Couldn't one buffer it again? With what?

Click to expand...

You are not completely right. The process ALSO takes place in well buffered paper, at least, that is what I assume. Unless a high pH completely blocks Pt/Pd prints catalytic activity, Pt/Pd will still convert the SO2 in SO3. The difference with non-buffered papers is that the buffered papers have a "back-up" alkali reserve, that will neutralize any formed acid as long as the buffer hasn't been exhausted, thereby significantly delaying the onset of any issues with acid destroying the paper base.

How long such a buffer lasts under "normal" conditions, I have no idea...

Again, any literature or scientific research links might be nice to see. One could setup an SO2 fumigation test of a Pt/Pd print compared to a "control" sheet of paper not coated with Pt/Pd. Might give interesting results... (I am in no position to do this myself)

Loris Medici said:

I've made my points very clearly. Relax and print / do your art Marco, don't be so anal, OK?

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One last remark:

Loris, you were the last person I would have expected to call me "anal" about this kind of stuff...

From all your regular posts here on APUG and Hybridphoto, I have the strong feeling you, just like me, are a person who devours anything or any form of (scientific) literature related to photography and alternative processes...

Dead Link Removed to discuss the longevity of his Argyrotype process versus Van Dyke Brown, a discussion topic on another forum you hadn't even started yourself!

Now who is "the anal person" here??? (I think we both are...)

Are some of the issues with Platinotype more of historical/conservator interest in that current, recommended methods to not include hydrochloric acid as clearing bath?
Is the catalytic properties of Palladium more of an issue at higher temperatures normally not found in print archives?
Does the recommendation for acidifying some papers for pt/pd usage actually lead to deterioration of the paper?

doughowk said:

Are some of the issues with Platinotype more of historical/conservator interest in that current, recommended methods to not include hydrochloric acid as clearing bath?
Is the catalytic properties of Palladium more of an issue at higher temperatures normally not found in print archives?
Does the recommendation for acidifying some papers for pt/pd usage actually lead to deterioration of the paper?

Click to expand...

Doug, all good questions!! Those are the ones I would like to have discussed and maybe even answered here in this thread... that's why I started it.

Marco B said:

...

So, if people feel the need to discuss and argue the longevity of silver gelatine prints, why on earth not discuss or argue the possible issues with other print types like Pt/Pd??? :confused:

I just don't get it... I also have the slight feeling that Pt/Pd printers, simply "don't want to hear it"... they invested time and money to get the longest longevity prints, and now someone is telling them there might (!) be issues in some cases they had not foreseen...

Click to expand...

Hi Marco,

I don't say lets not discuss it exactly, but (I think) it's pretty much useless for us photogs and/or collectors. I mean the possible negative effects showing up (if any) will take at least 4-5 generations of both groups. It's more a conservators' issue and this isn't a conservation list/forum...

Also as a practitioner of the medium (not current - but I was doing a lot of pt/pd few years ago. I just dumped it because my attention / interest just turned into pigment processes. Now I'm only thinking about pt/pd in the context where I'm also going to put some gum layers on top of it...), I confidently can say that my interest in pt/pd wasn't - a little bit - related to the longevity of the process, and I'm sure it's not at the top of the list of priorities of any other practitioner or master too. (It's important, no one will deny that, though.) It's all (well, maybe more) about the (unequaled) wonderful tones and smoothness we're able to get with the process... (+ handmade/tactile qualities + freedom of choosing / matching substrate to subject + image in / integrated to the substrate, not on top of it / separated + ... and so on...) Edit: You have to do few to understand that...

Marco B said:

...

Mike Ware is "not just everybody", he seems quite well respected, and undoubtedly has made some significant contributions to the alternative process community. Why would he risk his reputation telling nonsense about Pt/Pd? So if he says there have been documented cases of issues with Pt/Pd due to acidification, I do think this is something to listen to and possibly learn from.

Click to expand...

I have great respect for Mike Ware and admire him. I'm not saying he's telling nonsense (that's something impossible in my experience), everything he thinks and tells is very important to me. See the first paragraph for my (seemingly) bitter approach to the subject...

Regards,
Loris.

Loris Medici said:

Hi Marco,

I don't say lets not discuss it exactly, but (I think) it's pretty much useless for us photogs and/or collectors. I mean the possible negative effects showing up (if any) will take at least 4-5 generations of both groups. It's more a conservators' issue and this isn't a conservation list/forum... Loris.

Click to expand...

Loris,

Thanks for taking the time to explain yourself a bit further. Don't get me wrong, my intention was by no means to withhold anyone from practising the beautiful art of Pt/Pd printing (for whatever reason they may desire it, whether aesthetics, archivability or any other reason), by scaring them with stories about issues with longevity, but merely to inform and learn more.

However, I do not subscribe to the notion that this belong on a specialized conservation forum... APUG is just a "general" photography forum. All kinds of subjects are discussed here, and the longevity of silver gelatine prints is one of the topics that comes up on a very regular basis, and I think not without reason. So, personally, I see absolutely no reason not to discuss the longevity and conservation topics related to any other photographic process. It belongs on APUG as well.

Marco