Handbook of

Polymer Degradation

Second Edition, Revised and Expanded

edited by

S. Halim Hamid

King Fahd Institute of Petroleum & Minerals Dhahran~ Saudi Arabia

" ARC E L

n MARCEL DEKKER, INC.

D£XlER

NEW YORK' BASEL

19

Lifetime Prediction of Plastics

S. HALIM HAMID and IKRAM HUSSAIN

King Fahd University of Petroleum & Minerals, Dhahran, Saudi Arabia

1. INTRODUCTION

The deterioration of a polymeric material depends on how and to what extent it interacts with its surroundings. Outdoor uses of plastic products include buildings and construction, agriculture and horticulture, automobiles and airplanes, solar heating equipment, and packaging. It has been estimated that roughly half the annual tonnage of polymer is employed outdoors (1), where performance is often limited by weathering. Degradation of plastics during outdoor exposure is influenced to varying degrees by all natural meteorological phenomena. Heat, radiation

ultraviolet and infrared), rain, humidity, atmospheric contaminants, thermal cycling, and oxygen content of air, all contribute to the degradation of plastics subjected to outdoor exposure. None of hese factors are constant in anyone loca tion, and wea ther conditions vary widely with location. The useful lifetime of plastics needs to be predicted for planning their maintenance and replacement. To attain maximum accuracy in predicting the useful lifetime of an outdoor exposed plastic, all components of the anticipated exposure environment must be considered. This is best accomplished by conducting exposure trials in that environment (2).

It is now generally recognized that stabilization against degradation is necessary if the useful lifetime of a polymer is to be extended sufficiently to meet design requirements for long-term applications. The stabilization of the polymer is still undergoing transition, from an art to a science, as the mechanism of degradation becomes more fully understood. A scientific approach to stabilization can be approached only when there is an understanding of the reactions that lead to degra-

dation (3). . f

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\Vc;IIII":I'-illdIICl"l1 dq!I';ILJ.lllflll il1\ol,..:,> Ihc "lllllllt:II1l'UII" .ILl!!)11 ,d' suniighr, '),\),:;CI1, IClllpl'l'a!Url'_ :tllli h.rrmlu! ;11Ill'l~pill'J'i\: cll1i,'i\i<lIl~: uxid.u ivc dl'lcrioration of liJl'rtl1llpi:I"li..: p;rI~I11L'I'" dlll'illg PI'llc<.:""ill);, iuvulvc-, the "ill1ull<lIKIlU'> action of hcn t. mcchuuic.rl ";)I·l.:l'''. :111\1 ,).\ygCt1 (4). The lIlill/:llilll1 0)1' pla"lil'" ill outdoor apj1!il-:lli(!ll~ 11:1' ~r""11 Llpldl: with Illl: ov cru ll dC\l'lnpmclll Id' mdustries. and Ill'\\ commcrciu) ~IIHI induxmul rcqurrcmcut« IIJI' 111<)1'1.: il1c,~pCIl"iVL: :IIHJ durable 111<11c'r!;rl" OIIL' I)" t hc 111<1.1'11' 111'llhkllh !'.rccd hy (ill' pLtSlic pruLiuct'> u-,cd outdoors i" \\l':llhL'I--illlllll.:<.:tllkgr;tl!:IIIIlIL Till' ..:\ll'1l1 \)1' pLislIc dl..'h'r;ld~llii\1l can he evaluated in tcrrn-, oj' Ilh::t'lUrll1g ccruun prupcrtic-, c unsldl'l·lllg I) pnrillng c d exposure to t he 11:11', h weuther condiuun-; :lillI2) \;Ifinlls rcprescnuuivc luC:rliolh in a geographic I [)L'~I t jill),

ThL: ubiliiv to predic: crilicli prope n ie-, of wcuthcr-induced degraded plastics is or great importunce ;lllli USd'trIIKSS. [I helps ill determining the useful lifetime (durability) 01' the pla~li..: product'> for better planning ill maintenance and rcplucement. Predicrion olthc Ilfelime l!frlll~mers"llr lhl' lime to failure of specified pruperue , duriug Jong-tcrru ser: ICC. I' ,)1' greur .... ommcrciul importance. Thus, the hlgh6l permissible service ternpcr.u ure ;\1' the recommended lime of service under 0; peci tied condi l ions can be esiim.r led t o ,I~,ev, I h.: scope \)1' apl'! i c ,1 [ion or polymeric rnuteriuls. in particular. engineering thermoplastics (5.6)"

This chapter describes the main 1''' c tors affecting weathering degradation. advances being made in the lifetime predrcticnmethods for outdoor exposed plastics, and some case studies describing. the 17t'ctii~p~t!'klion 01' plastics weathered in a rieur equatorial regron.

II. ROLE OF WEATHER PARAMETERS IN WEATHERING

The r[-i 111:1 ry \\ c'~llh '[' r,ICI0rS respons: blc tor degr:lda rion reuc I ions in outdoor exposures 01' polvruers ~Ir<;! solar r.idiu tiun. uunosphcric oxvaen. ambient tcrnper.u ure. hurniduv . w iud. air pollut.uu». und coutu miuuuts. These factors act synergistically: 1 11<:' ret'o 1'<:::_ the: combined effect IS dilfereru r[UI11 those obtained by exposure to illdi\ idual compouenrs. The r,ll1l1\\ illg discussion is devoted (0 [he important went her pnrurneters 1l1:linly responsible I'm degralbliull reactions. This will help ill undersumding rile degr:1,bll,;n pl1':11I1111l'11:1 and their effect 011 lifetime dcrcrnuu.uiou or 11L>I;'Il1l'r~,

A. Solar Radiation

iVILl.,1 [l,'IYI1lL'ri~' m.uctials III~" their 1'll1I'L'I'IIL', Ill:1illl~' tn\ il1g III rhotooxidative "llad, This il11pli~'~:1 combined :1.:li\1l1 ,'I' ,l\\g .... n ;rild 'L1nligill un [heir chemicul structure. The liI!'I'L' ;rspclls ur slIllli:;ill suushim: dur.n iun. IlILt! sclur radiutioJ1: .ind ultraviolet ILl \-j rudi.u ion "::111 h~' l'-";L'L1 I,' qU:Illlit'y sunligh: :\:; an :[gent 01 dcrcrior.uiun. [l.-bl1Y ,"'lllll1l'I\:i,iI p,'h'Il1L'I"~ :1 ['l' ,iL'gnlLi.:d llllllilllll"S. primarily b<!~Jus<! ni' pllllr,,\iL'gr:ld:rlll11l. :1[ld ,',forh 11:1\''': been 1I];ldl' 1(1 rd:lt<.: 1 heir 1\::ii:il<lI1C': !O [he [lLlltlhu "r:illl1slllIlL'ItI\lIr~ t hcv "::111 \1 illl~I:11ll1 "",',n-L: 111L'\ luxe t hcir u~l'i·LlI pnrr.:rtl<!Snil' -e.uch ,'ur :1 qll'lllIil:lli\~L' rcl.uiou l'c'I\\l'l'll xuuxh un, IillLlr~ ,I ill! gluba[ solar r.uli.uu-u II:lS h",'11 ,I suh,l'c'l Ill' L"'Il'I,k'Llbk illl<.:rl'~t 1',:-;).

I"l." sol.n' [';llII.II;UII r..:;r,·ilill~ ":11"111', .";lIrl";ll·l· i,..; (lilil ,Ib,nil <,no:-h.llf 01 ll\,)-fliild, ii., v: ri Ill' .11 Illl' "lIll'l lil;lil, ,'1' lill' :IIIIl(lSI1!t"'rL'_ ru, lIlost deklcriuus

Lifetime Prediction 01 Plastics

701

"I" III,' 1.'11\'11',1111111.'111<11 1';lCII1I's ill Ilc;lllining pliCII<1I11<':II:1 i~ the ll\' ~L'L'li(l1l oj 1':1,11:111,111. II hich is rcspouxihlc 1',11' I ill' wc.uhcr-iuduccd lkgr:lli:J[i"11 "I' plastics (<J,IIl) l'hc sun :icntls ;1 coni inuou« sI1,'l'!r1111l ,'!' cl1ergy radiali,)11 1,1 the t.:;II'II1, II h":l'ch~ \ :If'lllllS lypt.:S Pi' r.uli.u iou :11'l' usu.rll, diITt.:I't.:IIII:I[L'd on [Ill' h.ixix Ill' 11lL' II ,IICIL'II:;lhs, The physicl! n.uurc ,)IIII":sL' r:H.llaIHlIlS is I Ill' ,,:IIllC, :1 IlL! thl'~r 1':lry only ill 1I<lll'kngth .uid. I 11 nl'j'll rc. their photon l'IlL'rg~', The 1\,llek'l1glh 11:1, :11l IIlI'L'rs..: rL'LI ticn II i I h q U,I n I urn L'llcrgy ( I I ), ThL' l',\ tr.uc ITeSI ri :11 r.idia rion or t he sun is l;lrs,'1 y CllllSI :1111 i 11 it s s ret'l 1':11 cumposi I i nil, lis i niensi t v depends on [ill' angle of incidence, The l'h:ll1gCS :IS a result u1' the lill ,)1' the carths :1i\JS und the rl1lalillll 01' the c.ui h in .1 tl:iily and unnuul cycle :11'1.' linked \I uh the geographic l.uitudc ,11'1111.' place tli' measurement (12),

The u t moxphcru modifies ihc xol.rr spcct rurn unevenly over the specirul range.

The ..:Il .. ,(t i:-. 11111['1.' pronounced ill the infrared lIR) am] U\' regions than il i:- in the vivible range. The rudia t ion II ;11 elcngrh ranges reaching the earth surface are from about 2')() to J4()U 11111 (13 15L The> )10rlil111 or the suns spectrum between ~(.lll :II1U ,100 11111 I, important to j1l1IYl1ler~ because it includes the highest-energy region und is t he on ly port i 011 1 h:1 t CII1 cause direct harm to u nrnod ilied polymers (161. The \ isi ble region or I he sl)I:1 r speer ru Ill, -100-800 11111, dues no 1 usually cause di rec I hurrn Il' polyme rs. bu t en n do so by in reruc I iOI1 wi I h se IlSi I izi ng SLI bsrances ill the polymers The I R poruon. less than ~OO rim. is ge nerally considered harmless in a pholochemicllleSii;e, but il may have a role in the rherrnul oxid.uive degradation of some polymers.

The L'\' portion of the radiation is mainly responsible Ic r the degradatio» of lJLII) rner-: the energy at visible and high wavelengths is tOO loll' to damage the chemical structure of a polymer. Because or its chemical structure every poly T11l'r is ~U,ce pi: hie 10 ph ot ochcrnical degrada tiou a I a particu lar 11:\ vele ng th. The a bso I'IJlJon 0 I' L' V radiu lion and its concorni tarn degrade ti ve effects va I'Y (0 r each indiv idual polymer. Stability is strongly dependent on the specific chemical and 11101- eculur SlfUCLUre of the polymer, vuriations in structure lead 10 differences in the a bsorptiun ranges of i nd j v id U<J I polymers, In theory, pure polyole nilS, such as pol: ;;'th: lene. do not contain functional groups that would be capable of absorbing L;\' radiation, However. polyolefins are ].;110\\11 LO absorb, and be degraded by. L'\' rilUI:IIIL)11 Sources of LV-absorbing chromophores are

Pol: mer structure

Feedstock or process impurities Resid uu I C~I tulyst

Thermal -pr ocessi ng degradu I ion prod ucts Amioxrdurus 'In<.1 uunsforrnuuon products Cl1]llr:111 t.,

Fillers

DtIlL'[' addit iv e-, (Ibme retardant. or other)

Ultra\ iolei tl1crgy is uvuiluhle from sunlight 10 break ma nv or the: chemical bonds ill organic compounds. Because 11l11.1 polymers should no: absorb at wavelength gre.ucr Ih:111 ~U() nrn. It has been assumed ih.u the ulorcrnenuoned sources ,)1' l,' V -,I bsorbi ng ell rumo phorcs presen till polvmcr-, ;1 re rcsponxihle rllr wca iheri ng (17), II ha, been di,>cll'iseJ thut it is LV13 ruditu ion with :1 shurtcr wavelength t hu t i~ 111'lil1l) n:,>p()J1~ihlc.: 1',11' rIWI()u;lm'lgilll:!, UI'>L'ol,mlll(lIl,. ;Inti I()s~ ,)1' mcchunic.r] )1["(1-

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pert ies, The sevcri tj or the cfl'ect or U v 13 levels 011 the Iifcti me of' polymer Jerends on both the. geographic location of' exposure und the susceptibility of' the particular rnaterial to UVB radiation (1~.Il)).

B. Atmospheric Oxygen

Residual double bonds in some molecules. such as polyethylene <Ire especially sus- ' ceptible to attack by atmospheric oxygen. although most polymers reuct very slowly with oxygen. However. oxidation is greatly promoted by elevated temperatures and UV radiation, and the reactions of polymers with oxygen under these conditions can be very complex (10). Oxygen is not usually considered as an experimental variable in the study or polymer weatherability because the' oxygen concentration in [he environment is substantially constant. Moreover, most weathering phenomena occur a t the surface o(fhe Ptastic. wh ich is in eq uilibri urn wi th air (21),

C, Ambient Temperature

Under extreme outdoor exposure conditions, a plastic sample may reach about 77°C. The temperature of an object in sunlight is usually significantly higher than that of the surrounding air. The difference between the air and surface temperature depends on factors such as radiation intensity. wind speed, object shape, and the nature of the material. in particular its surface finish. color, heat capacity. and thermal conductivity (22). The weathering process depends on temperature along with other factors, and the maximum temperature attained by the polymers is not sufficient to promote bond cleavage of am structures likely to be found in commercial plastics. The role of hear in the outdoor degradation of plastics is in accelerating processes otherwise induced. such as hydrolysis, secondary photochemical reactions. or the oxidation of trace contaminants (23), It is a well-experienced fact that deterioration rates of polymers in-the tropical zones far exceed those in temperature lones, Simulated wea the ring experirnen ts ha ve shown tha I the oxida lion rates of polyethylene exposed to JOO-om radi arion increase fourfold from 10-' to 50'- C (2-+) .

.-.......

D. Humidity

The signi fica nt role of wa ter in wea ther-ind uced degrudut ion 0 I' plas [ics lies in the combination of its unique physical properties with irs chemical reactivity (25). Water can have ttl least three kinds of effects that are important ['or the degradation of polymers. One is chemical, hydrolysis of labile bonds. .uch us those of polyesters or polyurnides: H second is physical. destroying the bono between a polymer and a tiller, such as glass tiber or pigment and resulting in chalking or fiber bloom. Rain ca n wash u way \1:\ rer-sol uble degruda tion prod uc ts. lrorn t he exposed surface, and moisture swells, soften" ami plasticizes selected plastics. A third is phorochemicnl. involving the generation of hydroxyl radicals or' other reactive species that can promote a host at' free rudicnl re.icrions (26),

Accu ru le L'I i 111,1 tologicu I d~lt[[ ~l re necessu rv ttl dctermi ne t he Cd uses u [' degradation a nd lor the development of' new :;tahilized pi:1Slic products with longer Ii kt i Illes. The s l:1 nd.: rd i Ilsi ru ll1e'IIIS ['or mens II ri Ilg the i III poruuu wcu thcr paru me ters should be located in the vicinitv 01' tile weathering [rials test sill: to have realistic profile ll[' metc()rnl,'~ir.:;li dati needed ['O!' corrclatiou .urd 1l1l)Jellilg.

Lifetime Prediction of Plastics

703

III. LIFETIME PREDICTION METHODS USED FOR EXPOSED PLASTICS

Polvmcrs l'\PllS,'d ill an outdoor environment need In be assessed Ior their dU1":lhllil:or lifetime. Prediction \11' the lifetime 01' ]1(llyllll'r l11aleri:d~ ill outdoor conditi lib i~ still a difficult I ruhlern. Researchers have tried to predict the life: imc (If pnlymers aged outside by .icceler.ued weathering leSlS with 11"\) types or methods These met hods Ill": I ude simula I ion and mechun iSI ic :1 pprouche». The si m u I:l! i on :1 [']11'0:1..:11 is norm <III: based on I he re leva nee 01' some observed phenomenon I h:l \ is dt'u uced rrom I he phy~ iC:l1 :llld chcrn ica] changes under n n i Ilci:1111' accelerated and 11<1 l u ru l ex pcsures. H owever. ill I he III echu nisi ic a pproach. I he (1 bserved pheuomeno II is controlled at .1 molecular level in t he polymer 111.1 I I' 1:\ , In a mechanistic approach the chemical n.uure and spatia"1 distr ihution or intermediate and final groups formed in polymer chain or brunches in the exposed samples are determined using spectrometric or microspectrornetric techniques. In this approach when a C0mm011 mechanism has been observed between kinetics and artificial aging kinetics. it leads to deierm iuing the req ui red acceler.u ion faclor.

A. Recen! Advances in Lifetime Prediction Methods

A reliable lifetime prediction method is of importance in terms or assuring the durability of stabilized plastics products in use today and to develop new plusiic formulations for expanding use in day-to-day life and engineering applications. Currently, progress has been made in the understanding or degradation and stabilization mechanisms. and also, some advances have been made in lifetime prediction methods, A brief review of the important methods used for durability assessment in lifetime prediction of polymers is given 10 promote an understanding of the field. Prediction of lifetimes or weather-induced degradation of stabilized polyethylene using artificially accelerated weathering and natural exposures in a tropical climate is discussed In detail. Some case studies of stabilized polyethylene (PE) films and polyvinyl chloride IPVC) pipes exposed in natural environment of Dhahran. Saudi Arabia are presented, Tidjani (31) III his Fourier transform infrared (FTIR r-based studies showed (hat the lack of correlation may be due to the differences in degradation mechanisms in accelerated and natural outdoor testing,

Outdoor aging is 100 slow to be useful in the development of stabilized formulation or for quality control of pia tic products. This ha led to the developrnent of accelerated weathering tests, Unfortunately, not all accelerated wea thering devices accu rarely predict the rela Ii ve dura bi I i ty of speci fie s ta bilized plastic products. Often It is desirable 10 perform accelerated weathering tests with the highest level or correlation and acceleration possible,

The commonly used accelerated weathering devices are weatheromeier Xenotesier. Suniester. QUY, UVCON, SEPA P, and EMMAQU , It has been reported that most or the accelerated weathering devices show poor correlation betw en the stability measured with the devices 'and til se or outdoors (17-29).

However. it CUll be said that in selecting the accelerated weathering method two factors <Ire of utrnoxt irnportn ncc. The-,e are correlation and {Icce/crillioll ol' thc accelerated test results with those or real-time outdoor tesl results Accelcrauon is a ractor that indicates how rapidly the wc.uhering lest Gill be conducted III a weathering device com pu red ,I'i l h I)L! I d 11m wc.u heri ng.

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One or the studies shows that the acceleration factor for photocxidation of polyethyierte depends on the dcgradntion pararnetcrs measured. For oxygen uptake, the acceleration [actor W;iS 2.5, and for curbouyl and end-unsuturation formation rutes the acceleration Iactors were [urger (30.) I), The differences between acceler<lteu and outdoor weathering may be due to a change in mechanisms. leading to a decrease of temperature or an increase or the oxygen pressure during accelerated weathering. These factors may lead [0 initiation of radicals through a charge-transfer complex (CTC) <lnd therefore, a better correlation with outdoor weathering, In accelerated weathering most of the oxygen is consumed through propagation reactions whereas in outdoor weathering most or the oxygen is con-

'sumed by an air initiation reaction by a CTC of oxygen. Basically. [he environmental factors, such as light intensity. spectral distribution, and temperature. have an influence on the degradation rates during exposures of polymers. These factors may lead to differences in oxygen uptake. changes in IR spectra. and loss or mechanical properries.

It is possible to achieve a good relation between an accelerated test and an outdoor weathering trial if the degradation-determining factors are controlled and accelerated in the same way to' have same reaction prevailing throughout the testing period.

For PE photodegradation, the basic mechanisms nre very wel) understood, However. there is a discussion going on a bou t the rela ti ve importance of the different reactions in the PE matrix. In PE the radical initiating capabilities or added ketones and hydroperoxide formed by thermal oxidation are low (32.33). The suggestion \1/a5 made that hvdrcperoxides in PE do not initiate photooxidation. because they decompose without forming radicals. But Gugumus (34.35) proposed an alternative mechanism of radical formation. He proposed that the hydroper oxide is the main source of new radical formation This is formed through CTC or the polymer with oxygen. Fractionation of the CTC leads to the formation of a IrClIls-vinvjene group and hydrogen peroxide. Hydrogen peroxide can initiate oxidation by thermal or photochemical decomposition. Other CTCs are also possible. which rnuy lead to unsaturation, or cross-links. instead of Il"IIlIs-vinyiene groups (36).

The conversion of oxygen into other products depends on the kind of exposure.

A higher oxygen uptake is necessary to bring about the same drop l'[" the elongation at brenk and un increase ofcurbonvl and eud-suturarion absorption in the IR spectra • ~ for (ll1tdl)0i'-ver~lIs accelerarcd weatheriug

II WCl~ suggested by Gijsrnun <"t ill. (37) that ill accelerated weathering: most or the oxygen is consumed through propugation reliction and gives all expected pro-

~~ In outdoor weathering, most 0'1' the oxygen is consumed by <Iq initiation reucrion caused by a CTC of oxygen. The higher conversion 01" oxygen by a ere during outdoor weathering 1l1~ly be due to higher stability of these complexes at low temperatures. Therefore. a decrease l)r temperature or an increase in oxygen pressure during accelcrtued weathering wil] result ill more initiation of radical form.uion through a eTC a nd. a:-; a re:>lIIL:1 better clHrel;tlion with Ollld,10f wc':tthaing is 11I1ssihlc.

The lii"clinll' prediction Dr elashll1lcrs cx poxcd 10 accclcru rc,l thermal condili"ll.' was studi,'" oy Gillen cl a l. (3~). l-or d,ISllllllL'IS aged in the air ell\ ironment, the long-term d,'gr:ld;l[iol1 usuully illV\I!v,'s ll.\ygL'1l (.'9).l\lll'Il1P[s han: been made to al"L'L'Il"r~lk lill"se rc.ictious by L',\r(lsill~ Ihl' 1II:llcrl;t!s 1,1 clcvrucd IL'IHl'er'IIUI"t'S. but a

Lifellme Prediction 01 Plastics

705

dll'i'lI';illll-lil11l1l'd oxid.uion IIL'l'ur~ 1-111 -I~L \L'l'l'il'l':ll...:d I 11 crm iI I :l~ill:: 'ILHlil'~ :II'C l'\lral",hll'd til lI~I.' ICI11PL'I':1 I 1I1"I.' c'Ol1diliUlb l-v lI~lI1g Arrhenius lifl'llllll' prv.lictiou 111l.'llwd" The 1'1.'1"1 1'1.', :Iccunling t o t hc Arrhcniu« method. lin: tcmpcr.uurc dl.'[1I.'I1- deuce "I' 1111.' r.uc Pi' :111 individual ,'hCIllIC:iI rcuct inn i~ ]11"'1',11'1 HIII:iI III 1.'\ p( - (./ R T). II here /;'" is 1 he :11.'11 \':11 ion c IIl'1'gy, R i:; [Ill' ide':t] g,l~ L'lll1~I:II1I. and ri~ lhl' :lb~ollitC tcrnpcra turc. III gcnn:d, p(lI~I1H.:rs 1,':111 be uescrih"d hY:I !'.l'riL" 11i' chemicul 1'1.':11..:1 ions, each asslIl11ed II) 11:1\ 1,' A rrhcnius behavior. K 111<.'IIC ;l11:iI:. ~i~ eli' I hcsc 1"l':I,'1 iOIlS I'CSU II~ i 11 :1 ~k<l dy, • .';t:III.' rn te ex pressi 1.111 , what' /:'" re prcxc II I ~ the effective .ictivntion l'llergy rill' the number "I' reuctions 111 the ul'gralbtilln, 11' 1\ t' ax-urnc Ih:1l 1111.' number ill' rcact ionx remains unchanged throughout the ternP"I'U 1 U II' 1':1 nue. :I I i lle~1 r rcl.u i onsh i j1 II'd I L'\ I~I be: ween I he I oguri t h III Ill' t he I illlL' I,) a certain ;IIlHHlIlt Ol-"I'llpl'rk. dl;lflge ,IIId I T, The value (\J' E., (':111 he obtained lrorn the ~1'~11e ,," the line, II' (11<.: rel.uive number \)J' degradnrion r<.':I,'tlon~ ch.uige II ith change III T, till' effective E, would be changed. a~ this c iJ:tIl;!I.' II ill result i 11 (l curved A rrehe 11 i us plot.

There .ire. however, certain limiuuion» 10 the Arrhenius method, For example.

Il is v.ilid I-,lr ultimate tcn~il(' elongation. hut JOl.'S apply (0 ulrim.ue teusile strength. .-\ no I he r pro blern \I'i til t he A rrhen i us :1 ppro.ich is I ha I the assum pi ion t h.u E" deri ved under the uccelerured conditiens-remuins c,'I1SI:111l at lower temperatures and ih.u these E" values C:IIl be lISl'UIO extrupolute lh<' accelerated results tl. 101\ -ternperatures usc conditions and ibereby allow the predicuons I'or longer dur.n ion. To conlirm rhis .rssumption. SC:I erul ycurs 01' exposures at I~'\\ temperatures wil] be needed until the elastomer \\ ill rail: thus, it becomes practic.rlly imp .siblc: An ulierunuve appro.tch to 1111.'l1i10l' oxygen cousumpiion r.n es at \ .lrIOUS temperuture s was adopted 111:11 verifies th,lI the same E., is suitable rOI" u~e in the low-temperature extrapolation region, This mel hod may be used for exposed samples having oxidation processes

- predominate the reaction mechanisms in tho: degradation (39), Elastcrner ic polymers a re u:-uall~ used at c I 05t' to room t ernper.u ure a nd a re mea n t lor 1011 g-term usage, Therefore. lifetime as .essment is of irnport.mce Cor such applicut ions. A common a ppr .. 'ach i 11\ elves accelera ti 11 g the chemical reacti n underlying t he degradat ion by t1 g mg a l seve ral eleva led tern peru I u res cl nd mcni tori ng I he degra d.11 ion 1 h rough change in ultimate tensile strength and elongation OIL break. The accelerated lugh-iernpera ture results are ex trapolated lL111Se temperature based 011 the Arrhenius method (43),

PVC i~ a \ er} important c0I11111odi1: polymer, Trabilco has tried to obtain lifetime estimates (-l4), The PVC cladding" as exposed in natural weather of Wei hrigton. I ew Zea Iii nd, Sam pies II ere abo exposed ina 11 a rtificially accelera led wea 1 hen ng device. Ch:1 nges ill i m pact SI ren g( h. duel i le-bri ule tr a nsi Ii 0 n rem perulure I DBTTI. yell )wne~s index chalk ing. .md tensile -n rength were monitored for the cxpnved cl.idding samples, The DBTT showx ,I definite trend, as it has larger t ncreases Ior both (he nutu ru II)" ,II1U a nlllLl<lII~ ex posed sa 111 pies,

Plusricizcd ,111U noriplusucizcd PVC lill11~ Me used <I., coatings. Exposure of PVC Formulations k'II.J to degrad.nion by thermal (4_- 47) 01- phctochemicul (4X- 50} jll'\lCC\SCS, but Ii or lIlt ich let n he ox i d.u i ve '11' 11 uno X I J., ti vc. 111 each of I he [oregouig l':I~C~ dchydrcchlorinutiun [)CCLlr~_ :IIlU pl'op,ig:tlioll Occurs ill :I sicpw i«: (/ip-t:lilllill<llinl1) l11;1I111(;l', The dchydruchlorination lcuds to Iorrnution or long, COiljllg'lt.:d p(ll~lller xcqucnccs ( Cl l C}! )11 III the buck bone. which gi\c: :1 red-brown l',llllr I" PVC,

706

Hamid and Hussain

Hollande and Laurent have studied color changes in plasticized PVC films by ex [10'img these in an accelerated weu ther i ng device a t 5()"C (51 J. L" V spectroscopy was used to follow degradation by measuring optical density (00) for absorption bands bet ween 250 a nd SOD nrn. These ba nus are cha racte ristic of polyene seq uences. The plasticized PVC films developed a darker color because the plasticizer also takes part in the discoloring of PVc. The 00 increases with aging time for plasticized PVC formulati ns.

Ethylene-propylene rubber (EP R) is used fo r electrical ins ula rio 11 purpose. A nev approach was used by Guegen et al. (52) to predict the lifetime of EPR It consists of building a graph (temperature-dose rate) in which four domains are distinguished. The concept of irradiation temperature synergism in the radiochemical aging is used in this study. This method needs both thermal and radiochemical aging experiments. It is then possible to define three (temperaturedose rate) boundaries separating four domains, each one representing a given lifetime prediction model. These tentative boundaries for EPR rubber have synergistic interactions between thermolytic and radiolytic initiation of oxidative degradation process. For natural weathering conditions there are no kinetic data available, therefore, a lifetime prediction has not been determined.

Substituted polyacetylenes are used as membranes for oxygen-enrichment process. These membranes encounter air at high temperatures As a result, they lose their mechanical properties owing to oxidation of the polymer. Gonzalez 1!! al., who used a kinetic model for the thermooxidative degradation process (53), have done lifetime predictions of poly(l-hexene) films exposed to high temperatures in an oven at 140~C. The weight loss obtained through thermogravimetry has been kinetically modeled. This model represents two opposing effects. including ao increasing weight process caused by polymer oxidation, and a decreasing weight process caused by volatilization of the oxidation products. This mechanism was proposed earlier (54). Once the weight loss is quantified. an approximate equation for the lifetime of polymers can be proposed as a function of temperature. The weighr loss varies linearly with chain scission .. which indicates that weight loss corresponds to a value of molecular weight ( [W) at any time and temperature. Consequently. a critical MW corresponds to a critical weight loss value. For this case critical weight loss of 2% has been assumed. Given the critical weight loss, a lifetime can be predicted at any temperature using the proposed equation as a fL\ncrion of temperature.

Polypropylene (PP} is a sernicrystalline polymer that is used in films, tapes, and injection-molded articles for a variety of commercial and industrial applications. The oxidati ve degradation or PP _ is a d iffusion-contro lied process. The extent of degradation will decrease with the increase in the degree of crystallinity and rno]- __ eculur orientation. following the effects of these parameters on oxygen diffusion (55.5bl. However. much of the oxidation occurs through radical chain reaction involving low- \W radicals produced by photolysis or thermal cleavage. The crystallinity and the molecular orientation also determine the mobility of radicals (57) and. therefore. control the rate lIt· terruinution through recombination or dispruportiun.uiun. Photooxidutive degrudurion uf isotuctic PP molded samples W:IS conducted hy ex posi 11)? them i \\ ;111 accclcru t i ng LI V device (5:\). The extent o]' degruduuon \\"a~ monitored by gel perrncu tion chrom.uogrnph (upe). FT[R, .uul ~"::\I1l\il1g electron-microscopy (SEMl. They suggexted that crystullinity was

Lile(,me Predic1ion 01 Plastics

707

the 111,1 i 11 1':lclor 1",lr COlli roll i 11g. the k inct i,',"; ,Ii' photodegrada t ion. The t rend observed for I he dTeCI \11- st ruct u re Oil 1 he c x lent oi' chemical degradation. 1H1I\l'\'er. I~ not reflected I n I hI' mcc 11:111 iC;J I hehn viur. The results or mel ting tern rel',lt lire or [Ill' recrvstullized modules were consistent With those by GPC and FTIR II'l the analysis-of-dept 11 profile. Th IS i nd i,',1 tes 1 h :11 I hey ca n be used as a guide Il) [he ex len t Or phot odegr a dation of PP.

In a 1101 he-r sl udy 011 s ta bi lized PP films (59). polypropylene fi lms were sta hi lized wit h Iowa nd high molecular weight hindered amine light sra bilizers (HA LS) and were ex posed to moderately accelerated condi tions in SEPA PI:: _ 24 umt. ultra-accelerated photoaging in SEPAP 50.24. and natural aging_ The FTJR spectrosccpy wus performed on the aged films and the maximum of the carbonyl absorption appeared at 17):,\ and J7J:\ cm-I (representative 01' acid groups) and a bsorpiion at :'1·077. 1640, and 910 em -I also appeared _ These absorptions may be assigned to vinyl group buildup that indicates photooxidation of ethylene segments of the ethylene-propylene copolvmer (EPR) Evolution of optical density relative [0 irradiation lime for moderate :;"'nd ultra-accelerated conditions has bee~ obtained, Similar variations were also observed for stabilized films exposed 111 outdoor wea thering.

Photodegradable PE films. stabilized with HALS. were also exposed 111 madera te accelerated conditions. ul tra-accelera ted photoaging, and na rural aging (59). The conclusions of this study include the following: I) evolution mechanism th roughcut wea theri ng . and accelerated aging allows can trol of relevancy of phenomenon. ~) simulation techniques showed irrelevant phenomena in accelerated conditions. 3) [he aging matr ix should not be considered as a homogeneous (photo) reaction at a molecular scale. and 4) the data collected at the initial time ll1 noriaccelerated conditions be extrapolated to the real lifetime of polymers using conventional kinetics. Therefore. experimental acceleration appears as a necessity in such studies. It was pOI nted out that deviations are generally due to either birn olecular reactions between inierrned ia te species. the concemra lions of which in real-time conditions are too low to interact. or 10 di (fusional processes of reactants that are slower under accelerated condi lions.

An other approach for deterrn i rung Ii relime is proposed using degradation profiles of thick high-density polyethylene (HOPE) samples exposed in an artifically accelerated apparatus and in outdoor weathering condition (60). The main objective of 111 is study was to fi nd t he critical degrada tion profi les tha I res ul I in the fail ure of the HOPE samples stabilized with a phenolic. antioxidant-type process stabilizer Samples were aged in Xenotesier 120(). ATLAS wea therorneter. and the outdoor Ilea t her of Florida and Delft. The Netherla nds. Degradat ion profiles were obtained by microtoming the surface and measuring the mechanical strength using microfil tensile testing system (MTTS). carbonyl and vinyl index applying FT1R spectrometry at 1712 cm-I and 909 [m-I, respect ively, and density measurements. The reo, ults showed that ex posed sam pies have 111111 ted degradation depth, wh ieh IS the maxim um depth a I which the degradat ion profile d i rrefS [rom the profile of a n unexposed sample However. sample exposed at Delft show an increase in degrada 11011 depth. TIle degradation de pth is i 111 portunt. ;IS i I l11:1y detenn me t he II feri me to I'(l ilurc (61,1'l:2). Wht:11 different cxpovurc conditions ure compared. the only vari.uions seems to he the depth <It which changes took place and the slope <It which tilt: degrt:c uf uegr,I(l<! \1 ()[I dccrcu vcd ["I"( imt he: surface [1111";1 rd [he m ida lc. Generally.

708

Hamid and HUssain

the degree ~ )1- dL:grada t i Oil i 11<.:I'L'U ~L:S, whc I'L'~IS till' SlllpL: dL'<.:n:aw, wh ile going from Xenorcster to wcatherorneter. tll l-Ioridu outdoor ex j10S LI IT_

The need to accclcrute the weathering condirior», hus led to the lkvclopment of several weathering devices r Tuhle I). These include the weatherometer, Xenotester, Suntesicr. QLlV. [IV('O:- -,', and SEPAP. Gijsman c l ul. (63) discusses comparison or UV degrudation 01' PE in accclenued testing and sunlight. It has been reported thut the sl<lhility measured with these devices shows poor correla lion with those measured in outdoor weather (27,(;4.65). This lack olcorrelation may be attributable lO the different degradation mechanism prevailing in accelerated and iutdoor testing (661_ The st udy shows the tollowi ng J11il i n concl usions: I) a cornpanson of the rate of degradntion in accelerated and Slim mel- outdoor weather showed that the accelerarion factor depends 011 the degradation parameter measured: 2) the acceleration lacror for oxygen uptake \\ <IS 2_5, and was larger for carbonyl and end-unsaturation formation rates; J) the differences in accelerated and outdoor weathering are probably due to it change in the mechanism leading to oxygen uptake. They suggested that. In accelerated weathering. most or the oxygen is consumed through the propagarion react I ns, whereas in outdoor exposures. most or the oxygen is consumed by an initiation reacti n caused by a CTC of oxygen ami the polymer, A decrease oftemper ature or all increa e in oxygen pressure during accelerated weathering will lead to more initiation through a TC and thus n better correlation with outdoor wea thering.

Lifetime prediction of H LS-stabilized LDPE and PP was attempted (67).

Two models. based on physical parameters, were used Ior estimation or HALS stabilization efficiency ill polyoiefins. That these models are empirical relationed, has been suggested (6R I. and theoretical model for addi ti ve los' pr posed (69,70). Moiscns model (68) IHI~ been rested lor HA LS-stabilized LDPE and PP with considerations that an efficient light stabilizer should be highly soluble in the polymer. whereas its di ffusion rate has to be mini mal. Ea rI ier a ttern pts to use th is model failed beca use I he audit; ve wus lost by dis. 01 ution ill a contac ling liq uid and not by evaporation from ihe surface Into air (71). But Sarnpers (72) considered the rate of loss of U'V-nbsorber trorn LOPE and showed a very good fit of the experimental data and g:lve gL10d predicted values from the model. Defining a critical stabilizer conccntr.uion has successfully used in the- other moue! Ior additive los) (69,70). The criticul concentration L,I' HALS is dilTerenl for PP and LDPE This difference could he related ttl different photooxidation initiation mechanisms of HALS-stabilized

ATL\S C.'\W carbon .irc wcat hcr oructcr ()-P;ltt.:1 t.,?tl V I J40 or _, I_~.-\ bulb)

.\ II \S si: TI'_ST l'PS bcuchtup \CIHIlI :\ J"L. \S (_'; (,:; xenon ;11-,- II \.',11 hcromcnr SUIlic"skr. l lannu

SI,I' \1' 12_2-1 lllll\l'I'~II_\ "I' Cklll1l1111-h:rr:llld SI-I' \1' 511.~-I, lIIlIH"'III "I ('krltllllll-I','rr;IIl\1 l'.vJI\I-\()II.,_ [)SI; l', 1-1-<'<11.:1 rcllcct u:

Carbon urc

1-'1 1I11 rcsccn I rcsui I .'\L·l1l)11 a 1"<':

:\,'11"11 ;1 rc

.\c'1\\1ll l.unp 1\1"Lil:r:llclY:icc..:kraling l II [-;I-;IL'l."cJ..:raling,

- S,'1.1 r conrcntr.u ur

Lifetime Prediction of Plastics

709

pnlYl'lhyielll' and polypropylene- .;;'l'L'!'\'~\'d :,~ Gucumus 17'1 I'hc l':lklll:IIl'tliil'l'time pl'l'dicth'lls lrorn the mod", .;,:rl"',: \1 ell w u l: IIII.' dat:1 oht.unrd trom diITL'ITIII ucccler.ucd weathering 111:ll'l1i11;;'.' 11 \1." ;11,;,' pointed mil th.u the J1h~·~.iL"<1i P:II'.nnctcrs could ;Iffe,'t the shnpe c ~jIT~::,klh" l'( }-l:\LS stahili7ilti'1ll performance on its initial conceutrarion in P;_It11C;'

Cross-linked polyethylene -.- ~"::"LlIl_\ i,ed flll" the m.rnulacture \11' cable insula 1 iOI1 a no pipes for h,'>\\ .ue: t r.u.sporr. The thermnl 1,\id:ll ion nr f~-ray-cross-linked polyethylene ··'.b ~;.:Ji<'J ::'. the tcmpera ture range l,(91) I~() C (--I), The durnuon of induction :,·;:,~i,~,: ·DIPI 11;1~ obtained using phenol depletion. ultirTI<tle eloncaticn. density. e<l~::-,ln~ I .:;;'\ el";'1l1em. color chance. and weight lo~s determinations. Tilt' Arrhenius 1.,'.\ \\,;- -'r~f'I:<,J [,1 Ji!Ter<'nl DIP values, Previously (he induction period was linkec :,' {[-_~, rC'~:,~ ,:1 stabilizer concentration (75 77)_ Phenol depletion i~ the only f __ -.1l1'~: ~r. t i:" i .111,1\\ ed defini ng a crit ical concentration, This method gives a .. 'IIe',: :J('lit:,~ value, which gives i1 :;,tfety margin in the prediction.

IV. LIFETIME PREDICTION OF POLYMER IN NEAR EQUATORIAL REGION

A. Mathematical Modeling of Weather-Induced Degradation

The weathering of plastics is deperccm ,':i almost all parameters of ihe environment (7,,-8 J ), The wea ther is variable j- ~:TI un:e [0 time and {rom place to place: hence, the outdoor trial results obtained it: ,::ifre~~nl seasons. years. or locations have been inadequate to fully ascertain the co~rad.;::on patrer n. Hamid and Prichard (82) conducted an extensive study using a ::l3th.:::tatic"l-modeling technique. that describes the weather-induced degradatio ; of :~:~ear low-density PE (LLOPE) material. The main objective of this stud _:fe :.; follows: to develop mathematical models ihar can descnbe the weathering :~:.'.I 0':::.1 to predict the lifetime and help in understanding the complex weathering .:::>grac.,lion 1'1 nomencn occuring in the material a a result of natural weathering (;;. I, LLDPE riln product: were exposed t natural outdoor weather of Dhahran. 5<1-:: A: .:·::ia flY a period or I year, Exposures were carried out on wooden racks fa ;::.11eC :~,cord;:lg to the ASTM 0 1435. The racks were adjusted 10 expose the plasr.; sar.:;,les iacing south at an angle of 45° from the horizontal (84). Samples wer ; .\ Jth'-:~a\\ n on a monthly basis.

TIle degradation was monu : -::d 1;-_ .errns of changes in mechanical properties. carbonyl groups. and percentage _~:;;'.:.::tnit~ or the exposed LLDPE films. The weathering site of Dhahran (26.: ~ '-'.: I J E I I' situated just north of the Tropic of Cancer on the eastern coastal :-·.::i . ~-' Sauci -\rabJa. The environment is very TIl uch des rt-Iike. The mean mon :.-.::. a -. :-~ilge [em pcra I ur e during July a nd August IS about 37' C. with a maximum i.:-~,pe:~:Jre reaching about 50 C. During the cool season, the mean monthly tempers __ ,e:, "hout ~(J C lower than the modest months The maximum monthly mean sol.: rac.eiion :- l1C(1r 4K() langleys. Annual precipitation totals are low. typically d_·:- I( ,I) mrn.

Three different models wert :::-\e; ;-:.ed tl' ~erre.,tlll the independent variables llj II tensile strength ITS), 2) carr ~:.I::- -wt h ,r\ J. and 3) percentage cryxlullinity (CYI in terms of the following dt~ cltk-' ·.;Ina:"k, average monthly UV 1"<ldi:lli,111

710

Hamid and Hussain

(UV), cumulative 1111)I1l111y UV rudiution, cumulutive total xula r radiation (CR), average totul solar radiation (RD), and aver,lgt: monthly temperature (AT),

A step-wise regression method was used to eliminate the insignilicant variables 185J\6) because the potential outliers or the meteorological parameters can misrepresent total degradation behavior (H7,XX), The computational analysis has been carried 0 lit us; ng a stu usuca I a n,ily~ is system (SA S I sort ware package.

IVl odcl I Modell]

TS = 210.52 - O.5/:) AT - O,8'+CU - 2.12 LV

CA = (l,22 - 0,] 15CU 0,14-+ V - O,OU-I RD + O,OOSCR

Modellli CY=<+3.JI-O,29AT+O.O, U+000008CR

The mechanical property was more dependent on the UV portion of the total solar radiation, carbonyl development was synergistically affected by UV and total solar radiation, and the percentage crystallinity was affected by CV, total solar radiation, and temperature. Humidity and other weather parameters played a less significant role in the weather-induced degradation of LLDPE properties.

B. Lifetime Prediction from Accelerated and Natural Weathering Trials Accelerated weathering of plastics can be achieved by continuous exposure to light, elevated temperature", and humidity. The intensity 0[' radiation by expo ure to high-energy wavelengths can accelerate the degradation proce (89). The data obtained from artificially accelerated weathering trial can be correlated with natural weathering trials using mathematical models and correlations (90), There are inconsistencies in the reproducibility ofweathering trial results for the material exposed at different times ina certain loca tion Correia tion of such da ta with those or artificially accelera t d weathering trials does not prove to be accurate, One of the major reasons is [he consideration given to the geographic climarologjcal data in the test criteria adopted in setting the artifically accelerated weathet~ apparatus ana also the variarion in natural wea ther conditions with time Furthermore. the variability of climatic conditions between various locations and at different times in [he same location make' it difficult to extrapolate natural weathering results from one I oca tion or time to a norher (91),

A weathering study was .arried out (92) on HALS- .tabilized LDPE film samples exposed at live different locations in Saudi Arabia. The details of the meteorological data i"L1r these sites are given in Table 2,

The main objective or this study was to develop correlnuon between natural ~1I1J artificial weathering, which can predict lifetime in a short time span for near-equatorial region. Natural weathering trial: on five CXpOSUI't: sites were carried out all aluminum racks designed [0 the ASTJ\l D 143.- (9~), for H duration of 2 years, Artificially acceierured weathering trials wen: carried nit in ATLAS Ci 65 xenon urc weatheromerer 1'01' soon h according tL1 the ASTM D 2565 (9'+),

The we.uherometer was set on automatic irrudiunce control mode, with an irrudiuncc level ,)1' 0 . .1:' W me at 340 11m. The dcur.ula t iun r.ue was monitored by meusuri Ill; COl rbon \ I a bsorhu nne: ill the region I lUU 17:'0 <.'111-1, The growth in cnr bouvl ,111;;01'11<1110': i'l)(' t h c samples exposed at live dilfcrenr "ilt:s is presented ill Fig. I Duri ng ,I no I he r .:X posu rc uiu I. chui n ~..:i"sio 11 :llld vross-l i 11 king rook place sim ultuucously (l)5), The riuc or cross-linking \\':IS higher u t the initial stages than

Lifetime Prediction 01 Plastics

Tnhll' 2

1\1 nx. I'vb~
mon I hl~ n1(lnlhl~
rVI 01:-' _ rcmp, I11C;11l soLn rclat I vc
III lOIS! lOy fad union humidirx
Latitude ( C\ ( lauglcys) ('y;-,)
~(,,-,2 4'.1.) ..JXO 90
25.51 4~.iI 575 77
::1.::9 4i'.0 520 g6
2~.2~~ 4..J.9 -'175 6g
Ii', IJ 3~.6 555 60 ~, Exposure Sil,·

lone

Dlw hru 11 R;\:u.Jh Jcddah Tabuk Bah:1

l','uslnl eastern Ccnt r a]

l-(1(1sl:11 western )i orthcrn S"ulhh·n

711

D. ~I
c.' - a .. h ..
.., .... Dh .. hn.n
u Jedd .. h
~ iC'.[N!I ...
-g e Riyadh
~ * Tabuk
s: c...oe
'"
>-.
to
c ....
-E
co
u
0,""
•
0 .0

••

"

1.

..

Exposure (months)

Figure 1 Changes in carbonyl absorbance of polyethylene samples as a func!lon of exposure time

the chain scission. However, chain scission dominated during the later stage (96). There was lower carbonyl growth during the initial 8 months of exposures. After t his period there was a step change in carbonyl growth The slower initial carbonyl development may be due 10 the acuve role of stabilizer played by HALS during early 51 ages of na lura I wea I hering.

Therrn a I ana lysis was carried out using DSC. The resul ts are presented in Figs ~ and 3 showi ng the cha nges in percen tage crystal] ini ty and crystal] inc-melt ternpera t u re( T m). respect i vely, A consistent behavior is exhibited in terms or T m for samples exposed at different location. However, an increasing trend in percentage crystallinity can be observed for all locations. Crystulliniiy increase has also been reported (97). and it has been indicated that imperfect crystalline region or LDPE are believed 10 degrade because of cross-Iinking, whereas chain scission predorn i nates in the a rnorphoux mat ri x (9R)_ This lea us 10 scconda ry crystal] iza I i on in <J 11 amorphous phase. wh ich is 1<1 tel' inhi hi led hy the decreasi ng mobi lily or chili ns o V," j ng 1 () bra nch ing and cross- I III king

712
..
..
••
..
u::
?:" ..
c:
1M
<'l
on ..
;>,
....
U ee
.. Jedd"h
.. e Rlylldh
* T"bu.k
... Hamid and Hussain

,.

..

,.

,.

""

..

...

Figure 2 Changes in percentage cr ystallinit , of PE samples as a 'uncuon ofexposure time,

1L1..------------------------------,

"I

'-_~- - B"hll

... Dh"hr8n ... Jeddah e Riyadh

110

".

11:1

""

1I1~- __ --_-~-_T--~-~-~--~-_r-~---~-~

10

II

11

,.

Ie

..

..

Figure 3 Changes III crystalline melting rernpcruturc ni' PE s.unplcs as a tunction of l'XrOSLIrc L nne.

11<, increase In crystallinity is generally attributed to [he degradation of ultra S t rong ..:11:1 ills, which i~ en used by ell il i 11 sciss I nil owi ng III r:I(Ji:1 tion-i nduced reactions (l)1.}1. The changes In molecular weigh! were determined by (,PC analysis.:\ drop of J(I"" 01' t he in i I i.1i va! uc 01' pen k molecular weight (1\11,,) W:IS observed Cor samples l'\!1ns..:d [or 2 vcu rv. This drop In '1r \\',1, :1 direct consequence Ill' chain sci,sion I'l';ICIIPI\:, that t ouk place,

1\11 cch .. 11 iL":d pn1pal ics, I he Ill. lsI i ruport unt p..:rr()['I11'11 ice charucteris lies. were dctcrmiucd <lI\d the changes in pcrCl'l1t:lgc cloug.n ion ,LI hrca k arc presented in Fig.

lilelime Prediction 01 Plastics

713

4, A <.:( n~i:·nLI11 miti.r] hch;l\ inr :lml 111':11 ;1 continuous drop ill pn)llcrlv 111.'n: observed, The ""IlSisl<.:111 h..:I1.1 vior muy he till': I,' I he dominance 01'1 111.' cross-liuk 11l,!'rc.icuons over II1L' chain sl'l~~i(lll during. rhc early sl<lges (100),

The "hang...:> in mechanical propel"! ics were also rnunitored for samples cxpl.)~l"Il in <111 .1 rl i liL'i;tll~ accclern ted WCLI t heri ng device. ,IS shown in Fig. :'i. A J1Crk~'1 1.'(1i"relation between natura] and ,lrtilil:iaIJ) ncceler.ued weathering is no! pr;lctiL";IIJ~ possible because not all the possible we.u hcring parameters can be considered in

Exposure Im011111> I

I.

,

............. ~- --

Figure 4 Change in elongation at break of polyethylene as a Iunciion of exposure rime.

I
500 'I ~'H , , 1 I i
1 •• ; ; I I
. I'i I' I
.~ III Ii ,
, !
~' 1 I
~ I , I" III 1
, ll 1
~ 450 . L HI 1I I
- 1IIIIi [11 I I
1
,. I " I III ,
I" i Ij!
.- Iii
,. I
.z · I,if "IJ ' II
400 • , : ~. I 1 i , , '''4 I HI' , ~- i i ,
- ~ -;-~i!- I i ,',I I ;1- + ~
, -;-11IIii-1 II
, I : ~ 1 j " I
I ! Ii 11 ; 1IIIIi I Iii I II
, I ,llrl i:' I I ' ,
,I' i , II l i '
I ]!I I
350 ' I 'lit I I II illl:
1 E 1E+02 .3 1E+03 1E+04 .3 1[+05
1:.\p""lrL'IIII'~ 1111 550

Figure:; (I>n1P:II'1\llll I)j fl"h':lilyiL'ilL' 'ill1l[lI~, l'\[l"'l'd III n.u urul ;111J ;lrlificlaJI) accclcr:III.'d c'IlI II"' uuncnt.

714 Hamid and Hussain

<Ill experiment design. Moreover, different materials respond differently to the accelerating parameters of the weathering environment (101).

The lollowing model were tried to correlate the data:

I. Straight line

~ Parabolic

3. Exponential

4. Cubic

Y=II+hx

Y :::::::: 1I + bs. (".\.2

Y = 11.\'/'

r = (I + hx + ex" + ".\'.1

The criteria for selecting a model were the value of ,.2 (coefficient of determination). The best model is that m I, hich has ,.:'. approaching 1 (I02/. SAS was u ed for all computational work.

The result showed that following parabolic model had the maximum r:'. value.

V.V = 5::'3.241 - [0075 x IO-t>XN + 110 x 10-'XN! r2 = 0.994

YA = 507.~58 + 19956 x 10-7 XA - 5.0 x IO-1i X A2 r2 = 0 78

where

y.v perce mage elongation at break value- I'or natural weathering

Y...J percen tage elcngati on a I break va lues ror artificial wen thering

XV natural exposure time

fA = artificial exposure time

Figure _- shows a change in mechanical properties for both natural and artificial exposure trials. The acceleration /£ICLOI" determined for the artificially accelerated weathering is about three limes that of natural weathering trials (5,000 h of artificial weathering = 14.000 hot-natural weathering). From this study it is shown that drop in mechanical properties can be considered as a quick means to predict a polymer's lifetime from urtificially accelerated and natural weathering trials.

C. Lifetime Prediction of Greenhouse Film Exposed to Outdoor Weather

Th~ most deleterious or the environmental factors in the weathering phenomenon is the UV portion or radiation. which is responsible tor the weather-induced degradation or plastics (1()3.104) arly luilures of greenhouse films in tropical climates cu lise hea I'> losses in lams or prod uct ion, p[:tSIIC rnu teriu Is. u nd opera tional illlarliption: maintenance replacements costs arc also incurred rtn repairing new urccunouxc Iii ms.

- 1\ ~Oll-tl[ll thick greenhouse tillll buxed on LDPE und suibilivcd with HALS II :I~ sludicd lor ils performance in uctu.d greenhouse environment ( [(5). The objectil c (11' lill, sunlv II':IS l<l corrcl.ue lhe n.uurul we.n hcrina trial d:II:1 \\ ith [hI:' weather Ulildilitln~ .nulcxpuxurc dur.iuon 10 asccrt.un the litcrimc or LDPF lilms exposed III :1 d<:sCi"I-likL' .:1;111:111.'. Greenhouse lilms wei',' exposed I'll[' .\ yc.ir» ill actual g['L'L'uh'lll.,CS :11 I)h:ll1r:ll1. The varialiollill totnl sobr rtuliatinn 1\';[11 lime ;11 exposure site n[' ()h:ti\l';[ll is shown in Fig. (1. S;IIHPics wen' withdrawn Oil a himout hly basis.

Lifetime Prediction 01 Plastics

715

Chnructcriz.u um (1 I' the wcuthcri Ilg Ii lm ~:1l11 pies wa S performed usi Ill'- t he cri t ic:iI performance propert ics l)(" tcnxilc strcll!;!lh and percentage elongation a\ I11"L':lk.

Till' durability ul' HALS- and Ni qucnche r-stnbilized LDPE greenhouse films ex posed nil :11 umin urn racks and u ISll ,'11 act un I green houses has been compared (I (J()l. This si Lld~ showed I hat IIll11s mounted in the actual greenhouse degraded more in comparison with films mounted on I he aluminum racks, The spectral emissions with \\"a elengt hs between 7 and 14 IIIIl are Important pan of energy losses from soil and til .... pl:111\5 inside a greenhouse. The partial prevention of this dissipation of the thermal energy from greenhouse film during cool night hours influences the degrad.u ion reactions in plastic films. Pesticides. based on sulfur and halogen compound s. GIll accelera te the degra dn t ion react ions. The chern ica I changes 111 terms of carbonyl absorban e are presented in Fig. 7. The higher values of carbonyl absorbance Ior exposed film on greenhouse versus exposure racks clearly indicate the severity of phot ooxidat i n react ions. The mecha nical property results _ how good correla lion with ITI R results. Figu re 8 shows the stress-at- brea k values for the samples exposed 011 racks and greenhouses. The film usually breaks at a point of contact with galvanized iron or ihe greenhouse frame.

A software package of SAS was used to estimate the unknown coefficients in the regression model (107) The following empirical models, given in Table 3_ are availa ble from the literature (108.109). The mean maximum and minimum deviations obtained for these models are presented in Table 3. Some of the relation. which gives good results for Dhahran, I listed 111 Table 4_

The investigation showed that model 2 gives lowest percentage mean deviation and is relatively simpler. A comparison of experimental data and ihe predicted values for rensi Ie trength as a function of exposure time j s shown in Fig. 9

Where, T, = tensile strength (MPa). T,,, IS lime 111 months, Co = 23.88 (tensile

?OO
IIS~O
~
o 600
""'ii,
<::
~ "',,"0
__j
<:: ""00
C
..
"":J ."'0
~
'" "00
~
_. ~"'O
~ :'00
2"'0
0 / .... 199:2
/ .....
/ <,
.....
'"
1991 ..... "-

\ \

-> -, '-

»" ""---'-

J /.990 ""

I /

I :...---

r

2

..

..

'0

'2

Exposure rirnc (h)

Figure 6 Vunuuon in total solar radiation with lime ,iI Dhuhran.

716

Hamid and HUssain

0,175

__ Exposed on racks

o ISO ~ Exposed on greenhouse

0,\25

::::'

Figure 7 Carbonyl absorbance versus exposure time for greenhouse film exposed on model greenhouse and aluminum racks.

30

____ Exposed on racks

lB -0-- Exposed on greenhouse

• d:
2
~
~
:::;
-"
./'
OJ
'-
:7. 20

2'

22

20

\8

Exposur« (1!lul1ll,,)

Figure 8 Sire-s ut brca k versus exposure 11I1\l: Ior greenhouse film e:-.;poscd on modd greenhouse and aluminum rucks,

I\k:11l dL'llaill>ll J\II ax. dcviu lion R.:f.
RL'!:lill'll (II II) I"~,,)
,., L\pIIJ( I rll S ,\S 1':llkLi h' L.-~oL,lnVI".·rt!.l: 7
8
I' - ;..: ,., <.:\1'1 IJt ) 1 .. 1,r) ~~()
('+ .1 1Ji" ) 14 () ~K,O 9
I' ~,'I'I Ufelime Pre dlc uon 01 Plastics

717

.5;'111[11.'

11,'. Rcl:111!\1l

MCJlIl M;I~.
deviation <1,'\'1:11 ion
(",,) (".,l
;_.~ X.I
~_:5 X.I
2_~ L) .3
41.7 L)~ \I i: = ('II + C,(r~I)+ ('~lr~II('\

~ T,= C,+(',(T~I)+('~(T\,1~

~ T, = C, + CltT~II'I~ + C"(h1l:'

4 T, = C"CXl'(-C,(TM):' + ('~(TM)

I~

o 0

,0

o IS-OHA-EXP_

I

10

- IS-OHA-CALC,

O~----~----r----4--~-+-----+-----r----~----~--~

11

16

,0

,8

J,

Ti me (months)

Figure 9 Experimental da ra and pred icied values of tensile srrengi h as a function of expo~Llre lime at Dhahran

strength of virgin samples at Ton =0), C" C: are constants. Also C, = - 0.149. C2 = - 0.000319_ The coefficient of determination 1'2 was 0,86.

The same form of model was also used to predict the percentage elongati on at break values, The following model was obtained for the percentage elongation at break as an Independent value USing the SAS package

PE = 517,5 - 4,438(T",) + O.0576(Tonf

The mea n <I nd max i mum devia II ons were I,]. and 5, I ';I.,. respect: vely. The coefficient of determination was 0.89, which is within limits for engineering purpose ( lOS).

D. Dura.bility of PVC Pipe in the Natural Environment

Polyvinyl chloride pipes used III Saudi Arabia are exposed to high UV dosilgc-170 190 K Iy! YC<t r. tern pera tu res or 13 50 C, rclat ive hum ill i! Y or .j 1- ~5'~" d ll.~( a nd other en vironmcntul factors d u ri ng Ira nsportu lion. xto rage, and USll ge During outdoor we.u hcring. complex 1·C:;11.:1 ions occur ill the presence or oxygen_

718

Hamid and Hussain

Degradation may start from chrornophcres in the polymer chain, but their preci e na 1 lire is questionable (107). U V radia lion exci les the polymer chain, causing radicals to [-orm thai further react with other chains of PV , causing dehydrochlorination, bond cleavage, and cross-linking [IOHj. Dehydrochlorination results in the formation or colored polyene sequences. which can be seen on the pipe surface a color changes. The radicals may also react with oxygen to start chain cleavage or cross-linking and Iorrn hydrcperoxide and carbonyl groups

A study was conducted (109) on white TiO:1-based pipe. containing lead stabilizers, by exposing them for 2 year' in the natural weather of Dhahran, Saudi Arabia and Florida. The objective of this study was to assess the service lifetime or PVC pipes weathered in natural weather of Dhahran and Florida.

PVC pipes are fcrmulated with a range of stabilizers to combat degradation effects caused by UV radiation and heat (110). The mean protection against UV attack is provided by titanium dioxide (Ti01) incorporated at 1-5':;', in pipe compounds. The pigment Ti02 strongly absorbs UV radiation at wavelengths below 720 nrn (lID). The energy as ociated with these wavelengths is 284-412 klima], which i enough to break the C-H bond (410 kJ/mol) and form an alkyl radical or break the C-Cl bond (315 k.L' mol) to form poleny! radicals. The incorporation ofTiO: inhibits the formation of radicals and subsequent phctooxidation However, complete stoppage' of the formation or radicals i not possible because radicals are also formed as existing polyenes, carbonyl groups, chain ends. and other impurities.

Degradation was monitored in terms of carbonyl group growth. changes in glass transition temperature (T~), and mechanical properties Figure 10 presents the changes in T~ relative to exposure time in Dhahran and Florida. A downward [rend of Tg is observed for both exposure sites. However'. the degree of drop in Tg is more for samples exposed at Dhahran. Tbis may be attributable to higher UV radiation doses. t~~"t__ 1~:l1Ul~idity Qlctors present in Dhahran.

------- O.,.hran

S9 __ Florid.

Figurl'llI l'hall!!.';s ill ;:(:ISS Ir:lllsiliolllC:Il1!,L"rallll-C n.:!;Hi",·!l'l·\I',lSur" 1111lL' !'''i' I Ill: ';.~I'oscd 1'1,'(' samples.

LileUme Prediction 01 Plastics

719

Till' Ul'l)0 ill .,~ ;!lso indic.ucs I Ill' dchydrochlorin.uion .ind oxidnt ivc dcurudu tiou n:;Il'1 ions occurred ill 1 ill' PVC The dehyd ruch lu rina: iun i"l';ICI ion C<i uses ;1 CI1<IIIgL' ill color I'rom \ hire In light brown, Prolonged exposure allnws 11lL' phorooxidiuion :llld cross-linking reaction III dominate (1 j I j 13).

An llVl'I'i111 inLTI':lslllg trend or carbonvl absorbaricc is observed Ior htllh sicks ,IS ~IW\l'l1 in Fig. j I. The extent or development or carbonyl groups is more :It Dhn hr;111 This C;I rbonyl t ra I1sl11 i IS electronic exci la Lion 10 I he vi 11;"1 ch loride un its, followed by the form ,11 ion 01' radicals, which degrade the p lymer.

Changes in mechanical properties are an authentic indica lor of in-service periormance of pipes. Figures 12 and J3 show the changes in stress at break and pertentage elongation at break with time.

The stress at break was lowered by 43';'-;, in Dhahran as compared with ~6j1"11l Florida within 24 months. Similarly, percentage elongation at break dropped by 66"·" for samples exposed in Dhahran and 49% [or samples exposed in Florida. The service lifetime determined in terms or loss in percentage elongation at break

is 47'Yr, in the initial I ~ months. However. it took 16 months of outdoor exposure

in Florida to drop to the same level of mechanical properties. This was also pointed out ill other studies; 6 weeks are enough to create microcracks On the surface of PVC pipes, which results in the loss of mechanical, physical, a nd chemical properties ... _ owing to the high UV dosages and temperatures that are encountered in the region . (114.1 I 5). Therefore, a 111 uch highe r level of Ti02 and UV -sra biliza lion are needed

t enhance the PVC pipe lifetime for use in tropical climates.

v. CONCLUSIONS

Prediction of the lifetime of polymeric material exposed in an outdoor environment can be achieved, but not with full accuracy. Basically two types of method. which

12
---- Dh~hran
10 --- Florid.
<J
:.> 08
<:
£
0
. ..., 06
s:
':":i
.--.
C 04
-s
U
02 OO+-~~-'-----.'-~~~-----r--~--r-~--~-----r~~

o

e

'2

20

28

Figure II Changes in carbonyl ubsorbancc relative to exposure time Ior the exposed PVC' sam pl~.,.

720
'2
38
34
,-,
C!.
:2 )0
-'"
'"' 26
"
Js
." 22
"-
v-
fJ
U1 '8
,.
10
0 Hamid and Hussain

, 2

,6

20

24

28

Exposure (monthv:

Figu re 12 Changes 111 stress at break relative (0 exposure time for the exposed PVC samples.

90
80
~
~'
-" 70
~
Js 60
."
SO
~
~J
.2 40
.u
30
20
0 e

'2

'6

20

28

Figure IJ Ch.mucs in pcrccru age elongation r .la nvc to exposure lime Ior the exposed PVC S:l111 flies,

ure bused 011 simulntiun .uul mechunisuc approaches. haw been used bv different rcscu rchcr-. The si III ulu t i()II upprunch is normally bused on I he re le vu Ill'C' or some observed phCIH1IllCIl111l I lui [ IS ded uced Irorn I he ph;. sieil ,I nd chemical cil;ll1ges ill all ;\l,tilici;dly accclcr.ucd and ,I n.uur.r] exposure. 111 mechanistic .rppruach till' chcmic.r) n.uurc and . ..; pil I iu l dixtributiun Ill" ill ierI\ll'di;lIL' ;l lid lil1,II groups formed ill l lu: PUIYIllL'1 chain !II' branches ill the l'XP1'~l'd .";:IIllPk's .uc dctcruuucd using spcctronu-t ric kLirlliqlll's, Liven the weathering kinetics uud ;tnilici:li aging kinetics (ilL' needed :ll'l'l.'!..:r:lt ion 1';1(l\lr- Gill be culcul.ucd.

Lifetime Prediction of Plastics

721

t)uld,),)r ;Iging i~ !I),' ,,1.1\1 In be useful ill development Ill" ~1;lhili/,ed 1",1rlllld;11 ions: I h"n:I'\1I·":. ,ll'l'l'!cr:lll'd :ll!i ug is very m uch rel) IIi red 1,1 .... ond uct II c;1111Crllll!1 na I~. The :ll\:el,'I":11 ion 1',1,'1 ,Irs Obi,] i ned [or 1 he pl],)[ ()(IX ilia (i OIl ol' polvmcrs II ill depend ,111 the lkgr;ld.IIHlIl parameters I11C<lSLlreu. Some of the import;1111 parumetcrs are oxygen uptake. c.uhouvl. end-unsaturation, and mechanical )11',)perties, II Iws been observed th;11 ihe experimental design or art ificinlly accelerated weathering is important hCC;IlISC \I'ry hll!1l acceleration leads 10 ;1 change in the me c linn ism 1 ha 1 leads to o.\\'ge11 II 1'1 a ke. In accelera led wca I her ing. most oxygen is consumed through :1 pr opag.uiou react 1\1n, whereas 111 outdoor we.uhering, most or the \.lXy g.:n i~ consumed h~ air initiauon reaction caused hy a charge transfer complex (eTC) ,11' oxvgen. II \\ ;1" ~uggt'~led t ha t <I decrease of temperature or un increase of oxvgen pressures during accelerated weathering might lead to more initial ion through ii eTC a ud I hen u bet tel' correla t ion wi til out door weu 1 heri ng.

TIle theoretical model proposed (,'r additive loss caused by exposure of polyolefins (69,70) and the ernpincal model (68) showed a very good fit l the experimental data with the predicted values. By defining a critical concentration. [he lifetime of the stabilized polyethylene formulation can be calculated from the proposed 111 ode! for the acceler.ned \\ e.uhering tria Is. The physica I parameters can In f"l uence I he dependence of' H ,-\ LS s[ ~1 hi liza rion performance on its initial concentrnuon.

Tn high-temperature applicauons I polymeric materials, a c rnmon approach is [0 accelera re the chemical react ion unde dying the aging a t eleva ted tempera lures and III oni 1 ori ug the degrada Lion through cha age in ultimate tensile strength and elongation at break, The accelerated high-temperature results are related to use tempera t ure. based on t he .A rrheni us method.

The lifetime of a polymer can also be determined using a kinetic model for ihermcoxidative processes, The weight loss obtained through thermogravimetry call be kineticallx modeled, The weight ion may vtlry linearly with chain scission, which corresponds to a value of molecular ",'eight at any time and temperature. Based on a cri I ica I weigh i loss of 2"" the lifetime can be predicted at any tempera lure,

The' ging polymer should not be considered as a homogeneous (photojreact r al a molecular cale. The data collected at the initial time under nonacceleraied conditions cannot be ex [fa pcla led 10 the real I i ret irne of polymers using conventional kinetics, For such cases. expcrirnernal acceleration is a necessity The deviations in the artificially accelerated and natural weuthering trial results are generally due to either bimolecular reactions between intermediate species. the concentrations of such in real-lime conditions are 100 low to interact. or to diffusion processes or reactants that are slower in ucceleruied conditions,

G iven I he lifetime evaluation I d' plil~lie st udy cond uctcd in ihe near-equatorial reg: on, the rul I owi Ilg concl usions huve been d ra \ n:

A weathering trial in nat ural weather is extremely necessary to obta in real-time performance data of stubilizcd plavi ics products, For lifetime evaluation of new plus! ic Iorm lila 1 ions na t II 1',11 weu ihering t riuls sho u ILl be cond ucted in 1 he well 1 hCIin which they will be used.

Mu thcm.u ic.rl modeling to1 represent independent v;It'i;lhk~ ur percentage dOllgaliol1 ;Il break. tensile ~trcllt!th, c arbonyl grnv v th, and prrccntugc cryxta llinit y ill tcrmx IIf dependent variu hlcs. including :ll'er;lge munt hly LlV radiation. L-UI1lLl-

I,ll ivc 11)I;iI .. ul.tr r.uli.u ion. ;11'l'I'ai!C IIlt;11 ,nl;lr r.u.lia tiun. nnd <l1L'1',I)!L' 11111111111;,

722

Hamid and Hussain

temperature, can be developed using regression techniques, Models developed for mechanical properties were more dependent on the UV portion or total solar radiation: carbonyl development was synergistically affected by UV and total solar rudiarion The percentage crystallinity was affected by cumulative monthly UV radiation, total solar radiation, and average monthly temperature, Other weather parameters playa less significant role in the weather-induced degradation of LLDPE.

The results of lifetime studies conducted in LOPE films 'how that data obtained from artificially accelerated weathering trials can be correlated with the nat ural \.\ ea thering trial data using parabol ic models Ior tensile strength and percentage elongation at break, The acceleration factor for accelerated weathering is about three times that of natural weathering trials (i.e.. 5,000 h of accelerated weathering is equivalent to 14,000 h of natural weathering),

Studies conducted on HALS-stabilized LOPE greenhouse film weathered on real greenhouses led to development of two models based for tensile strength and percentage elongation <It break as a function of exposure lime in months, The correla tions were good enough to serve the engineering ca kula ricns. Furthermore, the greenhouse film exposed on real greenhouse versus films exposed on aluminum racks suffered more. The reasons attributed for hizher degradation

--... - .....

011 the real greenhouse includes partial prevention of this dissipation of thermal energy-spectral emissions with wavelengths between 7-14 tIm-from plants and soil. and from film during night hours can influence the degradative reactions, Moreover. adverse effects of sulfur- and halogen-based pesticides on the H.-\LS

stabilizers can accelerate the degradation reactions in the films, .

PVC pipes stabilized with lead stabilizer showed faster degradation and lower lifetime for pipes exposed at Dhahran, Saudi Arabia compared with Florida. A service lifetime of about !2 months for Dhahran and 16-rrionrhs for Florida was obtained through natural weathering trial. A downward (rend of Tg, development of carbonyl groups, and a drop in mechanical properties are indicative of the dehydrochlorination and oxidation reactions, Dehydrochlorination reactions caused a change in color from white to light br wn owing to formation of polyene seq ueuces Longer exposure will ullow phorcoxida [ion and cross-linking to domina te in the PVC matrix. The pigment titanium dioxide strongly absorbs below 420 nrn, rhus it inhibits radical formation and .ubsequent phorooxiduriun. Pipes designed Ior ~l longer lifetime for near-eq uator region will need :1 higher level or Ii ut ni urn di xxide. together with other UY stabilizers.

ACKNOWLEDGMENTS

Th .... authors wish to ack now lodge the support 01' the Center Ior Rclirung "IlU PL'U-"dlo.:J1ll1:als or King Fahd Univcrsitv 01' Petroleum I{r l iucruls in couducting thl' t'L':>l'an.:1! work for' the f(m.:g:oillg ~Ilidle:;, Til' a ut hurs express th c ir th.inkx III 1\_ 1\\.11",)ul- for typing lhis work, Alirn Rizvi r,lf :lssist:lllCe in t 110.: cxpcrimcruul parts 1'1' thl' research work, and .I, H, Kh:11l I'ul' technical support ill the various research st tid il's,

lifetime Prediction of Plastics

723

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