Celluloid

Last updated

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]

Contents

History

Celluloid and sterling silver pen. Arco pen.jpg
Celluloid and sterling silver pen.

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.

Newark, New Jersey, industrial production complex of the Celluloid Company (c. 1890) US-NJ(1891) p568 NEWARK, THE CELLULOID COMPANY.jpg
Newark, New Jersey, industrial production complex of the Celluloid Company (c. 1890)

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]

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.

Old celluloid film rolls Old celluloid film rolls (5201105455).jpg
Old celluloid film rolls

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 founded the Keystone Dry Plate Works in 1879 with the intention of producing gelatin dry plates. [13] 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 15-inch-wide (380 mm) 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 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 and the Eastman Kodak Company obtained patents for a film product. (Ansco, 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

An antique celluloid doll Bebe celluloid.jpg
An antique celluloid doll
Table tennis balls 40mm table tennis ball Celluloid.jpg
Table tennis balls
A Seth Thomas black mantel clock, a typical late 19th century American style. The "serpentine" and "stone" of the pillars are made of celluloid glued to wood. Seth Thomas Clock Company mantle clock 1880.jpg
A Seth Thomas black mantel clock, a typical late 19th century American style. The "serpentine" and "stone" of the pillars are made of celluloid glued to wood.
Assorted tortoiseshell celluloid guitar picks. Celluloid Picks.jpg
Assorted tortoiseshell celluloid guitar picks.

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.

A late Soviet roly-poly doll from celluloid Nevaliashka.jpg
A late Soviet roly-poly doll from celluloid

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. [1] 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 ivory. [14] It was also used for dressing table sets, dolls, picture frames, charms, hat pins, buttons, buckles, stringed instrument parts, accordions, 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. Soviet roly-poly dolls were made from celluloid on smokeless powder plants until 1996, and table tennis balls – until 2014. "Parker Brothers... made some versions [of diabolos ] out of hollow Celluloid--which, because of its 'frictionless' properties, spun even faster than steel." [15]

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]

Flaming celluloid pattern on an accordion. Handharmonika.jpg
Flaming celluloid pattern on an accordion.

Celluloid was also a popular material in the construction of slide rules. 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 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

A fungus-damaged photographic slide A Fungi damaged photographic slide.tif
A fungus-damaged photographic slide

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

Related Research Articles

<span class="mw-page-title-main">Cellulose</span> Polymer of glucose and structural component of cell wall of plants and green algae

Cellulose is an organic compound with the formula (C
6H
10O
5)
n, 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 wall of green plants, many forms of algae and the oomycetes. Some species of bacteria secrete it to form biofilms. Cellulose is the most abundant organic polymer on Earth. The cellulose content of cotton fibre is 90%, that of wood is 40–50%, and that of dried hemp is approximately 57%.

<span class="mw-page-title-main">Explosive</span> Substance that can explode

An explosive is a reactive substance that contains a great amount of potential energy that can produce an explosion if released suddenly, usually accompanied by the production of light, heat, sound, and pressure. An explosive charge is a measured quantity of explosive material, which may either be composed solely of one ingredient or be a mixture containing at least two substances.

<span class="mw-page-title-main">Film stock</span> Medium used for recording motion pictures

Film stock is an analog medium that is used for recording motion pictures or animation. It is recorded on by a movie camera, developed, edited, and projected onto a screen using a movie projector. It is a strip or sheet of transparent plastic film base coated on one side with a gelatin emulsion containing microscopically small light-sensitive silver halide crystals. The sizes and other characteristics of the crystals determine the sensitivity, contrast and resolution of the film. The emulsion will gradually darken if left exposed to light, but the process is too slow and incomplete to be of any practical use. Instead, a very short exposure to the image formed by a camera lens is used to produce only a very slight chemical change, proportional to the amount of light absorbed by each crystal. This creates an invisible latent image in the emulsion, which can be chemically developed into a visible photograph. In addition to visible light, all films are sensitive to X-rays and high-energy particles. Most are at least slightly sensitive to invisible ultraviolet (UV) light. Some special-purpose films are sensitive into the infrared (IR) region of the spectrum.

<span class="mw-page-title-main">Cordite</span> Smokeless propellant, used to replace gunpowder

Cordite is a family of smokeless propellants developed and produced in Britain since 1889 to replace black powder as a military firearm propellant. Like modern gunpowder, cordite is classified as a low explosive because of its slow burning rates and consequently low brisance. These produce a subsonic deflagration wave rather than the supersonic detonation wave produced by brisants, or high explosives. The hot gases produced by burning gunpowder or cordite generate sufficient pressure to propel a bullet or shell to its target, but not so quickly as to routinely destroy the barrel of the gun.

<span class="mw-page-title-main">Nitrocellulose</span> Highly flammable compound

Nitrocellulose is a highly flammable compound formed by nitrating cellulose through exposure to a mixture of nitric acid and sulfuric acid. One of its first major uses was as guncotton, a replacement for gunpowder as propellant in firearms. It was also used to replace gunpowder as a low-order explosive in mining and other applications. In the form of collodion it was also a critical component in an early photographic emulsion, the use of which revolutionized photography in the 1860s. In the 20th century it was adapted to automobile lacquer and adhesives.

<span class="mw-page-title-main">Cellophane</span> Thin, transparent sheet made of cellulose

Cellophane is a thin, transparent sheet made of regenerated cellulose. Its low permeability to air, oils, greases, bacteria, and liquid water makes it useful for food packaging. Cellophane is highly permeable to water vapour, but may be coated with nitrocellulose lacquer to prevent this.

<span class="mw-page-title-main">Camphor</span> Toxic, waxy aromatic organic compound

Camphor is a waxy, colorless solid with a strong aroma. It is classified as a terpenoid and a cyclic ketone. It is found in the wood of the camphor laurel, a large evergreen tree found in East Asia; and in the kapur tree, a tall timber tree from South East Asia. It also occurs in some other related trees in the laurel family, notably Ocotea usambarensis. Rosemary leaves contain 0.05 to 0.5% camphor, while camphorweed (Heterotheca) contains some 5%. A major source of camphor in Asia is camphor basil. Camphor can also be synthetically produced from oil of turpentine.

<span class="mw-page-title-main">Billiard ball</span> Ball used in cue sports

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 properties such as hardness, friction coefficient, and resilience are important to accuracy.

Polymer chemistry is a sub-discipline of chemistry that focuses on the structures of chemicals, chemical synthesis, and chemical and physical properties of polymers and macromolecules. The principles and methods used within polymer chemistry are also applicable through a wide range of other chemistry sub-disciplines like organic chemistry, analytical chemistry, and physical chemistry. Many materials have polymeric structures, from fully inorganic metals and ceramics to DNA and other biological molecules. However, polymer chemistry is typically related to synthetic and organic compositions. Synthetic polymers are ubiquitous in commercial materials and products in everyday use, such as plastics, and rubbers, and are major components of composite materials. Polymer chemistry can also be included in the broader fields of polymer science or even nanotechnology, both of which can be described as encompassing polymer physics and polymer engineering.

<span class="mw-page-title-main">Smokeless powder</span> Type of propellant

Smokeless powder is a type of propellant used in firearms and artillery that produces less smoke and less fouling when fired compared to black powder. Because of their similar use, both the original black powder formulation and the smokeless propellant which replaced it are commonly described as gunpowder. The combustion products of smokeless powder are mainly gaseous, compared to around 55% solid products for black powder. In addition, smokeless powder does not leave the thick, heavy fouling of hygroscopic material associated with black powder that causes rusting of the barrel.

Alexander Parkes was a metallurgist and inventor from Birmingham, England. He created Parkesine, the first man-made plastic.

<span class="mw-page-title-main">John Wesley Hyatt</span> American inventor of plastic

John Wesley Hyatt was an American inventor. He is mainly known for simplifying the production of celluloid.

Daniel Spill 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 Parkes' invention Parkesine, the first man-made plastic.

<span class="mw-page-title-main">Bioplastic</span> Plastics derived from renewable biomass sources

Bioplastics are plastic materials produced from renewable biomass sources, such as vegetable fats and oils, corn starch and rice starch, straw, woodchips, sawdust, recycled food waste, etc. Some bioplastics are obtained by processing directly from natural biopolymers including polysaccharides and proteins, while others are chemically synthesized from sugar derivatives and lipids from either plants or animals, or biologically generated by fermentation of sugars or lipids. In contrast, common plastics, such as fossil-fuel plastics are derived from petroleum or natural gas.

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 majority of the thickness of any given film stock. Since the late 19th century, there have been three major types of film base in use: nitrate, acetate, and polyester.

Polyvinyl nitrate (abbreviated: PVN) is a high-energy polymer with the idealized formula of [CH2CH(ONO2)]. Polyvinyl nitrate is a long carbon chain (polymer) with nitrate groups bonded randomly along the chain. PVN is a white, fibrous solid, and is soluble in polar organic solvents such as acetone. PVN can be prepared by nitrating polyvinyl alcohol with an excess of nitric acid. Because PVN is also a nitrate ester such as nitroglycerin (a common explosive), it exhibits energetic properties and is commonly used in explosives and propellants.

<span class="mw-page-title-main">Cellulose acetate film</span> Base material for photographic emulsions

Cellulose acetate film, or safety film, is used in photography as a base material for photographic emulsions. It was introduced in the early 20th century by film manufacturers and intended as a safe film base replacement for unstable and highly flammable nitrate film.

Crystalate is an early plastic, a formulation of nitrocellulose, camphor, and alcohol invented in the late 19th century and patented by American inventor George Henry Burt. It is best known as a material for gramophone records produced in the UK by Crystalate Manufacturing Company, and for moulded billiards, pool and snooker balls, as produced by the Endolithic Company.

The Albany Billiard Ball Company was an American manufacturer of billiard balls based in Albany, New York. The company was founded in 1868, manufacturing for over 100 years, before going out of business in 1986.

The conservation and restoration of film is the physical care and treatment of film-based materials. These include photographic film and motion picture film stock.

References

  1. 1 2 Balser, Klaus; Hoppe, Lutz; Eicher, Theo; Wandel, Martin; Astheimer, Hans‐Joachim; Steinmeier, Hans; Allen, John M. (2004). "Cellulose Esters". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a05_419.pub2. ISBN   9783527303854.
  2. ↑ Andrea Picks: The Saga of Cellulose Archived January 24, 2010, at the Wayback Machine
  3. 1 2 Painter, Paul C.; Coleman, Michael M. (2008). "The Early History of Polymers". Essentials of Polymer Science and Engineering. DEStech>. pp. 7–9. ISBN   9781932078756.
  4. ↑ UK Patent office (1857). Patents for inventions. UK Patent office. p. 255.
  5. ↑ "Hackney Council - First Plastic in the World". hackney.gov.uk. 2012. Archived from the original on 4 March 2016. Retrieved 9 January 2012.
  6. ↑ 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.
  7. ↑ "US patent #105,338 issued July 12, 1870" . Retrieved 2014-05-07.
  8. ↑ "Plastics Historical Society". Plastiquarian.com. Retrieved 2014-05-07.
  9. ↑ Beaujot 2012, p. 147.
  10. ↑ Beaujot 2012, p. 149.
  11. ↑ Beaujot 2012, p. 148.
  12. ↑ Daniel Spill, Celluloid Manufacturing Company, United States. Circuit Court (New York : Southern District) Spill vs. Celluloid Manufacturing Company litigation documents
  13. ↑ "John Carbutt at Historic Camera - History Librarium". historiccamera.com.
  14. ↑ Grasso, Tony (1996). Bakelite Jewellery A Collector's guide. The Apple Press. p. 16. ISBN   1850766134.
  15. ↑ Orbanes, Philip (2004). The Game Makers: The Story of Parker Brothers from Tiddledy Winks to Trivial Pursuit, p. 48. Harvard Business. ISBN   9781591392699.
  16. ↑ <https://clockhistory.com/sethThomas/products/adamantine/index.html>.
  17. ↑ Ly, Tran Duy (1996). Seth Thomas Clocks & Movements. U.S. Books. ISBN   0-9647406-0-5.
  18. 1 2 "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>.
  19. ↑ Springate, Megan E. (1997) "Cellulose Nitrate Plastic (Celluloid) in Archaeological Assemblages: Identification and Care,"Northeast Historical Archaeology: Vol. 26 26: Iss. 1, Article 5.
  20. ↑ "Ask the Expert: All About Celluloid Rot—and What to do About It | Acoustic Guitar". 9 September 2021.

Sources

This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.