1. Definition Of Plastics 2. Plastics Fabrication
1. Definition of PlasticsØThermoplasticsØPolymers that are converted into shapesby processes involving flow of liquid(molten) polymer before solidification2. Plastics FabricationØ Compression molding – also used for thermosetsØ Polymer powder or monomers placed in one half of moldØ Application of pressure and heating melts polymer (or causesmonomers to react) to form shape of moldØ Cross-linking can occur, especially for thermosetsØMust melt at a reasonable temperatureØMust be flowable when moltenØMust be easily shaped or fabricated3. Plastics FabricationØVacuum moldingØHot polymer sheet placed over top of moldØVacuum pulls polymer to walls of chilled mold4. Plastics FabricationØInjection molding of thermoplasticsØGranular polymer melted in heated screwØForced through an opening directly into cooled moldr1
5. Plastics FabricationØInjection molding of polyurethane (thermoset)resins (reaction injection molding or RIM)ØSeparate compartments for polyol and isocyanateØFed into the mold where polymerization takes place7. Plastics Fabrication6. Plastics FabricationØExtrusionØForcing molten polymer through a die (shapedopening)Polymerpellets8. Plastics FabricationNIP ROLLSØBlow moldingØMolten polymer extruded through circular die to formbubble or parisonØAir injected, forcing polymer to walls of the cooledmoldØBlown filmØMolten polymer forcedthrough circular dieØAir flow forms bubble,shape controlled bycooling ringØBubble can be 7 ft indiameter and 30 ft tallØBubble collapsed viarollers to form wide sheets(films)ØSheets rolled up forfurther cutting and sizingFLATTENING ROLLSBLOWNTUBEAIR RING TOCOOL PLASTICDIEAIR INLETr2
9. Plastics FabricationØExtrusion coatingØMolten polymer extruded onto cooled substrateØForms solid film instantly upon contact with substrate11. Plastics FabricationØCalendering10. Plastics FabricationØCast film formationØMolten polymer extruded onto chilled rollØForms solid film instantly upon contact with roll12. Plastics FabricationØWire and cable coatingØMolten polymer pressed into thin film by passingthrough rollers with increasingly more narrow gapsr3
13. General Plastics UsesUses of ThermoplasticsPackagingBuilding and constructionConsumer productsElectrical equipmentFurnitureTransportation equipmentMiscellaneous32%141365426Uses of ThermosetsBuilding and constructionTransportation equipmentAdhesives, coatingsConsumer productsElectrical equipmentMiscellaneous69%84441114. Definition and ClassesContainers,lids, filmPiping, siding,fittingsPlywoodadhesivesØPlasticØPolymers that are converted into shapes byprocesses involving flow of liquid (molten) polymerbefore solidificationØPlastics can be identified and characterized bythe shape of their stress-strain t-toughØSoft-weak15. Stress-Strain Curve16. Stress-Strain CurveArea under curve total energy tobreakLarger area tougher polymerSlope measure ofstiffnessYoung’sModulusStress (psi)Yield pointYield elongationStrain (% elongation)r4
17. Stress-Strain Curve18. Definition and ClassesØHard high modulus (steep slope)ØTough high elongationØStrong moderate elongation and high modulusClass StrengthHighHighHighHighHard andtoughElastomers15 - 150100 - 1000LowNatural rubberModulus (psi)Percent ElongationCrystallinityPolymer examplePlastics1,500 - 200,00020 - 100ModeratePolyethyleneFibers150,000 - 1,500,000 10HighNylon19. Important PlasticsØHard and tough(CH2ØHigh density polyethylene, HDPEØManufacture ?ØPropertiesØLittle branching ( 7 per 1000 C atoms)ØHigh crystallinity (T m 135 o C, Tg -70 to – 20oC)ØRelatively opaqueØRelatively stiff, hard with high tensile strengthØDensity 0.94 g/ccElongationat BreakExamplesHighHigh density polyethyleneCellulosicsPolyamides (Nylon)PolyestersPolypropyleneEngineering plasticsPolyacetal, polycarbonatePolyimide, polyphenylenesulfide, polyphenylene oxidePolysulfoneModeratePoly(vinyl chloride) PVCImpact polystyreneStyrene-acrylonitrileHard andstrong20. Important PlasticsCH2)nØHard and tough(CH2CH2)nØHigh density polyethylene, HDPEUses of HDPEBlow moldingInjection moldingFilmPipe and conduitSheetWire and cableMiscellaneous35%221714615Bottles, gas tanksCrates, pails, toysPackagingWater and sewer,low pressure gasdistributionØEconomicsØ12.5 billion pounds produced in 2001ØCurrently about 0.48 per poundØCommercial value 6.0 billionØRecent growth rate: 5 – 6% per year, except for 2001ØHeavily recycledr5
21. Important PlasticsØHard and toughØPolypropylene, PP(CH222. Important PlasticsCH3ØHard and toughCH)nØPolypropylene, PPØManufacture ?(CH2Uses of PPInjection moldingFibers and filamentsDistributors and compoundersFilm and sheetBlow moldingMiscellaneousØWhat does isotactic mean?ØPropertiesØStiffer, harder, higher tensile strength than HDPEØTm 170 oC, Tg -10 oC (brittle at low temperatures)ØMore degradable by heat, light and O2 than HDPE due to ?ØStabilizers and antioxidants are requiredØDensity 0.91 g/ccOOCC O CH2ØManufacture ?CH nsileStrengthHighHighHighHighØTm 250 – 265 oC, Tg 70 oC60%3010Carpet backing,carpet fibers,ropesØHard high modulus (steep slope)ØTough high elongationØStrong moderate elongation and high modulusClass ofPlasticUses of PETSoft drink bottlesOther containersAmorphous and crystallizedContainers, toys,furniture23. Definition and ClassesnØPoly(ethylene terephthalate), PET31%30231123CH)nØ EconomicsØ16 billion pounds produced in 2001ØCurrently about 0.34 per poundØCommercial value 5.4 billionØRecent growth rate: 6.5 % per yearØRecycling may become important23. Important PlasticsØHard and toughCH3Hard andtoughElongationat BreakExamplesHighHigh density polyethyleneCellulosicsPolyamides (Nylon)PolyestersPolypropyleneEngineering plasticsPolyacetal, polycarbonatePolyimide, polyphenylenesulfide, polyphenylene oxidePolysulfoneModerateØEconomicsØAs a plastic, 10 – 15 % growth rate per yearØCurrently about 0.55 per poundØHigh recycling rateHard andstrongPoly(vinyl chloride) PVCImpact polystyreneStyrene-acrylonitriler6
25. Important PlasticsØHard and strongØPoly(vinyl chloride), PVC(CH226. Important PlasticsClØHard and strongCH)nØPoly(vinyl chloride), PVCØManufacture ?ØPropertiesØTm 140 oC, Tg 70 – 85 o CØLow crystallinityØGood chemical resistanceØDegraded by heat and light (Why?)ØExpected to be brittle or pliable at 0 oC?ØBecomes soft, tough polymer with 1-2 wt % plasticizerØPlasticizer dioctyl phthalateØPlasticized PVC27. Definition and ClassesØSoft low modulus (shallow slope)ØTough high elongationØWeak moderate elongationClass ileStrengthLowElongationat BreakHighSoft andweak76%6424CH)nSiding, roofing, gutters,water pipes, flooringCredit cardsØPlasticized PVC used in medical bags and tubingØEconomicsØAbout 14 billion pounds produced in 2001ØCurrently about 0.36 per poundØCommercial value 5.0 billionØGood growth rate in recent years (6.4 % per year) except2000-2001ØEconomics tied to which industry?28. Important Plastics(CH2CH2)nØLow-Density Polyethylene, LDPEØManufacture ?ExamplesØPropertiesSoft andtoughLow(CH2ØSoft and ToughLow density polyethyleneLinear low density PEPlasticized PVCIonomerLowUses of PVCConstructionConsumer goodsElectrical fittings, wire and cableHome furnishingsMiscellaneousClLowModeratePolyethylene waxesØHigh degree of branchingØ 60 branches per 1000 carbons – How are these formed?ØTm 115 oC, lower than HDPE and LLDPEØLow crystallinity high clarity for filmsØGreater permeability to gases than HDPEØDensity between 0.90 and 0.94 g/ccØReadily processed (flows well when molten)r7
29. Important PlasticsØSoft and Tough(CH230. Important PlasticsCH2)nØLow-Density Polyethylene, LDPEUses of LDPEFilmExtrusionInjection moldingWire and cableAdhesives and sealantsMiscellaneousØSoft and ToughØLinear Low-Density Polyethylene, LLDPEØManufacture ?Packaging, trash bagsPaper coatings59%1764410Squeeze bottles, toysØPropertiesØEconomicsØ6.9 billion pounds produced in 2001ØCurrently about 0.49 per poundØCommercial value 3.4 billionØFlat consumption due to competition from (substitution by)LLDPE31. Important PlasticsØSoft and ToughØModerate degree of branching due to occasional insertion ofcomonomerØHigher melting, lower clarity than LDPEØ More or less crystalline?ØHigher tensile strength (stronger) than LDPEØDensity between 0.91 and 0.94 g/cc32. The Three PE’sØComparison of the three PE’sØLinear Low-Density Polyethylene, LLDPEUses of LLDPEFilmInjection moldingRotational moldingWire and cableMiscellaneous72%96310Shrink wrap, packaging,heavy duty trash bagsØEconomicsØ7.6 billion pounds produced in 2001ØCurrently about 0.39 per poundØCommercial value 3.0 billionØHigh growth rate (7.4 % per year, except for 2000-2001),mainly by replacing LDPEr8
33. The Three PE’s34. The Three PE’sØStress-strain curves – Which is which?highly crystalline polymerLDPESCB: YESLCB: YEScross-linksHDPEamorphouspolymerFew short chain branches (SCB)Note the way the polymerstrands pack togetherWhich polymer is mostflexible? Why?LLDPESCB : YESsemi-crystalline35. Definition and Classes36. Important PlasticsØHard and brittleØHard high modulus (steep slope)ØBrittle low elongationClass ofPlasticHard andbrittleYieldModulus StressHighNo nØPolystyrene, PSØManufactureElongationat BreakLowExamplesPhenol-formaldehyde, ureaformaldehyde and melamineformaldehyde resinsPolystyrenePoly(methyl methacrylate)Unsaturated polyester resinsEpoxy resinsØPropertiesØTm 227 oC, Tg 94 o CØAmorphous, low crystallinityØFlammableØYellows in light – requires UV stabilizationØWhy is this polymer unstable to light?r9
37. Important PlasticsØHard and brittle(CH238. Plastics EconomicsØPlastics Material and Resin ManufacturingCH)nØ11 % of total for all of Chemical ManufacturingØPolystyrene, PSØHigh growth rate relative to other polymers 5048%1713976Plas. Matls & ResinsClear clam shellsOrg. Fib.-Noncell. 40Billions of DollarsUses of PSPackaging and one-time useElectrical and electronicsConstructionConsumer productsMedical productsMiscellaneousØEconomicsØ2.5 % growth rate from 1990 – 2000, -11% from 2000-2001ØAbout 6.1 billion pounds produced in 2001ØCurrently about 0.52 per poundØCommercial value 3.2 billionSynthetic RubberOrg. Fib.-Cellulosic 30 20 10 07085909540. Plastics EconomicsØGrowth Rates, except for 2000 – 0-5.6%2.5-0.52.98.64.73.54.60%ØHDPE 5 % AAGRØLLDPE 7 - 8 % AAGR – slightly higher than PPØLDPE 0.5 % AAGR16HDPE14Billions of PoundsØRecent growth ratesPolymer80Year39. Plastics EconomicsPlasticsPolyethyleneLow densityLinear low densityHigh densityPolypropyleneStyrene ile-butadiene-styrene & otherPolyamidePolyvinyl chloride & copolymersEpoxyTotal75LDPE121084.0 %68.4 %42089“Facts and Figures for the Chemical Industry”, C&E News,June 24, 2002, p. 63-6410.7 %LLDPE909192939495969798990001Yearr10
41. Requirements for FibersØHigh tensile strength (tenacity)ØPliable but low elongationØAbrasion resistantØHigh melting point (esp. for clothing)ØTm 200 oC (iron without damage) but 300 oC toenable spinning from meltØTg 100 oC so fibers soften when ironed at 150 oCØCreases removedPolymerPETNylon 6,6PANPPoTg ( C)7060105-5oTm ( C)26526532016543. Spinning of Fibers42. Requirements for FibersØFibers are pulled (drawn) during spinningØMelt spinningØWet spinning (polymer dissolved in solvent,filaments extruded into non-solvent)ØDry spinning (polymer dissolved in solvent, solventevaporates)ØDrawing orients amorphous regions, strongerfibers resultØDrawing makes fibers much stronger indirection of draw than across it (anisotropic)44. Requirements for FibersØSymmetrical, unbranched polymerØHigh crystallinity promotes linear molecularalignment – this is criticalØHigh cohesive energy (intermolecular forces)ØStrong intermolecular forces promoteØHigh tenacity, fiber strength, low elongationhydrogen bonding:dipole-dipole:HCHC NOOδ C OOδHHO HC NCHOcellulosicsproteins, nylonsδ C OOδpolyestersCHNδ- Cδδ C NδCHacrylicsr11
45. Requirements for FibersØRigid backbonestructures46. Requirements for FibersØRank these fibers by ids (aromaticpolyamides)Øhigh stiffnessØheat OOCH2CH2nOCnOØCompete with wireand glass fibersØForm rodlikepolymersOOCOOOCCnOOCCOOCH2OCH2CH2nOCH2ONHNH CCOnn47. Important FibersØNylonNHØManufacture(CH2)5OOCCnnylon 648. Important FibersC NH(CH2)6NHØDyeableØStrong, hard wearing fiberØWithstands high temperatureØHydrophobicnNHnylon 6,6ØNylon 6,6 formed by condensation polymerization betweenadipic acid and hexamethylenediamineØ280 – 300 oC under vacuumØAcetic acid terminates chains, controls MwØPropertiesØNylonO(CH2)4(CH2)5OOCCnnylon 6Uses of NylonCarpets and rugsIndustrialApparelO(CH2)4C NH(CH2)6NHnnylon 6,674%1610Belts, hoses,tire cordsØEconomicsØProduction relatively flat for past 15 yearsØ2.6 billion pounds produced in 2000ØNylon 6,6 is two-thirds of US market, nylon 6 is one-thirdØCarpet and rug markets increasing, other applicationsdecreasingr12
49. Important FibersØPolyesterØManufactureOOCC OCH2CH250. Important FibersØPolyesterOOCC OCH2CH2OnØInitial formation of oligomers by:nUses of PolyesterClothingHome furnishingsIndustrialØ Reaction of TPA and ethylene glycolØ Reaction of DMT and ethylene glycolØPolymerization at 200 – 290in vacuo with SbO3 catalystØFibers melt spun like nylon at about 260 oCoC50%2030ØEconomicsØPropertiesØReadily blended with other fibers (cotton)ØChoice of phthalate can vary tensile and elongationpropertiesØHydrophobic (does not absorb water)ØStains easilyØStatic chargeØLargest volume fiber producedØ3.9 billion pounds produced in 2000ØLarge production increases in 1970’sØRoughly same amount produced in 1980 and in 2000Ø Decreased slightly from 1980 – 1990Ø Increased slightly from 1990 – 200051. Important Fibers52. Important lyolefin(CH2ØIsotactic polypropylene prepared by Ziegler-Nattacatalyzed polymerizationØSome HDPE (from Ziegler-Natta catalysis) formonofilamentsØFibers produced by melt spinningØFiber strength achieved by high molecular weightØ Only weak intermolecular forces (van der Waals)ØPropertiesØLow density (0.91 g/cc) yield lightweight fiberØChemical and abrasion resistanceØGood insulating propertiesØNot easily dyedCH2)nØUses(CH2CH)n(CH2CH2)nØIndustrial (rope, belts, carpet backing awnings)ØHome textile (floor covering, upholstery fabric, blankets)ØApparel (sportswear, hosiery)ØDiapers (nonwoven fibers)ØEconomicsØLargest growth segment within fibersØSteady growth of 6 – 8 % per year since 1982ØSurpassed nylon in 1998ØClosing in on polyester as the highest production fiberr13
53. Fiber Production54. Important FibersØPolyester most important synthetic fiberØPolyolefins are rising star (PP)ØHighest growth rate – nearly 6% per yearBillions of 642070758085909500Year55. Properties of ElastomersØRequirements for ElastomersØCompletely amorphous, used above their TgØLow intermolecular forces allow for flexibilityØHigh modulus and strength when stretchedØOften crystallize when stretchedØLarge reversible extensions (several hundredpercent)Ø High localized chain movements, low overall movement of chainsrelative to one anotherØ Cross-linked chains prevent slippage56. Properties of ElastomersØPossess high molar mass to allow chainentanglements or are cross-linkedØGives dimensional stabilityØCross-linked with sulfurØReaction at allylic CH2CH2CHnSyCH2nHH2CCCH2CCH2ny 1 or 2slipr14
57. Important ElastomersØNatural Rubber, iene, BRC C(CH2Biological polymerizationAgricultural cropTg -70 oCPrimary use is auto tires2.2 billion lb/yr – all importedFree-radical polymerizationPrimary use is auto tiresAlso belts, hoses, gaskets1.33 billion lb/yrTg -110 oCHHCH2)n58. PolybutadieneReaction:nCH2CH CH CH2(CH21,3-butadieneCH CH CH2)npolybutadieneMechanism:(1) ROOR2RO(2)RO(3)RO CH2 CH2CH CH CH2ROCH CH CH2 CH2ROCH2CH CH CH2S -ButadieneRubber, SBR(CH2CH CH CH2)n(CH2CH)nFree radical polymerizationMechanism?Tg -65 oCPrimary use is auto tiresCompetes with NR1.93 billion lb/yrCH2CH CH CH2Vulcanization:(CH2CH CH CH2)nCH CH CH)nSS(CH259. Important ElastomersBiological polymerizationAgricultural cropTg -70 oCPrimary use is auto tires2.2 billion lb/yr – all importedCH CH CH2then (3), (3), (3), etc.Why is the Tg 40 oC lower than that of natural rubber?ØNatural Rubber, NRCH2CH CH CH2CH CH CH)n60. CopolymerizationØMany important elastomers like SBR arerandom copolymersØSequence of monomer insertion is completelyrandomØRandom arrangement of styrene and butadieneØSBR (styrene-butadiene rubber)ØCopolymer with 6:1 butadiene:styrene compositionnCH2CH nCH2CH2CH CH CH2CH CH2CH CH CH2CH2CH CH CH2r15
61. Copolymerization62. Important ElastomersØAnother important elastomer is formed byrandom polymerization of three monomersØAcrylonitrile, butadiene, and styreneØABS acrylonitrile-butadiene-styrene terpolymerCH2CH CH2CH CH CH2 CH2ØEthylene-PropyleneDiene Monomer, EPDM(CH2CH2)n(CH2CH)nCH3CH CH3CHdiene dimerCNCH2CH CH 2CH CH CH2CH2CHCNØPolyisobutylene, ButylRubberCH3ØThree monomers need not be present in the sameamount(CH2C)nCH3(CH2CCH CH2)1Ziegler-Natta catalystRandom arrangement of C2and C3 units createshighly flexible polymerDiene provides reactivesites for cross-linking0.76 billion lb/yrCationic polymerizationMechanism?Isoprene used to cross-linkPrimarily used for tubesand tiresCH3r16
Jun 24, 2002 · Elastomers Plastics Fibers Modulus (psi) 15 - 150 1,500 - 200,000 150,000 - 1,500,000 . ØGreater permeability to gases than HDPE ØDensity between 0.90 and 0.94 g/cc ØReadily processed (flows well when molten) (CH 2 CH 2) n. r8 . Plastics Economics ØGrowth Rates, except for 2000 – 2001 .
Mapping of global plastics value chain and plastics losses to the environment onment 2 Table of contents Table of contents List of Acronyms 4 Types of plastics 5 Executive summary 6 Technical summary 9 1 oduction Intr 17 1.1. Objective 19 1.2. General methodology 19 1.3. Report structure 21 2 Global plastics value chain 23
Engineered Plastics Cope Plastics, Inc. has hired John Thiel as director of sales - engineered plastics. Thiel joins Cope Plastics from All-State Industries where he . territory manager for Quadrant (formerly known as DSM) and has been working as a
KEY FIGURES* The European plastics industry includes plastics raw materials producers, plastics converters, plastics recyclers and plastics & rubber machinery producers in the EU27 3. KEY
FRP - Fiber Reinforced Plastics. FRP has been used alternatively to mean fiberglass reinforced plastics, fiber reinforced plastics and many other reinforced plastics. In this guide, it means plastics reinforced with fibers or strands of some other material. Ganged Woven Ravings - An FRP laminate consisting of adjacent layers of woven rovings .
definition, semi-formal definition and non-formal definition.Besides, definition by stipulation and expanded definition are also explicit definitions. 3.1. Formal definition. It provides maximum information at the highest possible level of precision. This is the traditional type of definition and it consists of three parts:
EEC Study of non-recycled plastics-August 2011 2 ENERGY AND ECONOMIC VALUE OF NON-RECYCLED PLASTICS (NRP) AND MUNICIPAL SOLID WASTES (MSW) THAT ARE CURRENTLY LANDFILLED IN THE FIFTY STATES EXECUTIVE SUMMARY Mechanical recycling of plastics has continued to grow in the United States, with 2.1 million tons of plastics recycled in 2009.
VALUE ADDED MULTIPLIER EFFECT RECYCLING 13. PLAS TICS. PLAS TICS Market data PLASTICS. 2015 2015 2016 2016 WORLD World and EU plastics production data 322 58 335 60 Includes plastic materials (thermoplastics and polyurethanes) and other plastics (thermosets, adhesives, coatings and sealants). Does not include: PET fibers, PA fibers, PP fibers .
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