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The History of Early Thermoplastic Materials "Click" to Login or Register 
IHC Vice President
Pitfalls Moderator
IHC Life Member
Picture of Edward L. Parsons, Jr.
posted
Acknowledgement

New information has come to my attention regarding plastic materials used for Hamilton Railway Special packaging. It now appears that polystyrene was used rather than nitrate-based plastics as had been stated previously. The product history has been revised accordingly.



Foreword

In researching thermoplastic materials used by the Hamilton Watch Company for making watch boxes and advertising items, I became intrigued with the history of early thermoplastic materials beyond the confines of horology and expanded my research to include all the commonly used early synthetic plastics, which resulted in the following history.

History of Thermoplastic Materials up to the Second World War

Pre-Plastic Materials


Before synthetic thermoplastics existed, the closest comparable substances were Gutta Percha, a natural resin from the Isonandra Gutta tree, discovered in 1842 by Dr. William Montgomerie, a surgeon in the British army in the East Indies, and Vulcanite, also called vulcanized rubber, a mixture of natural latex obtained from various tropical trees and sulfur, combined at high temperature. The vulcanization process was discovered in 1839 by American Charles Goodyear and patented in 1843. Vulcanite was first used to make jewelry, novelty items and waterproof goods, but it was almost always black. Color could only be added to the surface with dyes and shellacs. Gutta Percha was lighter in color and somewhat less elastic than Vulcanite. It was used to make early golf balls and electrical insulation, and also had numerous medical and dental uses, some of which persist to the present day. Like Vulcanite, Gutta Percha is a polyterpene, i.e., a polymer of isoprene. Both substances have the key property of all thermoplastics: the ability to be molded into any desired shape after being softened by heat, a shape that will be retained upon cooling. Gutta Percha can also be vulcanized and treated to produce a hard, white, very convincing ivory substitute that had many ornamental uses in the 19th Century. Today it is still sometimes used to make counterfeit scrimshaw articles.

Parkesine & Xylonite – Initial Unsuccessful Thermoplastics

The first truly man-made thermoplastic was an invention of English scientist Alexander Parkes. He unveiled Parkesine at the 1862 London International Exhibition. Parkesine, an organic material that could be heated and molded but would retain its shape when cooled, was made by dissolving cellulose nitrate, prepared by treating cotton fibers with nitric acid, in a solvent. Unlike rubber (or Vulcanite), it could be colored or transparent and could also be carved or molded into any shape. In 1866, four years after the exhibition, Parkes formed the Parkesine Company; it failed after only two years due to high production costs (even though Parkes had claimed it was cheaper than rubber).

A year after the Parkesine Company folded, an associate of Parkes named Daniel Spill tried to market a similar substance under the name Xylonite (from the Greek xylon, meaning "wood" — some of it looked like imitation wood). The Xylonite Company survived only five years and went bankrupt in 1874. However, Spill then formed the Daniel Spill Company and continued production of Xylonite, which was used to make imitation coral jewelry, among other things.

Celluloid – The First Successful Synthetic Thermoplastic

From the middle of the 19th Century the supply of elephant ivory became insufficient to meet the demand of the burgeoning billiards industry, so much so, that Phelan & Collander, who were American manufacturers of billiard balls, offered $10,000 for a suitable synthetic substitute - but, so far as is known, the prize was never awarded. John Wesley Hyatt and his brothers Charles and Isiah tried various compositions and patented several ideas; including an “improved method of making solid collodion” (collodion was a syrupy solution of cellulose nitrate in ether and alcohol). He was aware of the prior work on cellulose nitrate - particularly that by Parkes and Spill and of the beneficial effect of incorporating camphor.

Hyatt’s crucial breakthrough was the use of heat and pressure - heat melted the camphor making it into a solvent for the cellulose nitrate. This minimized the need for additional solvent and thereby eliminated most of the production problems experienced by his predecessors. Ultimately a hard, lustrous, ivory-like substance was produced which was dubbed Celluloid by the Hyatts. This innovation in approach was the reason why Spill's challenge to Hyatt’s patent was ultimately unsuccessful.

Hyatt participated in the formation of the Albany Billiard Ball Company, the earliest commercially successful plastics firm and certainly one of the oldest plastics companies in the world. The business was started in 1868 in Albany, New York, and is presently the only major manufacturer of billiard balls in the United States (in 1977, the company was renamed the Albany-Hyatt Billiard Ball Co.). Celluloid was successful as a substitute for ivory, long the prime substance in billiard ball manufacture. The Hyatt "composition" ball, with a celluloid base, dominated the game until the 1960s.

In 1870 the Hyatt brothers followed up on their initial success by setting up the Albany Dental Plate Company to manufacture dental plate blanks from the new material. In 1871 they started the Celluloid Manufacturing Company in Albany, transferring to Newark, New Jersey in 1872. A further reason why Hyatt's enterprise was successful where others had failed was that he developed machinery for working the new material - his “stuffing machine” was a forerunner of modern injection molding technology, which is the cornerstone of all thermoplastic manufacturing. He worked with machinery manufacturers such as Burroughs to make the first plastics processing machinery.

In the 1880’s George Eastman developed a transparent form of Celluloid as the basis for his revolutionary flexible photographic film, taking the place of the cumbersome glass plate negatives which previously had been the only way to make a photograph. To produce film, Celluloid was first dissolved in a solvent and then poured out over long glass tables. As the solvent evaporated, a thin residual film of celluloid was left, which could then be cut into strips and coated with photographic emulsion. Eastman first introduced this new film to the public in his ground-breaking Kodak camera in 1888. In 1891, Thomas Edison developed his new moving picture technology around an improved version of Eastman’s film to make the first modern motion pictures. Starting in 1908, Eastman introduced a more stable formulation based on cellulose acetate, which in time became the new industry standard.

Celluloid became the generic name for all cellulose nitrate-based plastics and its use as a substitute for amber, ivory and tortoise shell became widespread in knife handles, combs, hair brushes, mirrors and other toilet articles, boxes for watches and jewelry, various articles of tobacciana, washable collars and cuffs, numerous toys, table tennis balls, etc. Today celluloid is recognized as a category of collectibles unto itself.

Polystyrene

Polystyrene is a strong plastic created from erethylene and benzine that can be injected, extruded or blow molded, making it a very widely used and versatile manufacturing material today.

In 1839, a German apothecary called Eduard Simon first isolated polystyrene molecular chains from a natural resin, however, he did not know what he had discovered. It was left to another organic chemist, Hermann Staudinger, to realize that Simon's discovery could be used to manufacture a plastic polymer.

In 1922, Staudinger published his theories on polymers, stating that natural rubbers were made up of long repetitive chains of monomers that gave rubber its elasticity. In 1953, Hermann Staudinger won the Nobel Prize for Chemistry for his research.

In 1930, the scientists at BASF developed a way to commercially manufacture polystyrene. Badische Anilin & Soda-Fabrik (BASF) was founded in 1861. BASF has invented synthetic coal tar dyes, ammonia, and nitrogenous fertilizers and developed polystyrene, PVC, magnetic tape, and synthetic rubber. In 1937, Dow Chemical introduced polystyrene to the U.S. market.


The Hamilton Watch Company sold certain models of wrist and pocket watches in boxes which they called “ivory plastic” or “plastic,” including the famous flip-top cigarette boxes which came with 21 and 23-jewel Railroad Special pocket watches produced from 1940 until well into the 1950’s. In an earlier era, Hamilton was also well-known for their various advertising items printed on thin sheets of white celluloid. One of these items was identified as “celluloid card case” and another was identified as “celluloid covered booklet” in the 1908 Hamilton Material Catalog.
The bulk of the earlier plastic packaging material, from the 1930's and older are thought to be celluloid, but starting in 1940 the flip-top cigarette boxes were polystyrene plastic.

.
Bakelite - Material of a Thousand Uses

Bakelite is probably the most collectible — and valuable — thermoplastic in existence today. Many books have been published on this material, and a web search will yield hundreds of results.

Bakelite was discovered in 1909 by a New York chemist, Belgian-born Dr. Leo Hendrik Baekeland, the son of a shoemaker. He was 46 years old at the time, and had previously invented Velox photographic paper, which was bought by George Eastman for $750,000. This money allowed Baekeland to work independently from a home laboratory. While he was searching for an insulating resin to coat wires in electric motors and generators, he found that mixtures of phenol (C6H5OH) and formaldehyde (HCOH) formed a sticky mass when mixed together and heated, and the mass became extremely hard if allowed to cool and dry to form a substance that was highly heat-resistant, an excellent electrical insulator, and could be added to most materials (even softwood) to make them more durable. Baekeland called his discovery Bakelite and in 1910, obtained a patent and started the Bakelite Corporation.

He continued his investigations and found that the phenolic resin could be mixed with wood flour, asbestos, or slate dust to create opaque "composite" materials with different properties. Most of these compositions were dense, strong and fire-resistant. The only difficulty was that the material tended to foam during synthesis, which compromised product quality. Baekeland solved the problem with pressurized process vessels to force out the bubbles and provide a smooth, uniform product. Bakelite was initially used for automotive and industrial electrical and mechanical parts, finally coming into widespread use in consumer goods in the 1920s. Dr. Baekeland appeared on the cover of Time magazine on September 22, 1924, when he was president of the American Chemical Society.

Later in the 1920s, production began on bakelite jewelry; the colorful pieces were attractive and affordable to those affected by the Great Depression. They could be produced in various colors, but the most common were yellow, butterscotch, red, green and brown. Bakelite could also be transparent, or marbleized by mixing two colors. Coco Chanel featured bakelite items in her accessories collection, and the material was praised frequently in Vogue magazine.

The jewelry remained popular until production was halted in 1942 to concentrate on the war effort (phones, goggles, etc.). By the time the war ended, a new generation of petroleum-derived thermoplastics had taken over, and Bakelite became obsolete. Dr. Baekeland passed away in 1944 in Beacon, New York, at age 80.

Bakelite jewelry became fashionable again when Andy Warhol, a prolific collector of these pieces, passed away in 1987. His collection went up for auction at Sotheby's and fetched record prices.

Nowadays, you can find Bakelite pieces through many vintage and antique dealers. Bangles are the most common trinkets and often sell for about US$100-US$500 (or more); rings are harder to find, as they were less likely to have survived over the years (due to their small size). Some jewelers rework old pieces of the material to create new jewelry — the best-known of these artists are Ron and Ester Shultz, who create "Shultz Bakelite," which can be identified by its high gloss finish.

Although most sources say bakelite is no longer produced, there is at least one bakelite company in existence: Sumitomo Bakelite Group of Tokyo, Japan. Sumitomo is the present incarnation of Sankyo Co., Ltd., which originated plastics production in Japan in 1911 after Baekeland granted legal permission to his friend Dr. Jokichi Takamine.

Catalin - "the gem of plastics"

When Bakelite's 1910 patent expired in 1927, the Catalin Corporation began producing a similar material under the name — what else? — "Catalin." A new coloring method allowed them to add fifteen colors to the available range. They were famous for their Catalin radios; during the Depression, people would often give up their furniture before giving up their radios, which were an important part of daily life. Catalin replaced the wood and steel casings of radios, making them much more affordable — only about a tenth of the original cost. It has been estimated that about 70% of the "Bakelite" in existence today is actually Catalin.

The Clear Acrylics - Lucite & Plexiglas

Lucite was invented by accident in 1931 by chemists at DuPont’s research laboratories. It was crystal clear, resistant to water and ultraviolet rays, and was low density yet stronger than previous plastics. Around the same time, the Rohm & Haas Chemical Company discovered a similar compound, methyl methacrylate, and named it Plexiglas. Because Plexiglas was the main focus of R&H, whereas Lucite was not DuPont's primary product, Plexiglas achieved higher sales than its competitor. These materials became widely used as a nearly unbreakable glass replacement, known generically as clear acrylic plastics.

Like Bakelite and Catalin, Lucite and Plexiglas were used extensively in war supplies during WWII. In watches, Plexiglas and Lucite crystals were used to meet the military specifications requiring "unbreakable" crystals, and their use continued after the war in the less expensive watch lines. For example in the post-war Hamilton Model 15 stainless steel case, the "correct" crystal is acrylic plastic. Latter day acrylic plastics are still widely used in new and replacement watch crystals.

After the war, the plastics were used for jewelry and other items. Lucite rings were highly popular during the '50s and '60s, as were Lucite handbags. In 1993, DuPont sold its acrylic resin operations. The Lucite name now belongs to Lucite International in Southampton, United Kingdom.
 
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