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