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Index
COVER
TITLE PAGE
PREFACE
ACKNOWLEDGMENTS
LIST OF PLASTIC MATERIALS
1 THE ANTHROPOCENE
1.1 ENERGY FUTURES
1.2 MATERIALS DEMAND IN THE FUTURE
1.3 ENVIRONMENTAL POLLUTION
REFERENCES
2 A SUSTAINABILITY PRIMER
2.1 THE PRECAUTIONARY PRINCIPLE
2.2 MICROECONOMICS OF SUSTAINABILITY: THE BUSINESS ENTERPRISE
2.3 MODELS ON IMPLEMENTING SUSTAINABILITY
2.4 LIFE CYCLE ANALYSIS
2.5 THE EMERGING PARADIGM AND THE PLASTICS INDUSTRY
REFERENCES
3 AN INTRODUCTION TO PLASTICS
3.1 POLYMER MOLECULES
3.2 CONSEQUENCES OF LONG-CHAIN MOLECULAR ARCHITECTURE
3.3 SYNTHESIS OF POLYMERS
3.4 TESTING OF POLYMERS
3.5 COMMON PLASTICS
REFERENCES
4 PLASTIC PRODUCTS
4.1 PLASTICS: THE MIRACLE MATERIAL
4.2 PLASTIC PRODUCTION, USE, AND DISPOSAL
4.3 PROCESSING METHODS FOR COMMON THERMOPLASTICS
4.4 THE ENVIRONMENTAL FOOTPRINT OF PLASTICS
4.5 PLASTICS ADDITIVES
4.6 BIOPOLYMER OR BIO-DERIVED PLASTICS
REFERENCES
5 SOCIETAL BENEFITS OF PLASTICS
5.1 TRANSPORTATION APPLICATIONS OF PLASTICS
5.2 BENEFITS FROM PLASTIC PACKAGING
5.3 PLASTICS IN AGRICULTURE
5.4 BUILDING INDUSTRY APPLICATIONS
5.5 ORIGINAL EQUIPMENT MANUFACTURE (OEM)
5.6 USING PLASTICS SUSTAINABLY
REFERENCES
6 DEGRADATION OF PLASTICS IN THE ENVIRONMENT
6.1 DEFINING DEGRADABILITY
6.2 CHEMISTRY OF LIGHT-INDUCED DEGRADATION
6.3 ENHANCED PHOTODEGRADABLE POLYOLEFINS
6.4 BIODEGRADATION OF POLYMERS
6.5 BIODEGRADABILITY OF COMMON POLYMERS
REFERENCES
7 ENDOCRINE DISRUPTOR CHEMICALS
7.1 ENDOCRINE DISRUPTOR CHEMICALS USED IN PLASTICS INDUSTRY
7.2 BPA {2,2-BIS(4-HYDROXYPHENYL)PROPANE}
7.3 PHTHALATE PLASTICIZERS
7.4 POLYBROMINATED DIPHENYL ETHERS (PBDEs)
7.5 ALKYLPHENOLS AND THEIR ETHOXYLATES (APE)
7.6 EDCs AND PET BOTTLES
REFERENCES
8 PLASTICS AND HEALTH IMPACTS
8.1 PACKAGING VERSUS THE CONTENTS
8.2 PACKAGE–FOOD INTERACTIONS
8.3 STYRENE AND EXPANDED POLYSTYRENE FOOD SERVICE MATERIALS
8.4 RANKING COMMON PLASTICS
REFERENCES
9 MANAGING PLASTIC WASTE
9.1 RECOVERY OF WASTE
9.2 PYROLYSIS OF PLASTIC WASTE FOR FEEDSTOCK RECOVERY
9.3 SUSTAINABLE WASTE MANAGEMENT CHOICES
9.4 MECHANICAL RECYCLING OF PLASTICS
9.5 RECYCLING BOTTLES: BEVERAGE BOTTLES AND JUGS
9.6 DESIGNING FOR RECYCLABILITY
REFERENCES
10 PLASTICS IN THE OCEANS
10.1 ORIGINS OF PLASTICS IN THE OCEAN
10.2 WEATHERING OF PLASTICS IN THE OCEAN ENVIRONMENT
10.3 MICROPLASTIC DEBRIS
10.4 OCEAN LITTER AND SUSTAINABILITY
REFERENCES
INDEX
END USER LICENSE AGREEMENT
Table 1.1 Approximate Global Use of Selected Building Materials (2011 Data)
Table 1.2 Estimated Future Global Supply of Some Common Metals
Table 1.3 The Use Sectors, Global Reserves, and Production of Selected Critical Materials
Table 1.4 Classification of Environmental Pollution Events
Table 3.1 Glass Transition Temperature of Common Plastics
Table 3.2 Structure of Common Addition Polymers and their Applications
Table 3.3 Some Common Condensation Polymers
Table 3.4 Characteristics of Common Classes of Polyethylenes
Table 3.5 Properties of Different Grades of Polystyrene
Table 3.6 A Comparison of Properties For Polyolefins
Table 4.1 Choices Available in Selecting a Polystyrene Resin in the US Market a
a
Table 4.2 Commonly Used Processing Techniques for thermoplastics
Table 4.3 Commonly Used Processing Techniques for thermoset Materials
Table 4.4 Relative Energy intensity of Selected Plastic Processing Techniques
Table 4.5 Estimate of Plant Energy Distribution for Three Plastic Processes
Table 4.6 Comparison of EE Values and Carbon Emissions for Different Building Materials
Table 4.7 Energy-saving Opportunities in Plastics Processing
Table 4.8 Levels of Common Additives Used in Common Plastics
Table 4.9 Selected Examples of the Three Classes of Plastics
Table 4.10 Highest-capacity Bio-based Plastics by 2015
Table 5.1 Density, Modulus, and Strength of Materials Used in Automobiles
Table 5.2 Common Plastics Components Used in Automobiles
Table 5.3 Estimate of EE and GWP (kg CO 2 ) Per 1 l Package
2
Table 5.4 Embedded Energy, Solid Waste Generated, and GWP Per 10,000 Units of 12 oz Packages Manufactured
Table 5.5 Greenhouse Glazing Materials and their Characteristics
Table 5.6 A Comparison of Leading Materials Used in Window Frames
Table 5.7 The Thermal Conductivity and Environmental Performance Rating of Common Building insulation Materials
Table 5.8 Main Types of thermoplastics Used in Building Construction
Table 5.9 Candidate Wood Fibers for Wood–plastic Composites
Table 5.10 Main Types of Plastics Used in Equipment and Household Goods Manufacture
Table 6.1 Most Damaging Range of Wavelengths in Sunlight for Common Thermoplastics
Table 6.2 Location-dependent Enhancement in Photodegradation Obtained Using ECO Copolymer in Place of LDPE Laminate of Same Thickness (Andrady et al., 1993a)
Table 6.3 Main Environments in Which Plastic Litter is Found
Table 6.4 A Listing of ASTM Test Methods Related to Degradation of Plastics
Table 6.5 Summary of Estimates of Biodegradation of Polyethylenes in Natural Environments by Weight Loss Method
Table 7.1 A Summary of EDCs of Concern Relevant to Plastics and their Adverse Impacts on Human Health and on Animal Life
Table 7.2 Human Body Burden of BPA (only Studies with Sensitivity < ~0.1 Ng/g Reported)
Table 7.3 Examples of BPA Extraction by Different Liquids in Contact with Baby Bottles
Table 7.4 A Summary of Biological Effects of Exposure to BPA at Low Doses
Table 7.5 Common Phthalate Plasticizers and their Characteristics
Table 7.6 Typical Concentrations of DEHP in Water and Air
Table 7.7 A Summary of Effects of Human Exposure to Phthalates
Table 7.8 Some Examples of Nonphthalate Plasticizers For PVC
Table 7.9 The Solubility and Log K o/w for Common Classes of BDEs
o/w
Table 7.10 A Summary of Effects of Human Exposure to PBDEs
Table 8.1 The Embedded Energy and GWP of Selected Packaged Food Items (1 Kg Portions)
Table 8.2 Selected Barrier Properties of Common Plastic Packaging Films (25 μm Thick) Measured at 38°C
Table 8.3 Some Examples of Multilayer Films Used in Food Packaging
Table 8.4 Some Common Additives in Plastics Used for Packaging Food and Beverages
Table 8.5 Levels of Phthalates, OP, NP, BPA and DEHA (mean ± sd) in ng/L in the Different Food Packaging Items Considered in this Study
Table 8.6 Toxicity Levels of Monomers in Common Plastics
Table 8.7 Percentage of Component in Cold-pressed Orange Oil Sorbed by Different Plastics it was in Contact with for a 4-day Period
Table 8.8 Hazard Levels of Common Plastics Estimated from Monomer Characteristics
Table 9.1 The Plastic Types Mostly Encountered in the MSW Stream
Table 9.2 Breakdown of Different Classes of Plastics in MSW and their Recovery
Table 9.3 Yield of Products from Pyrolysis of Mixed Plastic Waste a at 440°C (dehydrochlorination Step was at 300°C for 30 Min)
a
Table 9.4 The Main Reactions Involved in Gasification
Table 9.5 Environmental Features of Plastic Waste Management Options
Table 9.6 Selected Examples of Thermolysis of Common Plastics Yielding Monomer and Mixed Fuel Gas/liquids
Table 9.7 Average Emissions from 87 WTE Plants in the United States
Table 9.8 Calculated GHG Emissions from incineration of Different Plastic Resins
Table 9.9 Indicators of Principal Environmental Impact Categories, as Evaluated for Five Plastic Waste Management Approaches
Table 9.10 A Comparison of Energy Used, GHG Emissions, and Solid Waste Generation to Produce Virgin and Recycled Resins
Table 10.1 Plastics Commonly Found in Ocean Debris
Table 10.2 Summary of Impacts on Marine Animals
Table 10.3 Degradation Agencies Available in Different Zones in the Marine Environment
Table 10.4 Summary of Results for Degradation of LDPE Control Samples, ECO Copolymer, and Metal-catalyzed Polyethylene Exposed in Air and Floating in Water at Different Locations
Table 10.5 Estimated Values of Log K PE/sw , Log K PP/sw , and Log K PS/sw for Selected Model POPs
PE/sw
PP/sw
PS/sw
Table 10.6 A Summary of Selected Studies on the ingestion of Microparticles by Marine invertebrates
Figure 1.1 Projected world population and population increments.
Figure 1.2 Rio Tinto (Red River) in Southwestern Spain devastated and tinted red from copper mining over several thousand years.
Figure 1.3 The ecological footprint of nations (hectares required per person) versus the per capita GDP of the nation.
Figure 1.4 Global energy use (open bars) and US energy use (filled bars) by source.
Figure 1.5 Hubbert’s original sketch of his curve on world oil production.
Figure 1.6 Sprawling solar energy complex in San Luis Valley, CO.
Figure 1.7 Comparison of the embodied energy (J/kg) and CO 2 footprint for different materials.
2
Figure 1.8 Estimated embodied energy (left) and carbon emissions (right) of classes of building materials globally consumed in 2011. See http://www.circularecology.com/ice-database.html.
Figure 1.9 Critical elements likely to be in short supply in the near future. The shaded boxes are those identified by the US DOE study (2010). The others are additional critical elements identified by a European Commission (2010).
Figure 1.10 Illustration of the life cycle of a product showing different steps. Residues are the externalities associated with each phase. Each phase also requires the input of energy.
Figure 1.11 Global average temperature variation and global CO 2 emissions over time.
2
Figure 2.1 Linear flow of materials supporting an expanding consumer base.
Figure 2.2 Sustainable development depicted in simple diagrams.
Figure 2.3 Schematic illustration of the emphasis in business planning and implementation.
Figure 2.4 Production possibilities frontier with illustrative placement of business entities.
Figure 2.5 Improving the environment quality of product also increases profit.
Figure 2.6 Investment in better technology allows the choice of simultaneous gains in both goods to be secured but at a short-term cost.
Figure 2.7 Definition of “life cycle” in LCA exercises.
Figure 2.8 An example of a polygon plot summarizing LCA results on three products, based on 15 attributes.
Figure 2.9 Sustainability matrix for assessing environmental sustainability.
Figure 2.10 Downgauging of polyethylene film in plastic garbage bag applications.
Figure 3.1 The polymerization reaction of ethylene yielding polyethylene.
Figure 3.2 Left : A ball and stick model of a section of a PP chain. Right : An AFM image of a single polymer chain suggesting flexibility. Reprinted with permission from Kiriy et al., (2002). Copyright (2002) American Chemical Society.
Figure 3.3 Approximate simulation of a polymer chain with freely jointed chain model. The value of r is the end-to-end distance.
Figure 3.4 Left : Schematic drawing of the molecular weight distribution of a polymer indicating the two averagesMn andMw. Right : Schematic diagram of the molecular weight distribution for polymer samples with low and high PDI.
Figure 3.5 Illustration of the stereochemistry in a vinyl polymer. Below each structural formula is an illustration of the stereochemistry with a “ball and stick model” for polypropylene.
Figure 3.6 Left : An illustration of crystallites embedded in an amorphous polymer matrix. Right : Crystallites in plastic crystals imaged by AFM.
Figure 3.7 The change in elastic modulus E of a semicrystalline and amorphous polymers with the temperature.
Figure 3.8 Illustration of different types of copolymers. Sections of polymer chains are shown and each circle represents a repeat unit. (a) Alternating copolymer, (b) random copolymer, (c) block copolymer, and (d) branched block copolymer.
Figure 3.9 Upper: Standard dog-bone-shaped test piece used in tensile tests. Lower: Tensile deformation of a rectangular test piece. Notice shrinking of the width. Direction of strain shown by the double-headed arrow at right .
Figure 3.10 Left : Change in shape of the dog-bone test piece. Right : Tensile stress–strain curves for glass bead-filled LDPE at different volume fractions of beads.
Figure 3.11 Left : Basic features of a DSC instrument. Right : A generalized DSC tracing.
Figure 3.12 DSC tracings of two blends of atactic and isotactic PP showing the area under the melting curve. The designations indicate the weight fraction of isotactic and atactic PP in the blend.
Figure 3.13 Flow chart illustrating the manufacture of polyethylenes and polypropylenes.
Figure 3.14 Left : An electron micrograph of a thin section of HIPS showing the rubber microdomains. Right : An electron micrograph of a thin section of SBR copolymer.
Figure 4.1 The timeline for development of the common classes of thermoplastic polymers.
Figure 4.2 Upper: world plastic production in recent years. Lower: pie diagram of world thermoplastic resin capacity 2008.
Figure 4.3 Plastic resin production in different regions of the world.
Figure 4.4 A generalized flow diagram of the plastics industry showing the three phases of activity.
Figure 4.5 Schematic diagram of an injection molding machine showing the reciprocating screw and different heating zones.
Figure 4.6 An injection molding machine and examples of molded products.
Figure 4.7 Upper: schematic diagram of a single-screw extruder. Lower: a sheet extrusion die for plastics.
Figure 4.8 A diagram of the bottle blow molding process. 1. Heated parison. 2. Mold closing. 3. Blowing air into mold 4. Cooling and opening mold. 5. Molded bottle.
Figure 4.9 Embodied energy for selected classes of plastic resin. The top part of each bar is for manufacturing energy (including recovered energy), and the bottom part is for material energy.
Figure 4.10 Percentage energy used as raw materials (the lower segment of the bar), in manufacturing operations (middle, grey segment), and in transportation of raw materials (upper black segment) in the manufacture of different plastic resins in the United States.
Figure 4.11 Total direct environmental damage as a percentage of revenue for several selected industries.
Figure 4.12 Major classes of additives used in plastics industry.
Figure 4.13 Dependence of the modulus of PVC on plasticizer content. DODP and DIDP are types of phthalates TPU is a thermoplastic PU.
Figure 4.14 Basic pathways to derive chemical feedstocks from renewable and fossil fuel raw materials.
Figure 4.15 A comparison of fossil resources and carbon footprint of conventional plastics with PLA and PHA.
Figure 4.16 Schematic of PHA production facility illustrating the recycling of solid and water waste into sugarcane field. Source: Based on information from Nonato et al. (2001).
Figure 4.17 Schematic diagram of poly(lactic acid) manufacture froml-lactic acid.
Figure 5.1 Fractions of different materials used in a 2011 light vehicle.
Figure 5.2 Effect of substituting plastic packaging materials with other packaging that provides the same functionality. Unfilled bars are for plastic packaging, and the filled bars are for a mix of other packaging. Life cycle energy consumption (scale on left) and life cycle GHG emissions (scale on right).
Figure 5.3 Plastic films used as mulch in agriculture.
Figure 5.4 Main uses of plastics in building applications.
Figure 5.5 A deck made of wood–plastic composites.
Figure 6.1 Principal agents of plastics degradation in the environment.
Figure 6.2 Regions of the solar spectrum reaching the Earth’s surface.
Figure 6.3 The cyclic autoxidation reactions for a polyolefin RH.
Figure 6.4 Development of surface cracks on PP surfaces on exposure to a filtered xenon light source (600 W/m 2 ) at 42°C and at different durations of exposure.
2
Figure 6.5 Action spectrum for the light-induced yellowing of mechanical pulp.
Figure 6.6 Effect of different solar radiation wavebands on the yellowness index of unstabilized Lexan polycarbonate film (0.70 mm) exposed to natural sunlight facing 26° South in Miami, FL.
Figure 6.7 Simplified schematic of the mechanism of UV stabilization by HALS. P refers to polymer chain.
Figure 6.8 Weathering of unstabilized LDPE films ( open symbols ) and enhanced photodegradable ECO copolymer ( filled symbols ) exposed outdoors in Miami, FL.
Figure 6.9 Two sets of data showing the relationship between number–average molecular weight and the percent retention of extensibility of degraded polyethylene. The upper set is for data on high-density polyethylene oxidized in oxygen at 100°C (Klemchuk and Horng, 1984). The lower set is for poly(ethylene- co -carbon monoxide) exposed outdoors at ambient temperature in air (Andrady et al., 1993a).
Figure 6.10 A schematic diagram of biodegradation of a solid polymer showing the two main stages of primary abiotic degradation to embrittlement followed by biodegradation of fragmented residue.
Figure 6.11 Diagram illustrating the potential enhanced biodegradability of only some bio-based plastics.
Figure 6.12 Weight loss curves for PHB and PHBV (films and pellets) incubated in tropical garden soil at two exposure sites in Russia: (a) Hoa Lac and (b) Dam Bai.
Figure 6.13 Respirometry experiment for measuring evolved CO 2 in biodegradation studies.
2
Figure 6.14 A biometer flask respirometer for carrying out mineralization studies. A respirometry curve for cellophane (regenerated cellulose sheet) compared to that of oak leaves.
Figure 6.15 Gas evolution data (filled symbols) plotted as percent mineralization for the biodegradation of bleached paperboard packaging material in a respirometer. Soil media (70 wt% humidity) with sewage sludge inoculum was used. Also included is a plot of the data (open symbols) as suggested by Equation 6.2.
Figure 6.16 Electron micrographs (a–c) showing the diversity of microbial flora on polyolefin debris surfaces exposed to marine environments. Micrograph (d) shows pitting around the microbes. All scale bars are 10 µm.
Figure 7.1 Approximate mean BPA concentrations in baby bottles and canned food or beverages compared to that in plasma and the placenta (Schönfelder et al., 2002).
Figure 7.2 Examples of non-monotonic dose–response curves. Above: Effect of tumor volume in mice on the BPA levels in drinking water shows an inverted-U response. Numbers on the horizontal axis refer to µg BPA/l of drinking water available to the mice. These correspond to 0–500 pg of BPA/kg body weight. Below: Suppression of adiponectin release from human breast adipose explants by BPA and estradiol (E 2 ). (Hugo et al., 2008).
2
Figure 7.3 Baby bottles and can liners may leach polycarbonate into food.
Figure 7.4 Modulus versus plasticizer (dioctyl phthalate) concentration for PS films. Two different techniques, indentation and strain-induced elastomer buckling instability for mechanical measurements (SIEBIMM), were used to estimate the modulus of the material. The latter technique is SIEBIMM, an optical technique for assessing the modulus of thin films of material.
Figure 7.5 Chemical structures of some common phthalates with their CAS numbers in parenthesis. DEHP, di(2-ethylhexyl) phthalate; DIDP, diisodecyl phthalate; BBP, butyl benzyl phthalate; DBP, dibutyl phthalate; DnPP, di- n -pentyl phthalate.
Figure 7.6 Intake of DEHP by source for an adult. Ingestion with food is by far the most important mechanism of exposure.
Figure 8.1 Bottled water sales in the United States is on the increase with a per capita consumption of 29 US gallons in 2011.
Figure 8.2 The energy use and GWG emissions associated with the production of material and fabrication of containers for milk (~1 l). The first segment of bar is for material production, and the second is for manufacturing. Drawn from data in Ghenai (2012).
Figure 8.3 Summary of interactions between plastic packaging and the food or beverage contents.
Figure 8.4 Plastic pyramid originally proposed in 1998 by Van der Naald and Thorpe.
Figure 9.1 The composition of the USMSW stream of 250 million tons generated in the year 2010.
Figure 9.2 Generation and recovery of the plastics in municipal solid waste stream in the United States. Source: USEPA.
Figure 9.3 A comparison of the heating value of plastics and conventional fuels.
Figure 9.4 Waste management options in United States (2010). The numbers in select boxes are for percentage of plastic waste in the MSW.
Figure 9.5 Different available recovery options for plastics waste.
Figure 9.6 Schematic representation of a pyrolysis process for plastics.
Figure 9.7 Basic recovery options available for plastics waste.
Figure 9.8 Chemolysis of poly(ethylene terephthalate) (PET) into chemical feedstock.
Figure 9.9 The general structure for PSDD, PCDF, and PCB are shown in the first row. An example of a congener derived from each of these is shown in the second row.
Figure 9.10 Relative environmental merit of different plastic waste management techniques.
Figure 9.11 The avoided energy and carbon emissions per kilogram of PET mechanically recycled. GWP (Global warming potential in CO 2 equivalents). The numbers from other LCA studies can vary slightly.
2
Figure 9.12 A general scheme for recycling of plastics recovered from MSW, illustrating closed- and open-loop pathways.
Figure 9.13 Recycling symbols. PETE is polyester (PET), V is vinyl plastics, and the “other” category covers all other resins.
Figure 9.14 Calculated concentration profile of the flavor compound limonene in PET derived from a postconsumer bottle of wall thickness 300 µm, containing a beverage with 1000 ppm of limonene, after 365 days of exposure at 23°C.
Figure 9.15 An illustration of open-loop recycling of PET into fiberfill.
Figure 10.1 Upper: Change in percent original tensile extensibility of polypropylene laminate exposed in air and floating in seawater at a beach location Biscayne Bay, FL. Lower: A floating rig used to expose plastics to surface water environment (in Miami Beach, FL).
Figure 10.2 A comparison of the rate of loss in extensibility of latex rubber balloons in Beaufort, NC (left) polypropylene tape in Biscayne Bay, FL (right) exposed outdoors in air and in sea water.
Figure 10.3 SEM images of different surface textures on plastic beach debris samples. (a) Flaking of surface, (b) vermiculite texture, (c) microfracture of surface, (d) surface pitting, (e) signs of initial degradation, (f) regions of preferential degradation, (g) horizontal notching from cracks, (h) deep cracks and fractures.
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