Scientific Principles:Polymers - 0 views
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The chemical reaction in which high molecular mass molecules are formed from monomers is known as polymerization. There are two basic types of polymerization, chain-reaction (or addition) and step-reaction (or condensation) polymerization.
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One of the most common types of polymer reactions is chain-reaction (addition) polymerization. This type of polymerization is a three step process involving two chemical entities. The first, known simply as a monomer, can be regarded as one link in a polymer chain. It initially exists as simple units. In nearly all cases, the monomers have at least one carbon-carbon double bond. Ethylene is one example of a monomer used to make a common polymer.
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The other chemical reactant is a catalyst. In chain-reaction polymerization, the catalyst can be a free-radical peroxide added in relatively low concentrations. A free-radical is a chemical component that contains a free electron that forms a covalent bond with an electron on another molecule. The formation of a free radical from an organic peroxide is shown below:
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The first step in the chain-reaction polymerization process, initiation, occurs when the free-radical catalyst reacts with a double bonded carbon monomer, beginning the polymer chain. The double carbon bond breaks apart, the monomer bonds to the free radical, and the free electron is transferred to the outside carbon atom in this reaction.
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The next step in the process, propagation, is a repetitive operation in which the physical chain of the polymer is formed. The double bond of successive monomers is opened up when the monomer is reacted to the reactive polymer chain. The free electron is successively passed down the line of the chain to the outside carbon atom.
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Thermodynamically speaking, the sum of the energies of the polymer is less than the sum of the energies of the individual monomers. Simply put, the single bounds in the polymeric chain are more stable than the double bonds of the monomer.
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Termination occurs when another free radical (R-O.), left over from the original splitting of the organic peroxide, meets the end of the growing chain. This free-radical terminates the chain by linking with the last CH2. component of the polymer chain. This reaction produces a complete polymer chain. Termination can also occur when two unfinished chains bond together. Both termination types are diagrammed below. Other types of termination are also possible.
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This exothermic reaction occurs extremely fast, forming individual chains of polyethylene often in less than 0.1 second.
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Step-reaction (condensation) polymerization is another common type of polymerization. This polymerization method typically produces polymers of lower molecular weight than chain reactions and requires higher temperatures to occur. Unlike addition polymerization, step-wise reactions involve two different types of di-functional monomers or end groups that react with one another, forming a chain. Condensation polymerization also produces a small molecular by-product (water, HCl, etc.).
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As indicated above, both addition and condensation polymers can be linear, branched, or cross-linked. Linear polymers are made up of one long continuous chain, without any excess appendages or attachments. Branched polymers have a chain structure that consists of one main chain of molecules with smaller molecular chains branching from it. A branched chain-structure tends to lower the degree of crystallinity and density of a polymer. Cross-linking in polymers occurs when primary valence bonds are formed between separate polymer chain molecules. Chains with only one type of monomer are known as homopolymers. If two or more different type monomers are involved, the resulting copolymer can have several configurations or arrangements of the monomers along the chain. The four main configurations are depicted below:
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They can be found in either crystalline or amorphous forms. Crystalline polymers are only possible if there is a regular chemical structure (e.g., homopolymers or alternating copolymers), and the chains possess a highly ordered arrangement of their segments. Crystallinity in polymers is favored in symmetrical polymer chains, however, it is never 100%. These semi-crystalline polymers possess a rather typical liquefaction pathway, retaining their solid state until they reach their melting point at Tm.
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Amorphous polymers do not show order. The molecular segments in amorphous polymers or the amorphous domains of semi-crystalline polymers are randomly arranged and entangled. Amorphous polymers do not have a definable Tm due to their randomness
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At low temperatures, below their glass transition temperature (Tg), the segments are immobile and the sample is often brittle. As temperatures increase close to Tg, the molecular segments can begin to move. Above Tg, the mobility is sufficient (if no crystals are present) that the polymer can flow as a highly viscous liquid.
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Thermoplastics are generally carbon containing polymers synthesized by addition or condensation polymerization. This process forms strong covalent bonds within the chains and weaker secondary Van der Waals bonds between the chains. Usually, these secondary forces can be easily overcome by thermal energy, making thermoplastics moldable at high temperatures.
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Thermosets have the same Van der Waals bonds that thermoplastics do. They also have a stronger linkage to other chains. Strong covalent bonds chemically hold different chains together in a thermoset material. The chains may be directly bonded to each other or be bonded through other molecules. This "cross-linking" between the chains allows the material to resist softening upon heating.
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Compression Molding This type of molding was among the first to be used to form plastics. It involves four steps: Pre-formed blanks, powders or pellets are placed in the bottom section of a heated mold or die. The other half of the mold is lowered and is pressure applied. The material softens under heat and pressure, flowing to fill the mold. Excess is squeezed from the mold. If a thermoset, cross-linking occurs in the mold. The mold is opened and the part is removed. For thermoplastics, the mold is cooled before removal so the part will not lose its shape. Thermosets may be ejected while they are hot and after curing is complete. This process is slow
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Injection Molding This very common process for forming plastics involves four steps: Powder or pelletized polymer is heated to the liquid state. Under pressure, the liquid polymer is forced into a mold through an opening, called a sprue. Gates control the flow of material. The pressurized material is held in the mold until it solidifies. The mold is opened and the part removed by ejector pins. Advantages of injection molding include rapid processing, little waste, and easy automation.
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Transfer Molding This process is a modification of compression molding. It is used primarily to produce thermosetting plastics. Its steps are: A partially polymerized material is placed in a heated chamber. A plunger forces the flowing material into molds. The material flows through sprues, runners and gates. The temperature and pressure inside the mold are higher than in the heated chamber, which induces cross-linking. The plastic cures, is hardened, the mold opened, and the part removed. Mold costs are expensive and much scrap material collects in the sprues and runners, but complex parts of varying thickness can be accurately produced.
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Extrusion This process makes parts of constant cross section like pipes and rods. Molten polymer goes through a die to produce a final shape. It involves four steps: Pellets of the polymer are mixed with coloring and additives. The material is heated to its proper plasticity. The material is forced through a die. The material is cooled.
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Blow Molding Blow molding produces bottles, globe light fixtures, tubs, automobile gasoline tanks, and drums. It involves: A softened plastic tube is extruded The tube is clamped at one end and inflated to fill a mold. Solid shell plastics are removed from the mold. This process is rapid and relatively inexpensive.
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In 1989, a billion pounds of virgin PET were used to make beverage bottles of which about 20% was recycled. Of the amount recycled, 50% was used for fiberfill and strapping. The reprocessors claim to make a high quality, 99% pure, granulated PET. It sells at 35 to 60% of virgin PET costs. The major reuses of PET include sheet, fiber, film, and extrusions.
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Of the plastics that have a potential for recycling, the rigid HDPE container is the one most likely to be found in a landfill. Less than 5% of HDPE containers are treated or processed in a manner that makes recycling easy.
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There is a great potential for the use of recycled HDPE in base cups, drainage pipes, flower pots, plastic lumber, trash cans, automotive mud flaps, kitchen drain boards, beverage bottle crates, and pallets.
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LDPE is recycled by giant resin suppliers and merchant processors either by burning it as a fuel for energy or reusing it in trash bags. Recycling trash bags is a big business.
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There is much controversy concerning the recycling and reuse of PVC due to health and safety issues. When PVC is burned, the effects on the incinerator and quality of the air are often questioned. The Federal Food and Drug Administration (FDA) has ordered its staff to prepare environmental impact statements covering PVC's role in landfills and incineration. The burning of PVC releases toxic dioxins, furans, and hydrogen chloride.
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PVC is used in food and alcoholic beverage containers with FDA approval. The future of PVC rests in the hands of the plastics industry to resolve the issue of the toxic effects of the incineration of PVC. It is of interest to note that PVC accounts for less than 1% of land fill waste.
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PS and its manufacturers have been the target of environmentalists for several years. The manufacturers and recyclers are working hard to make recycling of PS as common as that of paper and metals. One company, Rubbermaid, is testing reclaimed PS in service trays and other utility items.
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Table 3: Major Plastic Resins and Their Uses Resin CodeResin NameCommon UsesExamples of Recycled Products Polyethylene Terephthalate (PET or PETE) Soft drink bottles, peanut butter jars, salad dressing bottles, mouth wash jars Liquid soap bottles, strapping, fiberfill for winter coats, surfboards, paint brushes, fuzz on tennis balls, soft drink bottles, film High density Polyethylene (HDPE) Milk, water, and juice containers, grocery bags, toys, liquid detergent bottles Soft drink based cups, flower pots, drain pipes, signs, stadium seats, trash cans, re-cycling bins, traffic barrier cones, golf bag liners, toys Polyvinyl Chloride or Vinyl (PVC-V) Clear food packaging, shampoo bottles Floor mats, pipes, hoses, mud flaps Low density Polyethylene (LDPE) Bread bags, frozen food bags, grocery bags Garbage can liners, grocery bags, multi purpose bags Polypropylene (PP) Ketchup bottles, yogurt containers, margarine, tubs, medicine bottles Manhole steps, paint buckets, videocassette storage cases, ice scrapers, fast food trays, lawn mower wheels, automobile battery parts. Polystyrene (PS) Video cassette cases, compact disk jackets, coffee cups, cutlery, cafeteria trays, grocery store meat trays, fast-food sandwich container License plate holders, golf course and septic tank drainage systems, desk top accessories, hanging files, food service trays, flower pots, trash cans