Vinegar Syndrome: A warning for cel collectors

[sensei]

Yeah, I'm with you BuraddoRun. The issues Matt raises are serious and worth thinking about. It doesn't make sense to try to fix a potential problem with something that causes an immediate problem. Bottom line: cellulose acetate is chemically unstable and prone to spontaneous deterioration. But how quickly? And under what circumstances? There are too many variables to give a clear answer, and so your contact might well have been saying, "We can't guarantee that MicroChamber paper will prevent vinegar syndrome." For vintage Disney and Ghibli cels, the potential liability could be a pretty penny,

Given our present state of knowledge, no archival solution is known to be an ideal fix against this possibility. (Whereas MicroChamber paper does consistently and reliably guard against the yellowing of paper artifacts through age and exposure to the elements.) Professional consensus holds that this precaution can slow down the process before it goes into the acute phase.

Now the question is: can use of MicroChamber paper hurt cels? That's an issue worth shedding some light on. So far as I can see, as it's rated archival for photographic negatives stored directly against the paper, I would think that it would also be safe to place next to animation cels. Disney seems to think so too.

But it would be worth contacting the manufacturer to see what their recommendations are for amateur collectors.

[Rekka Alexiel]

This thread has seriously got me thinking about switching to paper. lol

This is one of those instances where my over-the-top paranoia kicks in, and I'm sniffing every single cel that I have. I've noticed some have a stronger paint scent (like nail polish) but I don't know if that's the same as this vinegar smell. If you say it's a clearly noticeable scent that would even stink up the room where the cels are kept, then maybe everything's okay.

What I have noticed, however, that some of the cels that have a stronger scent seem to be multi-layered and sometimes have this weird iridescent bubbling effect in between layers. For example, on first glance, this effect is clearly visible, but when you separate the layers once and put them back together again, the effect is gone. Is this something totally different from this vinegar syndrome thing or is it related?

I have one cel from Nazca that is heavily effected by this iridescent bubbling...and it has the strongest scent out of everything. I've noticed that a couple other cels near it have also got this same effect but only slightly. I've removed these cels from the rest just in case, but... I still don't know if this has anything to do with vinegar syndrome.

Anyway, I took a couple pictures to demonstrate what exactly it is I'm looking at, and since I wanted the details to be seen, these images are pretty big. And I don't know why these images are all upside down... *sigh*

Here's the first one of the Nazca cel: http://firesanctuary.com/images/cels/iridescent01.jpg
You can see the bubbling effect cover the majority of the surface.

And another from Gulkeeva: http://firesanctuary.com/images/cels/iridescent03.jpg
This one is not nearly as bad as the Nazca one, but it still covers a great majority of the cel and you can really see the funky colors that the bubbling effect has... STRANGE!

Here's a close-up of the funky iridescent bubble on the same Gulkeeva cel: http://firesanctuary.com/images/cels/iridescent02.jpg

And a couple of my own questions that I found some answers to...

And does anyone know where I might be able to find this MicroChamber paper here in Japan?
Would I be able to go into an art supply store have them?

I have not yet found a place that sells these products through a quick search for online stores, but I did come across various Art Care type of pages that at least mentioned MicroChamber paper (in Japanese):

http://www.cxd-japan.com/matboard-2.html
http://www.larson-juhl.co.jp/products/m ... lite2.html
http://www.tokyoconservation.com/art_keeper.html

Any clue what the product might be called?
マイクロチャンバー

[sensei]

I too have seen this Moire effect between layers of cels, but I don't know what it is. My guess is that it is relatively benign, as vinegar syndrome is accompanied by visible deformation and buckling of the acetate sheet.

But it is certainly true that even healthy cels are chemically active. That's shown by the way they damage cel bags, which indicates that they are constantly emitting some kind of fumes that make plastics deform and pucker. So I'd guess that it is a buildup of some vapor that is being given off by both layers of plastic, and which tends to build up in the space between, producing the "rainbow" effect. My inclination would be to slip a strip of MicroChamber paper between the layers, as far as possible without stressing the place where they are stuck together, to pick up this substance and neutralize it.

However, I'm still trying to raise someone at Conservation Resources International, the firm that invented and markets the product. Their website is pretty explicit about stating that the product has been tested successfully on animation cels and that it is safe to use on both paper and photographic (i.e., cellulose acetate based) products. However, Matt's message suggests that at least one of its customer reps was not so confident. I passed on this apparent contradiction in an email to their sales rep. site, but have not as yet received a response. If I don't get one today, I'll try their toll-free number to see if I can raise someone that way. Without having this issue resolved by the manufacturer, I'd say educated caution is prudent.

Their website does not list a direct supply source in Japan. However, you can order it directly from them in quantity, or perhaps get one of the Japanside arts suppliers to do so. Here's the info:

Conservation Resources International, LLC
5532 Port Royal Road
Springfield, Virginia 22151 USA
Office Hours are 9:00 to 5:00 EST

Phone: (800) 634-6932
Phone: (703) 321-7730
Fax: (703) 321-0629
E-mail: sales@conservationresources.com

[But as noted an email sent to the above address has not elicited a response to date...]

[sensei]

I have a reply from Bill Hollinger at Conservation Resources that clarifies some of the issues raised in this thread. It has a long section on the use of MicroChamber paper to preserve paper artifacts, so I don't want to quote it in full. (I'll send an unedited copy to anyone who wants it via PM.) But several parts are worth quoting and commenting on.

Dear Dr. Ellis,
We checked and we do not see a Bags Unlimited in our customer base. MicroChamber is our trademark and it is patented.

[Sensei comments: The product sold by Bags Unlimited is unambiguously the product of Conservation Resources. It bears the firm's watermark with it's name, logo, and patented trade name MicroChamber. But it's likely that they do not do business directly with Bags Unlimited, but sell in bulk to a middleman, who then sells lots to BU. That said, the rest of the letter does express some of the caution that the BU rep. expressed to Matt.]

If acetic acid is the cause of the problem you describe, MicroChamber paper may be worth trying, because the specialized zeolite (SPZ) we developed does remove acetic acid as well as the aldehyde precursor to acetic acid. It may also be plasticizers are a problem too, so as always the wisest thing to do is contact a conservator with experience in this area to see what your preservation options are.

[Sensei comments: That's a little more positive than the report Matt relayed, in that the Conservation Resources people don't think that their product would actively harm cels. In fact, the paper passes the PAT (Photographic Activity Test) so it will not negatively impact the medium (cellulose acetate) on which the cels are painted. However, Hollinger is careful to note that their product will help IF vinegar syndrome is involved. If the damage is caused by some other form of plastic instability, such as a reaction to or with the plasticizer added to the plastic sheet used for the cel, then perhaps some other strategy would be better. In that case it would be better to consult someone who knows more about cels than the Conservation Resources experts.

Hollinger then explains that MicroChamber paper was developed to deal specifically with issues dealing with preservation of paper, which was attacked not only from within by acidic substances added during papermaking, but also from without by environmental pollutants. He concludes:

Microchamber products provide another tool for conservators, like buffered paper and temperature and humidity control. The causes of deterioration are many and varied, and the tools people use to lengthen the useful life of an artifact should not be seen as a guarantee they will prevent further deterioration, but rather as something with the potential to help in this regard.

[Sensei comments: This is the way that I took the statement made to Matt that the company would not consider itself liable if a cel became seriously damaged even when MicroChamber paper was used to protect it. It should be considered as one among several prudent measures in storing such products, and not as a "silver bullet" safeguard.

Hollinger then calls attention to a published interview with Dr. Jim Druzik, senior scientist at the Getty Conservation Institute (which is partnering with Disney to establish clearer procedures for storing cels archivally), in which he states that the material used in MicroChamber products took up acetic acid and retained it more tenaciously than any other material tested, even "during influxes of high humidity." However, Druzik was working with photographs and works of art on paper, not cels. (This is a .pdf file that I can pass on in a PM to anyone who wants it.)

He also recommended that I contact a professional conservator at the National Gallery of Art (which I will do) and also gave links to the Northeast Document Conservation Center and to American Institute for Conservation of Historic and Artistic Works. Probably the GCI–Disney Collaboration would also be worth contacting.

This doesn't get us far, but it at least clarifies the potential role of MicroChamber paper in the archival process. Is it essential? Probably not, if the cels are being stored in controlled conditions and aired out regularly. Will it prevent vinegar syndrome or other serious forms of deterioration? By itself, probably not. But, Hollinger thinks, it would have the beneficial effect of picking up and neutralizing acetic acid both from the cel and also from the outside environment. That in itself won't stop the inevitable process of chemical activity in the cel material, but it wouldn't hurt to use it, and it would have the potential to help prolong its useful life.

I'll need to focus on the cel contest for awhile, but I don't mind if others follow up these leads and report back what they learn.

[BuraddoRun]

I do have another (hopefully) quick question[s], Sensei. I don't want to distract you from the contest (which I need to help with, too), but how do you know if a Microchamber paper had absorbed all it can and needs to be replaced? Does it change color or something?

[sensei]

This may not be very scientific, but I sniff it. It should not smell like anything, but if it too has taken up a definite vinegar smell, then it's probably saturated.

[Rekka Alexiel]

I may still be a bit paranoid about this topic, but what exactly did you mean by this in your original post?

a distinctive “washboard” rippling of the top of the cel around the central registration hole.

I just received a couple new cels and I notice that there are small cracks in the cel around the central registration hole that reach outward from the center. I don't recall ever seeing anything like this before, and oddly enough, a 2nd cel that I received in the same batch from the same series has the same small crack stemming from the center hole. This isn't what you were talking about, right? I've opened the cel bags and took a whiff inside; it does smell, but it's not an over-whelming OMG vinegar smell, I don't think. I hope I'm just being overly paranoid.... :p

[sensei]

What I meant was that the cel no longer lay flat but had shrunk somewhat in the space below the registration holes. That produces a pattern of ripples along the top that looks a little like an old washboard that ripples up and down. This scan shows an example of this:



I don't think what you're describing is related to vinegar syndrome at all. It is what I've seen described as "tap hole cracking" and is just a sign of physical wear during the time the cel went under the camera. Some cels get pulled off the pegs on the light table several times and then put back on (for instance, mouth layers during a long set of dialogue). Eventually the plastic starts to crack, especially around the central (circular) hole. I've commonly seen this part of the cel reinforced with a sticky "band-aid" that the camera crew put on these cracks to keep them from spreading too far.

So far as the odor goes, the sense of all the websites I've visited is that we really know too little about the chemistry involved. That's why the Getty's Conservation Institute is sponsoring some sophisticated lab work to try to grasp this on a molecular level. But in general the sense is that, whatever is being given off should be allowed to vent as freely as possible, without allowing it to build up around the cel. The source I raised at Conservation Resources emphasized, in a follow-up email received since the one summed up below, that cels should never be stored in an enclosed environment.

I'd say a prudent precaution that all archival sources would recommend is to let the cels air out thoroughly in a dark environment, turning them once so both sides can vent any built-up fumes. Then store them loosely with one side of the cel bag slit entirely down one side so fumes can continue to escape gradually.

[ReAnimator]

I can offer my perspective as a collector of vintage films, some of which have sadly succumbed to the dreaded vinegar syndrome.

First off, as others have said, you will have no doubt when you smell this very pungent vinegar scent. Once it has started, it cannot be stopped. It does not necessarily mean a death sentence (at least in the case of vintage film).

I don’t know if they work with cels (but it should) I have used something called A-D strips to either confirm your worst fears, or give you an advanced warning that vinegar syndrome is coming before the smell appears. From personal experience, A-D strips are extremely accurate (the makers won an Oscar in 1997 for inventing them). They are also extremely expensive.

Find them here if you’re interested in more info…

https://www.imagepermanenceinstitute.or ... /ad-strips

Another preventative measure I use with film is available through Kodak called “molecular sieves,” which basically suck the acid out of the air when your film begins releasing corrosive gases. They appear to be effective at slowing the rate at which vinegar syndrome accelerates…

http://motion.kodak.com/motion/Support/ ... ecular.htm

Lastly, as Sensei stated, the single most important way to avoid / treat vinegar syndrome is how the items are stored. Low light, cool temperature, moderate humidity.

In my case, I have several films professionally vaulted at 45 degrees Fahrenheit and 25% relative humidity. Combined with the molecular sieves, I’ve assured my films will outlive me by hundreds of years.

[cutiebunny]

Thanks for the article, ReA. I decided to check out the article as I was interested in buying them.

Until I read this -

Molecular Sieve is water reactive. Material can react with water liberating extreme heat.

This means that if you do live in an environment where there is humidity, you could come home to find your collection on fire due to the sieve's reaction with the moisture. One way to get around that would be to store your collection in airtight containers, but cels need to breathe. Granted, I'm sure the "on fire" reaction probably only occurs if you dump a gallon of water on it, but thinking about the material possibly heating up and that heat reacting with the cel doesn't sound good.

I guess, for now, I'll have to go with the Microchamber paper.

Thanks for the pic of the 'rippling' effect, Sensei. I have a few Toei cels that have this issue, so even though I don't smell anything funky from them yet, I'll separate these problem children from the rest of the campers.

[sensei]

Thanks, ReAnimator. Much of what we know about vinegar syndrome comes from vintage film conservators. It is especially problematic because film is typically stored in airtight cans with the acetate film strips wound around and around the spool in a tight mass that prevents natural fumes from venting. It also shows up in collections of vintage photographic negatives, especially when these are stored together in unventilated containers.

A quick check confirms that Kodak's "Molecular Sieve" technology and Conservation Resources' MicroChamber products use the same chemical neutralizer, a form of zeolite combined with an antacid buffer (typically calcium carbonate). From what I can tell, the "Molecular Sieve" product is a zeolite powder, while MicroChamber products bind the zeolite to a paper or rag board base. Their properties are similar, according to a Library of Congress Preservation Directorate report, with the powdered form being somewhat more effective in taking up acetic acid and retaining it.

However, the LOC report notes that proper ventilation is essential to their effective use. When tested in an airtight environment, the researchers found, "the volatiles emitted by degrading materials interacted with other items immediately adjacent, rather than being neutralized by the sorbent a few inches away" (p. 15). Both forms of zeolite were effective means of absorbing damaging substances, they concluded, "provided that their application is made with an understanding of their limitations" (p. 16).

This report dealt with conservation of paper artifacts, like most studies I've found. So far I've not found sufficient data on conserving cels, which obviously have a less predictable chemical constitution, more so than film. Still, this report suggests that the closer you can get the zeolite or zeolite-charged material to the cel, which is itself the source of the acetic acid and other chemical byproducts, the more effectively it will help increase its lifespan. Also that ventilation is essential to the effective use of zeolites.

[Rekka Alexiel]

Thanks for posting that image, sensei. I think I need to relax a little bit. I've gone through my whole collection and everything seems okay. I may enlist an artist friend of mine to locate some MicroChamber paper just in case... and new pocket sleeved cel bags...

[Sui Kune]

I just went through my Vinegar Syndrome cels and changed out their bags and Microchamber paper, and I'm happy to report that the Microchamber paper does an amazing job of absorbing the fumes. All my cels, even the two most pungent-smelling ones, have a lot less of a noticable vinegar odor than before I began bagging them with the Microchamber paper in front.

Of course, this is hardly long-term or conclusive in any way, but I just thought I'd give a report after 8 months. At the very least it's doing a great job of absorbing the fumes from the cels, which I'm happy with since I imagine it's still better than doing nothing at all.

[Rekka Alexiel]

I'm still having a difficult time finding this paper in Japan. If anybody has a clue where I can find it, please let me know. The art supply store I went to didn't have a clue what I was talking about.

[kathpatty]

Just back from sniffing my cel storage bucket..... No vinegar smell !!

but just ordered more cel bags for annual re-bag session