Fuel From Plastic Waste Introduction: Household items made of various kinds of plastic. Plastic is the general common term for a wide range of synthetic or semisynthetic organic amorphous solid materials used in the manufacture of industrial products. Plastics are typically polymers of high molecular mass, and may contain other substances to improve performance and/or reduce costs. Monomers of Plastic are either natural or synthetic organic compounds.
The word is derived from the Greek TIXaotLK??q (plastikos) meaning fit for molding, and TIXaor??q (plastos) meaning molded. It refers to their malleability, or plasticity during anufacture, that allows them to be cast, pressed, or extruded into a 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.
Aluminium, 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 thermosetting polymers. Thermoplastics will soften and melt if enough heat is applied; examples are polyethylene, polystyrene, polyvinyl chloride and polytetrafluoroethylene (PTFE). Thermosets can melt and take shape once; after they have solidified, they stay solid.
Department of Mechanical Engg, SKIT Page 1 Overview Plastics can be classified by 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 lastics. Plastics can also be classified by the chemical process used in their synthesis, such as condensation, polyaddition, and cross-linking. 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, and electrically conductive. Plastics can also be classified by various physical properties, such as density, tensile strength, glass transition temperature, and resistance to various chemical products. Due to their lastics 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 lectrically conductive to some extent, they are still no match for metals like copper or aluminium. Plastics are still too expensive to replace wood, concrete and ceramic in bulky items like ordinary buildings, bridges, dams, pavement, and railroad ties.
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; Page 2 each polymer chain will have several thousand repeating 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 customize the properties of a plastic, different molecular groups “hang” from the backbone (usually they are “hung” as part of the monomers before linking monomers together to form the polymer chain). This fine tuning of the properties of the polymer by repeating unit’s molecular tructure has allowed plastics to become such an indispensable part of twenty first- century world.
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). The 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.
Molded plastic food replicas on display outside a restaurant in Japan. History The firsthuman-made plastic was invented by Alexander Parkes in 1855 [7] ; 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, poWinyl chloride, polyethylene).
Types 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. Bois Durci is a plastic moulding material based on cellulose. It was patented in Paris by Lepage in 1855. It is made from finely ground wood flour mixed with a binder, either egg or blood albumen, or gelatine. The wood is probably either ebony or rose wood, which gives a black or brown resin. The mixture is dried and ground into a fine powder. The powder is placed in a steel mould and compressed in a powerful hydraulic press whilst being heated by steam.
The final product has a highly polished finish imparted by the surface of the steel mould. 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. Page 4 generators. He found that mixtures of phenol (C6H50H) 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 lastic 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 s radios, telephones, clocks, and billiard balls. The U. S. government even considered making one-cent coins out of it when World War II caused a copper shortage. 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.
Phenolic sheets, rods and tubes are produced in a wide variety of grades under various brand names. The most common grades of industrial phenolic are Canvas, Linen and Paper. Page 5 Polystyrene and PVC Plastic piping and firestops being installed at Nortown Casitas, North York (Now Toronto), Ontario, Canada. Certain plastic pipes can be used in some non- combustible buildings, provided they are firestopped properly and that the flame spread ratings comply with the local building code. 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 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 Page 6 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 uch current use as the substance of toy 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 y 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. page 7 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. [9] General condensation polymerization reaction for nylon It took DuPont twelve years and IJS$27 million to refine nylon, and to synthesize and develop the industrial processes for bulk manufacture.
With such a major 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, 1 1, 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, plain bearings, and because of good heat-resistance, increasingly for under-the-hood applications in cars, and other mechanical parts.
Page 8 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 aterproofed 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.
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. as 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. Toxicity Due to their insolubility in water and relative chemical inertness, pure plastics generally have low toxicity in their finished state, and will pass through the digestive system with no ill effect (other than mechanical damage or obstruction). However, adipates and phthalates are often added to brittle plastics like polyvinyl chloride (PVC) to make them pliable enough for use in food packaging, children’s toys and teethers, tubing, shower curtains and other items.
Traces of these chemicals can leach out of the plastic when it comes into contact with food. Out of these concerns, the European Union has banned the use of DEHP (di-2-ethylhexyl phthalate), the most widely used plasticizer in PVC. Some compounds leaching from polystyrene food Page 9 containers have been found to interfere with hormone functions and are suspected human carcinogens. Moreover, while the finished plastic may be non-toxic, the monomers used in its manufacture may be toxic; and small amounts of those chemical may remain trapped in the product.
The World Health Organization’s International Agency for Research on Cancer (‘ARC) has recognized the chemical used to make PVC, vinyl chloride, as a known human carcinogen. Some polymers may also decompose into the monomers or other toxic substances when heated. The primary building block of polycarbonates, bisphenol A (SPA), is an estrogen-like endocrine disruptor that may leach into food. Research in Environmental Health Perspectives finds that BPA leached from the lining of tin cans, dental sealants and polycarbonate bottles can increase body weight of lab animals’ offspring.
A more recent animal study suggests that even low-level exposure to BPA results in insulin resistance, which can lead to inflammation and heart disease. As of January 2010, the LA Times newspaper reports that the United States FDA is spending $30 million to investigate suspicious indications of BPA being linked to cancer. Bis(2-ethylhexyl) adipate, present in plastic wrap based on PVC, is also of concern, as are the volatile organic compounds present in new car smell. The European Union has a permanent ban on on the use of phthalates in toys.
In 2009, the United States government banned certain types of phthalates commonly used in plastic. Environmental issues Plastics are durable and degrade very slowly; the molecular bonds that make plastic so durable make it equally resistant to natural processes of degradation. Since the 1950s, one billion tons of plastic has been discarded and may persist for hundreds or even thousands of years. In some cases, burning plastic can release toxic fumes. Burning the plastic polyvinyl chloride (PVC) may create dioxin.
Also, the anufacturing of plastics often creates large quantities of chemical pollutants. page 10 except in life-critical fire suppression systems; see Montreal Protocol), the production of polystyrene contributed to the depletion of the ozone layer; however, non-CFCs are currently used in the extrusion process. By 1995, plastic recycling programs were common in the United States and elsewhere. Thermoplastics can be remelted and reused, and thermoset plastics can be ground up and used as filler, though the purity of the material tends to degrade with each reuse cycle.
There are methods by which plastics can be broken back down o a feedstock state. To assist recycling of disposable items, the Plastic Bottle Institute of the Society of the Plastics Industry devised a now-familiar scheme to mark plastic bottles by plastic type. A plastic container using this scheme is marked with a triangle of three cyclic arrows, which encloses a number giving the plastic type: Plastics type marks: the resin identification code 1 . PET (PETE), polyethylene terephthalate: Commonly found on 2-liter soft drink bottles, water bottles, cooking oil bottles, peanut butter Jars. . HDPE, high-density polyethylene: Commonly found on detergent bottles, milk Jugs. . PVC, polyvinyl chloride: Commonly found on plastic pipes, outdoor furniture, siding, floor tiles, shower curtains, clamshell packaging. 4. LDPE, low-density polyethylene: Commonly found on dry-cleaning bags, produce bags, trash can liners, and food storage containers. 5. PP, polypropylene: Commonly found on bottle caps, drinking straws, yogurt containers. 6. PS, polystyrene: Commonly found on “packing peanuts”, cups, plastic tableware, meat trays, take-away food clamshell containers Page 1 1 7.
OTHER, other: This plastic category, as its name of “other” implies, is any plastic ther than the named #1-#6, Commonly found on certain kinds of food containers, Tupperware, and Nalgene bottles. Unfortunately, recycling plastics has proven difficult. The biggest problem with plastic recycling is that it is difficult to automate the sorting of plastic waste, and so it is labor intensive. Typically, workers sort the plastic by looking at the resin identification code, though common containers like soda bottles can be sorted from memory. Other recyclable materials, such as metals, are easier to process mechanically.
However, new mechanical sorting processes are being utilized to ncrease plastic recycling capacity and efficiency. While containers are usually made from a single type and color of plastic, making them relatively easy to sort out, a consumer product like a cellular phone may have many small parts consisting of over a dozen different types and colors of plastics. In a case like this, the resources it would take to separate the plastics far exceed their of Active Disassembly, which may result in more consumer product components being re-used or recycled.
Recycling certain types of plastics can be unprofitable, as well. For example, polystyrene is rarely recycled because it is usually not cost ffective. These unrecycled wastes are typically disposed of in landfills, incinerated or used to produce electricity at waste-to-energy plants. 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 ill 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 Department of Mechanical Engg, SKIT page 12 German chemical company BASF makes Ecoflex, a fully biodegradable polyester for food packaging applications. Bioplastics Some plastics can be obtained from biomass, including: rom pea starch film with trigger biodegradation properties for agricultural applications (TRIGGER). from biopetroleum. Oxo-biodegradable Oxo-biodegradable (OBD) plastic is polyolefin plastic to which has been added very small (catalytic) amounts of metal salts.
As long as the plastic has access to oxygen (as in a littered state), these additives catalyze the natural degradation process to speed it up so that the OBD plastic will degrade when subject to environmental conditions. Once degraded to a small enough particle they can interact with biological processes to produce to water, carbon dioxide and biomass. The process is shortened from hundreds of years to months for degradation and thereafter process is not fast enough to meet ASTM D6400 standards for definition as compostable plastics.
Price, environment, and the future The biggest threat to the conventional plastics industry is most likely to be environmental concerns, including the release of toxic pollutants, greenhouse gas, litter, biodegradable and non-biodegradable landfill impact as a result of the production and disposal of petroleum and petroleum-based plastics. Of particular concern has been the recent accumulation of enormous quantities of plastic trash in cean gyres. For decades one of the great appeals of plastics has been their low price.
Yet in recent years the cost of plastics has been rising dramatically. A major cause is the sharply rising cost of petroleum, the raw material that is chemically altered to form commercial plastics. page 13 With some observers suggesting that future oil reserves are uncertain, the price of petroleum may increase further. Therefore, alternatives are being sought. Oil shale and tar oil are alternatives for plastic production but are expensive. Scientists are seeking cheaper and better alternatives to petroleum-based plastics, and many andidates are in laboratories all over the world.
One promising alternative may be fructose. Common plastics and uses A chair made with a polypropylene seat Polypropylene (PP) Food containers, appliances, car fenders (bumpers), plastic pressure pipe systems. Polystyrene (PS) Packaging foam, food containers, disposable cups, plates, cutlery, CD and cassette boxes. High impact polystyrene (HIPS) Fridge liners, food packaging, vending cups. Acrylonitrile butadiene styrene (ABS) Electronic equipment cases (e. g. , computer monitors, printers, keyboards), drainage pipe. Page 14
