Celluloid
Celluloids are a class of materials produced by mixing nitrocellulose and camphor, often with added dyes and other agents. Once much more common for its use as photographic film before the advent of safer methods, celluloid's common present-day uses are for manufacturing table tennis balls, musical instruments, combs, office equipment, fountain pen bodies, and guitar picks.[1][2]
History
Nitrocellulose
Nitrocellulose-based plastics slightly predate celluloid. Collodion, invented in 1848 and used as a wound dressing and an emulsion for photographic plates, is dried to a celluloid like film.
Alexander Parkes
The first celluloid as a bulk material for forming objects was made in 1855 in Birmingham, England, by Alexander Parkes, who was never able to see his invention reach full fruition, after his firm went bankrupt due to scale-up costs.[3] Parkes patented his discovery as Parkesine in 1862 after realising a solid residue remained after evaporation of the solvent from photographic collodion.[4]
Parkes patented it as a clothing waterproofer for woven fabrics in the same year. Later Parkes showcased Parkesine at the 1862 International Exhibition in London, where he was awarded a bronze medal for his efforts. The introduction of Parkesine is generally regarded as the birth of the plastics industry.[3] Parkesine was made from cellulose treated with nitric acid and a solvent. The Parkesine company ceased trading in 1868. Pictures of Parkesine are held by the Plastics Historical Society of London. There is a plaque on the wall of the site of the Parkesine Works in Hackney, London.[5]
John Wesley Hyatt
In the 1860s, an American, John Wesley Hyatt, acquired Parkes's patent and began experimenting with cellulose nitrate with the intention of manufacturing billiard balls, which until that time were made from ivory. He used cloth, ivory dust, and shellac, and on April 6, 1869, patented a method of covering billiard balls with the addition of collodion. With assistance from Peter Kinnear and other investors,[6] Hyatt formed the Albany Billiard Ball Company (1868–1986) in Albany, New York, to manufacture the product. In 1870, John and his brother Isaiah patented a process of making a "horn-like material" with the inclusion of cellulose nitrate and camphor.[7] Alexander Parkes and Daniel Spill (see below) listed camphor during their earlier experiments, calling the resultant mix "xylonite", but it was the Hyatt brothers who recognized the value of camphor and its use as a plasticizer for cellulose nitrate. They used heat and pressure to simplify the manufacture of these compounds. Isaiah Hyatt dubbed the material "celluloid" in 1872. The Hyatts later moved their company, now called the Celluloid Manufacturing Company, to Newark, New Jersey.
Over the years, celluloid became the common use term used for this type of plastic. In 1878 Hyatt was able to patent a process for injection moulding thermoplastics, although it took another fifty years before it could be realized commercially, and in later years celluloid was used as the base for photographic film.[8]
Imitating ivory
The development of celluloid was partially spurred by the desire to reduce reliance on ivory, with its shortages caused by overhunting.[9] An 1883 invention allowed celluloid manufacturers to imitate the distinctive graining of ivory, and by the end of 19th century celluloid was marketed as a lighter (and three times cheaper[10]) ivory substitute under the names "Ivarine", "Ivaleur", "French Ivory", "Parisian Ivory", "Grained Ivory", and "Ivory Pyralin".[11]
Daniel Spill and legal disputes
English inventor Daniel Spill had worked with Parkes and formed the Xylonite Co. to take over Parkes' patents, describing the new plastic products as Xylonite. He took exception to the Hyatts' claims and pursued the brothers in a number of court cases between 1877 and 1884. Initially the judge found in Spill's favor, but ultimately it was judged that neither party held an exclusive claim and the true inventor of celluloid/xylonite was Alexander Parkes, due to his mention of camphor in his earlier experiments and patents.[12] The judge ruled all manufacturing of celluloid could continue both in Spill's British Xylonite Company and Hyatt's' Celluloid Manufacturing Company.
The main use was in movie and photography film industries, which used only celluloid film stock prior to the adoption of acetate safety film in the 1950s. Celluloid is highly flammable, difficult and expensive to produce and no longer widely used.
Photography
English photographer
By 1889, more flexible celluloids for
Uses
Most movie and photography films prior to the widespread move to acetate films in the 1950s were made of celluloid. Its high flammability was legendary since it self-ignites when exposed to temperatures over 150 °C in front of a hot movie-projector beam. While celluloid film was standard for 35mm theatrical productions until around 1950, motion-picture film for amateur use, such as 16mm and 8mm film, were on acetate "safety base", at least in the US.
Celluloid was useful for producing cheaper jewellery, jewellery boxes, hair accessories and many items that would earlier have been manufactured from ivory, horn or other expensive animal products.
Shelf clocks and other furniture items were often covered with celluloid in a manner similar to veneer. This celluloid was printed to look like expensive woods, or materials like marble or granite. The Seth Thomas clock company bought rights for its use as a durable coating from Celluloid Manufacturing Company in September, 1880 and marketed it as, "Adamantine".[16] Celluloid enabled clockmakers to make the typical late Victorian style of black mantel clock in such a way that the wooden case appeared to be black marble, and the various pillars and other decorative elements of the case looked like semi-precious stone.[17]
Celluloid was also a popular material in the construction of
Celluloid remains in use for musical instruments, especially accordions and guitars. Celluloid is very robust and easy to mold in difficult forms, and has great acoustic performance as cover for wooden frames since it does not block wood's natural pores. Instruments covered with celluloid can easily be recognized by the material's typical nacre-like flaming pattern. Thick celluloid panels are cooked in a bain-marie which turns them into a leather-like substance. Panels are then turned on a mold and allowed to harden for as long as three months.
Formulation
A typical formulation of celluloid might contain 70 to 80 parts nitrocellulose, nitrated to 11% nitrogen, 30 parts camphor, 0 to 14 parts dye, 1 to 5 parts ethyl alcohol, plus stabilizers and other agents to increase stability and reduce flammability.
Production
Celluloid is made from a mixture of chemicals such as nitrocellulose, camphor, alcohol, as well as colorants and fillers depending on the desired product. The first step is transforming raw cellulose into nitrocellulose by conducting a nitration reaction. This is achieved by exposing the cellulose fibers to an aqueous solution of nitric acid; the hydroxyl groups (-OH) will then be replaced with nitrate groups (-ONO2) on the cellulose chain. The reaction can produce mixed products, depending on the degree of substitution of nitrogen, or the percent nitrogen content on each cellulose molecule; cellulose nitrate has 2.8 molecule of nitrogen per molecule of cellulose. It was determined that sulfuric acid was to be used as well in the reaction in order to first, catalyze the nitric acid groups so it can allow for the substitution onto the cellulose, and second, allow for the groups to easily and uniformly attach to the fibers, creating a better quality nitrocellulose. The product then must be rinsed to wash away any free acids that did not react with the fibers, dried, and kneaded. During this time, a solution of 50% camphor in alcohol is added, which then changes the macromolecule structure of nitrocellulose into a homogeneous gel of nitrocellulose and camphor. The chemical structure is not well understood, but it is determined that it is one molecule of camphor for each unit of glucose. After the mixing, the mass is pressed into blocks at a high pressure and then is fabricated for its specific use.[18]
Nitrating cellulose is an extremely flammable process in which even factory explosions are not uncommon. Many western celluloid factories closed after hazardous explosions, and only two factories in China remain in business.
Environmental hazards
Deterioration
Many sources of deterioration in celluloid exist, such as thermal, chemical, photochemical, and physical. The most inherent flaw is as celluloid ages, the camphor molecules are ‘squeezed’ out of the mass due to the unsustainable pressure used in the production. That pressure causes the nitrocellulose molecules to bind back to each other or crystallize, and this results in the camphor molecules being shoved out of the material. Once exposed to the environment, camphor can undergo sublimation at room temperature, and the plastic reverts to brittle nitrocellulose. Also, with exposure to excess heat, the nitrate groups can break off and expose nitrogen gases, such as nitrous oxide and nitric oxide,[19] to the air.
Another factor that can cause this is excess moisture, which can accelerate deterioration of nitrocellulose with the presence of nitrate groups, either newly fragmented from heat or still trapped as a free acid from production. Both of these sources allow the accumulation of nitric acid. Another form of deterioration, photochemical deterioration, is severe in celluloid because it absorbs ultraviolet light well. The absorbed light leads to chain-breakage and stiffening.[18]
Among collectors of antiques, the deterioration of celluloid is generally known as "celluloid rot." The chemical processes involved are not perfectly understood, but it is widely believed that the gases released by a piece undergoing celluloid rot can trigger celluloid rot in nearby articles of celluloid which were previously intact.[20]
See also
References
- ^ ISBN 978-3527306732.
- ^ Andrea Picks: The Saga of Cellulose Archived January 24, 2010, at the Wayback Machine
- ^ ISBN 9781932078756.
- ^ UK Patent office (1857). Patents for inventions. UK Patent office. p. 255.
- ^ "Hackney Council - First Plastic in the World". hackney.gov.uk. 2012. Archived from the original on 4 March 2016. Retrieved 9 January 2012.
- ^ Bassett, Fred, ed. (2009). "Albany Billiard Ball Company Records, 1894-1944; Bulk 1915-1944". NYSL.NYSED.gov. Albany, NY, US: New York State Library, NYS Education Dept. "Manuscripts and Special Collections" section. Archived from the original on January 5, 2013. Retrieved January 5, 2013.
- ^ "US patent #105,338 issued July 12, 1870". Retrieved 2014-05-07.
- ^ "Plastics Historical Society". Plastiquarian.com. Retrieved 2014-05-07.
- ^ Beaujot 2012, p. 147.
- ^ Beaujot 2012, p. 149.
- ^ Beaujot 2012, p. 148.
- ^ Daniel Spill, Celluloid Manufacturing Company, United States. Circuit Court (New York : Southern District) Spill vs. Celluloid Manufacturing Company litigation documents
- ^ "John Carbutt at Historic Camera - History Librarium". historiccamera.com.
- ISBN 1850766134.
- ISBN 9781591392699.
- ^ <https://clockhistory.com/sethThomas/products/adamantine/index.html>.
- ISBN 0-9647406-0-5.
- ^ a b "JAIC 1991, Volume 30, Number 2, Article 3 (pp. 145 to 162)." JAIC 1991, Volume 30, Number 2, Article 3 (pp. 145 to 162). Web. 18 Nov. 2014. <http://cool.conservation-us.org/jaic/articles/jaic30-02-003_3.html>.
- ^ Springate, Megan E. (1997) "Cellulose Nitrate Plastic (Celluloid) in Archaeological Assemblages: Identification and Care,"Northeast Historical Archaeology: Vol. 26 26: Iss. 1, Article 5.
- ^ "Ask the Expert: All About Celluloid Rot—and What to do About It | Acoustic Guitar". 9 September 2021.
Sources
- Beaujot, Ariel (2012), ""The Real Thing": The Celluloid Vanity Set and the Search for Authenticity", Victorian Fashion Accessories, Bloomsbury Publishing Plc, pp. 139–178, ISBN 9781472504517