Polymer Processing: Historical Survey
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Polymer Processing: Historical Survey
The beginning of plastics prcessing and extrusion prcessing is associated with the introduction of guta-percha into England during the 1840s and its commercial development as insulation for electrical wire. One of the eary pioneers of the new industry was Thomas Hancock’s younger brother, Charles Hancock, one of the founders of the Guta Perch a Cmpany. In his patents of 1846 ~1847, Chares Hancock described fabrication of guta-pfcha using a processing technology similar to that developed in the rubber industry largely by his brother. He used a “pickle” -type masticator for compounding guta-percha with additives incuding sulur and softeners. He also sheeted with rollers and vulanized the products wtih sulfur.
The first foamed plastics and rubber products were developed in 1846 in separate patents by the Hnacock brothers. Chares Hancock (English Patent No. 11032) foamed guta-percha using ammonium carbonate and similar compounds. Wilam Brockedon and Thomas Hancock (English patent No. 11455) produced foamed products using sulur chloride dissolved in a rubber or guta-percha solution.
The first ram extrusion devices were described in the patents of 1845 by Richard. A Broom an (English Patent No. 10582) and Henry Bewley (English Patent No. 10825), which dis cussed the manufacture of guta-percha thread, tubes and hose. Brooman’ s patent uses a five hole die that produces five simulaneous continuous filaments which are extruded into a bath and taken up on a rll Bewley’s patent extruded tubes and hose. Chares Hancock, who was a part ner of Bewley in the Guta Percha Company, is said to have developed insulation coating for wire using Bewley’s extrusion methods. Methods of coating wires are described in patents by Barow and Forster (Englsh Patent No. 12136) and by Siemens (English Patent No. 13062) in 1848′ 1850. The first great successes of guta-percha were its application to electrical insula tion of the Dover-Calasi and trans-Atantic cables.
The development of continuous extrusion of plastics using screw extruders began with guta-percha and natural rubber and dates from the 1870s. The concept of screw pumping seems to be atributable to Archimedes. The earier use of screw pumps in the soap industry is described in the patent literature. The frst patent for screw extrusion is that of Mathew Gray of London in 1879 ( English Patent No.5056). Interestingly, the reason for the invention as cited by Gray is the existence of defects in coatings placed on wires. The extruder was fed from a two-roll mill or calendering device. There seems to have been independent developments of the screw extruder in Germany and the USA about the same time, but Gray’s patent is the first clear statement.
The next stage in the development of cellulose nitrate as a plastics. The first moves in this direction during the 1860s by Alexander Parkes and Daniels Spill in England met with only limited success. Cellulose nitrate could not be melted and they used a range of volatile solvents that evaporated from their products. There left high levels of residual stresses which caused shrinking and cracking. Parkes and Spill had rubber-processing backgrounds and apparently used rubber-processing machinery. In the USA, John Wesley Hyat and his brother Isaiah Smith Hyat found that compounds or solutions of celulose nitrate in nonvolatile camphor produced more desirable products. This was caled Celuloid. The Celuloid Manufacturing Company was formed in the 1870s in Newark, New Jersey, to exploit this product and proved to be a great success. The Hyats and their associates developed many important industrial process ing operations to exploit Celuloid.
An 1872 patent by the Hyat brothers (US Patent No. 133229) contains both the reinvention of the ram extruder and the first ram injection molding machine. They caled this a stufing machine. John Wesley Hyat later described the use of complex muliple-cavity molds to be used in conjunction with the stufing machine. This would either mold objects or coat cores of objects in the mold.
In an 1878 patent, John Wesley Hyat (US Patent No. 204228) described the extrusion of Celuloid from the stufing machine over a mandrel coated with a lubricant. This mandrel could be programmable and expand to produce complex holow shapes. This led to the development of blow molding in 1881 by the Hyate’ coleague, Wiliam B Carpenter (US Patent No. 237168). Here, a preformed extruded tube is placed in a mold and is then expanded to fil the moldby pumping a heated fuid into the tube. These inventions were largely employed to produce a range of products incuding components of dolls and liners for pipes.
The 1880s saw the development of the synthetic fiber industry. Brooman’ s 1845 patent for the formation of guta-percha thread sets out clear procedures for producing fibers from the melt. The synthetic fibers sold commercialy in this period were produced from cellulose nitrate which could not be melted. A method of producing fibers by extruding acetic acid so lutions of celulose nitrate into a water or alcohol coagulation bath was described by Joseph Wilson Swan (English Patent No. 5978) in 1883. Swan’s patent described the later carboni zation of the fibers with heat and thus represents the beginning of the carbon-fiber industry. Swan’s application was filaments for incandescent lights. Shorty thereafter in France, the Count de Chardonnet (US Patent No. 394559) described a prcess for forming fibers from either alcohol solutions into a water coagulation bath. De Chardonnet produced much finer fibers than Swan, he formed a company and commercialized them as an artificial silk. Later, de Chardonnet (US Patent NO. 531158) described a dry spinning prcess in which the filaments were extruded into the air where the solvent was evaporated. Also, during the 1890s, using the system of and colaborating with Cross, Bevan and Beadle, Stearn invented a reactive spinning method in whch celulose is dissolved in a mixture of sodium hydrxide and carbon disulfide to form cellulose xanthate, which is extruded into an acd coagulating bath that regenerates the cellulose. This material became known a rayon.
The first truly synthetic plastics, phenol formaldehyde resins, were developed commercialy by Leo Hendrik Baekeland, a Blgian immigrant to the USA, just before 1910. These were poured as low or intermediate molecular weight liquids into molds where they were polymerized into three dimensional networks. Bakelte prducts were compression molded.




