bray of Congress Cataloging in Pubiation Data Strong, A Brent. Plastics materials and processing /A. Brea Strong, —Srd, Inthe: bitographia veferences and inde eNotes i Ph. Tile syidsssta os ene a? D> wetu uprany ‘hai 2onso1se76 rimepen es ESRI ee aoe a Speco eeeeernne eerie ae sone Shee ceaimaee ‘This book was set n Clearace by GOS Book Services, tani Highland. was printed ard bend by RR Doaneley. ‘The cover wat printed ky Phoenix Color Comp. ‘Sonyight © 2006, 2000, 1996 by Pearson Education, ne, Upper Salle River Now Jersey O74. ‘Pearson Pence Hl Alright reser Printed inthe United States of America. This publication i protected by ‘Copyright and permission shouldbe cbained ter the publisher prior toa prohibited reproduction, earn retrial ster or tastnsion in any frm of by any means, electron, mechanical, photocopying ecb, ot Ikevise. or iforaton regarding permissions wrt ta Rights and Permissions Depart Pearson Prontice Halls a trademark of Penson: Education, Tne. Pearson isa registered trademark of Pearson pe rence Hall isa roitred trademark of Pearson Béveation, Ine, Pearson Eduction Australia Pay. Limite esron Education North Ata Lid Parson Educacidn de Mic, SA de CX. Pearson Eduction Malla Pe Lid Pearton Eduction Ud. Pearson Education Singapore Pe Ltd Pearson Eduction Canada Led aaron Education Japan Contents ¥ Chapter » Chapter + Chapter 1 Introduction to Plastics. 1 Definitions of Plastics and Polymers 1 History of Plastics 3 Raw Material Supply and Pricing 10 Strategic Materials 13 ‘The Plastics industry 13 Uses of Plastics in Modern Society 16 (Case Study L1—The Development of Nylon 21 2 Polymeric Materials (Molécular Viewpoint) Introduction 25 Fundamentals of Mater 26 Bending al ‘Basic Concepts in Organic Chemistry 39 Polymers 43 Formation of Polymers $1 ‘Thermaplastcs and Thermosets 63 Copolymers 65 (Case Study 2.1—Moiifiations to Improve Teflon® Processing 3. Microstructures in Polymers 73 Introduction 73 ‘Solids, Liuids and Gases 74 Polymeric Solid State: Amorphous and Crystalline 75 30 Polymeric Caseous Sate 80 ‘Thermal Changes in Polymers 81 Polymer Length 95 Molecular Weight 96 25 66Mettindex 105 Shape (Steric) Eifects 108 ‘Case Study .1—Mechanical ‘of Density and Melt Index Properties of Pbjethlene (PE) as Functions 10 \VChapter 4 Mechanical Properties (Macro Viewpoint) 119 Introduction 119 Mechanical Properties in Solids (lastic Behavior) 122 Mechanical Properties in Liquids (iseous Flow) 123 ‘Viecoelastc Materials 129 Plastic (High-Strain) Stress Strain Behavior 132 Creep 139 ‘Toughness, Impact Strength, and Hardness 141 Reinforcements 144 Fillers 145 ‘Toughness Modifiers 148 (case Study 4. Tne Performance Testing of Trash Containers to Predict M6 \ Chapter 5 Chemical and Physical Properties (Macro Viewpoint) Introduction 151 Environmental Resistance and Weathering, 152 Chemical Resistivity and Solubility 158 Permeability 105 ‘lectrical Properties 72 Optical Properties, 176 Flammability 181 Plastic Kentification 169 ‘Case Stady 5.1—Using Carbon Black to Protect Polethylene from UV Degradation 19) ‘case Study 52-—Conductie Polymers 193 Chapter 6 Designing with Plastics 197 Introduction 197 Design Methodology 199 LayoubDrawing 208 Constraints 208 Material Choice 209, Prototying 214 (Case Smdy 6.1—Design of Plastic Stakes for Concrete Tit-up Walls 216 11 Contents U Chapter 7 Thermoplastic Materials (Commodity Plastics) Introduction 223, Polyethylene PE) 224 Polyethylene Copolymers 235 Polypropylene (PP) 230 Polyvinyl Chloride (PVC) 242 Polystyrene (PS) 247 ‘Aoys and Biends 251 (Case Study 7.1—Typical PVC Formulation 257 \/Chapter 8 Thermoplastic Materials (Engineering Plastics) Introduction 261 Celluosies 263, Polyamides or Nylons (PA) 265, ‘Acstals or Polyoxymethylenes (PON} 270 ‘Thermoplastic Pobesters(PETPBT) 273, Polycarbonate (PC) 277 Acrylics (PAN, PMMA) 279 Fluoropoiymers (PTFE, FEP, PFA) 281 High-Performance Mhermoplastics 286 (Case Study 8.1—Making Nonstick Flectrosurgical Blades 289 \y Chapter 9 Thermoset Materials 295 Introduction 295 Crosslinking 297 ‘Thermeset Types, General Properties, and Uses 304 Phenolics (PF) 306 ‘Amino Plsties (UF and MF) 309 ‘Thermoset Polyesters or Unsaturated Polyesters (UP) 312 View! Esters (VE) 320 Epoxies (EP) 321 ‘Thermeset Polyimides 25 Polyurethanes (PUR] 325 (Case Study 9.1—Thermoset Compsits for Wrapping Utility Poles / Chapter 10 Elastomeric (Rubber) Materials. 337 Introduction 337 ‘Aliphatic Thermoset Blastomers 341 ‘Thermoplastic Etastomers (TPE) 350 Fluoroelastomers 352 223 261 331PLASTICS Materials and ProcessingPLASTICS Materials and Processing ‘Third Edition A. Brent Strong Brigham Young University Upper Saddle River, New Jersey Columbus, Ohio oprSAY 200K Library of Congress Cataloging in Publication Data Contents Sere terials and Brent Strong. —3rd ed. Tenis and roceing/A = nan it MeTU itl Inds itogapica rrences ad inde, . Eavoisigat : saisgessTeates ny gut ; ade t &. 2ons04s876 dtr Debra Yar . introduc , SRSA ae oe Chapter 1 Introduction to Plastics 1 Frodision Cito Kena Ferg FrotuconCurdnatir: G&S bck Secs Ani Hila DefniionofPasticsand Pobmers 2 Dlr Cordnatr: Bane Brera Hisorref Plastics 5 (Gover Designer: Ali Mobrman ‘Raw Material Supply and Pricing 10 i StategeNaterals 13 ishing Manger Tec Sgn ‘ThePastics Industry 13 Uses of Plies in Modern Society 16 ‘is bok sen Cen y GS Bak See hn was printed and bendy RR. Dono. CaSte Li Theo orsbion 21 ‘ono ws pately Pox Ger Gor. ; . 2 Chapter 2. Polymeric Materials (Molécular Viewpoint) 25 cari © 2006, 20,1886 by Peon Edt inc, Ue Sie Ries No ey 07 Inoduation 25 feign Prete Hal ig evel Ped nthe Utes Sates vec spans ocd by Tnseducton ee 06 Epi andprmenserald Sone em te plas so ay pte erode sore Punlanenato ‘eto pte, orton nyo oy ty hears econ mca olocng een ot Bona oe ss Fron. Br fran srg penny wee te Ribs an Pistons Depron Buen in re Chen on i a nei Pann Basten, FouuonofPobmers 51 Fear? aegstered wader of Parone Tennsea temas 6 Ftc ls repseed ena fearon Can Tc. Remora nd Pearson Education Lid, Pearson Education Australia Pty. Limited Case Study 2.1—Modifications to Improve Teflon® Processing 66 FetionEdvcton Snore Ps Le fr Meesgnrae it f Eovaton ca PonvenBtucaon eon SoC , , : Faron eduaton pat earn Evan Naga Pe. Uk Chapter 3. Microstructures in Polymers 73 Introduction 73 Solid, Liquids and Gases 74 Polymeric Solid State: Amorphous and Crystalline 75 Polymeric Liquid State 80 Polymeric Gaseous State 80 Thermal Changes in Polymers 81 ues7ss4321 Polymer Length 95 isan o1s.aMssed Molecular Weight 95Contents costets MatIndes | 105 Chapter 7 Thermoplastic Materials ‘Shape (Steric) Biiects 108 i (Commodity Plastics) 223 eae Sindy 3.1--Mechanical Properties of Poletylene (PE) as Functions Irodadion 223 of Densiyand Met index 110 Pevetioe PE) 228 ns cas, i es (Macro Viewpoint) U1 obpropsene (PP) 239 \V Chapter 4 Mechanical Properties (Macro Viewpoint) etme a Introduction 119 Pobtyrene (3) 247 Mecha Properties in Solis (laste Behavior) 121 Aloysand Blends 251 echnical Properties Liquids Viscous Flow) 123 Case Stay71—Typicl PVC Formulation 257 Viscoelastic Materals 129 Fs igh Si Statin Bier 192 \/Chapter 8 Thermoplastic Materials (Engineering Plastics). 261 2 “Toughness, impact Stent, and Hardness 141 Introfucion 290 Reinforcements 144 Cellalosies 263, ee 1 Polyamides or Nylons (A) 265 ate, Cee you (Case Study 4.1— Testing of Trash Containers to Predict, esac otFobmetivenes P01) 270 tse Perfomance 46 Thermoplastic Polestes . Aeris (PAN, PMMA) 279, \v Chapter § Chemical and Physical Properties (Macro Viewpoint) 151 Flucropobrners (PTFE, FEB, PPA) 231 High-Performance Thermoplastics 286 Introduction 151 (Case Study 8.1—Makng Nonstick Bletrosurgical Blades 289 Environmental Resistance and Weathering 152 CChericl Resistivity and Solubility 156 IRE PERK Price @ipound) 075 0a OT] 140 SCAT For a new plastic material the pricing pattern has usualy been to el it fr uses that place a high valu onthe properties of the plastic otha high prices canbe justified. AS {ime goes on the manulacarer ofthe plastie develops more economical methods of man= ‘ctu andthe pie drop, which allows the development of ther uses Bently, the Solume and martet stably warrant the erection ofa fullsize manufacturing fly Father than the semiworks or il plane that areal used. The econeries of stale and inertable competion asta rule ina drama vice reduction forte plastic ver the ‘Subsequent fer yet and then a leveling of ofthe pice a the proces and consumption (demand) become eable andthe major uses are identified and demonstrated. The long- term rice hen becomes a fancton ofthe corapley ofthe process and the volume (35 alredy cscuseed). The price solume réstlonship is Musated in Figure 1. for several plastic and nonplcte serials. Ths ganeral inert ofthe curve inti gure confi {he strong gree volume dependence ofall thee materials, The devations from the Lin, which are generally eral, suggist thatthe proces complecty ta tor in the price, {though tia secondry fete hs. 9 (0S sin tame Be Figure 14. Pricey elaonship for ste and oer selec mata (1988 ts) lotndutioe to Piste: B ‘STRATEGIC MATERIALS ‘ne consieration often oversoked in the manutaetureof materi the laeation and lon tenn sability ofthe source of he principal raw materal an ster exal ingredients tums of soil unrest (such wars or economic emkargoes) or when the sup of atrial {is eontollad (suchas damonds or oi) the alabiy ofthe rw materials may dimiish, “Alematve stating mater or altematve finished goods must then be found expecialy for aplications tht are rate to national gals. Crary, irstance, was cat of For, the words supply of natural rubber during Word War I Because rubber ws tlt the ‘German gals 2 substitute ad to be found The result was enthticrabber a patil which served mast ofthe aplication previously served by natural ruber Ta the United States the Silesuply was cuto- This ws an impetus forthe eration of yon. Those ties oscil i ability were seo petiods st freed the development of new uses not previously en ‘Sone for esting materials. Non was designed asa sik substitute but became widespread ‘sa rope materi during WWI, eventhough its substitution for era, the previously dor ‘ankrope material ws nota major tage forthe original lon development. Because plastics are so ingrained in oder life and full so many critical appations {or national defense and other eational goal (i alos every cout), the avail of the raw materials shoul! be eained from a strategie point ofvew. As aeady discussed, ‘he prinial raw materia or most pasties sol Tat can certain bea problem ra a: ‘eral for most ofthe world. However, beease plastics make up only 2 small amouat oft cil consume, residual of fom ol ol fies coud be sed as an interim saute fr plastics inthe evene normal ude ol supplies were interrupt, Alternate sources of aw materials suchas agricultural products col, and aturl gas could als be expanded. The moro ‘ediments to the use of theze ltemate source are raw mete cet compared too and {he dificuly of corwertng some ofthe manutacturing sites forthe chemicals to accept he sera ter fed stacks. Therefore, plastics can usualy be made fer raw material {hat are generally avilable, although at a scmeuhat higher cost to protuee. ‘This station of relatively stable raw material soures aka exits for pape, dss, and some metals, especally on and copper Other metals, suchas chrom (asd in stainless ‘tel, ae far ls avaible and ve fewer alterate rata, and st, derfore, be ‘tociild or others secured for suategic purpose. ‘THE PLASTICS INDUSTRY ‘A ingram ofthe plastics industry is ven in Faure 15, with each ofthe mr fanetions represented ina box The interactions bebwen the various functions are stated by the ar- ros. The heavy arrows are the most common paths. Generally these interactions ress, ndthey are made inthe ietons shown by te atows, but sometimes the interactions are ‘Sooty intercompany transfers when a corapary bas inegated move tun oe fineion i ‘erally. The integration of several see is ute common ine pastes nce. ‘The resin manufacturers convert chemicals (rived fem crud ol carl as, ea, snd athe sources) into the basic polymer materials. Hence. these processes ae called polymerization processes.uw orton Fowe15 dagamot -—— ee Teta Mame 3 ae ‘These resins which require ferther processing tobe useful ae generally made age, highly intgrated exanufctuing faites that resemble il reinerie in Cer sie and ‘seape The enormeus investments require te bull such fais have rast general'y in large petrochemical companies becoming resin manafezurr Some af the mort wal Inown rxin mantfcroer are DuPont. Exxontcil, Don, Baye, BASE and Hstsman, anong may others, There are approximately 40 major ein pe with each resin typ Aifering from al othore according to the fundamental cherie ature ofthe pobre. ost ofthe resin types are available fom more than one resin manufacture Seve a the most common of these resin ypes are polyetilen,polypropyiene,pohtyene, poli lorie, slo, polycarbonate, polyurethane, nd postr Most ofthe proces used to make resins ae Mow procests that requte carl comuol over temperature, presure, fw rte, catalyst and oe associated paraneer ‘order to obtain te desired properties ato mirmize te production af unwanted side products. This text skips over most ofthese deals and cosiers only the most Basie Inodctin to Pes 6 ‘conczpsinpajmerzation (in the chapter on polymeric materi). This approach allows the eadecto appreciate the general way polars ae rade and understand the change a pelyner properties that are fror the pamerztion process. The emphasis ofthis eckson the mong ofthe verns ater thoy have bee polyericed. ‘The resins usually ext fom the polymerization reactor i one of thee physical forme igus, grandes, lake. The iqucs ae roughly the consistency of han. Te gals resemble ury soap powers in tetur, siz, and corsistency. The Rakes resemble un ‘cooked oatmeal rinstant poate fakes in teture and is I sld direct fom thereat, the liquid resins are general packaged in 5 galln, 55 gallon, ex ankcar containers. The ‘granules and fakes ae generally pocaged in S-poune bags, palltzeé carton, or y= lords (1000 pounds) in hopper trucks on al cars many cases, therein manafoturers end he grandes and ales through one tore srocss in order to make amore consistent producto ater processing anor to remove ‘contaminants, especialy schents, that might be present In this additonal precessing step the granules and fakes are converted into plies that are shaped like small rus ‘out 0.1 inch @ mr) in dameter and 0.2 inch Arar) tong ike spaghet that as been ‘hooped into very shor pices) This additonal processing le also gives the cesin manu facture an cpportunity to aja the average pellet properis by blending resins ofthe se polymer material from diferent hatches, Blending is oflen ch ease tan tying tofineane the esirmaking operation tel for each of ce mina diferences in procs {at might be offered. Every sin pes vallabe in many varieties, each of whichis made bya slighty diferent set of polmerzation races parameters or by Being of he materials from diferent polymerization batches. These varies difer slighty ‘om ‘ach ote in phsical properties but are similar in mal properties within each rein ‘pe Minor adits such as antenidants could alo be Blended into the polymer In the pelletiing step. ost resins are sal from the resin manulcturers drt tothe moldees. 12 male ows not uy fa age enough quantita be supe dest oe the resn manufacturer fo, paraps. cesires some special series nat provide by the resin manueturers, the rmolder might hay fom a resin distributor who typically bays i rgequanie snd then ‘Sips in sale lots. The reer may also ead sence suchas col matching, aiton of rocesing ais, o vinding. In these cases the moider would buy rom a compound. ‘The molders convert the resins (liquids, granules, falas or pellets) into the desired ‘topes by using ene or more plaste-moldig proces, Typical melding precsee ae ‘etruson, injection mong, empresion moleng and carting, Thee and other plastic. mong processes are discussed in desl inthis text. Mong companies tht have pute ‘ts their principal products usualy have many plas procesing machines tnd mak Sart in arg quate, Typical examples ofthese companis are plastic pipe extruders, injetion melders of automotive parts, or plastic toy manufetres, (Other molders are companies whose principal products something other than apas- tie but in which some pasts part or parts are used, These companies woule peal have only afew plastics procesing machines, Bemples of tis pe of comgary might be 3 ‘manuicurer of medial devices that ses speci plate fcc atplane marufoctares tho wse psi arts within the silane ra mall processor eho tes laste mil ues. ‘These essentially nonlastes companies may elect fo have an outsize compery do the6 Chapter Ome azlig fr then. Sach ouside cnpariss a ele job shop or stm molders i or alte sel nton mong nachna, on fret sex and sae a marcy wre ase hese prt components et procs hc te ste poner rica bcm ho CT he id mang ant pera, some ae * ada ca mae tanaresaped pars that ar say old compass hat en ping operation Tas peel aeady-lél yrs ae cl Fe eee estar ngi tortnce, uy ered set acum om fabreators Wr odo sun asa ose rome seu eae peal b= Tas i etic Balan te ito coh the bers hone at Ss or ie spel sees they ray aso by Som stk pats i Shue tap pst saps, och ashes, rye Bock ony and el yrs otters ay a tantra son tt canal with Bur, retg esc at io a tice opeions ave tinge rom ating bese they ae es Ta sac as ung toning, nara han Sania Senor taps by secondary mong. Fnshing asemblig al neaog ae at ng ye older or eboester bt can be covey camo ei weg eee arapechlzel operation. Conran ta at la rio the od aan ee ornare rare mans se an ile inthis Sein tp For ae a us il eacand spe forse her Fede hes, ee cub moe arts encom reo oer nee ma Componente lane rae ai sec pr dsr, nd Sion sy al lees Co ea er yale oe see ve tht ay poor oi eihing 9 For SSS ami weep nae erat PE in ey aap bone ofthe compen ct asker em. A homeowner de ES cfonacapaor ale epatoa drags pre stole ar Fs rey cer interesting age ech Ye. Te oo cat ie inky as een govig ot 3 ete SIs ark oe bing cation parts ofthe rans sc. ea oe fe immacon sore lees it dou the nba of hs Pea Eo uy continue outa the general ec USES OP RLASTICS IN MODERN SOCIETY Most cosumers haverelativel litle insight nto the charetristis of specifi pasties un ee Steal ty adversing For instance, many people ae unfair with nylon exept as (Site fer frosty, teas, and carpets Even then, they generals do not understand See Tein ot rin tat make Ira good ebsoe for these applicatins They may, How Seer betmore lamar with natural products such as cotton or wool, wnich mig orp Sear thine Sma. many consumers casa plastic materials int a general ategers TRA fen ferences in performance bat ae possible. Such a emument as “I broke ecru it sj laste” might be pial ofsuth a characterization. Inrodcton to Pais uw ‘The selection of a material fo a particular design is based on careful anaiss of eng neering properties 3 they rate tothe design function coupled with a consideration for the mantficturng expbiltes an ents ofthe msteal. Sines plastics resold materials ‘when in ial use. some characteristics of plastics, as compared to other sold materials, chiefly metas an ceramics, are Fisted in Append 1. The table of ype values fo several Important properties of plastics, metas, and ceramics gven in Appendix lustats the ‘wie range of valves both between and within the general chasifeaton of plas. Values [re compare otypia values for selected meas and ceramic, nit of his wide range ‘of plastie proper, some general characterises of plastics with Dpical advantages ard ssdvanages compared to metals and ceramics can be dented and are ust fr guide lines on peformanes. These goneralcharactenstics of patie are given in Table 13, "Note tat some characteristics ean be a ahaniage in one apation hut might be di adkantage in another application Pr instance, the low mating post of plates an impor tant advantage in processing becouse the molding canbe done at owes temperature than ae ‘arcmnon wh the shaping of meals and ceramics. However his sre low ating pint ako leads oa narrower usfl thermal range becuse los many oftheir benefit me anil properties a lover temperatures than do most metals and ceric. Therefor, te [tof characteris shouldbe reevaluated fer each aplication. Another auton ninterpret- ing Table 13 is thot here rach diversity within exch feof mater, which ends Ov [aps in properties between pts seals and ceramics. The table gies general ropertics _sseciated wih the pe ofaterl ands not necessarily representa ofl enters in that ‘ype In some application, the ned for apartculr propery or prepertis may’ beso dori- ‘ant tat othe, es Gesable properties ean or ought to be aces For instance, even ‘hough pass ry wear out much more apy than te, the high elongation and ood e- covery pats and the ability to form them te varcus Shapes has ed wa preface for sites (rbber for automobile es. The ride conor 's wort the asin one-term we. Plasies ar. by their sie nature, eapable of Beng formed. n genera, therefore, the ‘use ditates the frm ofthe paste pat. An if variety of fers ae achievable. Some pplcations have tadisonaly used standard forms, inclding shee lms, ros, tubes and pipes, bers, locks, and sabe. Table 13. characteristics of Pasies hon Capac io Meta and Gerais Sanam TaerapelDieoartage ow dersty ‘Tapes preduesilow arucual srengh Low mating pon ase of procesingLave! ust Berna ange pn cengaton ow thormal condctity Elect resistance ‘ow bitionoaigher 9p and lover old sang: ‘Good trea nsiaton Dispos nest 2207) ‘Good aici Ineuaten Does end! lcticty COptcaclarty (come ypes) Useihnous a a clear matera/Degrsation y anche si aes Use ino palming tit math cars Sevont senetity ‘Can be appiod a a slater be ated by eens ‘iste can te bumed/May cause fumes cfr hazare8 ‘chapter One Because plastics are s prevalent in the word toda, only apart of anoietons can be gon, Bven complete and comprehensive st of eurcet applications would Sich be outdated since te application of plastics i such 2 dyraricsegmentof inst Teh buang ta intended to show the breadth of patie aprlicatons ocross ary indus apd t iarate some applieations tat may be ite know, Packaging FP aos for thousands of diferent ood tems. These wraps an bea sage pasti or rat anaied Aas using up to seven ferent pasties and may be fee og te Bottles ard other container frites such as male saga rep sramnoo, medicine ig vd tmandry products, cleaning agents, inseiids, istiled water, microwable food, earl oon with see-through windows t tal how much ise inthe Doe) a8 Boed Biter yocs fr tools and small hardvare tes 1 Trash bags and grocery sacks, 1D Shrink wap for palletied containers, small ard display tems, and pratetve shl>+ ping ootngs. sa Foun packing for impact sensitive equipment such as computers, let instr rent and Rite Modical Cathars and other tubes that ass in proving entry to the bodys organs point ceplacement prs. Arif eg, fet, and ars 1D Xcry bles and other tems that mustbe transparent 2935. 1 Disposable surgical clothes and instruments 1D pesca hearts, lungs, and othe organs and sthetie bleod ese was, nd eure ‘ation materal or skin gai. sn Byee ames and Tenses. 1D Teothbreshes, combs, and other personal ear items Dental lings, bridges, and contngs "> Diagnostic equipment and tools Recreations! EPSoat lasts, ayia canoes, ands Tracts glfelts pols ovat, odo. olde, gears, acing cas, dune bugs, and enw Shei show, Sk ets sl poles, a boots, end et ch Gol bal exer, ol hb shat, nd gf cub ads Boyle par ies and ade, intron to Pace 19 ‘Tenties Clothing. Carpets. ‘Nonwoven fabrics. Diaper and othe disposables. Fibers used fr clothes either by themselves or blended with natura bers. ‘Netting for sors (basketball ocr Upholstered fabrics for rite, draperies, and vallaper tei Purniture, Appliances, and Housewares "Teshones and other communication equioment (Computer and small appliance cabinets or housings Foamasshoning, molded structs parts Luge. Paint Flor coverings (capes vinyl oon). Inston seating. Componeats of washers, dyes, refigerator, tabletops, picture npr at des ie op picture frames, clothes Met 7 Ronee enponers inadinges ch he Can ‘ib yrs eight Cant) us pe, a ested ote Tain mono nd eh a, Sex cae nat oes Tktedlne, Geni. crea whic inn ompoers Industrial Pipes, ves, and tas (especially for comasion pretation) Gears housing activation rods ‘Ahusives and contigs. Vibration arming pas ‘Wie inulton and deve connector, plugs, socket) ashes, sealants,Caster One atertaiament fr Musial instruments (guitars voting, crs). 1 Stereo and components. Cass for radios, tape players, asset tapes, and COS fVORtapesand housings Sinks, shower tals, plumbing fatures, Flori (iy and carpeting) Photo 14. Molded plesic Facer ana eacumer fs (Coney mA Ha Company) Inroction Pastis a cups, lates, and storage containers Paint Proactive tarps, tie-down bls, cords and rope ‘Owtdor signs and lighting covers ‘Tach containers and ater pails, buckets, and tanks. Pati hae serincreasing aplication in our madera woud (Photo 21), Some new applications of plastics coninat tobe replacements for other, more traionl materials (auch as replacement of aluminum sheets hy earborepeny composites in arlene struc ‘ures) Other applications are pss because ofthe unique popertiss of pasts (sich as Iubrietion fre bearings). The posites for plates use seem ends. case STUDY The Development of Nylon {fn 198, the DuPont Company hired a brillant Soysrold research chemist, Wallace Caroters, who had graduated with a PAD. (othe University of lina and then taught onfanic chemistry at Hinois and Harvard universities. DuPont agreed that Carthers sou be given the finest staan facies in ond to develo a concept that he had been teplorng He believed that he might be able to creaea gan lecle (large poyer) by 2 ew technique that involved series of condensation reactions (In condensation reas ons enoleeues combine oeeat lager molecules anda by-radact ralecale ke water, ‘tat condenses out ofthe reaction lke dew condensing out of the atmosphere ona hurd ening} Cather idea was to choose reactant melecues tha: hat two reace ends So that each mcecule could be chemicaly connected (bone) to two ethers. rected in Series ad if eotinued long enough he result would be a very long cain made up ofthe astng molecule al bonded together a pobre ‘DuPont agement alized that sucha mataral made up ofboeded merle woul be sie to raturaly occurring polymers such as sik. The research objectives for Carohers ‘wore, there, to epore the coneept OF tis new reaction (pure resarch) butt gp ‘ind hat the end esl shouldbe a usable produc lela synths slapd researc). "The soundness of Carthers concent was demonstrate in 1930 when his bl ase. ate, De Julian Hl cbsered that the compound a had ben tating in the elecuae stl {a dovice that removed the by-product and thereby encaurageé the condensation reaction to contin) had becoee tough and smi, yet elastic. Thare were properties long asso- cated with natural pelymors. The change of he reactants ito thee poverie materials ‘wat ler evidence tht Carother! team was on the ight wack, Carcthersramed the ne ‘materials “uperpoimers” About o wees ser, Hl made aceond ighly important dbsesation. Whilst ing ue properes of esd marin, Fl und rat when mete, het, mls ke ‘material could be pulled into afer shape that was not bt bt was tough and surprisingly Strong, Some of te Base research objectives had been met—a reaction to make a ply, the equipment to een the chain, anda song, pliable fiter—but the material il riedCharter One at co lw terpertue, een in hot water, and was sensitive to wormal cleaning Huis, ‘lynousy twas not yt ables fork The esearch tam had been working on reaction sytem that made a cls of organic chemicals known as ters. Alou these ‘would ater beoome a lige and important group of polymers further research was needed. orate, bth projects begged doe in tang to improve phic oper. ‘Corthrs Sesame dete and tuned stenton to vais e{ moles contig the onan ceria group aceene. He fl tat this system could lea toaster ber Tow pulled the wort athe heist ad ahough mary important chericals ‘were developed the synthetic rubber he sought was not orale. (Oe ote discoveries he Ice was anolthat ha the odor of muse highly pried iegeeintin perf hat 5p {othe obained ony fom the ras musk ovo Asta at almost prone eces) [At the urging of ie seoeats, Caothers reared to the const ofa gnthetie ik Fe concsied a more practical smtheis route and focused ona dierent clas of organic Choma the amides the [king connection isthe polymers On May 23, 1834, an. ‘ther suberpolyner” vas synthesized by tis ew technlque, This tine, Cacothers himself ‘emcestraied hom the-superpobmer” cou bo made nto aber Fs drew the ot viscous ‘ubwanee into 2 ayrnge and from the aedle aquired a tiny stream oft int thea. The ‘ating team cooled into a wip flament, as ine as those ofa spier's web. Te lustrous filaent fad exclent heat stl, withstood normal washing and cleaning, and vas feual in strength and play to sk and other natural ers such a cotton and wool. “Tere” sald Carothers walking into the office of the DuPont chemical irsctor in charge, "is your snthti texte er." "Te DuPont Company began an tensive efor to build an experimental or pl plant to produce slice quantities ofthe materials ut commercial tests ould be run. The ‘moter abel by Carotaers a 6 polymer was select as the mot promising fr imme {inte investigation frm the strc prac standpoint. Eventual, the plot plant po ‘diced the material and small-scale manufacturing was demonstrate, . ‘Or Octber 27,1938, almost 1 year ar the hiring of Caotrs, DuPont puch nour the development of" er fnew sythetc superpolyer fee whieh, among, ‘humerous applications lec ibers coli be sun of a stenadastity factor supa ing that of coon, linen, tal, rayon, o sk ‘Tis new group of shee materls base cn amide reactors was given the name sylon and quickly captured te imagination ofthe world. Newspapers aed the discovery {Sone ofthe mest important in the century of ees” The st product made from ‘ylon vas brits for toothorushes, Duo exited nylon stockings tthe 1938 World's Fas of New York and San Franiso.Nylen hosiery (qicydubsed “Tyfons) created a fensaion when, on May 15, 1940, the fst ited quantities wee placed on sale. This began the cmon ret” and during Ue ext 12 months appronimtaly 68,090,000 pars of _lenjlon hove were bought by American women, whose demand fr exesded the supp Fw if any, major inventions have been so imameiatay success as nylon. By the ed of 1841, DuPont bad yon plants in operation or beng bul caple of producing more {han 2 alin mile of lon arn daly. By 194, mast of the tothirasnes made inthe ‘United State half ofthe Habeas, ard sores of industrial and Household bres were ‘being bred with nylon flaments Nylon vas being used fr tenis and badminton ra. ‘gut stings, catheters sug sures, Shing lines, sical rings, wie inslation, Inodection to Plats 2 boltmel glues, seltubricating bearings and many wartime apliations suchas para chutes and rope ‘Caroter’scken death in 1937 cu short a career hat might have ade many other opr i Ser pl oven chara eli devs, Hany aa ee end apm auch parses or boting wih oppstty cngeé Ne en ined, Sra eases aides oon] 8 ‘intarplrsts ence anther of esonday bond Those beeen pol aon el Th a Seas te orc olen ae traced oe Fe tan orate ters eng tne fom Fa i lan inovantnecene exam oh aoe ee aren te praens f etaleenes te roving omer Bonde Serum cipher oats ee eee sc acct Cosranation bonding can ao Be portant in aoe ce ono ance nga mal es cers wt aro pian ade a ton tence ae ay snyoran in retin (othin) wera i en a ere pena ad rex with onde oor od tat crit toa ‘Sith uno rote ough estan When torn So elt nen cb one pre, ie an Be EE ae ae Spa mporart scons brs a expetalline bond wich fore sewn pes sk hn as resin Gi re SESE tat pratense mer arco deo ech oh SERIO ui eed cur med esti ta ca en oc a cicr—aece he meade owe Seta oa tre ined i ae dean Chott 3. Where ie thes srs Ths eurt the pbs lecl such 1 he tly poe ‘Ron nll calle serrs are ei ome : eS esa ancien oon dln he eal ft sonar uation oben. Te er iy ae ora A are avn a med seontany ed. Dube 8 ae hc wana soning tes dese xi bere a Ph, Fae ee Sioa. Tho iceolsrstractos incu wan der Wane forcesand induced poe stractions. Pomorie Matar (Melos Viewpoint 9 ‘The origin of van der Wan foeas hasbeen atbuted to the attraction that all mole cles have foreach eter, somewht ithe graitatonal attraction tat exists bebe al, bods The graviatianal tvaction i dependent upon the masses of the bodies and the dis tance bebseen then. Since molecules are 20 small (low tas), the onky way that these Fores can be sigalfcan is i the dstanes beeen the molecules are very short. Even then, he frees are quite weak-sevral ime lower netrengh han oni, metalic orc valent bonds ard evn much lever Un dgele bonds. Neverteless. when the molecules an pack closely together the large muraber of van der Wass feress that can frm wll result ta sable entlnestructre. Ifthe shape ofthe molecules prevents this close packing interatomic estances are tb large aod the van der Wels forces are‘t strong hough te pall Ue roolecues together and allow a sable eyataline structure to for ‘These shapeependen ects (alld sere ects) willbe disused in ore debater in thetex Tnduceé dipole attractions, the other tye of weak intermolecular atrecon, occur when apolar molecule ees into very else proximity oa nonpolar moleccle. When his ‘ctu, a momentary and very slight polaris induced in the nonpolar molacale Because ‘ofthe attracson of hs electrons forthe poste cece f the polar moles esting weak teraction that can lead to enstaline formation if sufficlent numberof hese inte in genera, the effect of crstaline regions on the properties of pajmer isto increase the melting point ofthe polymer, because more ener Is needed to fnpart totally re ‘overent to th polymer. These thermal interactions ate disuse in Chapter 3. Set- ‘odary banding wl als increas he strength an¢ the crep resistance of plastic materials borsse the molecules require more ener te slide relative a ech other. These properties, are assocised with the input of ener int the polymer mass. When any ener snp, the tendeny for mater to move vlate to each other's increased, bu this movernent is reste by th intormelecuiar attractions. These interactions and other mectanical properties wil be dicssed in deta in Chapter Sul ether internlecar forces fave bein ideried, One of te mast important is chain entangleram. Thee entanglement res dependent nthe eres bebieen atom ‘han on forces invobed with entire elecules which are seuss in Chapt BASIC CONCEPTS IN ORGANIC CHEMISTRY ‘One canon stent view that was prevalent before the age of modem chemistry cls fell eateries as ether living or nonlivng Anything hat had eves been living or Ut sas derived fom anything that had ever ved was considered part ofthe living dasifca ten) These to clasifcations were calle, respecte, orgenic and inorganic Chemists ‘studing organi materas noted that these materials were generally based on be cher [sry of the carton ator. Because ofthat connection between organic materia a carbon ‘dom chert, the study of carbon chemistry bscame own as organic cherry. The ‘Stuy ofthe chemisy ofa the other ats was led rarer cherry.) Toa), ary materials hased on carbon are totally syhedcand may never have Deen lke, bu thy are ‘Sl sued within she baad category called organic chemist.Caper Te “tat isso special about the chemistry of carbon that i il sould be classed seo rate dom all te other elements in the periodic tabi? Ta pat a lee the answer seme ‘atl Oe Sues are ao very many compounds of carbon, and tei mlecules can Be 30 {2.8 snd comple Mow plates are tased on carbon andar, therefore, part of organic eis. “Tha camber of molecles containing carbon is many times greater than the sub than eres etn carbon, These organ meleeles haw been vied nt amin based arse arangement of eafon and oler common ators into various characteristic ‘retying pers They general have no counterparts among the inagani compo For rac chemin is devoted to investigating te reactions ofthese families of eee Commun, ochdng the ays the atoms reaange an combine, and the prow es ofthe resultant new orgie molecules Carbon Atom Bonding carbon has an atone muriber of sic and therefore as sc protons in its maces and fn its cree ete at eleckronesoerunding te nucle. Two ofthese electro ae in te em Stu and do net enter into normal chemical bonding, he remaining fox aa rsdn the ovtey shell and ae avababe for boning (The esetron clouds of he Ge Re clectrone for atomae carbon were depicted in Figure 22) Normally elemental eae ghey for leans woul occpy he outer rb (By Fa» Carbon needs Hee Calton: to complet its outer sell and obain the stable Stat configuration. [Reto catbon uquies four more electrons (hy sharing) and will yay form four crete es cece per bond), Because cavdon isa nonmetal and ros of te othe ators ponte Sarpounds wath earbon are sa noameis, the pe of Bending betwean con eTthec atoms woul be covalent as iscsted previouh inthis choot, “Tne electron coniguretion ofan ator is changed when the atom becomes part of = molenae thi change eens because ofimarctons between the bonding otal: anal raeebinls The cas of carbon boning to four hydrogens otras the type of change a ori that scour when the some bind together ina CH, molecu proses itasated in Figure 20. Sea ting of oe carbon with the four yogens thee voles mast e satisfied in orden tr enioe the lwestenery, ose stable state Theze same rules aply to he Bord ing ofall atoms. The number af lectocs involved attests to sais the acta me {Hach bond has two electrons Sach bonding orbital raves a faraway from all other rials apes, within the Cnnurintofraintaining the proper bond distance withthe central tor, This ‘enarement arise rotate repulsion that eit between obi fa which ie eewons are prese ‘As indicated in Figure 2.1, this separation can Best be done forthe CH, case if the By: Eugtas move to te comes ofa tetrahedron with te carbon in te cena. The bon seokestas change shape inorder to accommodate the prferec spatial arangement, marc Mater (Moles Views) a Figure 210, Carson asm erg th ar yeroses lore form CH 0) Mollari (ater Saenger oes) Cotertedat penton: Bease tne new ons were re by ing dierent stom it! psn tis See Sean atch ow eas a ae fpr re Te ew hi Stal ate Wena! cunt pt onan Ao tole as een rel ofthe oranda ondngar cal molecaar orbital, “The electron confusion aout carbon cn so bu repeated with lero as dt, as hom in Pure fr OF, and eater orgie moll, CH Boh mae demonstrate bow ovale bond ae reeset by the eocmodot meod In CHUL CFpie 210), note aa chloro as ken he leo one of he rogers at {Sen ofthe ur Hoss rept by lato The rine stor hs een cetons if toouter hel porto bonding ne of theses use athe avant bod wie teh {serine srround the cviae lon, ler te colnt bonds fom beeen he Shlonre and evbon ators (each apm contig one eer Ue bond cerine ‘hve ta of igh secre oe shel, thi mig a ble eongartion at ght elesons in a cuter hel Te con in CHC a as eh eter shel Sica so on sabe. Th the enone Sond Sable when ecto fee share shown. The elerondt fro are smentat eset 1 wee a the gure 211. Carbon ators Send by elon bos « : : Se comet one arCiB ¥ £2E cotecona wee B # eMac (CH) (@ Choreanne (CHC2 sper To Table 21 Number af Sands for Toa Alors (ImportaninPlsis) Wise ner tions ie c 4 a 1 N 3 ° 2 s 4 ee 1 eninge of Figare 210, butte spatial orlentation is ot. Both representation gptems are commont sed ‘Many other toms can combine with carbon in conigurtions siniar to hydrgen and chlorine to frm various mocales, Ech atom has characterise bonding pate thet is ‘Eeated bythe marnber of earns in sonar sel, The vlens ofthe tom) Table 2.1 [sts the most common toms in organic chemistry and che numberof bonds each can or. Carbon-Carhon Molecular Orbitals Another key tothe large number and complexity of carbor-consning molecule s that Carbon can form bons with all. Such a molecule (CH, is ilustated in Figure 2.122. tn (GH; (alld ethane) the coment bands withthe nrogens were formed by the method ne ‘ erat pa eta CTS party (tates (bcceoromyene (Cy Figure 212 Bonding incarben molacoles. Polmeris Meter (lesa Vewsint) 8 previously described for CH, excep inthis case only thre hydrogens are boned to each ‘fie exrbons, That ete dat of the carbons with ely even outer hall electrons, One ‘ay forthe carbons o obtain the table oct configuration is for them to bord with each, ‘othe, Theelectron- Frmeoutoral represerations such as thoce shown in Figures 2.5, 27, 28,29, 211, and i which are commen among chemists but certainly are not the only 2-timensional pr restnaton methods. in general when te readers untaliae with organi chemistry, re compleiy ofthe repstetaton seems higher, Tis point an be sean by noting the est funeloal #r0up Ehoun in Figure 2.14 This functional group lables aromatic, shows al of te cabons Seu Slane nydrogene. For emerancedrheris this rereretation would he unneces, ‘erly complex and time-consuming to make. Those experienced chemists would most {HY cle simple representation, much lke that given as the ari funcional grou Jpatabore the oo previously ited, Note that none ofthe atoms i elit shown i this see eention The carbon ators are ineated by changes in ection of te ines (a Perc Mare Moloub Viwpsat) 8 None Paton Gg ne ii hase nob nite et nee S ony " eu noe iit ine Rg-o- bk Be tol asa ogame ° i Ree kate onat ° i Rote eta <> drone Ear devnsie Figure 214 Furctoal gos non nena. (Same ogee ao ee bos nite er spesy ane See ot ocang on hey atu efron gee. The ean ‘be any organic group) gener ‘ see mes ewe map npn yt ten sorter teats men ee io ireehcheccea esneiiaceenteetete Hence. this text wil occasionally use a seciabbrevated representation method that is n- Es eisai res mints gece ats ee Snopetnaaneuememem6 Charter Te epi shesstyOny in fe casesl esaisy paser roup ese reesedtsccusreitte pred sipe co ae cet bat cn be ae fur coils of hse uncial oe gern rsa be conn gsr? Ech lee Sd ofan teen witness ih fret rae tena eprint ray bese of Beaman tr ep Rebs span ssi Hee mone shaven ie 235, gue 2.15. rine meus caen. toe. sce see ra onjgin masting the eferences hy properties , Soh Sen terse rorgorews ‘ wen i HE gOmm teraz he 1H ed akook oto Lit we pene hh Paymere Mer (Nelo Vip) a chemi ommoniy used a ubbing alcohol. simply rerrnging the tome preserving ‘he sme number of earbos, hydrogens, and onygen) the maar becomes myth ether which canbe useé 2c an anesthetic By changing the arrangement and the wa tit the aejgen is bonded to the ear, bao tydrogen ae lac and the teria esomes acetone, a common sahent urd in applicators such as Sngerilplih remove Tae ouher rearrangements ofthe atoms im acetone (keeping the same number o exons) re- ful inthe formation of ath acuta (a set smelng cher used in prtues),pro- Pionaldetyde (gsharp-smeling chemical vale to cinramoe}, and propanne aid ‘hema eletad to vinegar. These varioes arrangement of tre arbors with Iyroges ‘nd ongensitustrate the macy properties that are possible with only minor changes the arangerrent ofthe atoms in these various molecules By ding oter atoms, nee ing the number of carbons and making other arrangements ofthe atoms neal init rumber of mnlecules can be formed, (ne fanetionsl group in Pigue 2.14 of particular interest hat should be discsed in ‘more deal isthe aromatic group. The pi (3 bond electrons in each double bod nat oy ‘overlap with the arb that share the double bond they also eversp wit the Roe ttetrons in adjoining carbons, loving these pi electrons to move i accel pattern ‘run the ing which reat in avery sable structure. The inital complexity epesen- tation ofthe aromatic malecule shows Ue electrons ai acre inside the hexagon fear bons, wich empaszs this cordate overiapping and delclzation of the eleeon. ‘These sivmembered rings are also called phenyl or beazo groups. Molecules that conta the aromatic grou ates to be aromati, (The term aromatic arose because mary ofthe molecules containing ths functional group have very strong ‘dors) Molecules that donot corain te aromatic ring are called aliphatic Al ts fne- tinal groups in Figure 2.14 except those labeled “aromatic” are allpate. Bene, carbon ‘xbon single and double toncs, carbo bonded to ewe, nitrogen, or anyother element ‘woul be alipatc In general onl melecues where six caroas are bonded together in 3 ‘ing structure where the ving has three double bons that alternate around the ing Would be considered aromatic. 1 several ofthese aromatic ings are attached othe lest, ‘aldo be nighlyaromstia. Molecules ean, therefore range rom highly aromatic thigh aliphatic. the characterises of aromatic and aiphati molesles wil be riportant nthe the lecal is art ofthe alkane fay The name chere= foe thane Tae ast molecule in the sae figure (Caso has two carbons and il ve thepreie eth” Howeve, this molecules acxrberrcavbon double bord and therefor lth etene fri ote that the ending fehane and ethene indicate te ferences io ‘hee ames) The est moleal all therefore be named ethens. The cer ame eer, sik sa sight ifeantraming stem but presenves many ofthe sams characteristics of ‘Taming the family pe. the number of arbors, and the surber of functional grou "Tae selenceofpljoers and plastics wlzes these names fr the sang and catego siction of paper atria te fr this reson that te fanetionsl groupe sn their ames are ntodueod inthis tet, “ust as two carbon atoms are bonded tagether in thane (C,H, Ue, our or many mere ‘analso bood ins chunk asrangement sematimes thousands of atoms long. These ons ‘ins of om are called polgmmers, rom the word origin meaning many its o arts. Polymeric Maris (ear Veweit) Figure2.16_ Throo-snensional prspotv eprecantatan of ebylene monomers {tino a paynar chan ecyeryiee) ‘The polymers are formed by ailing them up foes than very small units or individual soups called monomers, mearing.single nis Pigure216Hlusrates thre dimensional perspective representa of monemer bil toa polymer cba. ‘The nuber of atoms to which any one aor ca bond is determined acorting othe rues for table configurations four bonds inte case of earbon) as dsusied previously in this chapter. The proper number of electro fora stale configuration of a epresetatve ‘obymer is show. for each ztom in Figure 2173. Although the eletrondot notation i ()Senisbberinedsotion Figure 2.17 Represent poner chain stoning varcus netaton stom.Figure 2.18. Poyeners wah ‘Bot ot man cabo” thochan. ape srportant for x asic understanding ofthe boning this ethod of epresnting pobre momar foo so wre, Tarra shorter rthog (ele lf nan) in sch, i sre san Ue won show, use lstrad in gee 2.17. ei ane Oe earn uh represents to boring electrons ard that te number of leone i stood ey of ech atom s aggropriae forthe Se fat corsidee hous ely he gues fogs are inne. Ne tat exc carbon as eight lactone Beseeen ns of Bent erp ene ofthe ojees thee are four eects, When tis cours, 2 double the cans ae as nin crporearbon double bods. The semiatreiated notaton 9 ae altel in Figare 2.17e. In this system the Hyregen xs bonded to cabo ae treated to permit oeusngon the oer atoms, whichare asl ore moor aa corgi of he poe. eoerbe,howeset, thatthe drogen are realy ta ey ac ust nek snow) The parentheses geing through the bonds 2 the aa a ge (Reure 2170) inate tra the atoms shown we col 2 segment of anna yale fn In oral polymer representations, segment shown in saa ne a enn Figure 217 woul be the segment of the pobre ot pas ee he chat ober words the segment would be Bethe identical lino Fa in, Under these conditions te sme wuld be cle he repeat eit Feo epneseats he rab of uch wots cantina in the enire Foye. pati at ature fpbyer: eat the ators ser the rlvmer cn an gond 2a reaerectms along te cain and to atoms of the chain, Those atoms along the beth sald te backbone atoms and those ofthe in are alle pendant ae reece groups if sever toms ae grouped togethes The foneinsl groups Seem gure 214 canbe citer pendant groups or part of the backbone cal en prs cn ao have sors along the cin ef tt ae diferen from ce ee Stag ert isby far Ue most common. These noncattn cain alam ca 2 aa ae te properties of he pele. Sore payne wi aoncarbon sora aT sian at pigure2 1. The poet in Figure 2.169 i carborbasel ply (tat a ial atom along the cai), but nizogen and xen are aso pat of he aan a Pioreriusated i Figure 2.18 snot based on easton but rate silica, Sritogh aiconoced pobmers have some important applctions, the caboorased aa ear more gent ae are the price foes ofthis tex (Scone Pobymers are dicassed in Chapter 10) nse Gigeue previously inthe section on the perc table. whenever to ant Rave eferentSectronegtvts ae bonded the sharing af the elsizons may iors tat i, te eetrons may Spend more time nthe visit of one tom than in sere phe ther fe When neal sharing of electors ecu the Band is = we OnE ee 9 ah 1 nmi ta i | ‘ area fone Arnal known ctalyet apse of this type scaled the ZelarNatn cay ramet afer the developers of he sytem. These casts (1) promote be spretizadon, eae vent specie orientation reactions to occur, and (3) can ge the added bene 2 re escions Aether porta grou of cas, called themetallocenes as renee ad cent These catayts, ike te Zeer-Nata catalt force plymeriza tom ito specie spatal arrangements ty of tre atone. The avant of ae pets hat he shape ofthe cals abe changed at the moleclar lve that wre etng a wide varty of pobmers tobe careful and precisely polarized to specie Peal araagemens Te some eae, his capably allows pooner thatwere peo only ran ine to orm enaline sructares, Further, sme poostes ofthe poners ‘inbeHgnficandy enaneed by the ue of metallocene cia’. ‘tep-Growth Polymerization or Condensation Polymerization “the condensstion pelymerzation mechanism, sometimes called the Renzrowth polymer Tre seretcceanum,proceds by several stops tha ae it dere from the steps in BRCL sr addtdon pobmneiaton. Before describing the specific steps ip condensation YGibmsriation, some concepts Tegaring the reactions of functional groups (conning ra tation sta} should be considered, because these forma te bss of conderstion ac uation, The sus fundamental ofthese, bast concepts ise ration between onctional group that is iustrated in Figure 2.23, Tack stop in a condensation polymerization involves a zeactios between dsimias funetoral soups tut are yao roncmer molecules. These anetonal gous are soe (en Shouts from Ee mary ave in gai chemise to rect in the desired way nd icy cat eres nsdn he roing mater (Pure 2.14 ts several forsional ‘roups used t form comercial mporant posters) ee muon typeof easton in fning condensation pokes inves the for mali are new unalent bond bsbnesn the functional groups ané the simultaneous fT caanara smal molecule, suchas water which sa by-product of thereactin. (Te joining Figure223 Seams ncn sion ste aso Conena- Emr orese> growth poymerza ten reaction. Pobre Matera (oee Veweia) easton between (9) Reatne ofa sins oi oma a aie sa wae ctv moka itt rational bait need oot Sha the rove pnt ited sist, Sil neh an ao ah er iat oe nea ran ance ‘an react with an acd wo form an amide, again with waber asthe by-product. These me onsare reeset ed in Figure 2.23, bo These ree orpoeaton ocr ech monet nie mat ie ec fn sol ue (terse nooner wal ta cel nt in inglomrad Norones tht he bo gu te ieecna int eon cess aon eerste aston sheet sos Sane pi ames Titel emonesar phen gue 22 "ete tthe of hf er wh err cand egunetis Menton manomers Tse sel te) Enel mower tha cone we rcoomnation aeration (he 0 09 Tal mre ibe sine nappepate tome rt) eget rman ose ronteh22 sec tase fs conean arson om aspece poi: # ec and chon Figure 225. The para eden oretanton ration isco gen histori andcommercaleigafones Tecnu ato trl on coed tue feesn pero eae rs ‘Brame Ths mcin a a acl er ear ie nme omac guinea rere ap Tomo oh fog on ee of cb engi eBhtide welts woo 6) wt fe sane degion he rae Tore he ube of erin inshore as eth? aee vette . secs penee - oases, . sae 1 irtititile : me tii ttt PELLET sew if Tid eat" Lo roy OT me by, carbons. For simplity, the Kesamehylene diamine monomer wil be refered to a5 Snonomer A and the adil ai manerer wil be called “wonamerB “The see inthe condensation polymerization proces are as Siw Ri 1h se ifort menerere An Bach Paving too active sits, a intro- heed into the reaction veel, The materials are heated ane vignrously sired or agitated to fcitate the reaction. (M6 Inkiatr or catst is normal needed in condensation reactions) pe Figure 225 Condorason reson stipe to forma paamide (oven 6, Step 2. On end of monomer A reacts with one end of monomer and new bond is formed linking te two monomers, which begins the poymer chain. A molecule of water ‘condense i formed as 2 byproduct, as shown in Figure 2253. The reaction ootuts be ae of tibet tend fa and anne to et eens fs or] ups oeur witmat the cation of begrodect melee, touts thee econ ae Stop 3. Te beginning polmer chain ta active funtion groups on each offi eds. (tis is Because Both monomers had two ative ete before they reacted! Tn the caseChapter To shown in Figute 225, one en ofthe beginning polymer chain fan amtne group and the Sher end isan acid group. The amine group can react with one ofthe apis 26d monomers (poner B) ad th eid gr on the other end can react wth one of ed ‘ne monomers monomer Ale The raction of the acid end of the beginning polymer Bit rnocomer A's ilostrated in Figure 2.25 [nts reaction mono: Ais adéed to the ‘ealenng polymer, which exends the chain and forms longer pbymt Again amcesule rece Rested asa byproduct. Note that this reaction step isnot dependent upon any rosocs reaction step, in contrast othe chaineeaction mechanism cation gaye aaron ert a precou sep had to create ne re radial. For treason, this race ton method is caled stepwise polymerization. The water is removed by « special stilton pres asthe reaction proceed. ‘Sopa Te longer ples chain sl has reactive groups at both ents, Anam ca = acti the aed monomer (oonomerB) or an acid end cin react withan amine manemes ‘Teoconer alto prouve new bonds ad add to the chain to crate a etre poh pon mn Fgure22% Water i aghn made as a bp product. Ths pro:ess of eatin wih Nour Inger poles ean pocee, ia theory unt al the monomers have reacted, Lang peer chs can be formed but ae typically nots lon as with addon pobmeization ‘though the actual drensonal length ofthe chain i very small eeuse ators are <0 “erally is since at the rateral ew hs thousands of bonded units and the eles: ‘reaches unis into a poymer chain as signfcantl altered the properties of te mate- ‘als compared tothe orginal monomers. Step Not ony ean monomers react with each oer an with growing cans, to growing chains ean tact wth exch other. This would happen f the amine end of one Poly erin cto encounter and react withthe a end of another poly this happen, the qengliof the polymer chain cn grow very rapid because the procst joins lay cresteé Tong chains inant of adding a tngle monomer, Eventually, the cas wil become $9 Tee Sat farther enverent enabling the activ sites on the polyerstocoee into ose ey ior bonding w no longst posible. The reaction is then tennizated simply Pract which ncher reduces the movement and siows the tendency of he fantional [ous to weak The poyertzaion reseton can also be terminates by adding a materia {har has ony one active end. Thi is ealled quenching the reaction and is done afer {he poborers have reached the desired length. The quenching meri i sdf form cendeeaps. ‘ine the polymer chains become very lon, the end groups ar elavelywonportn as ar au polymer properties ace concered, arte plyers are best represented by @ ‘razed pobmer svuctue showing the eepet uni, thats, the smallest unit that reflec: {he base structure of te polyoneIn the case of condensation poymes, this repeat un 12 Shibanation ef the two monomers that wee asad to fore the pmer as indleated it Figure 2.254, These pobrners are named by using the prefi poly” with the name oft. ftps of fenesonal group erated. For instance, te action Between an arine and at Sues an amie, art othe pobrers ave elie rolyanies. Te name non is ist: ‘comaron mae for pobyamides. Tacome cass tne by-product not water, but tis almest aways small, stable mole ‘ale An temple fa by-product other than water is Ue rettionbebween phosgene 2 bie henal Ato form polycarbonate, Hydrochloric acid (Ci isthe by-product ober: Mater (eel Vewoit) a ‘Comparison of Addition and Condensation Polymers ‘Theron portion and conden pret rn ee bey aoe Thats dienes ae ermal in Table 23. , ct boson pretend codcon pymaition ths chaingronth mictanism. In aon pokmerizaton, ths poyoe: grows iach ‘ecornne ti nr arts sek earn oma se {Ete racy, dana aban pla get -er ie a ep cn mdse nos wen Ta of thar te major pe oman i a carci yk pe ona el oa te ge nen portion te here Re clones de bons te dng me econ contin py ‘ema ch one tae vo ete sesh ae acl rou kat ‘ater conde opal aia sr re ode pt Ton nooner ne wo val nce pues on ah fe Ths tome ime ha dle manometer 9 sh Os es but ote sae aetna be Gt monoe P acon Table23._ Characters of Adon and Condenaaton Polmerizson Matos “Ratan or ChanGrowth Condaneaion © Sap Gran Felymotzsion Poymersaion Fasmereronmecunien — Chairescion Sep Bsn eas Depensenn en proous sap Yeesequl Nowheepecort ors ‘ependent ents tr ued ve No “ypoot manor Conainscatorcarten rena (at acts Sebo bers fenton rss one ers urate sts : 2 (reser gir) por aero eset : ton yo et 2st rover By prodicttomad No vee aia) Nowtpectberatomes No ve ese mpraertaton onamer wines ne evar ored ipemorreeatunt usobonarcian oar ene never se Rebmerchanchancerces — Atenlongetane Many etry ang ine Brancing Posstle uty ane ot mer foxy + rane of ronemet_ Foy + mare of nw tnpolymerization to aces, the functional groups of the fist monomer most reset with the ‘inclonat graupy ofthe second menomer to form the polymer. Therefore, condensation Pobmerzation generally requires that to types of monomers be present whereas only ne tps af monomer need be present for ation pohmerizatic, (Condensation nol ‘heaton can also be ne whe a single wonomer has be diferent ond groups that wil ‘fly eae, These ae, however, ra) Trio of tse dferencis, some monomers polymerize bythe addition mechanism adhere thers polymerize hy te condersaltoncecharsm, No pobmer ean be formed by ‘oth mechanisms although a pobmer may be formed by one mechanism an¢ then ent into alter ection that uses the other means (This seen in rosin, to be di cessed later) “The formation of by-product condensate is spc in a condznsaton pobmerzation but doe not one in adstion polymerization reactions. Some minor products, such a6 Noy shorchainpoimer, maybe formed in sdton polymeriatin, bt these are the ‘Knut alisions beneen various fe racials formed during be cours ofthe reaction athe than ae a pect profs from each polymerzation ste. "The palmer formed For aditon pelymamzation cn be eprsented by She monomer without Ue eosble bond at with bre Bonds extending on either sik thus indicating tot ‘Tue is present. "Te baie palmer formed from condensation polymerization an be presented by bro sronamerejolned together as they would ben te pelymer ater the Crdenaate bas been etracted. "Soe iferences in the pelymes produced bythe dition polymerization and condenss- tion pymeraationprocsees cin by geen fom an eamination of thet mechanisms, Bex (us ofthe relatively sal amunt ef iiatr use in aditonrlymeiation, ony @ few las begin to rom. The cain action mechanism proceeds very ick’ especialy in the Sressnce aac ad vaults inf ver long chars na sor pero fine, Event {iy the monomer sents combined int the chains ad the eztion stops. Ta condesa Sk pulmedanson, ry to eferent monomers at mest can iia a tain. Therefore, tury chains are growing simaltaneously The grovth ofthese chains depends upon the Bins to encounter monomers or ether chine and vact fective. Bvensaly, che ‘monomers seal al reacted, bu bacase these chins til have active en, the grow {ng ehuins ean continue to react among thershes, thereby inessng the Length ofthe ‘Guin, Ths cain combination continues until the ehsine become long that farther moxe= tment fica, even atthe elated temperatures normally utd inthe pobmeriaion ‘races or una queneting agit is added. The leEhood of ery long chains, hereto, ove common wth aditon poymesiation tha with condensation andthe Hliood of Bing many polymer chain being formed is eter with condseation than wth adton, Polymerizations Other Than by Addition and Condensation Mechanisms ‘Senne pupaevzations ase reactions oth than a88on or condesstion. or insta, 2 ‘Eieogarate can eat witha cleo eo) to produce a polyuretere, No condensate formal inthis reaction. bot some rearrangement ofthe alm cccus when the bord be- tween the monomer formed. tom rearrangement alo o:eursin the formation of acetal Polyerc Materia Melee Viewpoint) & riba fon oman, er ti fr ming as nae Cheng tse rng yon wes sn ae tering opening cea ates ‘which can bond to other monomers and form a polymer. . These and evar ets fae brn se th experineraly and comme tipopmen ty te ese mur ofpebmreeedy ete ead thlonor ie crderstonpmeraon neo ‘THERMOPLASTICS AND THERMOSETS: Al plate, whether mad by aditon or condensation polymerization, canbe die ints ‘wo groups, caleé thermoplastics ant thermosets,Thermlaties ae sis at room temperature tht canbe meteor sftened by heating placed ino aol or other shaping device and then cools to give the desired shape, The terroplstis canbe reshaped at, sry tow by vehaating the port X Itchen araleg) to therwepsscs would be candy ‘wana (Photo 212), which soften and melt when heated When mele, they an be put into mos and cooled thus taking the shape of the mol. dsr, they canbe reeatnd ad veshoped many times, For instance the caramels could be reheated to3 met and then lnspole cred be dipped inthe caramel yet the apple Photo 2.15. Th czating ays on ‘he apple because the apple cols the caramel cating ‘Termoets an be eher Kgs or sls a room temperature, Whan placed nto a nel and then hen, they intl drop in viscosity (liquiy but then cure arden] wpe farther sting, has ging the died shape and sli properties. Mer coving if termes are re eae they wil sfen somewhat bt do nt mate ad, therefore, cannot be reshaped. A archon analogy to thermoces would be aca. The eter poured int the es pa roi {nd then place in the oven and heated Because the lqu cake batter cotane paler ‘materals that wl eosin when heated, the ek wil evenly harden cure. Wan the Teuid hasal soles, removed and cooled, but fhe cake is rheated, wl ot rere, bute degrade bur)-The bhavor ofthe eae is pia of Cero. ‘ho sath very diferent befvors would be expected to aise fom abasiediferencebe- tween thermoplastics and thermoses [nadton tothe normal covalent bonds thet jin the alors together in the palmer chain, the terms plastics also have event bonds that join the chains one fo another, Thsze bons baween chains have been given & special name, erosfinks, stated in Figure Figure 225, Creesneng olpaymer cus.Pobmere Mater (alec Vewoit) 6 Some polymers, such as many rubbers and ether eastomers, have properties that ae intermediate between thermoplastics and thermoset, This occurs Desase these Intermediate materials have only afew croslins. Thereore, some ofthe polymers may ‘ot be ted into others with cron and even if ted into others there ae so Crosslins thatthe mas of melecues wil wher heated, grea soften ard sme parts may fren melt. This situation mears tht the elastomers can be thought of as pally thermo- piste and party thease. Because ofthis intermediate nature of elastomers, thir compounding (mixin sive) and molding ae also somewhat difern: fom that of ether thermoplastics oF thermesets. Since eastmers do not fully met when heated, cornpounding is cone on the semi elastomers, usally by mining the ative and the polymer together in 2 powerful mixer Gomewhat like a bread dough miner) or by wing ale mil, fer ait ing the elastomer ie molded under heated conditions, ss Wiel o thermoset More ds ‘custon shout these ators wil be given in Chapter 10 COPOLYMERS Some unique pbs canbe created by mixing tngather mare monomer pes than the ‘minimum required t effect normal polmercaon, such as ming elplene emonome: and propylene monomer. Normal adtion polymesistion requires only one type of monomer to erate a polyner chan, wheres normal condensation polymerization nor mally regres uo moncmers, each with bwo seve ends. Waen mere than thee min ‘um numbers of rmenomer types are maxed, the polyae wl contin some combination Of the monomer bpespreseri. Polynes with mised monomers ae aed copolymers, nd they are, Uerefore characlered as having more than one type of repeat uit. (When ont the miimume of monomer tyes are presen, tat, when the nornal pojeer is rade, the polymers caled a homopolyaner) ‘Coplyeer in four general patterns canbe made by both the aio and the conde sation polmeriation methods, These are Mustrated Ia Figure2.27 fr the simpler ase of AERA YAY K A EX YR f Photo 21. (a) Caramels araegous to termoplstce. (9) Caame apples (roshaped themropssie), | (Random payer (Regu oesbensing copa (G).Cake thermoset). (Courtesy of BYU) ‘When the appropriate sites for reactions eis. rosin are normaly formed by eatin AK OKK KAYO Ye XK KK the polymer naar a proces: calle euring. The heating ives suet energy to exe the moltcule and enue Use to move cose enough together that atractions bebe thc bonding sites along the polymer chain en oer eauing the bond to form. Hence, ter ‘owe teil become Bim, Geel of “a” wit thermal erry. Te crosslinks can eth: be formed a the polymers thmselee are being formed or can be farmed betaeen speci sites slong esting polymer chains that can ji tageter in normal covalent bonds. Ther ‘moplatc materials which are characterized by not being croslinked wil sofen anc teceme mere pase” or pliable or melt with thermal ence Deal ofthe nature of ther ‘moplaste (commodity a engineering) and thermosets are given iniater chapters. (© Bleck epsimer (Get copolymer Figure 227 Copolymer paters tradition polymaizcton.hope Te cn polymerization, Some commercial copolymers, allo be discussed Iter in his Tee Scone butadiene styrene (ABS), syrene-ecrlontril (SAN), and ethyiene- SE cease (EVA). (Some opotymers canbe refered to as tenpoiymers, which res {Gut three monomer types are polymerize together) The determination of which ype of ‘Sober woud be formed i dependent upon the basis nature ofthe monomers and thelr SER vec, the conditions ofthe action (such a concentration, temperatures, ‘Bhatets, ets), and any specif mediations that might be mde tothe monomers or Sabine allowing the eopalmenzaion step tobe activated as sid ll these cond- fons ae used for various enpolyerzations. ‘One monomer, X. which coud pelymeriz alone, i mixed with enether monomer Y “which ould ake polymerize slne, The mature of monomers can produce & random Wefetbaner snare (igure 227, whee there spe pater in teasder ofthe monomers ‘Song the polymer chai. Thisis the most common coplymzr pattem sreetho pattern could bea regular or alternating copolymer pattern s shows i rigare 227% tn is patton the Manomers havea regula, alternating sxuerce, which fan be represented a2 XP, ete This pobmer shou ab be conse with normal henson payer, although the alternating patter i the ame, In the cepobmer case fhustated. too ation monomers were present (one more than the number needed to obmerint soa epsbrner wes mag, Beause copolymerization cequires more than the TRimam number of monomers, eopormer in condensation solymerization requires Tice movomers andthe resting polymer woul require at bast the pattem AB-C, ‘whereas the regular plyer getter is just AB. {hind typeof copper pte cccurs wher long sequencs of one monomer join tong sequences ofthe other monomer to fm te cain Tie pater is called 2 block epigmer shown ia Figure 226. Ths pater & characterized by several manomets of Soe poe in’ rom along th backoone flowed by several mancrers ofthe second te, ‘bo along the backbone, Such as XNA 6, “The urth pater 2 raft copolymer (Figure 227%) In this tye of copolymer, 2 polymer chai formed by one monemer (Xd then a ein of he other monomer (¥) Ipattched sea branch tothe mainbackbone, Te general, the properties of random and altemating copolymer: are averages f the proper ofthe te hornopelymas. The properties of blak ané gat. copones are nat ‘erage bat have sore characteristics Tk ene homopobymer compare and some prop- ‘pti Iie the other homopolymer. (CASE STUDY 2,1, = Modifications to Improve Teflon® Processing ‘Tonia cetered trademark ofthe DuPont Company forts glumes with a arbon Trcklons and fuoiaeccesses attached the carbons tal possible bong its. Mol- acs outa Ruorne and carb are cll’ laorsensbons This moles rpre= sented in Figure 2253. "the PTFE mater poietrafuoroatiyane, was discovered rather than intentoralty ‘mage A chest at Dufot oy Planks!) was working with ttrafuoeetlene (TE), Pojmerc Matern Moteur Viewpoint) 6 i 1 F Te (0 Pepe ol etree CFE, = piesaanonsen FE) i__ | ee oF Rie (9 Perteratony FFA) Figure 228 Fuecaroon pokes, 2, and ound on oe scan these re vas ey sgaetng tthe tavern etd te and td at twas usually hey an tty tank Shu dived fo unesand wy He at pen he tk and und ashe, vay powder the btm, ten red hatte FE nasa ronme that hd spent pl sean PTP he eating sl mara Berne Te has etoonenon cou Bond the stn oberon metod ee sapere an va tr contr The kf eye ex aes eral eer thane ope te The ner was found tobe ore an ste than te sale cogencxfen eth i er ee area PE at in obeniee ae rp y Suis n FIFE) To dina in porn ares se of the nature of the earbon-luorine bonds, mere anne tment clctrorgae fate stom hrf he carbone ond isha pl wt the pvt oar thee Hey th eetors ae el vey Sig th ance ole The ere te ver song nh pl te rn sae Chae te etalon the fctbone. The Rens es shi the eto and pay verso adc carr vl ri ec ns the plmar ery ner. This ners crestor race oper of Pt orice. PE ot ome ith one nse nt bum ror an Stoned Bee neous ele Shy wl ot nda erin eee IFS fering Bonds wth her raters ey fo things eno ard ths ben tore era in raleng ons sures cng pa The PTE ows roeChapter 0 rovened edges of the pan surace ving manufactre to ve a meshancal bond. No “Rete beds ormeds bees, the PTEE canbe rmoved by serena) PIPE chains ae very long, aight, and sf, allowing PTFE. rckales to pack to- ether iy, PTPS as Une Highest density of any lasts. Furthermore, temperatures Aerial cttct PTFS is unafecte by cold, remaining unchanged a teeperatures 3 ow BELGO'P (-258°0) only afew dugres above absolute zero, Likewise, resists high te ‘Scares PTFE does not begin to elt until 821°P (227°C) and then foes not become 8 Tiga, bozo trnstacent gl At erperaturee above this point. PTFE decomposes. Tis ctince to elevated teoperature Hae been both a benefit and & detrient for the ue of PEPE. Although allows PIFE tebe used in macy high-empeatue sppicatons i so Pins that PEPE i cific o process by noel thermoplastic provssing technigues that require melting of ke polymer. ‘radu, PIPE was made ito useful parts by packing he powder roa rold and then eating the tld under presse, to jut below the melting pent. This tesbment caused he Tijana pvt to ise together inte a solid mas common proces inmfasan cera ‘eesti. The aeabonoflarge ars was thereon diel Also he ime egret aie a pare vas very long compared with the tadiona Uhermopistic manufacturing ‘pootsea Thee, te DuPont Coraary sought way to aka polyrer thatthe ber cal properties ef PTR but woud be easier to process by traional pte manfactsring ‘icity to succes vaste escovery of pobhexaueropropsen PHP) a pobsner ‘Riel to PIPE: Ae sn in Figure 228, the PHEP i ased on prope (a thesaon PS father thn on eee. The rena polymer has a pendarexbon sto and fho- oP oat bonding locations This pendant group mean ha the hain as fr more Fea sn wil theeore, mata Sowerterpereture. This lowes reling point rest cesta the prosening toate ofthe polymer. The pendant group ao tans thi he raaeret tues same ofthe beneficial ropes characteristic of PTFE, PEP has greater 26 ‘Balun ior ater materi, is more elaczilly conductive, and is slovy altace by some Raclals fe should be remembered, however, that these properties are diminished wih xe Siecte PIFE. PHPP sil mush beter than other ptymers ial ofthese properties ‘DuPont found, however, hat a eopamer formed from mixing TFL monomer and FP rmovures bad poopie hat were intermadint betveen PTFE and PHFR teproved tobe 8 (oot compromise Te ew copolymer material was called Guorrael ethylene rovene Poo) and current in wie se Tis mater canbe moléed with rormal thermoplastic processing methods. cothe: pasty for improvement of PTFE is 2 macifestion that gives stihl higher sts for bonding with otuer mates. Tis canbe dove by adding omy to the ri chain si shown in Figure 228e. The oxygen allows the Muoyoearbon material to Jekd with ober materia, suchas with the mez in cooking pan This materi pefo- Meio (PEA is the basis forthe en, nonstick coatings that have en produced. Asn, Beit proces of PTFE ae einihed, but other properties sech as ahision er- age more svantgeous art ean ‘Other well pobre have been made by mining pure pobmarzed PTFE with other obec The are act copolymers beause the monomers are not mised but ater, the [ireauy pebmerzd plymers ar combined. A good example isthe mixing of PTFE. with sabanitene (PAL) 3 very song and hexe-resitant polymer. Tis mitre was found tobe ——— suMMary Pohmerc Marri (ec Viewpoint) 6 fl oars where mechani wer resin recat vas porta ch nob cast bangs: The Pa wes rest tthe ig tees pal fs opeon (Ge ght cat an PREY eed Te FE ‘count ents sng oe pres gn ehch menue a rs i ech ter nd ter ents ‘eTrcreite whose chee rein or ninick abr edi pre 21Fe canbe and. some compromise in rope istceale, PEPPER ors mire Of PT vith nother plya char Al might aca. Th et si ange of Saroearbon rea, each ving sme uae ad benlcalrpets at cn Be Ble to tach gpition ters ompoed oto, hich ze thmsces made porn tos {iSSon gw eh oc ple won dcp ste peo Stn. te wens neaton sto cn of eso ha ee oe Shed nudetan te cede re ranged wo es Meal tos ht Sn nebe efter a sete (cg evn te nt Elucef ints at ae mats Gr sue ec of pote el wih et ts ef geaco) Cage ma ol por te pe cae. rch oe por pce pc pel som scr Oy ogo Prot sea iets ute eect GSE dn Ech ions ur sie nar acres enue pes a te {en st lor a pa bc Tso es ihe cents cn bearaged na snl tle ba tha ned azo ther cemieal nantes an ator numbers Tis table called the peo abe because Site etal pone Priel petit oh tome se rina dpe ne arageet of the tego etn ange ale eee cfg acer ott toe fe elevesan te nyo ean say he rp eT ey le rend yt aon hl od sage Toate cher are th sons Gp upon on hel a3 oe ny or eons Parana ns is Shon coe cht oan so that ed ton he tc soo ar dass tans ttn he ate adhe tant bone ‘Rte toe ny andthe str npn ce sms eae oe Stoic tan pute aoa ot et ele an Son Erroll oes coin So tte one soe crt unter sta a une ole dco bh stn re ap the Son anis hoch hades omees ths sats ree hes Sor ttn to inccounscones et soars ha rt cece, ‘ian shee sco Ms cole oo and noe mata hang plme ve is pe lbo‘coger We ‘tothe extent tht the stms sare the bord unerualy, because one ato hy ve 3 rte ay for theese than te ty the Bon plat The aint fr leens a a cucnegatnty. Secondary bons bebrenmelecules can be formed that ae gale si cle than the lore, meal, oF covalent Bonds, Some sesondary Bonds ‘nde rc ofthe aacton of polar bondsbebeeen molecules. These are ealed Ser bonae or drogen bods nthe ese of water, te Ptegns ae postin com a tthe on ad wil fen ssendary bonds with he noe i oe wer rae Cer pes of atactions are van der Was forces and induced polarity race Gece both ef which are indviuaiy much weaker than elses primary or secondary bond at eee c are abet form may molecules offering sae and complet. Tere- ore te ay of carr tased molecules ald organic chests, hasbeen elven pei fo eto heve sx leczon, wih bo in anfaner sel and four in an outer seers Gates all leetons are general the only one that ete no chemi ea spe Re four outer she elecrons il form four covaont bends ans achieve a ers ce ton eoniguraion Since each covalent bond bas to alton, the sable co sane Gia conags of gt secon around each carbon atom and ie cale sale ote esa toms gin tay when they ae surounded by cght electrons in their outer shell at oupings of atoms that occur frequent in organic cherish have characteris: a Ee Sede cae asona groups The sty of thee group characters is 1 Bae fc of orgie chemistry ais the bass for the raring of ganic males inelding polymers. ae er can bond to theslves often creating Tog chins of carbons apt topethe atom Thee long stom eins are polars ad are formed by te bilding tere She dain Ror smaller ants, ale monomers. Two princi method for forming wer gre the nian pobraetization eto andthe cndensation plymerzaticn pane addin polneration general requires the prescnex ofa cacor-carvon dov- Fear fn ine monamet. Condenaton polymerization genrally ceqstes thst 0 Ne a cs each tative tes hat can eac even the moneret wares at are ethetic and that ae formed in oner to produce 2 useful proce are ches The ro forable terial scale ares, Pastis an be dvied into Bite youn —tneopiastes nd thermoset Termoplst are solid materials Gat see Pp mel and then placed ina meld and cooled to sly. Theos are aio haul starals hat are placed ito a rold an thes shaped and heated. This eating exes the material to resin ie ashcoare convert to use bsrauethe polymerization step has ben eae shed bythe pli en ranufactre, sulin ge tes resembling eines Freer a fy powder or fake, whieh is ofen proessed into stall pobmer Fre rr pout the sie of spiel, ang ace chapped into small pelts, These resins ate Saar atc who then (1) emt he material, @) mo into the varous Sana ead (a resi it to fam held properties dented the inked ct ‘Te lent ofthe pajmer caine produced by the ation pemerization andthe con dorian Wimerzation processes asa profound eft on te properties ofthe pel reser the monoers are wally gues ov igeids,the polymers are solids, often == wvestions Potmere Mater (bes Vewoint n wth meng sons of seen! hundred degre. tn Ger doeersoatbencmee Soa St er en ercet mata undergo crostnking ection whe tn he ‘takes longer than the cooling of thermoplastics. The Shad naterale cunt be sagen tan he lg of ere. Te ced wae Nien nal afer Opes mono es bri smonemers an oct, These payers ate led copaymers ard sal a proper ‘that are intermediate between the two types of nonmixed polymers, base epee 1 Deseret erences beeen the eon and ones EM at ers ecg sone sy the typeof bond nd the prot for pots et orca epected between potas Ka Soni (and ninth be are oi ber Sow teen ute lo ‘ tg cogaion of Kan Dy afr the bondi oro _ ty te pe of bond end te product forme exereé even meges dln (0, aden the bare ate ths bod Shaw he ealing ae ‘electron configurations of Mg and Cl after the bond hus formed. nee 5, Dacre te ope of boning between carton an caine 5 Wit svt ak inpan eprint? isthardr anak wy lg prac cae xn the cones Sonatolhnty wine beediten howtiaion neha 9. Daa th ond etncaon aa be inn ‘eolanaton ofthe mechunisen by which the various bonds are formed. What does the 4. tetera ol eer osetia cen wat ee racer a pera Wie lore eng a see Imran st ocean main desi eo ra 10, Vic pobmeration mahod. ation or conde we pera ation oF canes, ected 0 ret in 1, Desert crolining the resultant properties ta tl eeate 12. What isa copolymer and how are copolymers formed? ‘iho 1 te molar ieee hero ond eopite m? hig her wegh x pele cena le mop bwrtin pons yer Sug eb» coe 15, Deine fe rade and ein why ii co ec. === REFERENCES teen... Mandbokr ats raion, ders rem owns 198. [Bryson 1A, Plates Maries (2nd ed), New Yor: Var Nostrand Reinhold Company, 1970. Di ln: acre Por, nae Pe Tame PANE Cs a.caper Too rte, Nan ae ae 28. Seem Pe te Se ey gn oe ene CHAPTER THREE Ce " ale ues Chr, oe Sd a A ear ae . . "ike poo con ant erwin a Microstructures in Polymers “ae, 1990. CHAPTER OVERVIEW — — ‘This chapter sarins the allowing concepts: Solis, Heuids and gases “Amorphous and eystaline ‘Therwal transitions fet of themal changes en polymers Pobmer length, molecular weight (arerage molecular weight and molecular weight etehaton OAD). Physical and mechanical property implications of molecular weight and MWD Natt inde Steric shape) efoets INTRODUCTION ‘his chapter focuses on the shapes of large portions of robymer chains acting together snd the interactions bebeeen polymer chains, rather than on individual tome oF ‘all group of atoms along the polymer chains. This lee of fous is called the mero ‘sw; a epposed tothe meleculrvew ofthe previous chapter, The aco (an even ars) view, which loks af bulk properties of pomers, is scussed inthe felling two chapters. ‘Te lng ofthe polymer chun, Ue ways polymer molecules or cain interac wth ‘other chats, and the shape ofthe chan, eopeciliy asthe shape is hested by pendant ‘roups, are key parameters in deterining many pobyrer characteris, Incuding Selidfigud behave and crystals. The study of the miccostractre of rater L (cesta ee) iscalled morphoto. 3a Chaser ee ‘SOLIDS, LIQUIDS, AND GASES ‘Mattes can be described in terms ots pyc tate, that st seal eonon at any ‘one momen. The possible slates re Koons solid, au, and es. When in itsoli ate, ‘matter hasa fixed volume anda Seed shape. An exple would Bean ce cube. The ice cube ‘will ocapy te sume volume of space no matter how euch arr than the foe cube the Cortainer ay be. Parhermore. the cell maintain ts shape (cue) regardless of the shape ofthe container, provided the container sarge than thecube and ao other changes are mae, such as temperature ‘When ina liquid sate, matter has fed volume but nota aed shape. Water san ob- ‘ious wample of quid. When paced in a container, sh a3 evp, the war wil low to take the shane of he container If poured from acu into a ben te water wil change ts shape according. Te water wil, oweve, maintain its vlume, eventhough it might be placed ina much ager container "When ia gaseous stat, matter has miter afd ohare noc a feed shape, Steam or wat vapors the eorvesponding gas to fe and water When placed ia a cenaine, the fas ‘will tae te shape ofthe container and wil occupy the entire space availabe within the ‘ontaine. the sie or shape afte contane is changed, the gall change secorcing Mast types of mater ean be conver rom one sate t anotherby changing the ere ature of es commonly, changing the pressure. Pr instance, ic wil change into a qu at the reking point Water wil in tum change eto stam atthe Bolling point. The single ‘most important property that controls the state of material isthe fedora of movernent of it paricies (toms or mlocl). If the parle are highly resatad in thelr movements, ‘de matariais ely to bea slid the pariles can move independent in all ireeons, the materia is eb to bea gas Aqui isbetecen the two ia esto particle movement. or irtanc, in ee, the molecules ace locked in a hecedimensonal etl sructire with reltvely strong bonds hading each water molecule in lace raiveto its neighbors As hea is added to the ce ctl the atoms gun more energy and tei to wbrte ard move slighty. More hest wl result in more vibrations rotations and aber localized movement ‘ot veal the molecules ave more energy than the energy ascited with the rat structure bonds hold the molecles in place (These ar secondary bonds acting in three ioersons) When this enery point ached, the ie mel. However, evea afer melting there ae sil some secondary bonds acting between te now lqul ater molecules. These secondary bonds are generally nt thre dimensional and are, bees, weaker than in the solid case becuse the molecules are futher apart and secondary bonds are very stance ‘ependent. Hence, de molecules in the liuid state are “seresrtd” Wh added ener, the molecules continue to gin greater energy. which parts ure increases in vibrations rotation. and other movemerts, until eventually the energy ofthe remaling secondary bends sexcended andthe meses begin to acz completely idence, This the bo ing point. The molecules with energies above tis heling pont energy ate no lander ssc sated wth therst ofthe lees and are fret move she vithn he ante They wl therefore Sl the cereaine na random chon, characteristic of age. Acdional energy in ‘put ese al ofthe lid to bo, with no increase in erpertie ad becom ‘Adina energy cou sil be add tothe gaseous sytem, Ths wil continue cause ‘the molecules to vibrate, rotate, and move ntl eventually slice energy presen inthe ‘sytem thatthe bond ener is race When tht cur, te atoms in the emlecle wil icici ie Press % separate andthe mater will na lnger be eater but will revert te hycragen and omen Moms The point where the eovlen bonds are broken scald the decomposition pot, (Pu ter energy aetion could cceceably breathe store apart bt there energie ae eed with nocler reactions, suchas eer tom bombs, nd are heen the eps of thie et) Asthe number of atoms ina molecule nests, he marr oss for ese bone ing also increases. Hence, the amount of energy required io break thse bonds and convert the material fer sol to liquid alo incest, Polymers, wich ave very ong chairs of tome, wll gery racuie much mere anergy for each then change thn al, ne pobmere coset rte. Henes, thermal trator in plyners ccc at higher tore peratures than in srl nonplymarie oles, Other craters wn the oles that could increase secondary bonding (such 3b having polar shes Ut can for song Iyéeogen boa) wl lo inrease te thermal ants of mal covalent mati. Tonic solid (ceramics) and metalic sls (metals) can aso be melted if safcient em gy is aed to the astem to cause the bonds between the partes in the sli stuctre to separate. In these cases, the particles are atoms for fons), andthe bones that hold the aterals together ave the fnicor metalic bods discussed in Chapter 2. These bonds are ‘uch stronger than the secondary fonds that bold covlent sold structures together, Hence, the eneees require to melt ceramics and metals are generally euch higher than the energies required to mele small covalent solid, and the melding pont of ceramice and imeals are aso higher than covalent solids. (The eneris to break the primary covalene ‘bonds in covalent molecules are roughly the same as the energies to break art he ators in ceramics and metas. But inthe case of covalent molecules. hase energies ae ass sed withthe decomposition poin: ater than te meling poi) ‘Al the changes in sate (old tofiquid to gs) are reverse with the subtraction of en- ergy from the ster. Cases can be condensed to lds an ligne frzen to slide 2) ‘cooling, Most materials can be change fom one sate to another and bak repeated, with some imporant exceptions, which wil be chewed Iter, ‘The changes between the sold and Equisatas wit the adzition of energy ar impo. tant inthe understanding of pasties. As discussed i Chapter 1, the definition o «pase ‘material pes tat i use a solid bu at some ime has buen shaped or mc ints 8 useful shape. The shaping or molding is usually done when fein qui for. Hanes, most al plastics nave mace 2 wansivon frm the Hud to the shies, Nany of ee processes cicssed in theater chapar inthis text ious eiferant methods of ak fing thes transits POLYMERIC SOLID STATE: AMORPHOUS AND CRYSTALLINE, ‘The soli state of polymeric materia n same ways, more compe that the slid state of ‘mos ionic, metal, and sal covalent molecules. The complet in polymers asa be ‘ase solid polymer matarils can ext in two very distinct pes of eenigurtons. In ‘one ype, the polmer molecules are andomly coiled about each other with emanate’. tc a cooked Suchet would intartwin. (See Phato 3.1.) The srctare Spe caled amorphons. In the second type of eeniguraton, the poler molecules cn rack t>- ‘ether int regular, repeating structural pater, These rear packed regions are cal ‘egtals or rgtalline regions, Although no polymer is exmpetelycrytaline (having6 (Copter Thee Photo a1 Soashet shoving entanglement. (Couneoy of NU) some amorphous regions), hase with large concetrations of ersalline areas are sai to ‘ecapstalne of more accurately seminal. ‘Asernieryealline pobmer is pletured in Figure 3.1 in a two-timensonal representa: tion. Tis epreetaton called the fringed micelle model, iain many, but otal. of the properties of rstaline peers. One property not well explained this mode is the appearance af spherlite structures inthe Yay dilaton spectra Amedel in which the ‘elecles fold ino platlie stricres (See Figure 32), which sow from a central ‘uletion point, explains the growth pater tht forms the spherultes. This theory is {iled the laminarfspherlite model or more coramonly, te folded chain model. A- though the wo models have not bees Ally veconcie. it may be thatthe folded chain ‘modal is imaly te shape hat emerges wen the crtallne regions of the fringed micelle ‘model are slowed to grow stl into larger ental regons. opr ore Mo (6 Senieqyise eon (yds ioe Flgure32 Folded cain model or Shea sem ferrrtiegherate move! !pelser = Saye Mirstrctrs in Pobre 7 ‘The mast important (but nat the ony) feature of pelymer that determines whether it willbe amorphous or crystal is the shape ofthe polymer repeat wnt. the epeat unit ‘comple, epecally with large pendant sroups, the polymer cannot pack tight together and i be amorphous. Some of the most common amorphous polymers are pohstrene, acre. plyearbonate, and most copolymers. proximately half of the most common ‘commercial pasts are amorphous he pobmer repeat units simple andthe pendant groups are smal the polymer may beable te pack ight ard rysalline regions could be fored. The regions of ersaliiy re comjeed of fied chains held tageterby ental bonds Secondary bands)-These banding forces betwee the chains ar oaizes to the tightly packed erste ares and cea be ‘ae the costal structures, when they occur represent structures with lower energy than 2 tandem, nonenstaline arrangement ef te rsecle. Te lower ener isthe result ofthe ‘Roleula fring Bond, which releases ener The cpstaline sections are steed thought the plyoer with some apastuctured (amorpbaus) regiens between them ‘he amount of cylin in the polmer depends upon several faster. As already rentoned, the mot imporant she size and regulary ofthe pvt gous (the eruns tached wo the main polymer backbone) I these pendant groups are relatively smal and sre regula paced long the polymer chin, hey will ac interfere with each oher and the [ober chains can pack loser together Forces of atvaction an other simar intentions between polymers, such as hydrogen bonding, lo inerese ental. Some important Highly etlline pobrer are pljethylene (HDPE), acetal, and ylon. In adn to thera surutural factors, the enealiniy ef palynars alse depends upon molding or processing conditions. Cnstaliztion in plymer takes tie to cera. There= fore, factors such az coling rate can have strong fluences onthe acount of the rater {hal eyetalin, since below certain temperatures theres notsufciert molecular motion twallon the molecules to rearrange into close pcking configuration In some polymers, ‘mechanically suething the polymer wil do the chains int close proximity and, here- fore, induce crystallization. This phenomenon ithe bss forthe stretch biow melding process tha 6 used to cause crystallization in softdrnk bots, thus increasing their ‘Svengh and esstance toe dftsion ever what they would be famerphows ‘Some polymers wil only form crystalline srucsures when polymerized under very spe ‘al condlons, The mot important of these, and the dasscal eamole ofthe pe potyroprene. The relatively large pendant group on poipropyiene preveted trom en fallzing and so the pobmer lacked the strength and snes that would aise feo the ‘locely packed entaline regions. Hence. ery polypropylene had only Hnited applica- tions, However inthe 1940s and 1850, twas discovered that if plyprpslene were poy~ Ierzeé uring a peel catabst, eystaliztion would acct (This i dscused further in (Chapter 7) Recent catalyst developments (spectaly with meallocenes) have incated that many pobmersonee belived to only eds as amerphous polymers could he plyner- ized in such uy that eystalinestroctares would fr. ‘Te smcuntof cyan thatthe tla numberof tors weed in a crs satus ope ot number in amorphous regina evar sly nome ole, ‘ho ena tas place. in oes ial ofthe conditions are favorable, tainty ct Spsoch 100% buts more Hy tobe nthe 60 to 70 range As the material becomes more captain lz bores more ders. Especial in poletnlne and ober plastics with asper Tree wige ange of passble esas the density isthe mest commen metho of exresting “osallny. For instance, pabuylee wth a deo of 097 grams per centimeter! would Selnighedensty (HDPE) wheras& density of 092 gir would be Iew-denity pobetviene (LOPE). The folowing methods re commcnly used to measre spec gravy and drt f= Specific Gravity (ASTM D 792). This test determines the wight ofa sample fait nd then immersed in nate. The ato of the weights ithe sped gravity or the ent ofthe material compared tothe density of wats, Mest pasties have specie igewites inthe 09 to 2.0 range. Small spies about 1 nc) ae used in the estan fre suspended inthe wazer bya thin wire. ‘= Density-Gradient Techaique (ASTM D 1505). The density of matecls is deter Trned by comparing the point at which a small simple (usually 2 pele) wi ess Dunedin Mid of varying deity with tk suspension pints of sll gas oats of rove densities This method wie a canst gradient column prepared by adding wo Tusa igus lesuely water and ethanol) in varying concentrations so that more of te dene Equi smear the bottom ofthe column and more ofthe ess dense iid s ‘ear the tap The las ost of known dent are then eaefuly aed tothe con. ‘Toe fleas snk according to tir densities and, ty noting the depths. plot nth ‘vesus density can be etablished fer tho column, Then the plastic saroples ar a to dhe column an, by noting the dels a which they are suspended, ther density can beveal fm th elibvaton char, fer eome tne (usualy webs) the Huis inthe olumn tutualy diffuse and the cofuma must be refilled anérsaibrated, Acensy~ ‘radlene column ustated in Figure 33. sen es Balk Density (ASTM 1895). The bulk density ithe aporent density ofthe fratealthat the density ofthe material without compaction or woafcation. This proper) s important when te plastic materal isa powder ora flake, The test (yeaa re 33 _Oonay-gadlnt cnn etd deeming dns show he ta iv api of he colot clan i Mitre in Pyne ® conducted bycaeflly allowing the plastic to low ntoa beaker or othe container of noon volume. The excess material seraped off the top, nd Ue container with the raters weighed. The weight ofthe container ie subtracted fora Ue total weiz, And then density is lead asthe weeht per volume. A related property isthe bulk ‘actor, which is the bik density vides by the density ofthe plastic artltes mole Ing, Another related property i pourabty, which is areasur ofthe time reqired fora standard quantity of materal tow through a funnel of speciad dense. Resuls are given as gfx or pounds ‘+ Sieve-Analyss (Particle-Size) Test (ASTM D 1821). The ie ofthe patles andthe disibutio ofthe partici stzes ina prtcula baich can be importa Some proceses and in compounding For instance, rotational molding fasion can be Fighly dependent on theizes ofthe particle. Algo, when large sd ral prtiles are sed together, melting tends to be uneven and can resulin nonunifors mod fling nd surface defies such as orange peel The est to determine the size ditibtion of the particles ic imply to pour the powdered rata hough series of sieves with seriou opening sizes. The distribution is then determined by weighing the diferent Svs before and af the test. A shar usally i employed to facie passage the ‘material through the sieves ‘ry difecton is uf in detrminng the degree of ental borase Xe will avelop a characteristic atom whan Affacted trough a ena sacar, Ths ee teh igo sun to mega rye propre in mona and ceramics) infaedepetoropy ‘an alo be used to instigate rtlinity eae the wbratins and oations ofthe ators that are datected by infrared specvoscoy are aft by the cnstal structure and, therfore, {pps ight bigher energy els than do ely rotating and viting atoms ene, & Shi in spectrograph pct i detected when eneline regions are preee.Diererta ‘anningelorimety isanothe meted hatha been ws but nots Frequent se the others Because of the banding forces within a crystal, crystal fects mary piyscal prop. ses in wy that are sar to other intermolecular atraction already dscused. eile strength and sins, fr instance ae increased by erstalinity besause of he hgh sist. ance to movement inthe enstaline regons andthe need to overcome the intermolecular {ersaline fore. This resistance ean be very high in some eases, resulting ina rerked Increase in these properties over amorphous polymer araogs. For instarce, high-density Doyestene strong and sit enough tobe se-supportng even when uit hi fs {sod extensively for milk hotles. Low-density polyelipene is much more exible and is se widely for trash Bags. (Can you imagine the problems milk betes were made ofthe sme patc as trash bags ‘The effet of ersliiy On impact toughness somentut mace volved. The crs- talline sections of apodymer are notas fective in absorbing and ciating repack energy sare the amorphous regions because the atoms in the eystallne regions are taste to tomate, vat, and translate, This restriction on amie mavernent cases highly eye talline mater tobe ser and more Brite. Therefore, eventhough the strength in- ‘ceaze the impact toughness ten desretes fo high erin materia Several other properties areas fected by crystal 2 willbe discussed in Chapter For insanee, solubility of the pobmer is generally reduced in crysaline materi because of the compactness of the enstaline structure compared tthe amorphous9 hap These ‘elon. The compacinest retards the access of sohent molecules to the bulk of the ‘ryt ia baie property of plastic that shouldbe consider in the selection of ‘polymer for any sppicaion. Many palms ean be obtained ina rnge of ncainies, thus allowing the designer a wide choice of material properties. Anwther major effect of crystallinity isin there changes. POLYMERIC LIQUID STATE ober chains are generally so long that sgufcantintermlesusr entanglement ests te nthe gui stale. Tisetangeroctin the lui stat is exhibited in the igh viscos- ity ef the polymer mls ard solutions and in propery called mel xrength Viscosity is the veitance to flow thats present in all us. Some fis, like qui pobracs, have ‘ey high vseoskies which ark from the enangleent ofthe polymer cain, Akay ther- ral eet on viscosity i that as the temperature increases vse crops, Tis is aerial property in many past process because the viscosity aft mold ling and oer shap- {ng procasns nhc can most easily be controled bythe use of temperature, More wl besnid abot nico in Caza and Chapters 12-18, on the varias molding processes ‘Malt strength ithe property of polymer mls that relecs the alto soe iusto ‘spond to ten (galling fos. For intance, when 2 pljmer elt sein poured it ‘Shoiy rune out of te coneiner Ife container is sudenly tured uri, he Aw wil ‘Sop and some ofthe pobmer that hes already gone oer the edge the container might be fin bck ino it asthe pobmerinsie the container flows bacvaris. (Honey wil eit {tis me tendency to daa tack nto the cortaier) This propery ares because some of the pobmer molecules til in the eontaner are entangled with chose thathave already exted he ortaines Hence, the anes onthe ouside are dram back by the on inside. Tis properts ous nateistin low scsi rates such as yates Meltstengt san imporant proper) of pobmers that strongly ace such proseing maths: etrsion and casting tps of polyne liqud sates eit One ira pelymer met andthe others poles ution. Apbymer melts snpy the tate of guid polymer that aieved when asic formers tale peymer elution i formed when a poiymar is istoved in a solvent POLYMERIC GASEOUS STATE Because of the la nae of alos ina yore moles, perme: do nt es 8 fs stasteansruty dacs, when sal roles are the ui the Site changed tos py sie ting The increased eer us obisined wil as {Peal cis ornote ani fom hi nigra eventual brakes on ‘Tnctons and move anny i sy etn: This comers he ui ito 25h ppm athe 4, te ong tins be 9 move Snpobrnes st finger snes, en oso ore ei te bya dese nvsuiy) bt suru he stor lng ec begin fo iat Shoah Te becomes pus a moe chun woulhave fo cooley dengue fom Seiceand uch nary woe be Sede, Bling ois Seely creases he Marwan in Pobmaers a ‘ofthe molecule increases) However, atthe arnaunt of nee in the polymer stm i ne ‘reset try and boithe liquid he internal batons ineress ad bocce So ea ha the energy flowing along the poyrer chain exceeds the energy ofthe covalent bone, ‘When this ocars, the bond break and decomposition cenit. ance, bear a poe: il bolt form gas, wl decompo by breaking primary bonds. Polymer molecules can be swept up into as steam and ths achieve some of the properties normally asocated with 3 gas. Rarvembe, howeves, tha the pobrer tole: cals are carried by gas molecaes (such as nitrogen), much like a palymtrslation has palmer molecules surrounded by sven ‘THERMAL CHANGES IN POLYMERS Glasslike Sotid Phase ‘The responses of polymer materials to heat inputs are simi in some ways to thoce of sal molecules, as hus ben described in the secon on sls, iis, and gests. The ioe ‘ut of thermal exergy (heat) is both commen an very important for beri materia ‘Wien rolymers are heated, the basic nature ofthe pobmer i to move intemal fo absorb {he energy input. This intemal motion can be molecular tisting, vibrating, sething, ‘wanda, and other movements. The extent of theve maton is detected by arin the temperature of the pohmer. Some of these motion mode occur at lover energy inputs {Ban others (for insance, vibrating occurs with itl energy input), Buta he sont of energy input increases, all the motion modes become athe andthe temperature ines araty asa measure ofthis ineresed molcwar moten. ‘Ato temperatures, polymers ae sali, The motions of tame within a sei polymer ae inital imate to small movements (asually bration) ofa fe stom. the smount of est np inreases, these motions become bot larger fa amplitude and invohe more toms. Because ofthe imited amount of maton allowed in coli matin the easiest wy toabsor the energy isto mae ore ofthe toms along the polymer chain but lint ‘the motions to these that take up the lest spce ad energy—vibrations, rotations, and ‘isting. Hence, with moderate heat input the majcty ofthe atoms are ina mace of In- xed vibration, rotation, and bwsting. The properties ofthe pale dving this stage of heating ae litle changed ecet for an incrence inthe temperate ofthe polymer anda ‘minor increase in the space occupied by the polymer (voue}, Deas the motions ake slighty move space andthe atom ae foced apart. ‘Thermal Expansion Mort materials eoand when heated and contrat when cooled. Because plstics absorb ine pt enery through internal motors, the polmer chains usually mave spar allow for fins moton, Hence, plastis are Iie) to ewand more than merle or eae whe Feat Thischange in mension ofa materi wth np hat called thermal expansion andi usually measured as the ratio of the change ina linext dimension (uch a overall length tothe original dmenson per unt change in temperature. The veulting quantity2 Chapter Tree Figure 3.4. Tost appara (Gistometc uses fr measrog (petloon of iomal oepaion ers. scaled te cota of thermal expansion (CTE). The sso cosine ae ASIN De for nar and B26 for volume) ae condated by aca SEES abe tested na temperatareconvoled bo A uns laee atthe tale arden pac ba once sping The over of he ae od SARELD pp oo or ran elem mening Gece, Te sao irate ae ees sro core rodagt he ample ned ove he epee ange of nt opts wed ical tometer agra ofa test speak 3G Cae mauris gen fire 3 Tes species can beam 2 (0 5S inches ire Tal tone vo a ti ely wrt the tong deve Resale are gin Tenbwtegin oid CTE vale or pts rd meas are ire in Tae Cac CASES amo rnge 0.05 to n/a ch are mech ove tan fo eer pa se Gs There bon otc ch le into laste es an (ao aca Cte oft manu, The coon of fer rennet eel ce “ee er wil gency dre the CTE for pits bas the pba cas ae Tatonl trees tany bing esttdin ther movement be ers us Seandon ofa whe ot murtb ken i cosizaton en iain pet ere ga fe eed ee en sven apa ee Bertures nd ekg ina ron ge tere stig temperate thease ui cant uch nore bantu ntl andthe sce become oe, the CTE ‘evista abe cone when signing for sic, When aati ‘oblo21 Types Theml Conducios, Heat Capactos, an Crflets of Mena Bipanson fr Plstes and iis Migera Thema Condueeviy Heat Gapacty___Termal Expansion (CTE) Panic 00010008 Buubt*F —O4w OD Bue °F 8t0 12ingn.°F 10 (OSE Wn OAWOBRTT) [SiO TemleM*CX 10-7, Naa Swecbunay ai wOSBWbF — Bwainin x10 ot—soWin-K) (OA ASealg'C) (1 toLemleM "Ox 10% Meretrcurs in Pobre a 's formed, i is usualy at an elated temperate and vill shrink considerably when cone. Consequently, the mold en should be preweayoversaed vo tht the ‘area shrink to the cores eimensione. Creep 4s the poymer is eat further, translational mevemeats become more important. Tens Jaton movements occur when atoms move from one place es another in spee, beyond the movements of vibration rotation and testing wbich are centered about a taonary molecular poston. These increased movements slow the polymer chains to slowly dese tangle and to move apart, thus further incrasing the space bebe the atoms, Tsk cease in pace resus n'a decrease inthe strength of any seaondary Bonds that maybe present and a cecrease in the entanglement bebaen plymer eins. With these changes, the polymers movernent under applied erteral oasis increse In other wor, the slid polymer slowly moves under aplied leas. This phenomena ‘called creep. Creep becomes greater a the temperature ofthe pliner increases and ‘stheamount of secondary bonding and entanglement derest, Therefore, polymers that Ihave high secondary bonding, suchas costaline polymers, have ifereiy ls er29 than do amomhous poles, assuming ether factors are eal. Creep isalse reduced by igh entanglement, fy the presence of large pendant groups that inhibit movement by crosslinking, and by the laerene stilts of the bacione ofthe polymer These fess are diseased Ine in this chapter in the section on stoi (shape effets and in (Chapter 4 Heat Distortion Temperature (HDT) ‘Atsome temperature the plastic wil become so plable and so esi distorted unde oss that may not perform te function intende, especialy i thst uncon trata. The temperature at whieh this happens varie widely among, erent parce and among di ferent appliations. For instance, although ane plastic may Be“ishwashe se" it will nt distort 3 dishwasher teaperturs (about 120°, 50°C), another plastic wl us and deform. Therefore, the rst plastic materiale thermally sable at dihyacher tempers ture, but the second isnot In ancerintanes, Ove place may be very eutable fr caste tap cases in roma use but one wil distort when aft inside ea in the eur, "The designer of plastic parts should therefore, bs ane of the maximum sever! se temperature. Aromatic conent crosslink densi, estan and secondary bonding can allie the taperature at which distortion occa ‘Aeonveient tart the Deflection Temperature Under Load (ASTM DS4S) can be used to masure this upper ws temperature in this tes lustre in Figure 35, a simple of ‘he wane mater (5% % Iain} is placed in» heated bth of vines sore other liquid thats thecal stable athe temperatures tobe used, ows not eat wi he plastic, and wil transfer heat readily to the sample A specific weit (designated bythe testprocedur and dependent upon te type of paste material being tested) is then placee