Polimeri

Introducere:
Polimerii (sau macromolecule pentru chimiti) sunt o repetiie a unui motiv constitutiv (sau unitate) (M), unde M= CH2- (de exemplu). Gradul de polimerizare (n) corespunde numrului care exprim de cte ori este repetat mitivul : Mn. Lungimea caracteristic a unui lan este n jur de 1 micron. Exist polimeri supli (de exemplu, polietilena PE) precum i polimeri rigizi (ex. : poliparafenulena PpP). Scheletul polimerilor este stabilizat prin legturi chimice covalente, motiv pentru care polimerii nu se dizolv n soluii. Coeziunea ntre macromolecule este asigurat prin legturi fizice (Van der Waals sau de hidrogen), care se rup dac se nclzesc. Tab. .- Clasificarea polimerilor Cauciuc natural Celuloz naturali Colagen Lemn Os Polimeri sintetici Cauciuc sintetic Polietilen PE Polipropilen (PPRO) Compozite cu matrice polimeric

Structura chimic Arhitectura unui polimer este determinat de funcionalitatea medie F. Dac F=2 polimerul este liniar perfect ; dac 2<F<<3, atunci el posed un lan liniar ramificat, iar n cazul cnd 2,5<F<4, capt arhitectura unei reele (supl dac F este apropiat de 3 i rigid dac F este apropiat de 4). Polimerii liniari posed o anumit coeziune datorit legturilor fizice. Acetia se pot dizolva n anumii solveni. Prin nclzire, ei trec printr-o stare plastic, apoi una lichid (legturile fizice sunt rupte). Acetia sunt termoplastici (TP).

Polimerii cu arhitectur de reea au coeziune indus de asemenea de legturile chimice. Nu exist pentru acetia nici solveni i nici faza de topire. Prin nclzire unele ramificaii ale reelei se aga. Acetia sunt termodurificabili (TD). Polimerii TP sunt n general reciclabili i pui uor n form sub form lichid, n timp ce polimerii TD nu sunt reciclabili i punerea lor n form prin procedee automatizate este deosebit de complex. Izomerie i configuraii : Izomeria de poziie (dac motivul este disimetric) : cap-coad : ...-CH2-CHR-CH2-CHR-CH2-CHR-... polimer regulat; cap-cap : : ...CH2-CHR-CHR-CH2-CH2-CHR-... polimer neregulat.

Stereoizometrie: n cazul unui polimer vinilic unde planul format de ctre atomul de carbon considerat este planul de referin, atunci apare o tensiune de ntindere. izomer izotactic : grupul adiional R se regsete ntotdeauna la aceeai apropiere cu planul format de atomul de carbon ; izomer sindiotactic : grupul adiional R se afl alternativ alturi de un alt plan format de ctre atomii de carbon ; izomer atactic : dispunerea aleatorie a grupului R alturi de un alt plan format de ctre atomii de carbon. n primele dou cazuri exist o anumit tacticitate, n jur de 90%, dar niciodat 100%. Materialele care posed o tacticitate mare pot cristaliza, dar niciodat cele atactice. Proprietile lor difer funcie de gradul de tacticitate, de ex. : polipropilena (PPRO) 80% izotactic este solid la temperatura ambiant, n timp ce PPRO 100% este lichid la aceeai temperatur. Configuraia unui polimer nglobeaz cele dou izomerii. Copolimeri i ametecuri : Copolimerii : asociaz adesea dou motive constitutive mpreun : - copolimer statistic : : ...MNNMMMMNNNMNMNMMNMNMN... (material hibrid avnd proprieti intermediare) ; - copolimer - copolimer secvenial : ...MMMMMMMMMNNNNNNN... (material cu structur alternant : ...MNMNMNMNMN... (material foarte dificil de realizat). eterogen, care prezint proprieti asociative.

Amestecuri polimerice. Amestecurile polimerice, fizic, sunt contrariul copolimerilor a cror legturi sunt chimice. Comparaia este dat n fig. .

Amestecurile sunt mai ieftine, dar nu sunt posibile dect numai n cazul n care din punct de vedere chimic cei doi polimeri sunt relativ apropiai, fiind pseudocompatibili (de ex. : dou poliamide PE sau o poliamid PE i o polipropilen PPRO). Structura fizic : Conformaia : Aceasta este un aranjament de atomi n jurul legturilor simple. Macromoleculele avnd legturi multiple nu au dect o singur conformaie. Dou conformaii din cele mai des ntlnite sunt : zig-zag : ex. - PE i PTFE : elicoidal :ex. PPRO, ADN, ...).

O configuraie se poate schimba prin trecere ntr-un solvent. Faze cristaline : Statistic este aproape imposibil s avem o ordine a tuturor lanurilor, fazele cristaline nefiind n totalitate asigurate. Pentru a avea cristalinitate, polimerii trebuie s aib conformaia regulat = procentul de cristalinitate. Cu ct acesta este mai mare, materialul este semicristalin. Cnd este egal cu zero, pentru lanuri liniare i reele, polimerul este amorf. Dac este apropiat de 90%, ca n cazul poliacetilenei, polimerul este policristalin. Faze amorfe : Cnd sunt prezente faze amorfe exist posibilitatea unei ordini la distan mic, de aproximativ 25 . Ne aflm n acest caz n prezena unei faze amorfe rigide.

Proprietile polimerilor Proprieti termice Temperatura de utilizare a diverilor polimeri :

Siliconi

Azot lichid Polimeri obinuii PE, polistiren

Poliepoxy

2000C 4000C Polimeri termostabili Policarbonai Poliimide

Uneori polimerii lucreaz la temerturile de schimbare de stare, cazuri n care se utilizeaz proprietile manifestate de acetia la aceste temperaturi. Polimeri amorfi : n acest caz trebuie cunoscut temperatura de trecere n stare vitroas (Tv) a acestor materiale. Pentru aceasta se utilizeaz adesea analiza entalpic diferenial (A.E.D)

Fig. .- Tranziia fazelor amorfe mobile : (1) vitrificare lent : se stabilete o diferen fa de (2), o ordine local prezentat la temperatura de brisera. Pe curba (1) se observ un pic analog unui pic de fuziune. Exist polimeri total amorfi care nu au picul la Tg ; ei sunt compui din faze amorfe lichide. Ordinul de mrime al Tg este dat n tab. . Tab. .- Ordinul de mrime al Tg Elastomeri -100 -20 C 'De mare difuziune' 50 180 C Termostabili 200 300 C

Polimeri semicristalini : Ei au ntotdeauna un anumit procent de faze amorfe. Pe diagrama cp-T, fazele cristaline prezint un pic la Tc i/sau un pic de fuziune la Tm. n mod curent : Tg = Tm/1,5 (n K) (fig. )..

Proprieti mecanice n funcie de temperatura T proprietile mecanice ale polimerilor variaz mult. Mai mult, cele metastabile przint o evoluie a comportamentului lor mecanic n funcie de timpul (t). ncercri mecanice : Se disting deformaii mici (reversibile ) i deformaii mari (ireversibile). : Petites dformations: Domaine temps: s = efort sau tensiune (en N.m-) g = deformaia - Fluaj: s = s 0 (ncercare sub sarcin constant)

Este un test nespecific polimerilor, este scump, greu de realizat, dar aproximeaz destul de bine comportamentul real.

g /s = J : compliana (n m.N-1)

- Relaxarea tensiunii: s = s 0 (tensiunea de relaxare) Este un test nespecific polimerilor, este scump, greu de realizat, dar aproximeaz destul de bine comportamentul real.

s /g = G : modulul polimerului (n N.m-2)

n cazul general, G i J sunt diferite.

Deformaii mari: Se deformeaz un eantion cu vitez constant :

Fgi, .- Curbe tensiune-deformaie pentru diferii polimeri

(testul este foarte rapid, ieftin, dar necesit epruvete mari) Comportamentul elastic i vsco-elastic (se limiteaz la deformaii mici <10-3 m). Comportement lastique et viscolastique: (on se limite de petites dformations (<10-3 m) ) Pune n eviden

Policondensare (step polymerisation) : Este o sintez lent. Policondensarea liniar (fonctionalitate egal cu 2): a) Reacia de polimerizare: a+b c propagare cu ajutorul monomerilor: a-a + b-b a-c-b a-c-b + a-a a-c-c-a propagare cu ajutorul oligomerilor : a-c-c-c-b + a-c-c-a a-c-c-c-c-c-c-a

b) gradul de polimerizare: Dac se noteaz cu N0 numrul de molecule care trebuie rearanjate; x numrul de molecule ale produsului format, gradul de conversie va fi : p = x/No, iar gradul de polimerizare : G P = 1/(1-p). Logic, dac gradul de conversie tinde spre 1, gradul de polimerizare tind spre infinit : reacia de polimerizare este cvasicomplet. c) policondensare cu evoluie stoechiometric : exemplu : cazul poliamidelor : n HOOC-(CH2)4-COOH + n H2N-(CH2)6-NH2 (poliamida 6-6). Poliesterii i policarbonaii sunt de asemenea sintetizai prin policondensare cu evoluie stoechiometric. d) policondensare fr modificare stoechiometric : exemplu : poliuretanul n HO-R-OH + n O=C=N-R'-N=C=O -> [-CONH-R'-NHCO-O-R-O-]n Policondensare tridimensional (funcionalitate >2), n acest caz au reea tridimensional. 2n H2O + [-OC-(CH2)4-CONH-(CH2)6-NH-]n

Procedee de policondensare : a) policondensare n mas : Avantaje Fr aditivi de enlever Marche souvent Dezavantaje Vitez de reacie slab Temperatura crete n mijloc, din care cauz apar probleme de degradare

Policondensarea n soluii : Avantaje Multe locuri de reacii posibile, viteza de reacie este mult mai mare ; Bun control termic Policondensarea interfacial sau din emulsii: Dezavantaje Trebuie extrai adesea din solveni, operaie care este adesea delicat.

Avantaje - Multe locuri de reacii posibile, viteza de reacie este mult mai mare ; - lanurile formate sunt foarte lungi. Polimerizarea n lan :

Inconveniente - trebuie un control al reaciei - trebuie un solvent care fie acelai att pentru monomer ct i pentru polimer.

Aceste reacii sunt tipice polimerilor i sunt foarte rapide (de ordinul nanosecundelor). Exit dou moduri de polimerizare : ionic i radical.

Polimerizarea radical se face n trei etape : amorsare, propagare i finalizare (facultativ). Monomerii utilizai sunt de tipul XYC=CAB. Ei pot fi n acest caz fie vinilici, fie metacrilici. Faza 1 : amosarea, poate fi : Chimic prin nclzirea peroxizilor : - sistemul redox H2O2 + Fe2+ Z OH + OH- + Fe3+ Fotochimic : - prin aciunea direct asupra monomerului M care n acest caz se dezexcit :

M* -> R + R' prin disociere foolitic : H2O2 -> 2 OH prin fotosensibilizatori intermediari (fluorescena, de ex.).

Radiochimic : - aciunea unei raze electromagnetice (X, alfa sau beta) : AB -> AB* + e-, apoi prin disociere : AB* -> A* + B i n sfrit A* + e- -> A . Termic : Se utilizeaz n acest caz energia fononilor. Faza 2 : Propagare Aceast faz are loc n prezena monomerilor : RM + M -> RMM Faza 3 : Finalizare RMnM + R'MpM -> RMn+p+2R' Exist i o alt posibilitate : transferul radicalului : RMnM + solvent -> RMnM + solvent Cinetica polimerizrii Notm: Kp : constanta vitezei de propagare; Kd : constanta vitezei de descompunere ; Kt : constanta vitezei de finalizare : Vp : viteza de propagare ; [A-A]: concentraia n amorsori ; [M]: concentraia n monomeri; f : eficacitatea amorsorului.

Gradul de polimerizare mediu :

Notm : DP : gradul de polimerizare mediu ; Va : constanta vitezei de amorsare ; I : ntreg cuprins ntre 1 i 2 ; DP0 ; gradul de polimerizare fr transfer

Dac are loc o reacie de transfer, atunci :

Polimerizarea anionic i cationic: n acest caz centrii activi sunt anionii i cationii. Polimerizarea anionic: Amorsorul este o baz (NaOH sau KOH sau un derivat organomagnezian - CH3-(CH2)n-Li) sau un metal puternic electronegativ. Cazul polimerilor vinilici: Amosare : Propagare: Cazul monomerilor heterociclici : Polimerizare cationic : Amorsorul este un acid (tipic Lewis : BF3>AlBr3>TiCl4>BBr3). Cazul polimerilor vinilici : Solvenii utilizai trebuie s fie stabili n prezena unui acid. Acesta este adesea un solvent halogen sau hidrocarburi.

Polimerizare ionic coordinativ (coordineee)

Se caut s se obin un lan regulat. Se utilizeaz pentru aceasta un catalizator stereospecific (TiCl4 sau trietilamoniu ). Este sinteza Ziegler-Natta. Pentru PE, de ex. Polimerizarea este lent, la temperatur i presiune joase, care favorizeaz formarea PE de nalt densitate. Se utilizez aceast metod pentru sintetizarea polipropilenei izotactice, a EPR atactice, EPDM i acetilenei. Procedee de polimerizare ionic : Tipul polimerizrii Polimerizare n mas Avantaje Frecvent posibil Fr adiie de solvent Polimerizare n soluie Temperatur maitrisee Posibile reacii secundare Trebuie eliminat solventul n domeniul diluat reacia este prea lent Imposibilitatea de a avea mase molare importante Timp de reacie lung Polimerizare n emulsie Suprafee mari de contact, reactivitate mare, rapiditate mare Obinerea de mase molare importante - Maitrise de la temprature Trebuie eliminat solventul Trebuie separat polimerul i produsul de emulsionare dup reacie Dezavantaje Temperatur nalt i deci risc mai mare de degradare

Polimerizarea n suspensie

Temperatur maitrisee Polimer uor de recuperat

Formarea polimerilor : Aditivi : sunt lanuri scurte de plomeri, oligomeri sau mici molecule. Produsul final este un monomer. Umplutur (Charges) : sunt elemente organice i anorganice de 10 microni care nu interacioneaz nici ntre ele nici cu polimerii. Nu au un efect specific asupra proprietilor produsului final. Ranfort produc ntrirea polimerului original ; se obine un compozit polimeric.

Aditivi : - Plastifiani : mresc supleea polimerilor i reduc temperatura de tranziie spre vitrificare. Problema prinxipal const n faptul c plastifianii migreaz. Se utilizeaz n general ftalai, uleiuri

parafinice sau tricrsylphosphate..Pentru o bun adecvan ntre polimeri i plastifiant, parametrii lor de solubilitate trebuie s fie apropiai. Se utilizeaz aproximativ 10% plastifiant . - Antioxidani: contribuie la evitarea degradrii polimerilor n prezena oxigenului. Se utilizez n general diterbutilparacresol. Stabilizani termici : Sub efectul cldurii, PVC largue cu acid clorhidric devine casant. Se utilizeaz n acest caz piges de HCl pentru stoparea reaciei. On se sert n general metale grele (PB, Pa, sels de Cd, ...) sau uleiuri epoxidice care sunt mai puin toxice.

Stabilizani U.V. : Un foton U.V. are o lungime de und cuprins ntre 0,28 i 0,40 microni. Aceasta corespunde unei energii de 72 ... 100 Kcal/mol. Acest energie este suficient pentru a distruge o legtur a unui carbon teriar. Pentru evitarea fragilizrii polimerului se utilizeaz fenilsalicilat ale crui legturi teriare sunt mai slabe. Ce sont celles-l et non celles du polymre qui casseront. Ali aditivi : ageni ignifugani (de ntrziere a aprinderii) : fosfageni ageni antistatici : ageni higroscopici, acizi grai, lubrifiani, pelicule metalice permit creterea alunecrii l'coulement des charges i creterii conductivitii superficiale.

Pigmeni : anorganici (deni i opaci, voluminoi oxizi de fier ... ) sau organici (pentru strlucire mai mare sau mai mic). Ageni reticulani : pentru obinerea polimerilor tridimensionali (3D) ; Ageni de desprindere (ungere), lubrifiani : siliconi sau esteri ai acizilor grai ; Fungicide : pentru distrugerea microorganismelor care se formeaz n polimeri. Les charges: Dac les charges materialele de umplutur nu interacioneaz cu polimerii avem un polimer .......... polymre charg, iar n cazul n care interacioneaz uor avem de a face cu un polimer cu ranfort reticular (polymre renforts rticulaires). Dac interaciunea este mare se obine un compozit. Umplutur organic :

Carbonul (sfere cu diametrul de 80 microni) amelioreaz rezistena la U.V. i conductivitatea electric. Se utilizeaz totdeauna n elastomeri i poliolefine. Materialele de umplutur celulozice (fin de lemn, ... ) se utilizeaz pentru PVC i poliolefine.

Umplutur anorganic : bile de sticl de diametru de 40 microni, pline sau poroase, permit s se obin un polimer neted sau rugos, dup necesiti. silicaii (talc. Caolin. Mica, ... ) au un efect uor ranforsant.

Ranforsani : Acetia sunt particule de 50 microni n diametru cu ajutorul crora se obin compozite. Se folosesc fibre scurte (de ordinul unui mm ), fibre medii sau semiscurte (de ordinul unui cm) sau fibre lungi (fibre cu lungimea comparabil cu a eantionului). Fibre scurte i semilungi :

Se utilizeaz fibre din sticl (ranfort anorganic) sau din poliester i poliamide (ranfort organic). Dac materialele sunt supuse la solicitri de compresiune se utilizeaz fibre de sticl, care prezint avantajul creerii de legturi ntre fibrele de sticl i matricea polimeric. Dac ranfortul este repartizat aleatoriu se obine un material cu performan sczut, n timp ce prin asigurarea unui grad mare de orientare a ranfortului pe o anumit direcie se obin performane ridicate. - Fibrele lungi se utilizeaz pentru materialele de nalt performan i uoare. Sunt n general materiale oarte rezistente la ntindere, puternic anizotrope. Fibre din aramide : sunt foarte uoare, de performan sczut.Poliamidele aromatice au o comportare foarte bun la ntindere i la creterea temperaturii. Dar on ne sait pas les ensimer la matrice polymre, et l'humidit s'insre l'intrieur du matriau. Ex. Kevlar. Fibre de sticl : sunt de nalt performan, dar grele. Rezist foarte bine la compresiune, et on sait les rendre manipulables par ensimage. Fibre de carbon : uoare, au o mare rezisten la oboseal, dar nu sunt totdeauna utilizabile la compresiune.

Tehnici de prelucrare

Schma de principe du moulage par compression :

Schma de principe du moulage par compression transfert :

Schma de principe du moulage au contact :

Schma de principe du moulage au sac :

Schma de principe du moulage sous vide :

Schma de principe de l'extrusion :

Schma de principe de l'extrusion soufflage :

Schma de principe de l'extrusion calandrage :

Schma de principe du calandrage :

Schma de principe de l'enduction :

Schma de principe de Pultrusion :

Schma de principe du Thermoformage :

Polimeri industriali
Termoplastici Termodurificabili

Polietilene sunt compuse din carbon i hidrogen. Avantaje - Sunt izolatoare; - Neutre (incolore, inodore); - Relative biocompatibile ; - Totdeauna liniare (ntotdeauna termoplastice) ; - Uor de extrudat ; - Foarte suple, ideale pentru elastomeri ; - Bun rezisten chimic ; - Rezisten la eforturi ; - Slab absorbie a apei. Inconveniente - Lanurile alunec uor ntre ele i ca urmare nu pot suporta presiuni medii sau nalte ; - Aucune tenue en temprature - Aucune tenue aux U.V. - Nu suport carburani i solveni.

Diferite tipuri de polietilene PE

Polietilene termoplastice Dac densitatea este de aproximativ 0,92 ...0,93 g/cm3, este o PE de joas densitate (PEJD sau LDPE). Este utilizat pentru ambalaje, izolatori electrici de medie performan (aproximativ 100MHz) i n construcii mecanice(cnd are 40% cristalinitate, ate o foarte bun ductilitate). Se obine prin polimerizare n lan, suport presiuni de aproximativ 1kbar, masa sa molar este de circa 105 g.mol-1 . Se utilizeaz la fabricarea de filme, folii subiri, piese injectate, etc. Posed bn tenacitate i rezisten la ocuri la temperaturi sczute ; poate fi transparent. Puritatea nalt, capacitatea foarte bun de sterilizare, stabilitatea dimensional bun i transparena le confer aplicaii medicale foarte bune. Dac densitatea este de 0,94 ... 0,96 g.cm-3, polietilena este de nalt densitate (PED sau HDPE). Este sintetizat la joas presiune (50 bari). Masa sa molar medie este n jur de 10 6 g.mol-1 . HDPE posed rigiditate, tenacitate i rezisten la fisurare precum i o excelent rezisten la ageni chimici. Se utilizeaz pentru rezervoare de combustibil, diverse piese mecanice etc.

Reaction Injection Molding (RIM) Polymer reactants are pumped under high pressure into a mixing chamber and then flow into a mold at atmospheric pressure. The chemicals expand to fill the mold and to form the polymer. The foaming action of the reactant produces the pressure for replication of mold details (about 30-70 psi (207 to 483kpa), and the reaction heat speeds the polymer cure.(cycle times are usually less than 2 minutes) This process is usually applied to large parts (over 1kg) and polyurethane foams are the most popular molding materials. Many large auto parts, such as bezels, dashboards, and fenders, are made from this process. Fillers can be added to the reactants to improve the mechanical properties of molded parts.

Rotational Molding This is a process for making hollow parts by charging a metal mold with thermoplastic pellets, heating the mold, and rotating the mold. The plastic pellets melt as they contact the mold walls and form a shell that replicate the configuration of the inside of the mold. The process is schematically illustrated below. Molds usually rotate about two axes. This process is useful for forming large containers such as garbage cans. It is not as fast as injection molding, but tooling costs are minor compared with the mold requirements of high pressure molding processes.

Casting The process of forming solid or hollow shapes from molten polymer or from catalysed resins by pouring the liquid material into a mold without significant pressure, followed by solidification or curing. The mold is usually open at the top. This process is widely used on urethane and silicone elastomers to make roll covers, die springs, sheets, and the like. It is also suitable for making jigs and fixtures from filled polyester resins.

Solid Phase Forming Solid phase forming is a process employed with thermoplastic materials in which a sheet or similar preform is heated to the softening point, but below the melting point, and forged into a drawing ring by a heated die set; the still warm preform is transferred in the draw ring into a cooled draw die, and a plug draws the part to the finished shape. The steps in the process are illustrated below. A lubricant is applied to both sides of the preform to assist the draw. Depth of draw ratios can be 1.5 or higher, and the forming in the solid phase is said to enhance strength over parts formed by melting techniques.

Stereolithography Stereolithography is one process in a category of fabrication processes that are termed free form fabrication Processes. In this process, illustrated below a computer controlled laser is used to selectively polymerize a liquid resin to form a part. A platen is given a thin coating of liquid resin by dipping or spraying; the laser traces the shape of the part at a vertical slice height of a few microns. This action polymerizes the resin. The part is recoated, and the process is repeated at another slice height. This process is repeated until a three dimensional part emerges.Another variation of this process is the laser fusing of powder. A platen is coated with athin layer of powder, and the laser fuses the powder in the shape of he part. The emerging shape is given another coating of powder, and the process is repeated.The usual material for sterolithography is a UV curable polyurethane resin (rigid). The powder process can use nylons, polycarbonate, and a wide variety of thermoplastic materials. Both techniques are used to produce plastic prototypes without hard tools or even drawings. The part can be made from computer data files (CAD). Functional tests can be made on the part before any capital is invested in tooling.

Calendering The process of forming thermoplastic sheet or film by passing the material through a series of heated rolls. The gap between the last pair of heated rolls determines the sheet thickness. The material is usually blended and plasticised on separate equipment. Elastomer sheets are often formed with this process.

Thermoforming

A method of forming polymer sheets or films into three dimensional shapes, in which the sheet is clamped on the edge, heated until it softens and sags, is drawn in contact with the mold by vacuum, and cooled while still in contact with the mold. Vacuum is not always necessary. Sometimes the sheet is simply draped over a mandrel. Sometimes matched metal molds are used. Thermoforming is ideal for low volume production of containers, machine guards, and other parts with suitable shape.

Compression molding A method of molding in which the molding material, usually preheated and pre-measured, is placed in an open mold cavity, the mold is closed with a cover half or plug, and heat and pressure are applied and maintained until the material has filled the cavity and cures. This is the most widely used process for thermosetting materials. Because curing of thermosetting polymers is a time-dependent reaction, cycle times are usually much longer than in injection molding.

Transfer molding A process usually applied to thermosetting materials, in which the molding material is put into an open cylinder, and the material is heated and transferred under pressure into the part cavity. It is a modification of compression molding.

Injection Molding A process in which granular polymer, usually thermoplastic, is fed from a hopper into a heated barrel where it is melted, after which a screw or ram forces the material into a mold. Pressure is maintained until the part has hardened. The mold is opened and the part is ejected by some mechanism.

It is by far the most important technique for mass production. The major disadvantages of the process are that not all polymers can be processed (most thermosets), and the metal molds are very expensive.The basic process is also used for coinjection of two different polymers. There are two extrusion barrels and injection systems. A shot is made with one polymer, and second a shot with a second polymer can be used to surround or surface the part made in the first shot. Coinjection is often done to achieve a cosmetic effect or to alter use properties.

Blow Molding A process of forming a hollow articles by blowing hot polymer against internal surfaces of a split mold. Usually a tube (parison) of heated polymer is extruded down the center of a closed mold. Air is then injected, and the heated polymer expands in a fairly uniform thickness to form the desired shape. This the process used to make plastic bottles and containers. It is fast and usually used only on thermoplastic materials.

Extrusion The process of forming continuous shapes by forcing a molten polymer through a metal die. Extrusion is used to make structural forms such as channels, bars, rounds, angles, tracks, hose, tubing, fibers, films, and countless other forms. It is very fast and usually applied only to thermoplastics. With special techniques, two different polymers or different colours of the same polymer can be coextruded. This process is being used with increased frequency to make specially shaped weather stripping. A variation is used to make plastic bags. (blowing)

Polymer Composites Composites are from a commercial standpoint made from matrices of epoxy, unsaturated polyester, and some other Thermosets, and a few Thermoplastics.

The reinforcements are glass, graphite, aramid, thermoplastic fibres, metal, and ceramic.

The combination of the two materials makes a composite.

The reinforcement can be continuous,woven,or chopped fibre; conventional composites contain from 20% to 50% by weight glass or other reinforcement.

The percentage of reinforcement in advanced composites can be as high as 70% these materials usually use epoxy as the matrix material and graphite is the most reinforcement.

Development of Polymer Composites

Polymer Composites

Matrix

Reinforcement

Thermoplastic

Thermosetting

Plastic Fibres

Carbon Fibres

Glass

Ceramic

Metal

Polyetherimide Polyphenylene Sulphide, Polyether Sulphone etc.

Epoxy, Unsaturated Polyester, Phenolic, Polyamide etc

Polypropylene Aramid

LO E Hi E

E Glass S Glass

S1C AL2O3

Cut Wire Powder

These are the types of reinforcement schemes used in making Polymer Composites

These are the types of reinforcement schemes used in making Polymer Composites

Chart to Show Comparative

Strength of Composite Materials and Metals by Density.

Recycling of Plastics In 1988 The Society of the Plastics Industry (SPI) established voluntary guidelines to code plastic containers so that they can be easily sorted fro recycling. The system is very simple. The SPI recommending that all 8oz and larger containers and all 16oz and larger bottles have a symbol molded on the bottom to indicate the type of plastic that it is made of. The symbols established for this purpose are shown below. They consist of a triangular chasing arrow with a number in the centre and an acronym for the type of plastic used in its manufacture. Recycling of Plastics

1) PETE Polyethylene terephthalate. 2) HDPE High Density Polyethylene. 3) V 5) PP 6) PS 7) OTHER Materials Processing When processing a material it is possible to alter a materials properties. This is predominantly done by modifying: --- Grain structure --- Composition --- Heat treatment Having previously covered polymers and composites we shall be concentrating on metals/alloys. Cold Working Processes Cold working processes are ones that are performed at temperatures below the recrystallisation temperature of the metal. During cold working the crystal structure becomes broken up, and distorted and the materials become work hardened. The mechanical strength is increased and the material becomes harder and more brittle. Electrical resistivity is also increased. Cold Working Processes Polyvinyl Chloride/ Polypropylene. Polystyrene. Means any plastic that is not one of the above. 4) LDPE Low Density Polyethylene.

 Reasons for using cold working processes are: ------------To obtain the necessary combination of strength, hardness and toughness. To produce a smooth, clean surface finish in the final operation. To obtain a greater dimensional accuracy. To improve the machine ability of the material. The disadvantages of cold working are: ------The material quickly work hardens. Interstage annealing and other related processes.

Cold Working Processes Some examples of cold working processes are: ------------------------Deep drawing Drawing of wire and tubes Cold rolling of plates, sheet and strip Spinning and flow turning Stretch forming Cold heading Coining and embossing Cold Forging

Cold Working Processes

Hot Working Processes This is the process that is carried out at a temperature well above the recrystallisation temperature of the metal. At this temperature recrystallisation will take place at the same time as deformation. There is no work hardening. The metal is more malleable at high temperatures. The main disadvantages of hot working are: ------The surface condition is usually very poor. Accuracy of dimensions are difficult to obtain.

Hot Working Processes

 Some examples of hot working processes: ------Various Forging processes Various Casting processes

Hot Working Processes

Hot Working Processes

Hot Working Processes

Hot Working Processes