A celluloid question

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kenb
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A celluloid question

Postby kenb » Fri Aug 10, 2018 12:44 am

I know all about the pitfalls of celluloid and am experiencing some problems right now with a celluloid knife. What I wanted was thoughts on newer modern celluloid handled knives. I know that no one has a crystal ball and can look into the future, so this question could be answered with just opinions, and I understand this. I have an opportunity to purchase a Case Christmas Tree Cheetah (celluloid), and a Case Gold Sparkle Cheetah (Is it celluloid?). I'm really attracted to the Christmas tree knife. It's celluloid, but modern celluloid. Does anyone know if this material has been made more stable in our modern era, or is it still the same old miserable stuff. The gold sparkle knife looks to be celluloid as well, but I don't know this for sure. I'm really on the fence with this purchase. I have some pretty old celluloid knives that are still in great shape and a few that are bad and one that is only about 20 years old that is deteriorating. I rarely sell knives, I keep them, so it would be a knife that would be in my collection for years to come. I was just looking for some insight before I make my decision. I haven't purchased a celluloid knife in quite a few years because of their reputation, I usually pass over them. What are your thoughts. Thanks.

Ken

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Mumbleypeg
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Re: A celluloid question

Postby Mumbleypeg » Fri Aug 10, 2018 1:04 am

Since no one seems to know what triggers celluloid to self-destruct, or what causes it, I have to doubt that the material is more stable now. ::shrug:: Anecdotal evidence would say it's not - for example the German Bulldogs with celluloid handles, and the Case Classics (all but a few of which were actually made by Queen, to Parker's specifications).

Case goldstone is celluloid, and fairly well known for outgassing. Is gold sparkle something different? Christmas tree and candy stripe seems to be some of the more stable stuff. YMMV. And that's why I don't buy anything celluloid unless it's inexpensive - you could wake up one day and find your money has gone up in gas. ::facepalm:: With celluloid you never know.

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Quick Steel
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Re: A celluloid question

Postby Quick Steel » Fri Aug 10, 2018 1:06 am

Ken that is a very good question that I also have been kicking around for a while. I've been staying away from celluloid for the obvious reasons. You might check with Case and ask if they are still using celluloid or are the covers possibly acrylic now.

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Re: A celluloid question

Postby Gunsil » Fri Aug 10, 2018 1:06 am

I don't know about the ones lately made by Case, but the failure rate of the celluloid used in the "Case Classic" knives seems to be way higher than that of antique celluloid knives.

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Dinadan
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Re: A celluloid question

Postby Dinadan » Fri Aug 10, 2018 2:06 am

This discussion kind of makes me wonder why anyone still uses celluloid. I have only a few celluloid knives. Only one is outgassing (a Bulldog) and it is the newest celluloid knife that I own. I have not clue about the answer to Ken's question, but I will not spend a lot on a celluloid knife. On the other hand, if I like it and the price is right, I will buy it and take my chances.
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Re: A celluloid question

Postby edge213 » Fri Aug 10, 2018 3:16 am

Not sure what you mean by new.
The Case candy stripe from the early 2000s can outgas. Although the ones I have , have not gassed yet.
Case " goldstone" does outgas.
The new gold sparkle is kirinite, it does not out gas.
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TwoFlowersLuggage
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Re: A celluloid question

Postby TwoFlowersLuggage » Fri Aug 10, 2018 3:50 am

I'm absolutely with you on not understanding why any knife mfr would bother using celluloid. There are a zillion different synthetic materials, and many that could mimic all the cosmetics of celluloid without the problems.
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tongueriver
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Re: A celluloid question

Postby tongueriver » Fri Aug 10, 2018 1:46 pm

I had no idea that anyone was still using celluloid. I knew that some German knives were using it far more recently than logic would dictate, but CASE? :shock:

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XX Case XX
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Re: A celluloid question

Postby XX Case XX » Fri Aug 10, 2018 1:59 pm

When it comes to buying a knife made with celluloid, old or new, there's only one way to look at it:

"Place your Bet & Roll the Dice". It's literally that simple.

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Re: A celluloid question

Postby espn77 » Fri Aug 10, 2018 3:08 pm

I think I have close to 200, 1920-40 Remington celluloid knives and I've only seen one that was gassing. It was purchased in a large group and I don't own it any more. Not saying they couldn't start at anytime but the way I store my knives it doesn't bother me to own the old ones.

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Re: A celluloid question

Postby Mumbleypeg » Fri Aug 10, 2018 4:18 pm

tongueriver wrote:I had no idea that anyone was still using celluloid. I knew that some German knives were using it far more recently than logic would dictate, but CASE? :shock:

I'm not aware of any celluloid production from Case in the past 30 or so years but I could be wrong. Some Case Classics had celluloid covers but as has been discussed here in other threads those were made by Queen as one of Jim Parker's many (sometimes controversial) marketing schemes when he owned Case.

To my knowledge more recent Case synthetics have used acrylic, G10 and perhaps other modern materials. If I'm wrong I'm sure someone will correct me. :lol:

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Re: A celluloid question

Postby Sanders Knives » Fri Aug 10, 2018 9:32 pm

Journal American Institute for Conservation: Celluloid Degredation

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From the article: Page 1

.1 INTRODUCTION
ONCE A celluloid object has been fabricated, it becomes subject to the chemical, physical, and biological forces of its environment. The visual appearance of deteriorated celluloid varies. Celluloid that has been protected from undesirable environmental conditions will deteriorate according to the mechanisms inherent in its own structure. The cellulose nitrate molecules continue to crystallize around the loci created by the pressures used in manufacture. Camphor molecules are squeezed out, often to the surface where they will sublime at room temperature. This sequence of events leaves celluloid very brittle, cracked, shrunken, warped, collapsed, crumbling, discolored, and crystallized. Celluloid that has been exposed to undesirable environmental conditions is apt to be even more discolored, warped, swollen, softened, mushy, and coated with droplets or a film of nitrate salts and their acids.

When celluloid objects are fabricated with other materials such as metals, glass, textiles, and paper the problems of degradation are compounded. The deterioration products of celluloid are often corrosive (nitric acid) and react readily with other materials in proximity.

As mentioned, celluloid's inherent degradation or aging process involves the recrystallization of cellulose nitrate molecules and the expulsion and sublimation of camphor. Environmental conditions generally alter this process by enhancing degradation of the cellulose nitrate molecules. Degradation through thermal, chemical, photochemical, and physical means generally leads to lower viscosities and softer rather than more brittle celluloid. Conservators must find the balance between these two processes if celluloid objects are to be preserved.



3.2 FORCES OF DEGRADATION
Celluloid deteriorates as a result of four degradation processes: thermal, chemical, photochemical, and physical.



3.2.1 Thermal Degradation
Thermal degradation of celluloid involves the breaking off of nitrate groups in the cellulose nitrate molecule. As a result, nitrous gases are evolved. The following reaction equation shows the probable mechanism whereby the weak -O-NO2 bonds are broken, leaving NO2 gas, aldehydes, and alcohols.



Fig. .

Selwitz indicates that nitrogen-oxygen bond cleavage takes place at temperatures above 100°C and when the molecule is exposed to visible and long-wave ultraviolet light (Selwitz 1988, 25).



3.2.2 Chemical Degradation
Chemical degradation can result from acid or alkaline hydrolysis. Acid hydrolysis involves the fission of glucosidic links in the cellulose nitrate molecule. With cellulose nitrate, this reaction is very slow and results in the reduction of the average molecular chain length of the cellulose nitrate molecule (Miles 1955, 268). Acids may be present as a result of synthesis, manufacture, or environmental conditions.

Chemical breakdown of the cellulose nitrate molecule by alkalis is more rapid than that by acids—often called denitration—the following reactions show the results of alkaline degradation (after Miles 1955, 286).






Alkalis may also be present from synthesis, manufacture, and environment.

Alkaline hydrolysis produces a wide variety of low molecular weight oxidized compounds. Inorganic nitrates, ammonia, cyanides, carbon dioxide, oxalic acid, maleic acid, glycolic acid, and malonic acid have all been recorded as deterioration products (<a href="http://cool.conserva...ml#bib11">Miles 1955, 278). Basic pigments added to cellulose nitrate lacquers were found to increase the rate of deterioration through nitrate loss in accelerated aging (Hercules 1955, 44–48). Acids may have been added to mixtures to neutralize alkaline pigments such as bone black, oil black, and nigrosine (Hercules 1955, 44–48).

Aside from acid and alkaline hydrolysis, some metallic oxides are known to cause irreversible gelation of cellulose nitrate in solution (Chao 1934, 99–102). Lacquers, glues, and badly deteriorated celluloid can be irreversibly gelled by oxides of lead, calcium, arsenic, tin, iron, copper, and zinc (in order of decreasing effect). Many lacquers contain tartaric, citric, or maleic acid as a gel inhibitor. Early tubes for cellulose nitrate adhesives were made of lead, which gelled the adhesive so that it would not set. This discovery led to the knowledge that certain metallic oxides could gel cellulose nitrate (Miles 1955, 291–92).

Selwitz points out that due to its structure the cellulose nitrate molecule is highly polar. This “extraordinarily high nonionic polarity” is also a contributing factor to the high instability of celluloid plastics (Selwitz 1988, 2).



3.2.3 Photochemical Deterioration
Photochemical deterioration is relatively severe in celluloid due to the ability of the molecule to absorb strongly in certain wavelength ranges. The far ultraviolet is readily absorbed by celluloid. The maximum and complete absorbance occurs at around 2536 cm−1 (Miles 1955, 287). Different wavelengths of light have been found to deteriorate celluloid by reducing the viscosity and/or chain length of the molecules (Miles 1955, 291). The results of strong absorption can be seen as yellowing, embrittlement, and softening. One interesting breakdown mechanism apparently involves the disintegration of the nitrated glucoside ring structure by exposure to far-ultraviolet radiation (Selwitz 1988, 25).



3.2.4 Physical Degradation
Physical degradation of celluloid can be caused by thermal, chemical, and photochemical deterioration, loss of volatile constituents like camphor, and external physical stresses from fabrication or housings. Many objects appear to collapse on themselves as a result of the entrapment of harmful deterioration products in their interiors. The trapped gases accelerate deterioration in the immediate area and essentially consume the inside of the objects (Sirkis 1982).

The thermal, chemical, photochemical, and physical breakdown of celluloid constitutes a set of highly interrelated decomposition reactions and mechanisms. Light, alkalis, acids, and certain metallic oxides can be very detrimental. The primary environmental contributor to celluloid degradation, however, appears to be moisture. Water is required for most of the aforementioned reactions. Water also has the potential to create physical stresses due to the isotropic nature of celluloid and its capacity for water absorption. Worden discusses a close relationship between nitrate content and absorption of water by cellulose nitrate (Worden 1911, 2:974). As the nitrate content drops (i.e., in degradation) cellulose nitrate can absorb more moisture from the atmosphere, increasing the rate of many water-dependent reactions (also see Miles 1955, 158–59) (Hercules, 1955, 36). This characteristic indicates that celluloid plastics may be more sensitive to moisture than are other more highly nitrated cellulose nitrate materials.

Sanders Knives
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Re: A celluloid question

Postby Sanders Knives » Fri Aug 10, 2018 9:33 pm

In summary:

The thermal, chemical, photochemical, and physical breakdown of celluloid constitutes a set of highly interrelated decomposition reactions and mechanisms. Light, alkalis, acids, and certain metallic oxides can be very detrimental. The primary environmental contributor to celluloid degradation, however, appears to be moisture. Water is required for most of the aforementioned reactions. Water also has the potential to create physical stresses due to the isotropic nature of celluloid and its capacity for water absorption. Worden discusses a close relationship between nitrate content and absorption of water by cellulose nitrate (Worden 1911, 2:974). As the nitrate content drops (i.e., in degradation) cellulose nitrate can absorb more moisture from the atmosphere, increasing the rate of many water-dependent reactions (also see Miles 1955, 158–59) (Hercules, 1955, 36). This characteristic indicates that celluloid plastics may be more sensitive to moisture than are other more highly nitrated cellulose nitrate materials.

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TwoFlowersLuggage
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Re: A celluloid question

Postby TwoFlowersLuggage » Fri Aug 10, 2018 9:56 pm

Hmm, so it sounds like putting some desiccant with the celluloid knife, in a well-sealed bag, inside a box away from the light, might be a good idea.
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Re: A celluloid question

Postby Jacknifeben » Fri Aug 10, 2018 10:31 pm

I have owned the knives for over 30 years no problems. Enjoy them just about every time things are not going right.
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