CHAPTER 1

INTRODUCTION

The word plastics has been deeply ingrained into our society and culture, tothe point that many consider this the age of plastics. The word itself applies tomaterials that can be shaped and formed, however, today we use it to describea polymer which contains additives, such as pigments, fillers, antioxidants, andUV-protectors, to name a few. Polymers are materials composed of molecules ofhigh molecular weight. The unique material properties of plastics and versatileprocessing methods are attributed to their molecular structure. The ease withwhich polymers are processed and with which one can consolidate several partsinto a single part, as well as their high strength - to - weight ratio, make them themost sought after materials today.

1.1 STATISTICAL DATA

In the last century, plastics have gained significant importance in the technologicalas well as economic arena. Fig. 1.1 compares the production of plastics' resinsin the past 55 years to steel and aluminum. Before 1990, the figure depicts theproduction in the Western World and after that year, when the iron curtain camedown, the worldwide production. Table 1.1 presents the per capita polymer resinuse, by region, for 1980 and 2002 as well as the projected 2010 yearly production.

In general, the plastics industry can be broken down into three distinct sub-categories:

Plastics resin manufacturers and suppliers Plastics product manufacturing (Original Equipment Manufacturers (0EM Plastics machinery (Machinery supplier)

The over 18,000 different grades of resins, available today in the U.S., can bedivided into two general categories - thermosetting and thermoplastic polymers.Of the over 31 million tons of polymers produced in the United States in 1993,90% were thermoplastics. Figures 1.2 and 1.3 show a percentage break down ofU.S. polymer production of thermoplastics and thermosets, respectively. Each is

Table 1.1: Regional Break-Down of Per-Capita-Plastics Use in Kilograms

Phenolic & other taracids34%

Polyvinyl chloride &copolymers

19%

Thermoplasticpolyester

4%Acrylonitrile-

butadiene- styrene3%

All others4%

Urethane24%

Polypropylene18%

Linear low densitypolyethylene

8%

Urea18%

Low densitypolyethylene

15%

1.2: Break down of US thermoplastic production into common types.

1.3: Break-down of US thermoset production into common types.

Statistical data

2010

1 Introduction

2000

4.54.25.14.38.53.06.52.8

1990

Annual % change (2002-2010)

1980

3714630.5136241082410

2010

Year

2610520.597

12.585

14.58

2002

1970

10457.5408.55023

1980

1960

- Polymers (Density 1.1 g/cm')/!/

_ Polymers (without synthetic rubber and fibers)Steel (Density 7.8 g/cm') / ./

- Aiuminum (Density 2.7 g/cm')/1 /,

//'// .//

/:~_........1--/'~-7~- ----

...... ----~ .-J.-./----==-~-~........-:::::/ ~---------- - -------

,.-.-.-------- - ------------- --.---------- -o

1950

25

WorldwideUSLatin AmericaEuropeEastern EuropeJapanSouth East AsiaAfrica Middle East

Region

50

200

250

75

225

175Et:,g 150'E-'= 125t:o

g 100-0ea.

2

Today, the plastics industry implements polymers in a wide variety of ap-plications as shown in Figs. 1.4 and 1.5 for thermoplastics and thermosets, re-spectivelly. As depicted in the figures, packaging accounts for over one-third ofthe captive use of thermoplastics, whereas construction accounts for about halfthat number, and transportation accounts for only 4% of the total captive use ofthermoplastics. On the other hand, 69% of thermosets are used in building andconstruction, followed by 8% used in transportation.

broken down into its most common types. Of the thermoplastics, polyethylenesare by far the most widely used polymeric material, accounting for 41 % of theU.S. plastic production.

Figure 1.1: World production of raw materials (after Ehrenstein).

Figure 1.5: Break down of US thermoset applications into common areas.

5

137,800112,10095,30094,90089,10074,40070,00052,80051,70050,900

No. of EmployeesStateCaliforniaOhioMichiganTexasillinoisPennsylvaniaIndianaNew YorkNorth CarolinaWisconsin

Rank12345678910

and plastics categories

Regional Break-Down of Per-Capita-Plastics Use in Kilograms

Plastics are organic and semi-organic materials that have as their main attributea very large molecular weight. These very large molecules, or macromolecules,give them their distinct properties and material behavior, when compared to othermaterials used in manufacturing or found in nature.

Figure 1.6 presents the classification, break-down and provenance ofplastics.As presented in the figure polymers can be placed into either a thermoset, ther-moplastic or elastomer category. Thermoplastics in turn include a special familywhich is relatively new, called thermoplastic elastomers. However, all these ma-terials have in common that they are made of huge molecules. Some of thesemolecules are uncrosslinked, which means that each molecule can move freelyrelative to its neighbors, and others are crosslinked, which means that "bridges",or physical links interconnect the polymer molecules. Thermoplastics and un-vulcanized elastomers are uncrosslinked. Vulcanized rubber, or elastomers, andthermosets are cross-linked.

Thermoplastics are those polymers that solidify as they are cooled, no longerallowing the long molecules to move freely. When heated, these materials re-gain the ability to "flow", as the molecules are able to slide past each other withease. Furthermore, thermoplastic polymers are divided into two classes: amor-phous and semi-crystalline polymers. Amorphous thermoplastics are those withmolecules that remain in disorder as they cool, leading to a material with a fairlyrandom molecular structure. An amorphous polymer solidifies, or vitrifies, as

The transportation sector is one of the fastest growing areas of application forboth thermoplastic and thermosetting resins. In the U.S. alone, plastics encom-pass a $310 billion industry that supplies 1.4 million jobs. Table 1.2 presentsthe top 10 states in the U.S. in terms of number of employees. These 10 statesemploy almost 60% of the US plastics workers.

1.2 POLYMER AND PLASTICS CATEGORIES

1 Introduction

Packaging32%

Tranportation8%

BUilding &construction

14%

Others14%

Consumer &institutional products

13%

Building &contruction

69%

Other11 % Electrical

eqUipment Consumer &4% institutional

products4%

Exports12%

Transportationequipment

4%Furniture &furnishings

5%

Figure 1.4: Break down of US thermoplastic applications into common areas.

4

Figure 1.6: Classification, break-down and provenance of plastics in materials science.

it is cooled below its glass transition temperature. Semi-crystalline thermoplas-tics, on the other hand, solidify with a certain order in their molecular structure.Hence, as they are cooled, they harden when the molecules begin to arrangein a regular order below what is usually referred to as the melting temperature.The molecules in semi-crystalline polymers that are not transformed into orderedregions remain as small amorphous regions. These amorphous regions withinthe semi-crystalline domains lose their "flowability" below their glass transitiontemperature. Most semi-crystalline polymers have a glass transition tempera-ture at subzero temperatures, hence, behaving at room temperature as rubberyor leathery materials. On the other hand, thermosetting polymers solidify bybeing chemically cured. Here, the long macromolecules cross-link with eachother during cure, resulting in a network of molecules that cannot slide past eachother. The formation of these networks causes the material to lose the abilityto "flow" even after reheating. The high density of cross-linking between themolecules makes thermosetting material stiff and brittle. Thermosets also ex-hibit a glass transition temperature which is sometimes near or above thermaldegradation temperatures. Compared to thermosets, elastomers are only lightlycross-linked which permits almost full extension of the molecules. However,the links across the molecules hinder them from sliding past each other, makingeven large deformations reversible. One common characteristic of elastomericmaterials is that the glass transition temperature is much lower than room tem-perature. Their ability to "flow" is lost after they are vulcanized or cross-linked.

Unlike other materials such as metals, plastics have numerous grades andvariations of every type of resin. These variations include different addi-tives, fillers and reinforcing fibers, to name a few. Early on, plastics werelauded as the "material made to measure"; today, this has become realityand an everyday attribute that we take for granted.The strange molecular structure of polymers leads to peculiar behavior notobserved with other materials. Such behavior includes viscoelasticity andother non-Newtonian effects during deformation, such as shear thinning.These characteristics not only affect how a final product may performin its lifetime, controlling how we must approach design, but also theactual manufacturing process, such as mold filling, extrusion die flow, etc.This will often lead to residual stresses, as well as molecular and fillerorientation, which causes anisotropy in the final part. General materialscience of polymers is covered in Chapter 2 of this handbook. Severalstandard tests are available to evaluate the performance ofa material. Thesetests are described in detail in Chapter 3 of this handbook.

During design and manufacturing of a product, material cost often be-comes the most influential parameter. However, today we must also factorin ecological and environmental aspects. These include the effects of ad-ditives such as solvents or certain flame-retardants on the health of factoryworkers, as well as the environmental impact in general. In addition, theproduction of a product must keep in mind that the material used shouldbe recyclable. Recycling issues are also introduced in Chapter 2 of thishandbook.

One of the great advantages of polymers is the low energy required duringmanufacturing. The melting, shaping and solidification all take place in anintegrated fashion. Chapter 4 presents the various plastics manufacturingtechniques, as well as material preparation and post-processing procedures.

The design, performance and recyclability of a product is directly coupledto the choice ofmaterial and its additives as well as chosen processing tech-nique and corresponding processing conditions. This can be referred to asthe 5 P's: Polymer, Process, Product, Performance and Post-consumer life.Design aspects are covered in Chapter 5, plastics materials are presentedin Chapter 6, and plastics additives are covered in Chapter 7.

cross-linked elastomers at room temperature are significantly above theirtransition temperature, they are very soft and very compliant elastic solids.

Although this handbook heavily concentrates on thermoplastic polymers, wetried to incorporate thermosets as well as elastomers whenever necessary

fitting. Finally, the following generalizations can be made of plastics andserve as a general guide to this Plastics Handbook:

1 Introduction

Ceramics (ionic bonds)Polymers (covalent bonds)

Synthetic polymers

Elastomers (rUbbers)

/ ----------=--1 OrganiC! I Inorganic (glass)/ ~

"'---c-h-em-iC-a\-'=:"'-1 1----="-Bio-iO-gi-ca\--

+ t__C_h_em-;-iC_a_\_-,I 1---Bi-O\-09-ica-I--

tThermosets

Monomer prod"uction

Classification

Dominating atoms

Polymerization

Bonds

Type

6

Table 1.3: Alphabetical overview of co=only used acronyms for plastics

In the plastics industry it is common to define a polymer by the chemical familyit belongs to, and assign an abbreviation based on the chemistry. However, manytimes instead of using the standardized descriptive symbol, often engineers usethe tradename given by the resin supplier.

This book uses the standardized notation presented in Table 1.3. The symbolswhich have been marked with an asterisk (*) have been designated by the ISOstandards, in conjunction with the material data bank CAMPUS. The plasticspresented in the table are presented in detail in Chapter 6 of this handbook.Furthermore, the acronyms presented in Table 1.3 may have additional symbolsseparated with a hyphen, such PE-LD for low density polyethylene, or PVC-P forplasticized PVC. The symbols for the most common characteristics are presentedin Table 1.4.

Table 1.5 presents the most commonly used plasticizers and the symbolsused to describe them. Plasticizers are also covered in detail in Chapter 6 of thishandbook.

1.3 PLASTICS ACRONYMS

9

Continued on next page

Chemical notationCOC-CopolymerCellulose propionateChloroprene rubberCasein formaldehyde, artificial homChlorosulfonated polyethylene rubberCellulose triacetateDiphenylene polycarbonateEthylene-propyleneEthylene vinylacetate rubberEthylene acrylic acid ester-maleic acid anhydride-copolyEthylene buteneEthylene butylacrylateEthylcelluloseEthylene copolymer bitumen-blendEpichlorohydrine rubberEthylene chlorotrifluoroethyleneEthylene ethylacrylate copolymerIonomer CopolymerEthylene methacrylic acid ester copolymerEpoxy Resinsee EPDMEthylene propylene diene rubberEthylene propylene rubberPolyethylene oxide tetrasulfide rubberEpichlorohydrin ethylene oxid rubber (terpolymer)Ethylene tetrafluoroethylene copolymerPolyetherurethane rubberEthylene vinylacetateEthylene vinylalcohol, old acronym EVOHFurfurylalcohol resinPolyfluoroethylene propyleneFuran formaldehydePerfluoro rubberFluoro rubberPropylene tetrafluoroethylene rubberPhosphazene rubber with fluoroalkyl- or fluoroxyalkyl grHalogenated butyl rubberHydrated NBR rubberIntrinsically conductive polymersButyl rubber (CIIR, BIIR)Isoprene rubberStyrene isoprene rubberLiquid crystal polymerLiquid silicone rubberMethylmethacrylate acrylonitrile butadiene styreneMethacrylate butadiene styreneMethylcellulose (cellulose derivate)Melamine formaldehydeTetrafluoroethylene perfluoromethyl vinyl ether copolymeMethylfluoro silicone rubber

Acronyms

AcronymCOPCPCRCSFCSMCTADPCE/P*EAMEAMAEBEBAECECBECOECTFEEEAKElMEMAEP*EP(D)MEPDMEPMETETERETFEEUEVAC*EVALFAFEPFFFFKMFKMFPMFZHIIRHNBRICPIIRIRIRSLCP*LSRMABS*MBS*MCMF*MFAMFQ

1 Introduction

Acrylonitrile-butadiene-styreneAcrylate rubber, (AEM, ANM)Acrylonitrile-chlorinated polyethylene-styreneAcrylic ester-ethylene rubberAcrylate ethylene polymethylene rubberAcrylonitrile ethylene propylene diene styreneNitroso rubberAcrylonitrile methylmethacrylateAcrylonitrile butadiene acrylateAcrylonitrile methacrylateseeACSAcrylonitile styrene acrylic esterPolyesterurethane rubberBromobutyl rubberButadiene rubberCellulose acetateCellulose acetobutyrateCellulose acetopropionateCresol formaldehydeHydratisierte cellulose, ZellglasChloro butyl rubberChlorinated polyethylene rubberCarboxymethylcelluloseCellulose nitrate, CelluloidEpichlorhydrine rubberCyclopolyolefine-Copolymers

Chemical notation

Continued on next page

ABS*ACMACSAECMAEMAESAFMUAMMAANBAANMAAPE-CSASA*AUBIIRBRCACABCAPCFCHCIIRCMCMCCNCOCOC*

Acronym

8

10

AcronymMMAEMLMPF*MPQMQMSMUFMUPFMVFQNBRNCRNRPAPAll*PAI2*PA46*PA6*PA61O*PA612*PA66*PA69*PAAPACPAEPAEK*PAlPAMIPAN*PANIPARPARAPARIPBPBAPBIPBMIPBNPBOPBT*PC*PCPOPCTFEPDAPPDCPDPE*PE-HDPE-BMWPE-LDPE-LLDPE-MDPE-UHMW

1 Introduction

Chemical notationMethylmethacrylate exo-methylene lactoneMelamine phenolic formaldehydeMethylphenylene silicone rubberPolydimethylsilicone rubbersee PMSMelamine urea formaldehydeMelamine urea phenolic formaldehydeFluoro silicone rubberAcrylonitrile butadiene rubberAcrylonitrile chloroprene rubberNatural rubberPolyamide (other notations see Section 6.7)Polyamide from aminoundecanoic acidPolyamide from dodecanoic acidPolyamide from polytetramethylene adipic acidPolyamide from e-caprolactamPolyamide from hexamethylene diamine sebatic acidPolyamide from hexamethylene diamine dodecanoic acidPolyamide from Hexamethylene diamine adipic acidPolyamide from hexamethylene diamine acelaic acidPolyacrylic acid esterPolyacetylenePolyaryletherPolyarylether ketonePolyamidimidePolyaminobismaleinimidePolyacrylonitrilePolyaniline, polyphenylene aminePolyarylatePolyarylamidePolyarylimidePolybutenePolybutylacrylatePolybenzimidazolePolybismaleinimidePolybutylene naphthalatePolyoxadiabenzimidazolePolybutylene terephthalatePolycarbonate (from bisphenol-A)Poly-3,3-bis-chloromethylpropylene oxidePolychlorotrifluoro ethylenePolydiallylphthalate resinPolydicyclopentadienePolyethylenePolyethylene-high densityPolyethylene-high molecular weightPolyethylene-low densityPolyethylene-linear low densityPolyethylene medium densityPolyethylene-ultra high molecular weight

Continued on next page

Plastics Acronyms

AcronymPE-ULDPE-VLDPE-XPEAPEDTPEEEKPEEKPEEKEKPEEKKPEI*PEKPEKEEKPEKKPEN*PEOXPESIPES*PET*PET-G*PF*PFMTPFUPHAPHBPHFPPI*PIBPISOPK*PLAPMAPMIPMMA*PMMIPMPPMPIPMSPNFPNRPOPOPOM*pp*PPAPPBPPCPPE*PPIPPMSPPOX

Chemical notationPolyethylene-ultra low densityPolyethylene-very low densityPolyethylene, crosslinkedPolyesteramidePolyethylenedioxythiophenePolyetheretheretherketonePolyetheretherketonePolyetheretherketoneetherketonePolyetheretherketoneketonePolyetherimidePolyetherketonePolyetherketoneetheretherketonePolyetherketoneketonePolyethylenenaphthalatePolyethylene oxidePolyesterimidePolyethersulfonePolyethylene terephthalatePolyethylene terephthalate, glycol modifiedPhenolic formaldehyde resinPolyperfluorotrimethyltriazine rubberPolyfuranPolyhydroxyalkanoatePolyhydroxybutyratePolyhexafluoropropylenePolyimidePolyisobutylenePolyimidsulfonePolyketonePolylactidePolymethylacrylatePolymethacrylimidePolymethylmethacrylatePolymethacrylmethylimidePoly-4-methylpentene-1Poly-m-phenylene-isophthalamidePoly-a-methylstyreneFluoro-phosphazene rubberPolynorbornene rubberPolypropylene oxide rubberGeneral notation for polyolefins, polyolefin-derivates uPolyoxymethylene (polyacetal resin, polyformaldehyde)PolypropylenePolyphthalamidePolyphenylenebutadienePolyphthalate carbonatePolyphenylene ether, old notation PPOPolydiphenyloxide pyromellitimidePoly-para-methylstyrenePolypropylene oxide

Continued on next page

11

12

AcronymPPPPPQPPS*PPSU*PPTAPPVppyPPYRPPYVPS*PSACPSIOAPSSPSU*PTPTFE*PTHFPTTPUR*PVACPVALPVBPVBEPVC*PVCIEVAPVDC*PVDFPVFPVFMPVKPVMEPVMQPVPPVZHPZRFSAN*SB*SBMMASBRSBSSCRSEBSSEPSSEPDMSISIMASIRSISSMAB

1 Introduction

Chemical notationPoly-para-phenylenePolyphenylchinoxalinePolyphenylene sulfidePolyphenylene sulfonePoly-p-phenyleneterephthalamidePolyphenylene vinylenePolypyrrolPolyparapyridinePolyparapyridine vinylenePolystyrenePolysaccharide, starchPolysilicooxoaluminatePolystyrenesulfonatePolysulfonePolythiophenePolytetrafiuoroethylenePolytetrahydrofuranPolytrimethyleneterephthalatePolyurethanePolyvinylacetatePolyvinylalcoholPolyvinyl butyralPolyvinyl isobutyletherPolyvinyl chloridePolyvinyl chloride-ethylene vinylacetatePolyvinylidene chloridePolyvinylidene fluoridePolyvinyl fluoridePolyvinyl formalPolyvinyl carbazolePolyvinyl methyletherPolymethylsiloxane phenyl vinyl rubberPolyvinyl pyrrolidonePolyvinyl cyclohexanePhosphazene rubber with phenoxy groupsResorcin formaldehyde resinStyrene acrylonitrileStyrene butadieneStyrene butadiene methylmethacrylateStyrene butadiene rubberStyrene butadiene styreneStyrene chloroprene rubberStyrene ethene butene styreneStyrene ethene propene styreneStyrene ethylene propylene diene rubberSilicone, Silicone resinStyrene isoprene maleic acid anhydrideStyrene isoprene rubberStyrene isoprene styrene block copolymerStyrene maleic acid anhydride butadiene

Continued on next page

Plastics Acronyms

AcronymSMAH*SPTCFTFEHFPVDFTFEPTMTORTPA*TPC*TPETPE-ATPE-CTPE-OTPE-STPE-UTPE-VTPO*TPS*TPU*TPV*TPZ*UPUP*VCEVCEMAKVCEVACVCMAANVCMAHVCMAIVCMAKVCMMAVCOAKVCPAEANVCPE-CVCVACVCVDCVCVDCANVDFHFPVFVMQvuXBRXCRXFXNBRXSBR

Chemical notationStyrene maleic acid anhydrideAromatic (saturated) polyesterThiocarbonyldifluoride copolymer rubberTetrafiuoroethylene hexafluoropropylene vinylidene fluorTetrafluoroethylene hexafiuoropropyleneThioplasticsPolyoctenamerThermoplastic elastomers based on polyamideThermoplastic elastomers based on copolyesterThermoplastic elastomerssee TPAsee TPCsee TPOsee TPSsee TPUsee TPVThermoplastic elastomers based on olefinsThermoplastic elastomers based on styreneThermoplastic elastomers based on polyurethaneThermoplastic elastomers based on crosslinked rubberOther thermoplastic elastomersUrea formaldehyde resinUnsaturated polyester resinVinylchloride ethyleneVinylchloride ethylene ethylmethacrylateVinylchloride ethylene vinylacetateVinylchloride maleic acid anhydride acrylonitrileVinylchloride maleic acid anhydrideVmylchloride maleinimideVinylchloride methacrylateVmylchloride methylmethacrylateVinylchloride octylacrylateVinylchloride acrylate rubber acrylonitrileVinylchloride-chlorinated ethyleneVinylchloride vinylacetateVinylchloride vinylidenechlorideVmylchloride vinylidenechloride acrylonitrileVinylidenechloride hexafiuoropropyleneVulcanized fiberPolymethylsiloxane vinyl rubberVinylesterurethaneButadiene rubber, containing carboxylic groupsChloroprene rubber, containing carboxylic groupsXylenol formaldehyde resinAcrylonitrile butadiene rubber, containing carboxylic grStyrene butadiene rubber, containing carboxylic groups

13

Table 1.5: Commonly Used Plasticizers and Their Acronyms

Continued on next page

Commonly Used Symbols Describing Polymer Characteristics

15

Di-n-octylphthalateDinonylphthalateDioctyladipate, also diethylhexyladi-pate, DEHA no longer usedDioctylphthalate, dioctyldecylphthalateDioctylsebacateDioctylazelateDiphenyIkresylphosphateDiphenyloctylphosphateDipropylphthalateEpoxidized linseed oilEpoxidized soy bean oilOctyldecyladipateOctyldecylphthalateParaffin oilTributylphosphateTrichlorethylphosphateTrikresylphosphateTriisooctyltrimellitateTrioctylphosphateTriphenylphosphate

Chemical notation

DOP, DEHP, DODPDOSDOZDPCFDPOFDPPELOESOODAODPPOTBPTCEFTCFTIOTMTOFTPP

AcronymDNOPDNPDOA(DEHA)

Plastics Acronyms1 Introduction

DioctyldecylphthalateAlkylsulfone acid esterBenzylbutylphthalateDibutyladipateDibutylphthalateDibutylsebacateDicyclohexylphthalateDiethylphthalateDihexylphthalateDiisobutylphthalateDiisodecylphthalateDiisononyladipateDimethylphthalateDimethylsebazateDinonyladipateDi-n-octyl-n-decylphthalate

Chemical notation

AmorphousBlock-copolymerBiaxially orientedChlorinatedCopolymerExpanded (foamed)GraftedHomopolymerHighly crystallineHigh densityHigh impactHigh molecular weightImpactLow densityLinear low densityMetallocene catalyzedMedium densityOrientedPlasticizedRandomly polymerizedUnplasticizedUltra high molecular weightUltra low densityVery low densityCross-linkedPeroxide cross-linkedElectrically cross-linked

Material characteristic

DODPASEBBPDBADBPDBSDCHPDEPDHXPDIBPDIDPDINADMPDMSDNADNODP

Acronym

SymbolABBOCCOEGHHCHDillHMWILDLLD(M)MDoPRUUHMWULDVLDXXAXC

Table 1.4:

14

Osswald Baur . BrinkmannOberbach . Schmachtenberg

InternationalPlasticsHandbookThe Resource for Plastics Engineers

HANSERHanser Publishers, Munich Hanser Gardner Publications, Cincinnati