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OVERVIEW of Plastics

Plastic is the general common term for a wide range of synthetic or semisynthetic organic amorphous solid materials suitable for the manufacture of industrial products. Plastics are typically polymers of high molecular weight, and may contain other substances to improve performance and/or reduce costs. The word Plastic derives from the Greek (plastikos) meaning fit for molding, and (plastos) meaning molded. It refers to their malleability, or plasticity during manufacture, that allows them to be cast, pressed, or extruded into an enormous variety of shapes—such as films, fibers, plates, tubes, bottles, boxes, and much more. The common word plastic should not be confused with the technical adjective plastic, which is applied to any material which undergoes a permanent change of shape (plastic deformation) when strained beyond a certain point. Aluminum, for instance, is plastic in this sense, but not a plastic in the common sense; in contrast, in their finished forms, some plastics will break before deforming and therefore are not plastic in the technical sense.

There are two types of plastics: Thermoplastics and Thermosets.
  • Thermoplastics will soften and melt if enough heat is applied; examples are polyethylene, polystyrene, and PTFE.
  • Thermosets do not soften or melt no matter how much heat is applied. Examples: Micarta, GPO, G-10

    Overview:
    Plastics can be classified by their chemical structure, namely the molecular units that make up the polymer's backbone and side chains. Some important groups in these classifications are the acrylics, polyesters, silicones, polyurethanes, and halogenated plastics. Plastics can also be classified by the chemical process used in their synthesis; e.g., as condensation, polyaddition, cross-linking, etc. Other classifications are based on qualities that are relevant for manufacturing or product design. Examples of such classes are the thermoplastic and thermoset, elastomer, structural, biodegradable, electrically conductive, etc. Plastics can also be ranked by various physical properties, such as density, tensile strength, glass transition temperature, resistance to various chemical products, etc. Due to their relatively low cost, ease of manufacture, versatility, and imperviousness to water, plastics are used in an enormous and expanding range of products, from paper clips to spaceships. They have already displaced many traditional materials, such as wood; stone; horn and bone; leather; paper; metal; glass; and ceramic, in most of their former uses. The use of plastics is constrained chiefly by their organic chemistry, which seriously limits their hardness, density, and their ability to resist heat, organic solvents, oxidation, and ionizing radiation. In particular, most plastics will melt or decompose when heated to a few hundred degrees celsius. While plastics can be made electrically conductive to some extent, they are still no match for metals like copper or aluminum.[citation needed] Plastics are still too expensive to replace wood, concrete and ceramic in bulky items like ordinary buildings, bridges, dams, pavement, railroad ties, etc.

    Chemical Structure:
    Common thermoplastics range from 20,000 to 500,000 in molecular mass, while thermosets are assumed to have infinite molecular weight. These chains are made up of many repeating molecular units, known as repeat units, derived from monomers; each polymer chain will have several thousand repeat units. The vast majority of plastics are composed of polymers of carbon and hydrogen alone or with oxygen, nitrogen, chlorine or sulfur in the backbone. (Some of commercial interests are silicon based.) The backbone is that part of the chain on the main "path" linking a large number of repeat units together. To vary the properties of plastics, both the repeat unit with different molecular groups "hanging" or "pendant" from the backbone, (usually they are "hung" as part of the monomers before linking monomers together to form the polymer chain). This customization by repeat unit's molecular structure has allowed plastics to become such an indispensable part of twenty first-century life by fine tuning the properties of the polymer.

    Some plastics are partially crystalline and partially amorphous in molecular structure, giving them both a melting point (the temperature at which the attractive intermolecular forces are overcome) and one or more glass transitions (temperatures above which the extent of localized molecular flexibility is substantially increased). So-called semi-crystalline plastics include polyethylene, polypropylene, poly (vinyl chloride), polyamides (nylons), polyesters and some polyurethanes. Many plastics are completely amorphous, such as polystyrene and its copolymers, poly (methyl methacrylate), and all thermosets.

    History of Plastics:
    The first human-made plastic was invented by Alexander Parkes in 1855; he called this plastic Parkesine (later called celluloid). The development of plastics has come from the use of natural plastic materials (e.g., chewing gum, shellac) to the use of chemically modified natural materials (e.g., rubber, nitrocellulose, collagen, galalite) and finally to completely synthetic molecules (e.g., bakelite, epoxy, polyvinyl chloride, polyethylene).

    Types of Plastics:
    Cellulose-based plastics
    In 1855, an Englishman from Birmingham named Alexander Parkes developed a synthetic replacement for ivory which he marketed under the trade name Parkesine, and which won a bronze medal at the 1862 World's fair in London. Parkesine was made from cellulose (the major component of plant cell walls) treated with nitric acid and a solvent. The output of the process (commonly known as cellulose nitrate or pyroxilin) could be dissolved in alcohol and hardened into a transparent and elastic material that could be molded when heated. By incorporating pigments into the product, it could be made to resemble ivory.

    Bakelite®
    The first plastic based on a synthetic polymer was made from phenol and formaldehyde, with the first viable and cheap synthesis methods invented in 1909 by Leo Hendrik Baekeland, a Belgian-born American living in New York state. Baekeland was searching for an insulating shellac 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. He continued his investigations and found that the material could be mixed with wood flour, asbestos, or slate dust to create "composite" materials with different properties. Most of these compositions were strong and fire resistant. The only problem was that the material tended to foam during synthesis, and the resulting product was of unacceptable quality. Baekeland built pressure vessels to force out the bubbles and provide a smooth, uniform product. He publicly announced his discovery in 1912, naming it bakelite. It was originally used for electrical and mechanical parts, finally coming into widespread use in consumer goods in the 1920s. When the Bakelite patent expired in 1930, the Catalin Corporation acquired the patent and began manufacturing Catalin plastic using a different process that allowed a wider range of coloring. Bakelite was the first true plastic. It was a purely synthetic material, not based on any material or even molecule found in nature. It was also the first thermosetting plastic. Conventional thermoplastics can be molded and then melted again, but thermoset plastics form bonds between polymers strands when cured, creating a tangled matrix that cannot be undone without destroying the plastic. Thermoset plastics are tough and temperature resistant. Bakelite® was cheap, strong, and durable. It was molded into thousands of forms, such as radios, telephones, clocks, and billiard balls. Phenolic plastics have been largely replaced by cheaper and less brittle plastics, but they are still used in applications requiring its insulating and heat-resistant properties. For example, some electronic circuit boards are made of sheets of paper or cloth impregnated with phenolic resin. Bakelite® is now a registered trademark of Bakelite GmbH.

    Polystyrene & PVC
    After the First World War, improvements in chemical technology led to an explosion in new forms of plastics. Among the earliest examples in the wave of new plastics were polystyrene (PS) and polyvinyl chloride (PVC), developed by IG Farben of Germany. Polystyrene is a rigid, brittle, inexpensive plastic that has been used to make plastic model kits and similar knick-knacks. It would also be the basis for one of the most popular "foamed" plastics, under the name styrene foam or Styrofoam. Foam plastics can be synthesized in an "open cell" form, in which the foam bubbles are interconnected, as in an absorbent sponge, and "closed cell", in which all the bubbles are distinct, like tiny balloons, as in gas-filled foam insulation and flotation devices. In the late 1950s, High Impact Styrene was introduced, which was not brittle. It finds much current use as the substance of signage, trays, figurines and novelties. PVC has side chains incorporating chlorine atoms, which form strong bonds. PVC in its normal form is stiff, strong, heat and weather resistant, and is now used for making plumbing, gutters, house siding, enclosures for computers and other electronics gear. PVC can also be softened with chemical processing, and in this form it is now used for shrink-wrap, food packaging, and rain gear.

    Nylon
    The real star of the plastics industry in the 1930s was polyamide (PA), far better known by its trade name nylon. Nylon was the first purely synthetic fiber, introduced by DuPont Corporation at the 1939 World's Fair in New York City. In 1927, DuPont had begun a secret development project designated Fiber66, under the direction of Harvard chemist Wallace Carothers and chemistry department director Elmer Keiser Bolton. Carothers had been hired to perform pure research, and he worked to understand the new materials' molecular structure and physical properties. He took some of the first steps in the molecular design of the materials. His work led to the discovery of synthetic nylon fiber, which was very strong but also very flexible. The first application was for bristles for toothbrushes. However, Du Pont's real target was silk, particularly silk stockings. Carothers and his team synthesized a number of different polyamides including polyamide 6.6 and 4.6, as well as polyesters. It took DuPont twelve years and US$27 million to refine nylon, and to synthesize and develop the industrial processes for bulk manufacture. With such a major investment, it was no surprise that Du Pont spared little expense to promote nylon after its introduction, creating a public sensation, or "nylon mania". Nylon mania came to an abrupt stop at the end of 1941 when the USA entered World War II. The production capacity that had been built up to produce nylon stockings, or just nylons, for American women was taken over to manufacture vast numbers of parachutes for fliers and paratroopers. After the war ended, DuPont went back to selling nylon to the public, engaging in another promotional campaign in 1946 that resulted in an even bigger craze, triggering the so called nylon riots. Subsequently polyamides 6, 10, 11, and 12 have been developed based on monomers which are ring compounds; e.g. caprolactam.nylon 66 is a material manufactured by condensation polymerization. Nylons still remain important plastics, and not just for use in fabrics. In its bulk form it is very wear resistant, particularly if oil-impregnated, and so is used to build gears, bearings, bushings, and because of good heat-resistance, increasingly for under-the-hood applications in cars, and other mechanical parts.

    Natural Rubber
    Natural rubber is an elastomer (an elastic hydrocarbon polymer) that was originally derived from latex, a milky colloidal suspension found in the sap of some plants. It is useful directly in this form (indeed, the first appearance of rubber in Europe is cloth waterproofed with unvulcanized latex from Brazil) but, later, in 1839, Charles Goodyear invented vulcanized rubber; this a form of natural rubber heated with, mostly, sulfur forming cross-links between polymer chains (vulcanization), improving elasticity and durability. Plastic is very known in these areas.

    Synthetic Rubber
    The first fully synthetic rubber was synthesized by Lebedev in 1910. In World War II, supply blockades of natural rubber from South East Asia caused a boom in development of synthetic rubber, notably Styrene-butadiene rubber (a.k.a. Government Rubber-Styrene). In 1941, annual production of synthetic rubber in the U.S. was only 231 tons which increased to 840 000 tons in 1945. In the space race and nuclear arms race, Caltech researchers experimented with using synthetic rubbers for solid fuel for rockets. Ultimately, all large military rockets and missiles would use synthetic rubber based solid fuels, and they would also play a significant part in the civilian space effort.

    Polymethyl methacrylate (PMMA), better known as Plexiglass acrylic. Although acrylics are now well known for their use in paints and synthetic fibers, such as fake furs, in their bulk form they are actually very hard and more transparent than glass, and are sold as glass replacements under trade names such as Acrylite, Perspex, Plexiglas and Lucite. These were used to build aircraft canopies during the war, and its main application now is large illuminated signs such as are used in shop fronts or inside large stores, and for the manufacture of vacuum-formed bath-tubs.

    Polyethylene (PE), sometimes known as polythene, was discovered in 1933 by Reginald Gibson and Eric Fawcett at the British industrial giant Imperial Chemical Industries (ICI). This material evolved into two forms, Low Density Polyethylene (LDPE), and High Density Polyethylene (HDPE). PEs are cheap, flexible, durable, and chemically resistant. LDPE is used to make films and packaging materials, while HDPE is used for containers, plumbing, and automotive fittings. While PE has low resistance to chemical attack, it was found later that a PE container could be made much more robust by exposing it to fluorine gas, which modified the surface layer of the container into the much tougher polyfluoroethylene.

    Polypropylene (PP), which was discovered in the early 1950s by Giulio Natta. It is common in modern science and technology that the growth of the general body of knowledge can lead to the same inventions in different places at about the same time, but polypropylene was an extreme case of this phenomenon, being separately invented about nine times. The ensuing litigation was not resolved until 1989. Polypropylene managed to survive the legal process and two American chemists working for Phillips Petroleum, J. Paul Hogan and Robert Banks, are now generally credited as the primary inventors of the material. Polypropylene is similar to its ancestor, polyethylene, and shares polyethylene's low cost, but it is much more robust. It is used in everything from plastic bottles to carpets to plastic furniture, and is very heavily used in automobiles.

    Polyurethane (PU) was invented by Friedrich Bayer & Company in 1937, and would come into use after the war, in blown form for mattresses, furniture padding, and thermal insulation. It is also one of the components (in non-blown form) of the fiber spandex.

    Epoxy - In 1939, IG Farben filed a patent for polyepoxide or epoxy. Epoxies are a class of thermoset plastic that form cross-links and cure when a catalyzing agent, or hardener, is added. After the war they would come into wide use for coatings, adhesives, and composite materials. Composites using epoxy as a matrix include glass-reinforced plastic, where the structural element is glass fiber, and carbon-epoxy composites, in which the structural element is carbon fiber. Fiberglass is now often used to build sport boats, and carbon-epoxy composites are an increasingly important structural element in aircraft, as they are lightweight, strong, and heat resistant.

    PET, PETE, PETG, PET-P (polyethylene terephthalate)
    Two chemists named Rex Whinfield and James Dickson, working at a small English company with the quaint name of the Calico Printer's Association in Manchester, developed polyethylene terephthalate (PET or PETE) in 1941, and it would be used for synthetic fibers in the postwar era, with names such as polyester, dacron, and Terylene. PET is less gas-permeable than other low-cost plastics and so is a popular material for making bottles for Coca-Cola and other carbonated drinks, since carbonation tends to attack other plastics, and for acidic drinks such as fruit or vegetable juices. PET is also strong and abrasion resistant, and is used for making mechanical parts, food trays, and other items that have to endure abuse. PET films are used as a base for recording tape.

    PTFE (polytetrafluoroethylene) (aka Teflon®)
    One of the most impressive plastics used in the war, and a top secret, was polytetrafluoroethylene (PTFE), better known as Teflon, which could be deposited on metal surfaces as a scratch-proof and corrosion-resistant, low-friction protective coating. The polyfluoroethylene surface layer created by exposing a polyethylene container to fluorine gas is very similar to Teflon. A DuPont chemist named Roy Plunkett discovered Teflon by accident in 1938. During the war, it was used in gaseous-diffusion processes to refine uranium for the atomic bomb, as the process was highly corrosive. By the early 1960s, Teflon adhesion-resistant frying pans were in demand.

    Polycarbonate - Lexan is a high-impact polycarbonate originally developed by General Electric. Makrolon® and Tuffak are tradenames high-impact polycarbonate plastic made by Plaskolite.

    Biodegradable (Compostable) Plastics
    Research has been done on biodegradable plastics that break down with exposure to sunlight (e.g., ultra-violet radiation), water or dampness, bacteria, enzymes, wind abrasion and some instances rodent pest or insect attack are also included as forms of biodegradation or environmental degradation. It is clear some of these modes of degradation will only work if the plastic is exposed at the surface, while other modes will only be effective if certain conditions exist in landfill or composting systems. Starch powder has been mixed with plastic as a filler to allow it to degrade more easily, but it still does not lead to complete breakdown of the plastic. Some researchers have actually genetically engineered bacteria that synthesize a completely biodegradable plastic, but this material, such as Biopol, is expensive at present. The German chemical company BASF makes Ecoflex, a fully biodegradable polyester for food packaging applications. Gehr Plastics has developed ECOGEHR, a full-range of Bio-Polymer Shapes distributed by Professional Plastics.
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