Print display life expectancy of Cibachrome/Ilfochrome vs RA-4

Photo Engineer said:

... I don't wish to hijack this thread with dye stability material. I do have the data and references, about 1/2 inch of them, sitting next to me right now, and will be glad to quote them for Sal or anyone else. But I want a separate thread started by Sal so that I can do it without interfering with this one. I do this out of respect for their great task and the interest of those following a dedicated thread.

Here are 3 comments though:

1. Predictions are very hard to make, especially if they are about the future! (either Bohr, Berra or Twain - take your pick)
2. Sal, I dug these up just for you - if we do go on and I have to scan in these answers, then you owe me big time... Muahahahahah
3. Starting references: Bugner, Oakland and Willard - IS&T journal.

PE

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OK Ron, here's a new thread. I'll be most interested to see how the Azo-based silver dye-bleach paper fares compared to RA-4 (both Fuji and Kodak) under identical accelerated fading test conditions.

Please forward your invoice to me at 343 State Street, Rochester, New York 14650. Not really, I'm just showing off how that address is burned into my memory.

Sal Santamaura said:

Please forward your invoice to me at 343 State Street, Rochester, New York 14650.
Not really, I'm just showing off how that address is burned into my memory.

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So that proves you were a Postal Service letter carrier in Rochester, right?

Back when I was doing Cibas, the expected life was 100 years.
That was for prints in an office environment with moderate lighting intensity.

- Leigh

Cibachrome uses a dye destruction process while the RA-4 process creates the dyes. In the Ciba process the same commercial dyes used to dye fabrics are used. These are quite stable even to moderate amounts of light. The same cannot be said of the RA-4 process.

Let's start with Arrhenius. His equation states:

Arrhenius' equation gives the dependence of the rate constant of a chemical reaction on the absolute temperature, a pre-exponential factor and other constants of the reaction.

Where

• k is the rate constant
• T is the absolute temperature (in Kelvin)
• A is the pre-exponential factor, a constant for each chemical reaction that defines the rate due to frequency of collisions in the correct orientation
• Ea is the activation energy for the reaction (in Joules)
• R is the universal gas constant

But, he only considers one thing, as causing an influence and that the material behaves!



This is a good example and is a yellow azo dye in a gelatin matrix.



And this is a bad example. It too is an azo dye in a gelatin matrix.

And this is a test of 2 dye coupling products which show 100 years good keeping, but --- wait for it ---- only if Ozone is excluded. If Ozone is present, then stability falls markedly and product "B" becomes a bit better than "A".

Where does this sort of data come from?






Kodak and Fuji offer the most comprehensive - and peer reviewed studies.



WIR offers self published data with no peer review. As noted, spectral distribution is not included, nor is any seasonal data which is included in the Kodak and Fuji publications.

Now, all I can offer on Azo dyes is the fade of some inkjet materials as it seems that, as I said before, Ciba/Ifochrome is a dead product and has not been studied for years. However, I can comment on my previous post citing some yellowing. When Azo dyes are split the -N=N- bond becomes 2 -NH2 bonds on 2 molecules and these can decompose and form yellow materials if not washed out properly. In addition, poor washing can lead to this problem and so faults in the process (mine apparently in this case) can cause problems even with extreme care. It seems that these dye bleach products are very sensitive to yellowing just as old chromogenic prints were.

How is this for a start?

PE

The Arrhenius equation appeared just fine in my post until I made it! Sorry.

Gerald C Koch said:

Cibachrome uses a dye destruction process while the RA-4 process creates the dyes. In the Ciba process the same commercial dyes used to dye fabrics are used. These are quite stable even to moderate amounts of light. The same cannot be said of the RA-4 process.

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You are correct Jerry and that is why additives are placed in the coupler solvent along with selection of chemical structure and other tweaks to make stability such that it is now approaching or exceeding the Ciba/Ilford products. You cannot rest in this world or science catches up with you.

That will come from my ICIS notes of 2006 later on if there is interest.

For one such case see Lestina - USP 3,432,300.

PE

Photo Engineer said:

...How is this for a start?...

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It's a basis for informed speculation; I'm not qualified to do the speculating. To reiterate what I posted in the other thread about Wilhelm's results:

Sal Santamaura said:

...the comparison between Cibachrome/Ilfochrome and Fuji Crystal Archive is made under consistent test conditions. Whether his 'years of display life' figures are completely accurate or not, they do provide a useful relative ranking of the products' light stability...

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Unless someone -- not me -- conducts similar tests on both products at lower illumination levels, I'll have to rely on Wilhelm's ranking, which is consistent with my own experience displaying Cibachrome and Crystal Archive prints side by side in a fluorescent-illuminated office environment for more than a decade. The commercially processed RA-4 samples were not visibly different at the end of that period, while the Ilford samples (processed scrupulously by me) exhibited obvious fading.

Wilhelm offered data with no peer review. Take that as you may. Fuji and Kodak subjected their data to peer review. This is significant if you understand the "science" of publication of technical data.

However, you must understand that there has been a great advance in chromogenic dye stability and it continues to a certain extent. Also, there is little interest in the products you espouse due to the fact that they are obsolete.

OTOH, since you observe obvious fading of Ifochrome samples vs RA4, this should tell you something.

PE

Photo Engineer said:

...there is little interest in the products you espouse due to the fact that they are obsolete...

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My communication skills must be broken today. I don't "espouse" Cibachrome/Ilfochrome at all and never have. Every time this subject comes up, I post only to point out that RA-4, in my opinion, is very superior to Cibachrome/Ilfochrome for prints on display. That opinion was formed from both the published Wilhelm data and personal experience.

In addition to finding the extreme surface gloss of Cibachrome/Ilfochrome aesthetically distasteful, I was always skeptical of claims that it resisted fading on display. That's why I made prints on it and conducted my own uncontrolled, non-scientific, non-peer-reviewed trial next to RA-4 prints. At the end, I was satisfied that there was no reason to put up with the gloss since RA-4 lasted longer in the conditions of importance to me.

Photo Engineer said:

OTOH, since you observe obvious fading of Ifochrome samples vs RA4, this should tell you something.

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I expect that's due to incorrect processing.

I have many Cibachromes made over 30 years ago that are unchanged.

- Leigh

Photo Engineer said:

...OTOH, since you observe obvious fading of Ifochrome samples vs RA4, this should tell you something...

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Leigh B said:

I expect that's due to incorrect processing...

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Nope. Your expectation is not met. See post #7:

Sal Santamaura said:

...the Ilford samples (processed scrupulously by me) exhibited obvious fading.

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I always use fresh chemicals, one-shot, in accordance with the manufacturer's directions. Those Cibachrome/Ilfochrome prints were no exception.

Sal,

Of course you THINK you developed everything per the instructions.

You realize in the absence of independent confirmation that's a circular argument.

Since your results are at variance with my own, and with countless published reports...
There's strong reason to call into question the processing method, display method, or observation.

- Leigh

Leigh B said:

I have many Cibachromes made over 30 years ago that are unchanged.

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I can add to that!

Three metre long mural Ilfochrome Classic prints produced in 1976 by master printers at (now defunct) ChromaColour Pty Ltd in Adelaide/South Australia, were on permanent display in their gallery (Ken Duncan, Peter Lik, Peter Dobre... many others, but these were the heavy-hitters of that time and for decades after), and commercial galleries around Australia since 1976 — that's 40 years, to this date. Illumination in their, and in all of the galleries where prints were consigned to, is per low voltage UV-stabilised halogen lamps additional to ambient room illumination (there are specific lighting specifications given to photographers about this). Much of the framed work is unremarkable in terms of the materials used, but my own prints were always framed with UV-retardant glass (TruVue). Nobody has ever barked about fading Ilfochrome prints because it just has not happened. If it is happening, I very strongly suspect it is a result of processing, not materials!

I have yet to witness any fading or deterioration of these large mural prints (in addition to many others produced to a huge variety of sizes). Dibond or woodb-mounted prints may have an entirely different life expectancy (though most are coated at the finished step), but they are still strikingly beautiful to look at. These are not amateur productions!

I have little interest in controlled environment or lab testing (or Wilhelm's widely discredited and disproven research), as repeated often so far in this thread. My interest is in real world display of the finished product — 'then' (decades ago) and now. I doubt photographers and master printers would go through the trouble and expense of producing an Ilfochrome Class print knowing, if it was true, it was going to catch brown rot in 20 years and be shit-poor to look at. That is a shibolleth. As is a lot of this talk about Ilfochrome not living up to its longevity.

As for RA4 prints, these gems do look superior to Ilfochrome Classic side-by-side, and that's a common statement from viewers and galleries. And their life expectancy? Why the debate? Rather than beat about the bush, enjoy the view! Be happy with the fact that Ilfochrome Classic and RA-4 prints will easily outlive most people here.

Photo Engineer said:

For one such case see Lestina - USP 3,432,300.

PE

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That patent claims improvements in light stability in numerous places such as: When the diffusible-image dyes are mordanted in such receiving sheets containing our stabilizer compounds, they exhibit marked improvement in light stability.
My bold, there is no, as far as I can see, link to any published work substantiating that claim, presumably that is "allowed" in patents?
Not saying of course they don't work but "marked improvement" unqualified is not helpful.

Leigh B said:

...Of course you THINK you developed everything per the instructions.

You realize in the absence of independent confirmation that's a circular argument...

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I don't "THINK" my processing was (and is) scrupulously in compliance with manufacturers' instructions, I know so. It's not an "argument," it's a fact. Attempting to cast aspersions is a deflection. How about addressing the topic rather than changing the subject.

Leigh B said:

...Since your results are at variance with my own, and with countless published reports...
There's strong reason to call into question the processing method, display method, or observation...

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That your results differ could easily be the result of display conditions different than those I described. There's no reason to question my processing method or observations. I've already dismissed your processing aspersion.

Poisson Du Jour said:

...Much of the framed work is unremarkable in terms of the materials used, but my own prints were always framed with UV-retardant glass (TruVue). Nobody has ever barked about fading Ilfochrome prints because it just has not happened. If it is happening, I very strongly suspect it is a result of processing, not materials!...

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It would not be inconsistent with Ron's comments about different illumination levels if Cibachrome/Ilfochrome prints, when framed under UV-absorbing glazing and having illumination intensity/spectra strictly controlled, exhibited longer display life expectancy than those in the trial I performed did. Typical consumers don't hang photographs that way.

People do 'bark' about how their Cibachrome/Ilfochrome prints faded, i.e. failed to live up to the hype, after they've been displayed for some years. However, those who sell and/or re-sell such prints always jump to discredit the 'barkers.' Financial interests seem to trump objectivity.

Again, changing the subject by denigrating my processing doesn't help your case.

Poisson Du Jour said:

...I have little interest in controlled environment or lab testing (or Wilhelm's widely discredited and disproven research), as repeated often so far in this thread. My interest is in real world display of the finished product...

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The specific glazing and illumination conditions you cite are a very controlled environment, one not common in the real world display of prints. Wilhelm's research has been questioned with respect to method, but not "widely discredited and disproven."

Poisson Du Jour said:

...I doubt photographers and master printers would go through the trouble and expense of producing an Ilfochrome Class print knowing, if it was true, it was going to catch brown rot in 20 years and be shit-poor to look at. That is a shibolleth. As is a lot of this talk about Ilfochrome not living up to its longevity...

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It's unclear what "Class" refers to in that quote. Cibachrome/Ilfochrome was, before the digital photography era, marketed as a way to obtain long-lasting prints from transparency originals. The materials and chemistry were used in individuals' darkrooms as well as commercial photo labs.

I've had no issues with Cibachrome/Ilfochrome prints in dark storage. Ron described that problem; if interested, please ask him about it.

Poisson Du Jour said:

......As for RA4 prints, these gems do look superior to Ilfochrome Classic side-by-side, and that's a common statement from viewers and galleries. And their life expectancy? Why the debate?...

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This all started in the Ferrania thread. As a reminder, here's the sequence of posts:

Nzoomed said:

...I get all my film scans printed on Fuji Crystal archive, (RA4) i believe this is the closest thing to cibachrome as far as dye stability goes...

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To which I replied:

Sal Santamaura said:

On display, it's not even close to Cibachrome/Ilfochrome. It's far, far more stable.

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Then others disagreed with me. As always, I persisted in pointing out that Cibachrome/Ilfochrome doesn't live up to its hype about long life on display in typical consumer conditions. Ron asked that the discussion be moved to a separate thread and I complied. So here we are. That's "why the debate."

I never initiate these Cibachrome/Ilfochrome exchanges. They only occur in response to claims (or parroting of such claims) by those who probably have a financial interest in the sale/re-sale of Cibachrome/Ilfochrome prints. In my opinion and experience, RA-4 prints not only look much better than Cibachrome/Ilfochrome prints, they also last longer on display under typical consumer conditions.

Sal, sorry for that poor choice of words. I merely meant that you had some interest in exposing the real information. However, I must agree with you when you compare recent RA4 products with the last version of Ilfochrome regarding stability. Even older versions showed poor dark keeping and these were processed up to standards with good chemistry and good washing. In fact, the purpose was for side-by-side show and tell in KRL of Ciba/Ilfochrome, Ektacolor Plus and Ektaflex which dates the tests. These have been kept in the dark for over 30 years after the few meetings at which they were shown.

As for Lestina, Greg was an organic chemist who came up with the idea of attaching antioxidants (in chemicalese - free radical chain stoppers) to the coupler, or making liquid versions to use as solvent. (USP 3,698,909) This latter work does offer some stability data for those interested, and Ektacolor 30/37 papers in 1970 were the first to use both methods with a new coupler and solvent. Unfortunately, the effort by management cut out the stabilizer to have a 2 step process, and thus got bad cyan fade and pink stain. (proper pH throughout a color process is critical!)

For B&W work, look for work on the RIT web site under IPI (Image Permanence Institute). Some of that work is also quite fascinating.

Now, back to fade... Note the reciprocity above. At different temperatures, fade of dyes is vastly different. These, under other circumstances, are quite similar to those used in printer inks and Ilfochrome, they are azo dyes.



This is an azo dye. During bleaching, all of the N=N bonds are clipped, in this case, 2, and the remains must be washed out. If not, they yellow. Calcium in the water can replace the Na ion and cause a precipitate and eventual yellowing of the residue.

PE

Photo Engineer said:

You are correct Jerry and that is why additives are placed in the coupler solvent along with selection of chemical structure and other tweaks to make stability such that it is now approaching or exceeding the Ciba/Ilford products. You cannot rest in this world or science catches up with you.

That will come from my ICIS notes of 2006 later on if there is interest.

For one such case see Lestina - USP 3,432,300.

PE

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As the Red Queen says to Alice in Through The Looking Glass "... it takes all the running you can do, to keep in the same place. If you want to get somewhere else, you must run at least twice as fast as that!"

OK, this thread is getting interesting.

First thing ill say is we has a family portrait taken in 2002.
I have no idea what type of paper it was printed on, but I expect it was an RA4 type paper, but obviously this predates products such as crystal archive.

I know it has a protective covering over the print, like some sort of plastic, it actually started to bubble off one corner in the first year, but they said it was easy to fix and it appears its just stuck down with some sort of adhesive?
Either way, they fixed it and its never given any trouble.

However, it is starting to show real noticeable signs of fading over the last few years, I would say its probably shifting to cyan if anything.

IDK if they can do a reprint, providing they store the negatives, but im interested to know what sort of paper it is.

Second thing i want to ask is what "methods" the manufacturers use to test their products to make such claims of 100+ years life?

I expect they just put the prints under strong UV lights and/or subject them to high temperatures, but how reliably can you replicate these conditions in such a short space of time?

Subjecting something to high UV for a short space of time cant be the same as low amounts of UV over 100 years for example?

EK uses natural tests in homes all over the world. In addition, they use SANS (Simulated Artificial Nortlight) and a High Intensity fade station. All of these have the spectral distribution tracked at all times. Samples are compared periodically at intervals for fade.

More recently, tracking of and inclusion of Ozone and Sulfur Dioxide are part of the testing.

In addition, samples are heated to 140 F at 70% RH and 90 F 10% RH for wet and dry oven keeping

Dye loss of C/M/Y and neutrals are tracked quantitatively as is any increase in Dmin.

Both Kodak and Fuji watermark their paper on the back. Ilfochrome is on a plastic reflective material. Other manufacturers and many inkjet manufacturers do not watermark their paper.

These short times at high temperatures or intensity are not really indicative in many cases because the Arrhenius equation only considers one variable. See the above graph for reciprocity failure in fading of some inkjet azo dyes.

PE

There are just so many potential variables that I gave up on believing accelerated aging tests a long time ago, including what Wilhelm postulated.
I printed Cibachrome almost from the day go until it became no longer available, along with RA4, and have watched the results under quite a variety
of tests conditions. For example, if I go to my portfolio boxes, Cibachrome prints over thirty years old look like they were made yesterday, while the

... (hit wrong button)... while the ra4 prints are stating to conspicuously yellow. Ciba prints hung in strong INDIRECT mountain sunlight for 25 years
also look almost new. But strong UV from either direct sunlight or halogens takes its toll pretty fast. I know how to window-light-fade them in a week, experimentally, using dreadfully wrong mounting ingredients. The nice thing about Ciba is that all three dyes tend to fade at the same rate, so a bit of fading barely shows, at least up till the point the dyes are seriously stressed and about to tumble of the edge of the cliff, and then a shift in noticeable, generally toward the cyan. Now I'm watching various flavors of Fuji "Crystal Archive" paper. It seems
to be an excellent product but perhaps the marketing contains a bit of wishful thinking. It wouldn't surprise me if a bit of yellowing starts within twenty years. But they're allegedly more light stable than Ciba. Only time will tell. I probably won't be around myself long enough to give an answer.
But anyone who goes around extrapolating that such and such a color media will last for "so-many centuries" is basically a snake oil salesman. It will
be up to people in those years to decide retrospectively, after a true representative track record.

Sal - I've tested just about every alleged UV-inhibiting glazing or treatment that could be thought of. If any of them extend the life of a Cibachrome
more than 5%, I'd be surprised. The secret is to simply avoid UV.

DREW WILEY said:

...The secret is to simply avoid UV.

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I long ago took a different course. After performing my own light fade trial in the conditions of interest to me, I simply avoided Cibachrome/Ilfochrome.

I dont know what our family portrait was printed on 14 years ago, but it is shifting significantly towards the blue spectrum.

A family portrait produced commercially on early canvas has faded so the extensive print retouching displays that lost art to perfection.