MAN`ŁD(a \łDj|^\ induction time and oxidation induction temperature
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MAN`ŁD(a \łDj|^\ induction time and oxidation induction temperature
MAN'ŁD(a \łDj|^\ ' R]TTInj,cĄMU'' ^''orTFp': Interlaboratory test on polymers: determination of oxidation induction time and oxidation induction temperature by differential scanning calorimetry that d'e d.EminatiÓn dańon ińdudjon time (o]T) kśsindiĆafu dIoJT involv.s a hiEh dcgrcc ol nnĆdhińty in r$Pe.t iol low ol7 YrIuś 'Thh wolld sĆń to exteńely cr'ii.al siBt fi.ańe lor .l!a Fcdicljons of Polyol€fin Parh Dcte!ńinDg oxidatiÓn indu.6on rńPgafur.(olr)oub th dore be a valuable'llcrni 6vc lo! lss śibilizcdpolyolcliN (low olT 1tlu4) in Falhcular HowNcr' o]l ńssutmmr chally indicates thai ihe abjljty t, dśhnguish bcn'ccn differenr sanpls dcd.is6 drrsticalrv as oITr dab in.rasc ccnenlly, thc Nalułted data can b. Jsed lo r*ińate th! restlb oI iFhouse and eYtłnal o'Tlor memutemenb and th.' .ońP ibiliry Thś repo should theEforc supPo day tonay wolk iń analytici l l'bore ioics whete ox idaiio n ińduchon valud areneaŚ!red by Dsc I<ey sÓd3: ińiellaboEto'-v tc Polycthylcnc' oxidaiion ńduchon hme, oxi_ ' śi.al valuation oI ńcasurcmenb, differen_ li\i cońtol PurPGes {olk or liictimc an inbrlabotbry te66 on (o]T) oldaho. indudion tlne ańd oxidation Edu.hon icnp.nhtrc (onr), organized by EMPA, st callcn, irc Ptesenled. IMPA sl callcn org'nizs lhesc kśson polymeriĆ nabńals cvgy lvo ycaE The Pałi.ipanh ale usually indusbbl lłboratoris a shfutE lhai ieś,rsearlr and develop Polyńgi. ńit* rńls' The presented intrlahoratory tst took Pla.c m 993 and 1ó in 200ą mainly froń lndusty rnd rese .h o]T ańd olr ol foul diffcrni 8rads of Polyethylene by di{ferendal *annjn8 Glo.mcĘ (Dsc)' ]']F n€aŚLtd data wde ollcdcd by EMPA and aMlvzed uŚing a ro bu*sbbtical meihod nl. Repparability and reproduci bilityd a wcrc ofsp€.ialinbresL In thń the resulh of b) thc.juipmenrand rhcanalyhcl iBbumcnh, thc c.luiPneni łnd lhe iBbU d th. olihration oi .Ifrd dldng rh. br Fro.c. i.nperafure, h!ńldjN' ljght' pol d) the cnYironn€ntal durĆ, iŻ jnflu.|c of Thc factoB mrnhon.d ihove arp n hcm itrvd" sfiibed by Ćakulahn8 the main chłeblisti. ińt!ńb.. nloly lesulb, the iobJn śandżld sŻ tfactoN a), b), c) and d)ar.idcnii..1_repea! 'bility .onditiont rnd thc rcbus aBility ofEpIodu.ibility śnIfadoĘ a), b),c).n,l d) are vłied reprodu.ibir y .ond irions I. Thesoure atut signili -.a..c ol lhes€ ańd orhc! śatiśi.al Irbontory teŚtś arc dcfin.d in Fi8' ] ' on. lsinE rhe co(c linjb.Th€sevallĆŚaie dcfin.d a3 follows r= R.Pealabili9 lińit (l =2 B.5l):Thclin'ekŚ ŚPondińg Mct inpo ani IadÓn that Ploduc dĆviihons b€_ than oI €qual 60 thc absoluic dil1em rcsulh obbined und rcPealłbilirv expeded io bc wrhi n r probability o f 9s r, =R.Prcdu.ibilitylinil (R =2 3 śi):Thcvaluc -R ks u'an or cqual io the absolrte di E* lsllts obiain.d lndł lePloducibiljty condiiions ł ht'b lth! r&ribqh{h e fur khi nay b€ exPcdld io be within a Pbbability of 95 1 Final]y,lheratiÓn/'isa ń.asu!cof th.!uJliiyolth. ńeasurnenł p.lońance o' thc p + tl'gr.,u * I g I .---t Fis.1. carcklbl belw\ rlislnd lłlE k,,,l d sR) inbdaborabw teŚ itlelt For -8ood" aid tliable inter labÓntÓry lesb the tńo should b. wthin a Bngc ol about 2-3. rfnlr>4 rhas ro b!.sumed, rhaibsid* thc abovc mcnłjoncd p.nnd6s i) d) Óther palam. Ers ,nlru.n.c thc rcsulrs si8niri.. *andard deviaiion of repmdu.ibility G^) k ł1ńoł .n tircly .ontollPd by a major.ontib fined interlabrralÓry t*tÓndirioN' In this PrcsenbtioĘ not ońly rhe Wcllc$ablishcd jńd PoPuhr o]Tme ureńe 5dts.u$.d butthcdJ. cially foI o]T m.aslteńelr a Ic\! and ds łc avlil' iblcoablc1)'Thesequcn.eof rstand diz.do]Tr€ł suFmeŃ UsinE psc ncihod amrtlin8 io EN 723 is oJl lin€d in Fi8' 2' A srmPle of ihe Polymer (apProainatly 15 ng) is Placd in a clean aluminum Pan. AfĘr Posi , plishc n.icrials b h€ ab izcd to . grciter or l€sł exi€ni a8aimt oxidahon and cnvilonncntłl influen.€s' A simp]. ńerhod b ch(* ihe efiicim.y of th lizjngsyś.mnsed, is lo delemjn€ F.rabre of rhc ńol. nave EsPeciłlly lor Polyolefins, oJTand/o! orT' ńca. quality .onhol pu! Poses as a quick sdeenin8 ń.rhod b ch{k ihc acti vity of lh. Us.d *abiljzłion syscń Thc oIT measuremgnt isnośPoFUlarln lhiscasc. Many puhli.ariÓns deal $nh th[ quc ion l2l r€nt parańetct on thc Prc.ision b..n i nvestisa tcd ln dehil13, ala tiÓn of lJchmc Prediction 1or Polyol.fin t5] ln '!be5 frucn.ing param.hn whi.h nas b bc ncnrioncd ir thk connediÓn at. sańple weiFht, lmpuritis kala_ lyiical dfed)' sańPle slrfa.c and shrpc, nushing Eas and flux' heating.atc (orÓand isoth€rmal tenpła ture (oJ, To mi.imlzc thcsc ciicds th€ te* prÓ giamńe wasa.curately pPsciibed for all lh€ Parńci FiŚ' 2 s.hlndi d4ml Płi ] bęfud1 bBt k 1il"tiar Ó| olr B ll1[ flru) atl b hńn, ń dr *l2ł a| Ifu n a| 'r rńptł;oń|dplanrJion ox!8 tiÓning the un.overed sańPlc Pan toscthcr with an cńPty lcfcren.e Pan in a rllbrated Dsc-ovcn' a |iło. gen atmosphł. i5 e*ablEhcd in ihc mełsu $ c.ll' Thcn' thc shple and the .cfcrcnc arc hPłted npidly (at Icaś = 20 K/ńin) to ihc tcnPcnl v ue js tÓ be dcbmin€'l' wnen iI€ Golhmal ś.Pof 3 ł in Fig' 2) the abcPhcle is swikhed to oxygcn ind lhc DSC-ovcn is hcld at thc same rempeniurc until an cxothmmal signal (ondahon). b€rc.%nized fteon set of this oxidliion si8nłl .orresp Fis 3 klm n dksnh Óf lh. dlkń,|ińli\ r| a]r' ń ltt dśdknpnt!rt o1annp*ł;al (dpl Rli," _ sc tkl) iin. as stard lndero nNesĄ. or?'i5 dcbmlncd ó lh ata dcfiMd rct Połohic 6y Dfi!4 {l fush8 Flcqucndy howNer, ilre oxjdation sigMl is less.i Prcsed thal indi.abd in FĘ 2'ń tjon of ł clear]y d€Iined onset trńPerarlle difńolt FiŃin8 a suitŃl€ measurhg i.np.nfut. rhe iso' themal phase oIt€n 66$ I!*her diffi.ukic'o!wth oJT measuremenh x rhe @ńPerable n lm low iherc js a subslańtjal indease in the duntion of lhe measureńenl d if ih. bńPłafore śioo high oxidłtion takes Pla.. inmediat.ly aIie' lh. inhoduclion oI oxygen' l'h. oĄset Enperabrc ot rhc dermpcition signal (it cao no mosramm. urc onft or thc uually nor clcally B pmsed i'r oIT neasu.cmmb (: k ne.Esary olT Poini in ihe the. d(ompGitiof is Frnrll , ro si\E dn ovF\ cw thc rsul6. signal as rhe onser 1ol tn. I < -.t'''] tine r: deEmińż A-j|ńń1 obvious, that ihc ol-r'method ned up th€ nssurcmenb and in lhc majotiry ÓI gives d.ar defincd onset poinh ca$ t Four ommer.jal grads of polyethylcnc wrh dilfcr. .nt hvck ol śabiliradon wgc cho for the olTlod them elials) tcst Gcc TabIe 3 lor cxact dś.liPtio| of ]1le mafutjłk wł. ŚĆhcr.d iń such i Ęy, thłt a boald nng€ of oJT Valus,suibblc k, Ędusbiłl aPpliĆahons, was ĆoveĘd (o'T Yalucs bcfuccn somg indlction lcmpgaforc (o]-a) is €valu atcd in accordan€ wilh Fig. 3 Thesanpl.isheatd upontinuouslvOr r0"c /nin) undd a p@ oxyscn (or .ir) sas flo The oxidation R$u16 0fo\daLon ndudion rine (orll The inletlabontoly les daia 01rhĆ o]T Valucs ir. s!ńmrizcd in Tabl.4' Frdń the d Pcsiblcbe ablisl rhat rhc rcp.abbilily łnd r.PloduĆi bility o1 thĆ orT valu6 dcPcnd on the oder of ma8ni fud. of the n.dian valu€s of ih. sanPlcs Tnc b Ćr thĆ o]T ńedian values' thc €rcatcr thc rclative values G' relahvg śnĘlative) ol lhe śandad dcvńhoŃ This conelfton bŃmcs dcalet if rhe daia of lhe actual ńg k* are conpared with dala froń olhet infurlaboraiory seen for the telalive rePfudlcibihy $andłd d.viatio| Gi relativ.) in palti.ulai Evcn a b rang. ÓI ]0 lo 20 ńin 5eń5 io b€ Ple the Śł valucs lisc significantly GclahYc rcPoducibility standard devi ioN 8reatel than ó0'r;l) Evaluiiions ol o]T values oI ih. sanPl€s with vcry low *abilizcr amount (orT bwd than ]5 ńin) m 8atded as oińcal' onc Poslbilty b sionorOITinth Gsc.ould lcńPsafuI. bc to in order to jnomse l: to i hnc rc8ion ibovc Re,ulrsoloxidation inductionr.nperiiurs (orT') n'_A blĆ ó' ń } ey dłżof thc ]abolJloł fo+ ' 'bh n.d froń Theshnd'rd dNjahons of 'h bc Table 6 secm to b.Icśonłblc 9ń a! oldm of mi8niiude as lhose Iabolatoly lcśs'wtere i.npenh'rc wcrc cvalu.t.d by mełB oi Dsc mssutem.nls Peraiur€ me*ltńenb, it i5 ló, 7l quie In th. casc oi tcm_ relatilc valucs G, rcktivc an,l sx rclahvc) sbnsly dc Płnd on rhc fumpcBhrc scale lsd FoI jNtancc, if a]r solute tenpeEturcs (Kclvin silc) arc uscd in ou! inrer d dcviihon Nould becońe smal lci Anolhel plopGal .ou ld bc lo dcfi'r c th c mcltins poini of wery mrorial as dre zerc poini of thc lcsPc.tivc ori measJremglł In this case the relativc ; ; i'tedabÓratory hsl, wc dc.idcd " hL.[Ń"Myb+p-6.-d bj hcrcforc' łll fu hff discusions ]d .omParisols of ielati!€ lcmperahm ł Po n rh. s. ańd sł r6ułs The lober rhe o]T valuą the u rsPondin8 to th€ .enli8rade sal€, tc.au{ it ń quitc sTM Frm rhe dab in Table 5, is r.nden.t what innaen.e rh. ol7 eslbśańtiauy Indr to comPrtisn ofolTmd EĘater oi' dła Tabl. 7 slnńanŻes rhe ńedńń !a viations G" śR)and rchhvcabndżrd dNi;tiÓns G' icla Tib lc 7 o[ lid o]i ńdbi 6fusi ldlddNbtbisG'reLtM'|5{ĘDtŃjldftbt lE sńPlcs and fuo oxidł rinE sŻ lclatjvc and s& telalive vahes o1oJT and orT'dab it can bc sen lhłi the dynaniĆ neaslrcn.ńr (o,7') n rclaicd b sĘniIi_ tivą sR relative) of rhe 1otl .antly sńaller rclahvc siandłd d slahc o/T method' It js buP for both cmes' i.. the Ępeal Jb'l'! nJndard.lsiiho' an.{reProdu.b'l'ly*andŹrd sPrcrrion,rhi orT' EEJnd \hvuld bc PreGrcd Addł'onJ]\ J]so l]re ęt śnon(rblc llEr loi oiT' m€a5liń abiliiy bcr{ccn individual sanp cnily wilh rising bmPrratlr.''fl1is coEelańon śshown dP ly in FiE 4' The fÓlr PE intllaboĘbry l6ts sim_ PIeŚ ar. Plottd hclc as o]T/o]T'dngnm with rhe m€ Fig 4)' Tl'Uś'lhc d frcrcnh ion be oĄtfi e\ <E r thc..scoilhco]/ !m l rcr ivc *rndrrd dcvnhoN impc + mal s]vc ih! ime ol'' l*i, t ,h," "lł],.gl .onhin a diffcrcnt anount or.iid .onbaśb thai, ii is pNsiblc t, distinsunh thc $mPlcs by way oI ihe oIT laluś(ordilraic axh) dcspit. high rclative *andard dcvńhons Finallv rhc ł /rmtio for boih nssu o,T ) fJ"l.od oll -^ple! i. d*e to rh. rc,lutrcd rd cxpectedra$eoI2 3Ginglcvahcsoln/rtłbulaicdin Tabb a and Tabl.6) Th. ncasu ng pcrformame ot all Palhopanb s€em kJ bc rathcr good a|d ihc reprcduĆi biriry limft n is turiinuen.cd by unknown and un.on dĘn valucs as r, ! valles łnd lhe leprodu.ibilin, *an_ dard deviationś Gn) a5 ud.giainry brE. ll cal be cl€arly se.n d'ar dre b rhc cxPoncnhal c indi.ateŚ what ĘFcatab it]' rd andaŁl dcvi'tjons and whit .om. sFondin8 limitŚnu*he bkcn lntoi(olniwhlnoxida ijon indu.tion lińc or tcmPcnlut Pc omcd aing D6c ncihod' Al a glinm, ih. l.poł sh ou ld drr.Idc providc suPport for day bnły wÓrk iń inłlyli.al lahÓratoncs wherc olT daia ar. measur.d The dab from lhis oJT inbrlabotatÓry te* dcńo| sb e d'at lhc dciernimtion ÓI thc tine sl'ows a sub .niialvarialiÓn lLeŚ' PŹ njcu lally lor vły low o,7 valu s H oc' onl], a tdddon of lh. EmPłłurc i f lhc FńlhłmJ] PhŃc lI < Żl0ucloli redudon ol thc o ńc6uńn3 d'anbei could ucrcasc thc diff.rPntiibility of sinilar sańPls. Thc hi8h valms ol repeabbility and iepbd!Ćibifuy andatd deliations al5o shos' thai thc sĘ fińńcc of oJT neasltnenb' .J wnh rcs.rd io qualit-v .onhl or liIetinĆ P!.di.tjons of polyoIclh pł s, i5 to bc vis.d tadEr d|tĘlly Pati.ularly 1o! vcly low oll valL'cs (polyohlins with low sbbiliŻe6 on.cnbalion) th€ dynamiĆ PrÓG olT valus ftis iinally leads ro an ovcrlap oI ihc cnol baE .onernińg abs.i$a (ovslappin! IPAion in tehp.lafure $cms lo be a EÓod altcrMlivc. But' ihc oli drta also show dcarly that diff.r.n vjdual s ń p lcs raPidly vhąr o/ valucs in_ 'l€.reas* The Pres.nt rcpo tProd!.jbilily ris.4' x, fłrn af on pI'uhtŚ k!,1tl,1 . ) o| ,h hW PE lń:: k! llPl.s unh lh! rt\pÓ ! )d d dfuirlirnś k 15 !nąlknll'', inń (funt tPl1nn drcBposftiol ol plaśicwith tule (dorcd rine in Fig.4), orT v 24o oc led to a mulative a.Óh tive surcd AcN1:łowLEDcMENTs Th. euthaauish b thonk: rr. M' wńd ńo hańkd tlt _ lalislt &|iŃft L nnd il lh. tzbbdalty Br dń yndućd th.l6ulb PrńEd Mpa&smd na uks uhitn suwlzn ńŻ 7o. -ml idt |furnćiĄw al br Ś wllk8 t ł mtdih |rd a| d rye ALL lhz pĘns l1us 1 Frtt,ła^b and 2aaa)' who P.: "Robu* StaHsridl Medb& h lntrlabe ńlory An'lyd.ar sbdi6" in "Rob!* shtisii.s, Dah Anary3iś, and cÓnpuler lŃtriw Methods" (ed' Lis.he. rdre Nores i! sbiiltic 009t spinss vłlłg,NewYÓrk1996,P'Tr 265' 2. Pauquct J' R', TÓdeh R V,Dr iofu ąnd ApplLclioG of ondJiiDn lndudjon TjmP lom h Qlality conholofPolyolehtr" 4Ż!9lnĘF nied.r H.), 3' nati@ar wire !. c,ble symPsium, 1993. wauius s'] /igfu. M.rŹ',l' oEh r99' 21r' 1o3. Materi.ls by Thernal AnalytiĆal T€.hniq!es", 5' 6' Geblei H': XlEtslorź 1939.79.9. AfÓlter 9, sónid M', wanp0ł Z s.nmid M', r''{Ólfu s', Rifu E'3. 2m1 236 Na ]0' ó05 A