Cristallized Celluloid Pens - A Tibaldi Trasparente Ruined

[Kaweco]

Hello Pen Friends

I don`t believe in the suggestion of outbreaking nitric acid. I think the answer is given in Tom`s posting: The celluloid crystallizes! Celluloid is a mixture of collodium (Di nitrocellulose, not "Gun- Cotton, this is Tri Nitrocellulose) and Camphor. These compounds build a liquid, yes, actually celluloid at normal temperatures is a liquid with a very very high viscosity. There are other mixtures with similar structures like sealing wax or window glass, when a high percentage of potashium carbonate is used. The surface tension keeps the form. The fatal damages occur in transparent celluloid only and IIRC transparent celluloid is made by adding alcohol as an additional compound to the mixture (Römpp or Ullmann?). This might generate a quasi- crystalline structure which hardens after the alcohol drove out after years. So it could be a systeme immanent non reversible problem of transparent celluloid.

I found a cigar box containing old pen maker tools. The workers made handcrafted drills and used materials from their working environment like galalith, celluloid or hard rubber. These tools had been kept in the same way at the same temperature and humidity for many decades but only the transparent handles crashed!

http://i844.photobucket.com/albums/ab1/Thomasnr/toolsmisc.jpg

Kind Regards

Thomas

[penboard.de]

Hello Pen Friends

I don`t believe in the suggestion of outbreaking nitric acid. I think the answer is given in Tom`s posting: The celluloid crystallizes! Celluloid is a mixture of collodium (Di nitrocellulose, not "Gun- Cotton, this is Tri Nitrocellulose) and Camphor. These compounds build a liquid, yes, actually celluloid at normal temperatures is a liquid with a very very high viscosity. There are other mixtures with similar structures like sealing wax or window glass, when a high percentage of potashium carbonate is used. The surface tension keeps the form. The fatal damages occur in transparent celluloid only and IIRC transparent celluloid is made by adding alcohol as an additional compound to the mixture (Römpp or Ullmann?). This might generate a quasi- crystalline structure which hardens after the alcohol drove out after years. So it could be a systeme immanent non reversible problem of transparent celluloid.

I found a cigar box containing old pen maker tools. The workers made handcrafted drills and used materials from their working environment like galalith, celluloid or hard rubber. These tools had been kept in the same way at the same temperature and humidity for many decades but only the transparent handles crashed!

http://i844.photobucket.com/albums/ab1/Thomasnr/toolsmisc.jpg

Kind Regards

Thomas

 

HI Thomas,

interesting input about the extra alcohol added to create transparent celluloid.

But well, it definitely is an acid, evaporating in the evironment, and damaging, in case its kept in a closed box.

How else would all the metal parts corrode so heavyly ?

It attacks the pens around the one "infected" as well, the nearer the other pens are, the more damage results.

And I talked to Visconti about the problem, they have analyzed the happenings - with one sure conclusion - its acids doing the damage. and its mostly the transparent parts being attacked.

 

Best regards

Tom

[Vintagepens]

A well-established cause of premature failure of celluloid is when the nitrated cellulose is not thoroughly washed and de-acidified before being plasticized with camphor.

 

But even well-made celluloid can deteriorate eventually -- especially if improperly stored, with transparent material much more vulnerable. And when it deteriorates, it does give off nitric acid -- this is again well-established, and thoroughly documented in the specialist literature. The nitric acid will corrode metals, and will also greatly hasten the deterioration of any other pieces of celluloid exposed.

 

Alcohol is a standard solvent used in celluloid production. It is not specific to transparent celluloid. The greater vulnerability of transparent celluloid would appear to be due to the absence of the stabilizing and UV-screening protections offered by opaque pigments.

[ashbridg]

 

...so how should one define "well ventilated"?

 

Michael

And is more ventilation better? If you take the pens apart they can get air inside the cap and barrel. I store my celluloid pens in an open pen tray on a shelf so they get plenty of air. I do disassemble them before storage. Whether the extra air does any good, I don't know, but it can't hurt.

 

Ashby

[pen2paper]

Great thread.. thanks for the additional photo.

 

Thanks David for weighing in here - you always detail exactingly, where I ramble-on forever.

So then, may I inquire for all here who wish to be good caretakers of their celluloids, and especially their collections of vintage writing instruments, what is your preferred method of storage? Short term, long term?

[Vintagepens]

If I were setting up a pen museum, I'd store celluloid pens uncapped and at refrigerator temperatures, with enough space between pens and in the storage units to allow for air circulation and exchange.

 

For the rest of us, I think most pen cabinets are just fine in allowing for air circulation. Main thing is to isolate any pens that show signs of deterioration, and to make sure pens are thoroughly dry before being put away. High temperatures and high humidity are to be avoided.

[pen2paper]

Appreciate the participation of All here! Thanks!

[Kaweco]

...... And when it deteriorates, it does give off nitric acid -- this is again well-established, and thoroughly documented in the specialist literature. The nitric acid will corrode metals, and will also greatly hasten the deterioration of any other pieces of celluloid exposed.

 

Alcohol is a standard solvent used in celluloid production. It is not specific to transparent celluloid. The greater vulnerability of transparent celluloid would appear to be due to the absence of the stabilizing and UV-screening protections offered by opaque pigments.

Thank you that`s very interesting. Is it possible to post a link from the original literature to enter a scientific discussion? It actually might be that a photolytic reaction through the transparent celluloid at a wavelength under 240 nm splits off an O- atom at the nitroester group. The nitroso- compound is labil and exhausts NO. The NO oxidizes again with air- oxygen and reacts with air humidity to nitric acid. But is the nitric acid terminating the celluloid? Ok, ok, it is an oxydizing and highly corroding agent, but collodium and gun- cotton is MADE with conc nitric acid in common with conc sulphuric acid....

so: treating the fountainpen with lye extracts the acid but it possibly doesn`t prevent from the origins of the damage.

What to do? Keep the fp`s in a dark room? That is not necessary. It would be good to avoid ultraviloett light from sun AND from halogen lamps and quicksilver lamps in showcases. (!) Use normal window glass, it is not transparent for UV.

Is a refrigerator storage necessary? I think not. Photochemic reactiones are thermal forbidden and thermal reactiones are photochemic forbidden.

Point 2. Is anything known about mushroom attac? This is well known in old cameras. Lens combinations had been glued together with natural resins. Some species of mushrooms eating the resin left a spiderweb- like pattern in between the lenses where tey had been crawling through.

Kind Regards

Thomas

[Kaweco]

Hi all

A sudden death of an interesing talk???

Maybe this could help:

http://cool.conservation-us.org/coolaic/jaic/articles/jaic30-02-003.html

Kind Regards

Thömas

[clear1]

Sorry to revive an old topic.

 

I see the celluloids out gas the acid gas. Then, I wonder if it's safe to touch the celluloid pens that started outgassing, or to have them nearby on the table on open air? I heard nitric acid gas is quite harmful to skins and respiratory system. Any advice?

 

But well, it definitely is an acid, evaporating in the evironment, and damaging, in case its kept in a closed box.
How else would all the metal parts corrode so heavyly ?
It attacks the pens around the one "infected" as well, the nearer the other pens are, the more damage results.
And I talked to Visconti about the problem, they have analyzed the happenings - with one sure conclusion - its acids doing the damage. and its mostly the transparent parts being attacked.

[WaskiSquirrel]

Sorry to revive an old topic.

 

I see the celluloids out gas the acid gas. Then, I wonder if it's safe to touch the celluloid pens that started outgassing, or to have them nearby on the table on open air? I heard nitric acid gas is quite harmful to skins and respiratory system. Any advice?

 

 

 

It would be in pretty low concentration with these pens, especially when moved to the open air. The damage you see here is from years of exposure.

[clear1]

 

 

It would be in pretty low concentration with these pens, especially when moved to the open air. The damage you see here is from years of exposure.

 

Hi, thanks for the advise!

 

I got a Stipula celluloid pen, severely corrodes its inner metal parts in a few days when assembled. Even in the open air disassembled, its surface gets a little bit foggy in a day. It seems to be outgassing constantly, even though it may be small amount. I've placed it on my room's book shelf, but I'm afraid it may be bad. I love that pen, but this nitric acid seems pretty dangerous. So I'm worried.

[Seney724]

By far the greatest risk, given what you have described, is to any other celluloid pens in the room. Best if there are none.

 

What are the conditions like in the room where you are keeping this pen??

• Cool, dry, well ventilated rooms are the best conditions for celluloid pens.
• Warm, humid, poorly ventilated rooms are the worst.
• And, in either case, no exposure to direct sunlight for long periods of time each day.

 

If it is a well ventilated room, I do not think there is any significant risk to you.

If it is a small, enclosed space with poor ventilation and where you spend a lot of time, it might be..........