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Author Topic: Are there any 100% cotton glossy/luster papers without TiO2?  (Read 4224 times)

mearussi

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I'm trying to find out whether there actually is a truly "archival" glossy/luster type paper available.
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deanwork

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #1 on: July 26, 2019, 08:08:31 pm »

Hahnemuhle Photorag Pearl and Hahnemuhle Photorag Baryta.


I'm trying to find out whether there actually is a truly "archival" glossy/luster type paper available.
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MHMG

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #2 on: July 26, 2019, 09:13:15 pm »

Hahnemuhle Photorag Pearl and Hahnemuhle Photorag Baryta.

+1, the first two papers that come to mind for me as well :)  Also, Canson Platine, Red River Palo Duro Soft Gloss, Epson legacy Platine.

There are others as well no doubt. Aardenburg Imaging & Archives needs to start compiling a list. It only takes time and money ;)

Easy to sort OBA-free media with a low cost UV-LED "flashlight". Or refer to the Aardenburg light fade test database or Ernst Dinkla's extensive spectral data sets for modern media at http://www.pigment-print.com/spectralplots/spectrumviz_1.htm for guidance on OBA-free media.  Choosing OBA-free media is thus a straight-forward and enduser-verifiable way to avoid media which exhibit light induced low-intensity staining (LILIS) regardless of any TiO2 content.

If the media is both OBA-free and TiO2-free, then a spectrophotometer like the Xrite i1Pro2 can pick that up by inspecting for fall-off or lack thereof in the 380 to 420 nm range. Both TiO2 and OBAs cause a sharp downturn in the spectral reflectance curve in this wavelength range, hence it is hard to deconvolute the curve if one or both are present.Thus, X-ray fluorescence (XRF)  or other analytical techniques are required to identify the TiO2 in the presence of coatings also containing OBAs. That said, essentially all resin coated (RC) photo media contain both TiO2 and OBAs, hence as a class of media, RC photo papers all exhibit the LILIS  media yellowing phenomenon to varying degrees and thus should be considered only moderately "archival" at best, non "archival" at worst.

The media manufacturers could help in a big way to sort these material choices out and provide more media that don't have the LILIS problem, but I'm not sure they would want to willingly share this information, and at this point in time, I'm not sure they even understand the LILIS problem exists....it all takes time. Don't shoot the messenger ;D

cheers,
Mark
http://www.aardenburg-imaging.com
« Last Edit: July 26, 2019, 10:00:41 pm by MHMG »
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mearussi

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #3 on: July 26, 2019, 10:12:50 pm »

Thank you both, I'll have to take a look at them. The only one I've ever used is the Canson Platine so I'll have to compare that to the others.

Does anyone have a favorite?
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BrianWJH

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #4 on: July 26, 2019, 10:13:12 pm »

Here's another one, Felix Schoeller rag silk satin.

Brian.
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MHMG

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #5 on: July 26, 2019, 10:46:55 pm »

Thank you both, I'll have to take a look at them. The only one I've ever used is the Canson Platine so I'll have to compare that to the others.

Does anyone have a favorite?

Photo Rag Pearl. Tests well for longevity with all the current OEM pigment ink sets, and has a unique yet homogeneous (not obviously paper grain-oriented) surface texture I'm very fond of, separate and distinct from other non RC luster/gloss type media. OBA-free with high CIELAB L* max whitepoint and only slightly warm white (CIELAB b* value approximately equal to 2.0 under D50 illuminant). Excellent L* min (Dmax) and low bronzing and differential gloss (as good as it gets without additional spray coatings) when used with current OEM printer manufacturer ink sets.

cheers,
Mark
http://www.aardenburg-imaging.com
« Last Edit: July 26, 2019, 10:54:51 pm by MHMG »
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mearussi

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #6 on: July 27, 2019, 07:15:04 am »

Photo Rag Pearl. Tests well for longevity with all the current OEM pigment ink sets, and has a unique yet homogeneous (not obviously paper grain-oriented) surface texture I'm very fond of, separate and distinct from other non RC luster/gloss type media. OBA-free with high CIELAB L* max whitepoint and only slightly warm white (CIELAB b* value approximately equal to 2.0 under D50 illuminant). Excellent L* min (Dmax) and low bronzing and differential gloss (as good as it gets without additional spray coatings) when used with current OEM printer manufacturer ink sets.

cheers,
Mark
http://www.aardenburg-imaging.com
Sounds like a good paper for me to check out.
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Alan Goldhammer

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #7 on: July 27, 2019, 07:43:29 am »

Though it is a bit on the warm side, I do a lot of printing on Museo Silver Rag.  It has a really good black point.
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deanwork

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #8 on: July 27, 2019, 09:51:27 am »


Yes, by all means Mark’s ( and Ernst’s plots data) are the best references for paper white info. I’ve never read anything by a paper supplier that is at all useful.

Mark, I am a little confused about what pigment whiteners are being used in the Canson Platine and Epson cloned Platine and Breathing Color Lyve media. I thought they used titanium white pigment, similar to what is used in acrylic artists paints. What exactly is Ti02. I know it contains Titanium pigment. How does it differ from what is being used in Platine.

By the way folks, you can ignore Wilhelm’s longevity data as it is listed for rc media full of oba because he has them listed as some of the most permanent of any of the papers made.

John






+1, the first two papers that come to mind for me as well :)  Also, Canson Platine, Red River Palo Duro Soft Gloss, Epson legacy Platine.

There are others as well no doubt. Aardenburg Imaging & Archives needs to start compiling a list. It only takes time and money ;)

Easy to sort OBA-free media with a low cost UV-LED "flashlight". Or refer to the Aardenburg light fade test database or Ernst Dinkla's extensive spectral data sets for modern media at http://www.pigment-print.com/spectralplots/spectrumviz_1.htm for guidance on OBA-free media.  Choosing OBA-free media is thus a straight-forward and enduser-verifiable way to avoid media which exhibit light induced low-intensity staining (LILIS) regardless of any TiO2 content.

If the media is both OBA-free and TiO2-free, then a spectrophotometer like the Xrite i1Pro2 can pick that up by inspecting for fall-off or lack thereof in the 380 to 420 nm range. Both TiO2 and OBAs cause a sharp downturn in the spectral reflectance curve in this wavelength range, hence it is hard to deconvolute the curve if one or both are present.Thus, X-ray fluorescence (XRF)  or other analytical techniques are required to identify the TiO2 in the presence of coatings also containing OBAs. That said, essentially all resin coated (RC) photo media contain both TiO2 and OBAs, hence as a class of media, RC photo papers all exhibit the LILIS  media yellowing phenomenon to varying degrees and thus should be considered only moderately "archival" at best, non "archival" at worst.

The media manufacturers could help in a big way to sort these material choices out and provide more media that don't have the LILIS problem, but I'm not sure they would want to willingly share this information, and at this point in time, I'm not sure they even understand the LILIS problem exists....it all takes time. Don't shoot the messenger ;D

cheers,
Mark
http://www.aardenburg-imaging.com
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Alan Goldhammer

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #9 on: July 27, 2019, 10:33:36 am »


Mark, I am a little confused about what pigment whiteners are being used in the Canson Platine and Epson cloned Platine and Breathing Color Lyve media. I thought they used titanium white pigment, similar to what is used in acrylic artists paints. What exactly is Ti02. I know it contains Titanium pigment. How does it differ from what is being used in Platine.


TiO2 is Titanium Dioxide, a common white pigment used in lots of applications.  It has an excellent white point which is why it's used in lots of commercial paints.  Unfortunately, for our purposes it it is not as inert as once thought to be and can decompose over time with light exposure.  The other commonly used chemical whitener is barium sulfate found in baryta papers.  I have not seen any papers in the scientific literature that point to chemical breakdown issues analogous to titanium dioxide.  Barium sulfate has a long history of use in photography for improving the reflectivity of paper.
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mearussi

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #10 on: July 27, 2019, 11:45:47 am »

TiO2 is Titanium Dioxide, a common white pigment used in lots of applications.  It has an excellent white point which is why it's used in lots of commercial paints.  Unfortunately, for our purposes it it is not as inert as once thought to be and can decompose over time with light exposure.  The other commonly used chemical whitener is barium sulfate found in baryta papers.  I have not seen any papers in the scientific literature that point to chemical breakdown issues analogous to titanium dioxide.  Barium sulfate has a long history of use in photography for improving the reflectivity of paper.
TiO2 acts as a catalysis producing ozone from the NOx in the atmosphere. In a confined space, like the inside of an enclosed picture frame, the ozone builds up and over time will degrade the paper and ink. This is why any paper containing TiO2 cannot be considered archival if it's going to be framed. The effect will be worse if acrylic is used instead of glass since acrylic passes more UV. Conversely the effect can be attenuated if a UV blocking glass or plastic is used. But best yet is just to use a paper without TiO2. 
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Alan Goldhammer

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #11 on: July 27, 2019, 02:24:04 pm »

TiO2 acts as a catalysis producing ozone from the NOx in the atmosphere. In a confined space, like the inside of an enclosed picture frame, the ozone builds up and over time will degrade the paper and ink. This is why any paper containing TiO2 cannot be considered archival if it's going to be framed. The effect will be worse if acrylic is used instead of glass since acrylic passes more UV. Conversely the effect can be attenuated if a UV blocking glass or plastic is used. But best yet is just to use a paper without TiO2.
I think this is a little more complicated.  I just took a look at the paper by the French scientists.  Yes, there is formation of ozone but the paper I'm reading notes that it requires a clear surface of TiO2 for the reaction to take place.  They used glass plates coated with TiO2 and exposed the plate to a synthetic atmosphere.  They used near UV light in one test and sunlight in a second.  It's important to note that TiO2 is the bottom layer in inkjet paper, coating the paper base and the ink receptive surface is on top of that.  I'm unsure what the level of nitrogen oxides are in a typical indoor viewing environment but it may not be high enough to matter much.  In addition, the illumination source may not have enough energy at the surface to make a big difference.  All this being said, there is a risk in using TiO2 coated inkjet paper in terms of print permanence.  As to how much color degradation will take place and over what time period remains to be determined.  If you are concerned about long term stability of inkjet prints it is advisable to avoid such papers.
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deanwork

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #12 on: July 27, 2019, 03:25:00 pm »

I am still unclear as to which kind of whitening agent is used in the Canson Platine and Canson Rag Photographique, or the Breathing Color canvas media? Are they some kind of proprietary formula?

John
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MHMG

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #13 on: July 27, 2019, 03:26:37 pm »

I think this is a little more complicated.  I just took a look at the paper by the French scientists.  Yes, there is formation of ozone but the paper I'm reading notes that it requires a clear surface of TiO2 for the reaction to take place.  They used glass plates coated with TiO2 and exposed the plate to a synthetic atmosphere.  They used near UV light in one test and sunlight in a second.  It's important to note that TiO2 is the bottom layer in inkjet paper, coating the paper base and the ink receptive surface is on top of that.  I'm unsure what the level of nitrogen oxides are in a typical indoor viewing environment but it may not be high enough to matter much.  In addition, the illumination source may not have enough energy at the surface to make a big difference.  All this being said, there is a risk in using TiO2 coated inkjet paper in terms of print permanence.  As to how much color degradation will take place and over what time period remains to be determined.  If you are concerned about long term stability of inkjet prints it is advisable to avoid such papers.

When resin coated photo papers were introduced in the late 1960s-early1970s, notable field failures in the PE/TiO2 layer started to be reported soon thereafter, namely cracking and delamination of the PE layers in prints on display, yellow and reddish micro spots of silver tarnish forming in B&W RC papers, etc. The industry responded by incorporating more anti-oxidants and other chemistry changes in the PE/TiO2 coatings. Research into these issues pointed to the TiO2 as a photo reactive material where the light exposed TiO2 generated free-radicals which in turn created hydrogen peroxides which in turn tarnished the silver particles in B&W RC prints as well as embrittled the PE.  After another decade or so the photographic industry had finally "tamed" these issues, but only to the extent that the color chromogenic dyes in popular RC color photos would fade noticeably before the PE/TiO2 showed cracking, yellowing, and/or delamination. Hence, dye stability rather than RC media deterioration was once again the limiting factor in print longevity during that era.  Also, because the residual color couplers in silver gelatin RC color prints had thermal staining/yellowing issues of their own, and many prints weren't always processed correctly which also contributed to yellowish stain formation, any observed yellowing of the RC paper was always attributed to these mechanisms, not the OBA/TiO2 yellowing connection (LILIS). Hence, it's only in this modern inkjet era where residual color coupler chemistry and/or poor processing has been taken out of the print longevity litany of concerns and high quality pigmented inks can withstand much higher light exposure doses than chromogenic color dyes of the 1 hour photofinishing era, that we are now beginning to rediscover the inherent material limitations of RC media.

kind regards,
Mark
http://www.aardenburg-imaging.com
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Alan Goldhammer

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #14 on: July 27, 2019, 03:55:58 pm »

I am still unclear as to which kind of whitening agent is used in the Canson Platine and Canson Rag Photographique, or the Breathing Color canvas media? Are they some kind of proprietary formula?

John
I have tried both Canson papers.  They do not have any OBAs and the Canson website says that Rag Photgraphique is treated with adding natural minerals to the paper during processing.  It does not say what these are.   Both papers have the same whiteness according to the product sheet.
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MHMG

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #15 on: July 27, 2019, 03:58:14 pm »

I am still unclear as to which kind of whitening agent is used in the Canson Platine and Canson Rag Photographique, or the Breathing Color canvas media? Are they some kind of proprietary formula?

John

Yes, proprietary no doubt which gives certain fine art inkjet media on the market today a very high whitepoint L* value and a near neutral color without resorting to OBAs, but this chemistry also produces a strongly alkaline coating which in turn makes the inkjet receptor coating susceptible to phenolic yellowing... yet another  yellowing issue unrelated to the LILIS yellowing phenomenon (I hope to publish an advisory on phenolic yellowing and how to avoid it in the near future :). More research needed, however).

My XRF evaluation of Platine and several other papers back in 2015 was not extensive enough for me provide you any more insight on the whitening pigments used in Platine other than to say I did confirm these whitening pigments did not incorporate TiO2. That was the "smoking gun" I was looking for in the various papers I tested. Testing required renting access time to a portable XRF at a local conservation lab here in Massachusetts (i.e., the Williamstown Art Conservation Center). Funding has kept me from pursuing this work any further, but again, I was looking for the TiO2 and OBA connection and XRF helped me connect those dots. In fact, I also looked at some of the so-called "Baryta" papers, like Canson Baryta photographique because they showed evidence of the lILIS problem as well in my light fade testing at the time.  Sure enough, a number of the glossy/luster papers sold as "true Baryta" contained some barium sulfate, but, wait for it, they also contain TiO2 hence more evidence that OBAs and TiO2 don't play well together in modern media.

cheers,
Mark
http://www.aardenburg-imaging.com
« Last Edit: July 27, 2019, 04:12:31 pm by MHMG »
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Alan Goldhammer

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #16 on: July 27, 2019, 04:18:25 pm »

Yes, proprietary no doubt which gives certain fine art inkjet media on the market today a very high whitepoint L* value and a near neutral color without resorting to OBAs, but this chemistry also produces a strongly alkaline coating which in turn makes the inkjet receptor coating susceptible to phenolic yellowing... yet another  yellowing issue unrelated to the LILIS yellowing phenomenon (I hope to publish an advisory on phenolic yellowing and how to avoid it in the near future :). More research needed, however).

Wouldn't any phenolic yellowing come from residual lignin in the paper or do the coating materials contain aromatic hydrocarbons that are subject to oxidation? If it is the coating, is there a difference between matte and gloss papers?
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deanwork

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #17 on: July 27, 2019, 04:25:03 pm »

Interesting. So these papers are sensitive to nitrogen dioxide in the environment that causes phenolic yellowing. ND coming from gas heating, air conditioners, ozone auto fumes, chemical floor detergents, certain plastics, etc.

So for them, showing behind glass or plexi is critical, and exhibitions of mounted work with no protection is asking for trouble, especially with the magnetic attractive qualities that inkjet receptor coatings add to the mix.

Rag Photographique and Platine being 100% cotton should have no lignin.





Yes, proprietary no doubt which gives certain fine art inkjet media on the market today a very high whitepoint L* value and a near neutral color without resorting to OBAs, but this chemistry also produces a strongly alkaline coating which in turn makes the inkjet receptor coating susceptible to phenolic yellowing... yet another  yellowing issue unrelated to the LILIS yellowing phenomenon (I hope to publish an advisory on phenolic yellowing and how to avoid it in the near future :). More research needed, however).

My XRF evaluation of Platine and several other papers back in 2015 was not extensive enough for me provide you any more insight on the whitening pigments used in Platine other than to say I did confirm these whitening pigments did not incorporate TiO2. That was the "smoking gun" I was looking for in the various papers I tested. Testing required renting access time to a portable XRF at a local conservation lab here in Massachusetts (i.e., the Williamstown Art Conservation Center). Funding has kept me from pursuing this work any further, but again, I was looking for the TiO2 and OBA connection and XRF helped me connect those dots. In fact, I also looked at some of the so-called "Baryta" papers, like Canson Baryta photographique because they showed evidence of the lILIS problem as well in my light fade testing at the time.  Sure enough, a number of the glossy/luster papers sold as "true Baryta" contained some barium sulfate, but, wait for it, they also contain TiO2 hence more evidence that OBAs and TiO2 don't play well together in modern media.

cheers,
Mark
http://www.aardenburg-imaging.com
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MHMG

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #18 on: July 27, 2019, 04:45:45 pm »

Wouldn't any phenolic yellowing come from residual lignin in the paper or do the coating materials contain aromatic hydrocarbons that are subject to oxidation? If it is the coating, is there a difference between matte and gloss papers?

Traditional photographs have never been observed to exhibit phenolic yellowing AFAIK, but it's a well known issue in the conservation of textiles. The key ingredients are an alkaline environment (garment being washed in an alkaline detergent and not completely rinsed), a phenolic compound like BHT which is often added to plastic (like garment bags used to cover textiles in storage), and NOx. Put these ingredients together and phenolic yellowing will occur. With microporous inkjet coatings, the porosity plus alkalinity of the ink receptor coating is the perfect incubator. The phenol compounds diffuse into the media from sources like adhesives, BHT in plastic bags, some paint fumes, dry mount tissues, etc. NOX arrives via air borne contamination and absorption into the microporous coating. And bright yellow stains can then form, in a matter of only hours or days, but sometimes it take a bit longer. Traditional silver gelatin processes process out as nearly pH neutral, so the alkalinity needed to boost the reaction isn't there. Phenolic yellowing of modern media, as far as I can tell, is a new symptom for photo conservators to wrestle with that has arrived on the scene with microporous inkjet receptor coatings.

Over the years I have seen numerous examples of bright yellow stains appearing under hard-to-document environmental conditions on inkjet prints in the real world, and I didn't understand the cause until recently.  I also couldn't replicate the problem in my lab until recently. Now I can, and that's the first step in truly understanding how it gets caused in the real world. The manufacturers advise customers who have had the problem just to just stick the affected print in sunlight for a few hours, and the yellow will fade back to colorless state (that's largely true, but still an unsettling proposition to the print owner). Anyway, it's time for me to set up some more controlled studies in order to figure out what the range of susceptibility is for the variety of inkjet receptor coatings used in inkjet printing today.

cheers,
Mark
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mearussi

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Re: Are there any 100% cotton glossy/luster papers without TiO2?
« Reply #19 on: July 27, 2019, 06:29:27 pm »

Ouch Mark, I hadn't thought of dry mount tissues as a source of contamination. So what do you use instead to hold the print flat?
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