Celluloids are a class of materials produced by mixing

nitrocellulose Nitrocellulose (also known as cellulose nitrate, flash paper, flash cotton, guncotton, pyroxylin and flash string, depending on form) is a highly flammable compound formed by nitrating cellulose through exposure to a mixture of nitric acid and ...

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 contemporary uses are table tennis balls, musical instruments, combs, office equipment, and guitar picks.

History

Nitrocellulose

Nitrocellulose-based plastics slightly predate celluloid.

Collodion Collodion is a flammable, syrupy solution of nitrocellulose in ether and alcohol. There are two basic types: flexible and non-flexible. The flexible type is often used as a surgical dressing or to hold dressings in place. When painted on the skin, ...

, 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 Birmingham ( ) is a City status in the United Kingdom, city and metropolitan borough in the metropolitan county of West Midlands (county), West Midlands in England. It is the second-largest city in the United Kingdom with a population of 1. ...

, England, by

Alexander Parkes Alexander Parkes (29 December 1813 29 June 1890) was a metallurgist and inventor from Birmingham, England. He created Parkesine, the first man-made plastic. Biography The son of a manufacturer of brass locks, Parkes was apprenticed to Messenge ...

, who was never able to see his invention reach full fruition, after his firm went bankrupt due to scale-up costs. Parkes patented his discovery as Parkesine in 1862 after realising a solid residue remained after evaporation of the solvent from photographic collodion. 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. Parkesine was made from

cellulose Cellulose is an organic compound with the formula , a polysaccharide consisting of a linear chain of several hundred to many thousands of β(1→4) linked D-glucose units. Cellulose is an important structural component of the primary cell w ...

treated with

nitric acid Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available nitri ...

and a

solvent A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for ...

. 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.

John Wesley Hyatt

In the 1860s, an American,

John Wesley Hyatt John Wesley Hyatt (November 28, 1837 – May 10, 1920) was an American inventor. He is mainly known for simplifying the production of celluloid. Hyatt, a Perkin Medal recipient, is included in the National Inventors Hall of Fame. He had nearly ...

, acquired Parkes's patent and began experimenting with cellulose nitrate with the intention of manufacturing

billiard ball A billiard ball is a small, hard ball used in cue sports, such as carom billiards, pool, and snooker. The number, type, diameter, color, and pattern of the balls differ depending upon the specific game being played. Various particular ball p ...

s, which until that time were made from

ivory Ivory is a hard, white material from the tusks (traditionally from elephants) and teeth of animals, that consists mainly of dentine, one of the physical structures of teeth and tusks. The chemical structure of the teeth and tusks of mammals i ...

. He used cloth, ivory dust, and

shellac Shellac () is a resin secreted by the female lac bug on trees in the forests of India and Thailand. It is processed and sold as dry flakes and dissolved in alcohol to make liquid shellac, which is used as a brush-on colorant, food glaze and ...

, 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, Hyatt formed the

Albany Billiard Ball Company The Albany Billiard Ball Company was an American manufacturer of billiard s based in Albany, New York. The company was founded in 1868, manufacturing for over 100 years, before going out of business in 1986. History In the 1860s, John Wesley Hya ...

(1868–1986) in

Albany, New York Albany ( ) is the capital of the U.S. state of New York, also the seat and largest city of Albany County. Albany is on the west bank of the Hudson River, about south of its confluence with the Mohawk River, and about north of New York C ...

, 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. 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 Newark ( , ) is the most populous city in the U.S. state of New Jersey and the seat of Essex County and the second largest city within the New York metropolitan area. 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.

Imitating ivory

The development of celluloid was partially spurred by the desire to reduce reliance on ivory, with itsshortages caused by overhunting. 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) ivory substitute under the names "Ivarine", "Ivaleur", "French Ivory", "Parisian Ivory", "Grained Ivory", "Ivory Pyralin".

Daniel Spill and legal disputes

English inventor

Daniel Spill Daniel Spill (11 February 1832 – 1887) was born in Winterbourne, Gloucestershire, England. He became a rubber and an early thermoplastics manufacturer. For over 20 years Spill had pursued the goal of making a successful business from Alexander Pa ...

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.Daniel Spill, Celluloid Manufacturing Company, United States. Circuit Court (New York : Southern District) ''Spill vs. Celluloid Manufacturing Company litigation documents'' The judge ruled all manufacturing of celluloid could continue both in Spill's British Xylonite Company and Hyatt's' Celluloid Manufacturing Company. Old celluloid film rolls (5201105455)

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

John Carbutt John Carbutt (1832–1905) was a photographic pioneer, stereo card publisher, and photographic entrepreneur. He came to be the first to use celluloid for photographic film and to market dry-plate glass negatives. He was born in Sheffield, Engl ...

founded the

Keystone Dry Plate Works The Keystone Dry Plate and Film Works was founded by John Carbutt in 1879 in Philadelphia, and its 113 Berkley Street location was constructed in Germantown in 1884. The factory became the location for his pioneering work in new photographic tec ...

in 1879 with the intention of producing gelatin dry plates. The Celluloid Manufacturing Company was contracted for this work, which was done by thinly slicing layers out of celluloid blocks and then removing the slice marks with heated pressure plates. After this, the celluloid strips were coated with a photosensitive gelatin emulsion. It is not certain exactly how long it took for Carbutt to standardize his process, but it occurred no later than 1888. A sheet of Carbutt's film was used by William Dickson for the early Edison motion picture experiments on a cylinder drum Kinetograph. However, the celluloid

film base A film base is a transparent substrate which acts as a support medium for the photosensitive emulsion that lies atop it. Despite the numerous layers and coatings associated with the emulsion layer, the base generally accounts for the vast majorit ...

produced by this means was still considered too stiff for the needs of motion-picture photography. By 1889, more flexible celluloids for photographic film were developed, and both

Hannibal Goodwin Hannibal Williston Goodwin (April 21, 1822 – December 31, 1900), patented a method for making transparent, flexible roll film out of nitrocellulose film base, which was used in Thomas Edison's Kinetoscope, an early machine for viewing mot ...

and the

Eastman Kodak Company The Eastman Kodak Company (referred to simply as Kodak ) is an American public company that produces various products related to its historic basis in analogue photography. The company is headquartered in Rochester, New York, and is incorpor ...

obtained patents for a film product. (

Ansco Ansco was the brand name of a photographic company based in Binghamton, New York, which produced photographic films, papers and cameras from the mid-19th century until the 1980s. In the late 1880s, ANSCO's predecessor, Anthony and Scovill, bo ...

, which purchased Goodwin's patent after he died, was eventually successful in a patent-infringement suit against Kodak). This ability to produce photographic images on a flexible material (as opposed to a glass or metal plate) was a crucial step toward making possible the advent of motion pictures.

Uses

Seth Thomas Clock Company mantle clock 1880

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. In these applications it was often referred to as "Ivorine" or "French Ivory", after a form of celluloid developed in France with grain lines in made to resemble

. It was also used for dressing table sets, dolls, picture frames, charms, hat pins, buttons, buckles, stringed instrument parts,

accordions Accordions (from 19th-century German ''Akkordeon'', from ''Akkord''—"musical chord, concord of sounds") are a family of box-shaped musical instruments of the bellows-driven free-reed aerophone type (producing sound as air flows past a reed ...

, fountain pens, cutlery handles and kitchen items. The main disadvantage the material had was that it was flammable. It was soon overtaken by Bakelite and

Catalin Catalin is a brand name for a thermosetting polymer developed and trademarked in 1927 by the American Catalin Corporation of New York City, when the patent on Bakelite expired that year. A phenol formaldehyde resin, it can be worked with files, ...

. Table tennis balls were made from celluloid until 2014. "

Parker Brothers Parker Brothers (known by Parker outside of North America) was an American toy and game manufacturer which in 1991 became a brand of Hasbro. More than 1,800 games were published under the Parker Brothers name since 1883. Among its products wer ...

... made some versions out of hollow Celluloid--which, because of its 'frictionless' properties, spun even faster than steel." 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 called its celluloid clock material "adamantine". 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. Handharmonika

Celluloid was also a popular material in the construction of

slide rules The slide rule is a mechanical analog computer which is used primarily for multiplication and division, and for functions such as exponents, roots, logarithms, and trigonometry. It is not typically designed for addition or subtraction, which ...

. It was primarily used to coat wooden slide rule faces, such as in early A.W. Faber rules, as well as cursor end pieces, such as in Keuffel and Esser rules. 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 A bain-marie (; also known as a water bath or double boiler), a type of heated bath, is a piece of equipment used in science, industry, and cooking to heat materials gently or to keep materials warm over a period of time. A bain-marie is also ...

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

, nitrated to 11%

nitrogen Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...

, 30 parts camphor, 0 to 14 parts dye, 1 to 5 parts

ethyl alcohol Ethanol (abbr. EtOH; also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound. It is an alcohol with the chemical formula . Its formula can be also written as or (an ethyl group linked to a hyd ...

, 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 In organic chemistry, nitration is a general class of chemical processes for the introduction of a nitro group into an organic compound. The term also is applied incorrectly to the different process of forming nitrate esters between alcohols an ...

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."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. . 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, leaving the plastic as brittle nitrocellulose. Also, with exposure to excess heat, the nitrate groups can break off and expose nitrogen gases, such as

nitrous oxide Nitrous oxide (dinitrogen oxide or dinitrogen monoxide), commonly known as laughing gas, nitrous, or nos, is a chemical compound, an oxide of nitrogen with the formula . At room temperature, it is a colourless non-flammable gas, and has ...

and nitric oxide, 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 Ultraviolet (UV) is a form of electromagnetic radiation with wavelength from 10 nm (with a corresponding frequency around 30 PHz) to 400 nm (750 THz), shorter than that of visible light, but longer than X-rays. UV radiation ...

light well. The absorbed light leads to chain-breakage and stiffening. 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.

References

Sources

External links

"Celluloid"
Plastics Historical Society
"History of Plastics"
ociety of the Plastics Industry {{Authority control Cellulose 1870 introductions 1862 establishments in England English inventions Film and video technology Plastic brands Thermoplastics