Document mqMzq8dqw9xoLyYVxGzOqGkq4
AR22c -- 1315
`Spreading of Aqueous Solutions of a Mixture of Fluoro- and Hydrocarbon
Surfactants on Liquid Hydrocarbon Substrates'
ntReh Dpib, cGmyoCopii Now Tork 0507 ReedFury 17, 198: stldy 0.1906
Jlhhvcevpetsritmedaei rietnirniaa irsoofsognA vninoosntreofmcat tionsdt4mc) f p T rt eo t ofr ero oepn
AlthoughmanyRsotupduieshav be reported {f6inosmont)hoefhtihgeh soruorcuarbaocnivuiayet(aonwissuartftahcee
o(n1-t3h)e,sstudries aon tpdhuereshipreasdninogngopfusroolhutifionss, Sloow slurofacne teensrioan,nco(u1p5l-e3d0wditvhn/teheml.owThini.
G10 beoscaerceddespeite iempnorotannt i4n-du8sriaaplpaeps. _ sturbascriatepinstoernfac(e1,-a3llyonw/setmheyAtFFhFlsoiluotionn,
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on he fu suf provides aon clneiyfost mThee prhacticaeltwmeeofttehfoemwowsenlbloknnoawnnd
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Tar"neAsFtTngrexneeeraglluy Acointnaign emiRxetuernees ooff hhye. 8Ttenolcldoaufnsdtsheerofsmasunundaiicnanmotfset(ea10f)n.ondtawmeeennt the
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ctt e 60 Cats sd ute ce cSiolntydroeesrof chhetaandrcnbme proorpeerryady
fernittehrse
a fiecriemnitn(e1)PededfionnetdhaesFark oot.
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emo
Saavedra (reading ofuid 3000),
[1]
SabcnadisaeAtrseimianla(o6nnahipepapacr1abtdehahKee.lfNdsice0oscosn
Whedr ahndd. y epetheea .faacned evenihmi:n RF2h1e sPrATiEEES 0oaoffoccoosmmmmberedcrrial nadndexcopfeerl
bSfpoaontniaislancoonussisopnrabdeitnweweinlotchceurwhoenASUIsS
iLhneSsoarcaadabbilsteooff varviaoriuosus mmiixsttuoosrffhebyys Keene and heptane n oi Sad only
voolmvTeheesn.sicueiatdsntsaastpbesecptrseoafdifsapeono5tansoos"l8y P(5C, 4jojPi0o3ns70bSbeteweLnen tioherempaspetroednadaaeblrileintyneasndtdedth.e .
240 Inthe catoefpusre AsO AE i. he satin ts of seven soe
Of spreading has been fh 10 be PIOPOT- omg of FC-129, 3 commercial fluorocarbon
plhteicaeotendiealndt.oittnhobbgeoeswap4ueraeiranddtiohnioegnnso,prfeK1ahdmDaietnsdsgaiesmsp)ueerniadscoennxtt LL sL urCfaCctaL nte , eanvdoearn.(miiRTxAht(eGuryC)eTtaoAnfdBapsrebrefellcuomiehreovaedme-
uthand mercial nionnsd aoof he {Leven th resin te and oe
oidSuhefrepsleauscnttdaeaesnc)acnetSnoomRerMbtcoIolGsOnscd.teeomsmtoiirhoctmonyhcaeendctortaopteiioadnt the expanding merce nd thre
LC reading coeficient. rTheya, hnowsevecro,ndciednnto:t 17pS1i 00we he ivedies d he spreing
:
ShhaosuernlespopnilhrtehmsotsienFgoieohendThlke
$088 solutionsof8 commcrci ares ty dir
time dependenceof the spreading coeficient yu qaouiative relations between the rate of
duc to the dynamic responseofthe surfactant oreong"ang the experimentalparameters
molecules 10 the expanding interfaces can. in 1 1yed in the spreading. such a thespread-
theory, be expressed as
ing coefficient, dynamic surface tension, and
{"ThoseamSre tethiemdrcepseenoddfenmucateucaalwnlsslblolibleywbB de. 0quatnheti )sorf tthe sapnrt deadhiengnuairde "wtaapancegd
in Innaactl,heeGnisdlprren "eathdiansglagHpseunoddfaisnpnrdgeaatdhniendsgthsuuecbhor5c.0 lcmoaedsnisncegmn,m t oofurtd eexhaeprceeore nEtdxsopannvssiooofnodofnttihhe
CreosNmpeoonnrdiainntgryaslpdr(eea1fd)itnagnndcdoLeeiolndaorEd(s1a1)NdvBreeetn csoesostpepsuofbSareusin Fuk io he ur :
if(6ag1c)itiaon dstuhtirhoesnrusioosnmodnprotshceasrbrbwcoaindnuindthofee iur
exaretnasTaL
foWfrroomomadimohanenaapdolisnt(5u)ofipnvvieerwsotfeoefdeslsheepviarsppoeroreaaatddinio.nng csuormTfmhaeceriacnmitiaslsotAsdPFionfchoiosnrtcyeannwdishyCdk2in0co6aw8rnb,5o5n
ropes of some commerol ATES 80 "Th wale manoiscres by 3M. Souions
a3
SPREADING OF SURFACTANTS ON SUISTRATES
1
=
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+ dveetBnircidcedelewshhceerrieepxip(oenr,oimfetnhtealapppraorcaetduusrehawsabseans
5
=
ftoolmleowtse.r Tvahs sreetcoorndear oifhmeebaIsRe. s10percetardotphhe
absorbance at the wavelength comesponding
:ra.
S0"tsTheheeqCIu-RHivsatsreatdcjhu(s~te2d9t5o0rcema"d)2o6f1t0haebssourb--
:
we b2a7n5cecwmithopaennemaprteya.teTstheltes(t6cclml cwaasmehre,n
i. 1. Sechevmatirc dCagCRofuelsTpC o:tVA, v5.i larbetsdoarwbniactnhcee1woafs05a.ofrsT.uhrbisastr1syahtcderubasnatnectdehetverueeladiconargn.
`Totee aiotNGr.smoWnhgtFeS. (460 5.5 roenspdosndtso0a3ssurface reaof he aqueouslm.
ofthis conceinaannritf rcaawtaete,Were adroo"rpThwfeisteeesttshpraroeuagdhaingnseoelTduhltieeo(nev2a2a6s)dthteortahpepplsiuaerd-
sutsaetdesi,nmthie ssproetafdirngpeteaxspneeriamnednYtsIOANsKAuNbE nyaycoatin hteheacpobntreofnheth1e 0 coelfhie spueclhe8
1is5ne5nvacdraiytonu/sacmvraonaltgue2me5of)psr.uorpMfoarctieioLnexsniowtoenrsue (eu2prs4iea5dene10. 01oandfotohrmen,surAftsactheoejutmsotamleolonwntedtihaecromsploentpeedroroplfhevety
and hexanewereao used 0cutend Rhee TCL imasdrecording on thIRveas
t0hes1ur8fadcyentjeenms)io.nrangeof thesubstrate (198 Methods
uSworauusnsrelacdyocntoaonrtf.oaltTlhfeheldeoswbusybroslaiutrtsaiyootrfnia0nw.gsae1s7cpamoupmymppmpllii,eentdue,nlctyoiwnlhctiitocnh.h.e
Determination of sreading rate. wTaheneasp <c1aogdewwiahstehveisdpernecaeddfbiym.ihTehiesdcucotmipoenteofctohve
0me adienromfiao nne ItRhespserccatardoiehgotsompeteer.cqcuiopprnpeessd b53orcaalnonsc.aete1o0n2t6h0 aFbsoirbangcheowcuslsemrthee e50-%
coaenpllot(rhTeCc).ocnTocnhetenitenrxuapoteuirsoinmomeofnntitathlorthieyncdghrnboicyqaurIeiRb.sobnoafssutebhd.e CC3oXvdPeEr,aRgMecEplNosbinatttowohdniecihnceuwravtsehewusaaevsdecrtoahngrseotursguphcroteueatddtibhnyeg
-
rte. Sine tmheeomvaaopoonrlcoancaenatsiioenn oifn hthee Mfesisinmg t-hraccboofsthevosuaebrst.arbfeu,nactGilnoansscofitenhse
Shiaiuocrobauasneie mcraeneadbsadursifeeatdcleiyotffhtrh1oempsruohpbeesttrsceeca,orrtedhe,er OShfeExYaRanSer)ohuwaserdeihauemseddteertospcowrftietshhhetassevhueebriagtlhatHm(s-cigccholtonl--y
TomtoGesermin th area spreading ete. A EcTlSl. Trh saAurl:usofitnhgewcyacsloehneexarne nintshidee tshte.
sp
essa iE Ws then completely covered with the
(CAoSmTm1a18n130).mamta Le Padus SaPcrecacdovlermaget,hearenbdytcnrcoemeaasfptroancidtiinnogngaalbseurr.-
:
2H
2
mo
Fi. 2.Tp dermiafaeieoensnie for50%coreig) 0 tes
abbainacienewdasis rsehado.wnThien Fcial.ib3r.aTtihoen acbusrovrebatnhcues viamleunetsofo0.5d6etwearsmiunseedthtehrSoOu%ghcoouvtertahgee.expTehre. cohnooiucreporefltihmein5a0r%y ocbosveerrvaagteiownassthmatadupe1o hbaisesd coonvemrsagteotfhtehseprseuabdsitnrgatwe.as reasonably radial conIdntihtiiosnstoufdycthonssapnrteadaipnpglsipcaeteidonundoefrtthhee Spreading liquid i definead
Ie
ab RY gooof 2- A\ | o
dog i--som ni mgeosion cpuofdo toecdeeacoif
xis A/2 0 Va 1378teens. [3] sHesre theistitmhee arveeqruaigreedarfcoarlhsperc0ad%ingSsuprofccde, sctorvaetreasguer,faacnedinA hiettheestocpeeln(a27r.5 ocfmt)he ub. surTfhaceedceotveerrmaignea(tiiso)notfhetrfhorteicmonfsotithuteesSt0h%e majMoeraspuorrteimoennotftohfeeeixpberriimuenmtsaonfhdidsasumde. ssptrfeaacdeintgesnsoilountsi.onTshaendsutrhfeacseubtsernastieosnswoefretahlel mTehaesiunrierdfuascianlg ttehnesiWoinlslbeeitmwyeepnlattehtsepcrhenaidqiuneg.. sthoeluriionngsamentdhtohde.subTshteratpersewseernecemoefasthuereubndy. sauvbositdraabtleemsaprdeeadthfemWsikoenltmhye spulraftaecemeotfhtohde unsuitable fo the interfacial tension mea.
solDuytinoanmsiwcerseurdfeatceertmeinnseidonussionfgtthhe sdpyrenaadmiincg datroorp w(e1i2gh.t method developed in our labosprAeladliengmsepaeseudrweemeenpteirntcorhmiendgath2os5eoCfthe
c 28
SPREADING OF SURFACTANTS ON SUBSTRATES
10
ResuLTS AND DiscusSioN wtahsosfooufntdhe0sboewcsopnrseiadderianbglcyaslees.s Sroimael ptahratns
me"nTthoeeifetxhpseersiopmreenatdsailnpgreessepuedsc3osf.thefuFnconnmcetaisounreoo:ff o46f55t0hseObsospeorrenvaeddionftghtaihtemthhisghhsopswrueeradfda"icnneggteesnprseiieondngo"fsuItthse
gBso chic of the concentrations of the AstrEateMs (yI,n>a2n3d adypnpjaemr)toderveiaacthes fpolmanth:e
A ohoceof the conceantratiaons Of56 inudseptehndesntpofrheesspaeaeddebieecnonmogens opfratschticaully
LsOh) neloaera PutesedOe BI. ahatvsi.orThweilcabuesfoufthtehris eixmaimtiinngedsplraetaedrinign
t tespreat dingspec prs CONMECHon with the. discussion of the dy.
in Fi. sr average ofa Ist thre ea. mie WT enon ccospreading
sureThemvereticnalbt arss ont.he data points PPefomena (Fig.
ininddhiieceatesrtehaetsitnagndeardd deavipatpioen aofbrethe
mean
nar
[hePAlplEitahiNTceaSeustr5egiSoingIohnRtthiEen6s%riysou lutis olnlcnainnhge
Rea las coon snes function of the substrate surface tension, vo. TA=kit mah 1)
`ctaahneudses6cd%atbtseyorluottfhieotnh.meadrTahtkaeesdpe raoergeuai lrbaeerln ioitbeisveteesdrvs ie0ndtobhnee SS[2i]ynca(en1dn=o[42]s,2)pra=enadd0ionintgctoahcnebcuaerssssuh(moFpxwtnio=nfr0t)ohmawtEhatesh.ne cSopnrceeandtirnagtpeadtsteornoonf tohne hfgmh-ssuorfstceh.stheingiholny oSfurifamcee tdeunesi1onothfetlhe sauobfsmtcurattukealisnodleupbelntdyent Ssupbrsetardatiensg.(Thhieghspsrperaedaidnigngpcaocftioctifetnehtesms) Gsmts. htheatime Tame of this spreading experimen,
|so
os
1
od
1
Fc. 4. Ava edo ee 5.3 clon fe si cinof bs
144
mo
xSU
h|
hET0Cc.HC550..sSSsumocufitthneemoafchieeoa2ds3c8nla reiiooofnf3napsictynceuit wss crocmelntisoshon3ne omuroesonnReosifn
Famki(ra-[+nrlantl=t=Ol)) =kira= Zr =
(fac=ial toenfsitohnestw(ovuvea)luessn.d the sum (Ty Equation [5] showsthat he average spread
a Slim 0 Tohfethcexspiictoenxpr(1ession
oinf
15) tthheestihmoevdeecpOeUnUdNeOnNcSe
iSn sipued(1is= d2i)rstpyrepardoiponrgtcioosnaflcetontth.eHeqouiw. evir,ditealnso cofnutnacitnisona opfarhaemesutref,acktoa,ntWhciocnh
tiiselrifyanctiefanledcaetsdpse0cbtsu,tintTdhhieceardteeyfnonraoemtittchhees(umnurtsuuaialonaSdn0ii1snn0 gSseeemnmrcseetoisfoetnh.eertshprvteeabtdyienmgeapnthioeinaotmnegne ahoen the eenodny:.
sftiantiitce ivamlueess.hoTuhled rbeesutlatkseonf3slicneqaurilrebgrrieosmsioonr analyses ofthespreadingspeeddat ae SUM:
Io1txtpheisaipmost,acrfseisnsiructive 10 cxamine ovthe dynamic surface behavoifohre sur.
amarritzheedmienaTsaubrleed 1s.uArflascei(nvc)luadendditnheTaibnle1es s{cracdvintgepnheuniomsencso.mFisgomre54ssshsoaawsnasen
(ilssnttai)onsutrhfacseum(s1.0o0f) tahnedtiinmtee-rdaecipaelndtennt
ResiinnARaEegiorn Ans
sfiaocnasnt(1pl4ov)ieodfatswoa sfoulnucttiioonnsooffatgiimve.enTswuo. concentrations, C, and C;, above he critical
Temi micelle concentration are compared, When
S w1v 0u m w0S 6 G1u93n M WSI0mE6d0D+27 reftahecohsenusmtohpeflstacheeud otfnwotchte eseuorfenfatcohensfosasuifs8busiorsifutbanoscett(ravsnan0tt)e *
o3_00Mo C2o4 1m2a Sin9ig4ss3ii0n theerewadinng cocnoceennttbebceocmoemsesppoosties,ie,
iSuenfehmnd re iccqedn tice (6 vb hSpereaaudainignmaeknteopflahcies. sTphoentiamneeourseqrueiraeddifnogr
atape 17. 3 3
SPREADING OF SURFACTANTS 0% SUBSTRATES
1s
cWioetnlidloiintnigoncs,toahirneferod,oss,pporenbatedacinongcm.oessOentseesir(ntnieg<cowonin-l. aridilgchasyuurisanc-emnsteideoenpoeFsnusdbpsertnerataSdtiepnc5gksdipnnreccoioln
Cfoaecotcamnxtpmamnouinvnligeitnshetrrpaocmsetbheecobnmleksosnftstoheenu:fro FinglTbh.eehapvrivoiroousbyrmeantoifohneed4isiolnoiosnpr(e1a.d
io n ptehcr teexdtahmpsn orsgeivdee aatFnssae.h5d2mtohCussant1i.o9n
ofcthaen hnoowrtxcrxepaadnayiuonndrsood on he bu Both hr 54 and 35 csentally prs
dmeeptstqeucikrmhatprbostdhicntcioonrehasv.e hTen 1ahratmEcheealanydthdeimceaaome lnatanssis.i3bbeeeaenn
t{epheeirnsamrriesssnpeeacutt,hbetehbrohefiiitmivproerertrtneaStnportfespardaairainagmneestteearenldtduhtaniotoendnersa- t1S0hecumosmpeiprea(art1de4i)n(sgtht8gsp.pgee(end3i.(Cn7To)hnecyisncaaintco vieorosnnelybt reeloatdnetd
fruaaeintiobtfceanaiouornnedodfyctniheaoSnmTi(RRcS,TaRau)n.rdmaItsnhicteoeinrcaidmarn.,. dthiuTeadlbeo|mSshhooewInssWphrSHteEadhieSngunsEux0pc(ePresrts-si0onssprros.f
ShlFoieglunarteiow5nililltbehscthsetasbprrheeaeddiyng emofceas. wSiohenels.ciThuheitmhirmteafscualrcetenvsaainoldnuseeoffswtaehco6esndof
COnFdothirnuwcioinanhgii,gaehnRi2S2oT(Rn,,hataGsrvhoiosorpmoefrosuipteoisou.nm S3%-,hhs1anbdeoe.n1o%nutdse.dithohanraFwaernCe m2erasoma0rperde6gc.sAai1
TvShneiessspprreaasadicnaganerb.eesasepofdint0gh Gssuartfsiacoen ttoehnnslsiouan.s uhocmeltha1vatheer3,CCcTMhu.CeraeCfMO(C1no5ws(shv/odaweyleThmoenee.d
(ShS4he5eo+rS+rpn7o(%n)ia.a1nAcs)soutshoeApssmeaurscfedacioenngteenncsssoinuonnrdoiyfnitotehnosweios4uunbd-thfSnotruoedsyaalnml1ethrSeoevseolmtuhtioCnsHSIusuCeed4nsfdorasnthhdoewmspieresardilang
CSShhroewtcn hinteFerenao4nciTonhfgetiheentecsrutobetscesreen,shtapwAeithhaehande hpeS coonenh1i i3erpapaireoae nmcedteer10kpybeienaEntogfedhd]eefroeanptreencsedngeyt.s
vTPiaigehrrwibwle,hyeonhndtoetwhsevablbeectohrmtae.ecaepcrheosopetnhssignprtley.s nsmaemeicddpseandFcinsc.asn2donmfdhre fSshpcrCelaodeinnogscnetsotr5he1e
c5oPi2reptenihdateod2unistnl7gyo4fdrmettsheFecegwsnidluSibbnb.geiOcrpoomrsSteiuuophnrcasocfatitathnleeyocsumrdvtbeehs.,e. d(SEeoqp.Fnen[i2dh]ea)ngtmcacepuyroobefrneserhseenepelahahcreeedeabrayaatndstdhieocfcohnreceecanetlyraentei::onn
CsSioisvnenthheegpfoalaesnmrealealucmoytmpphaersetddmnvgirnceohneeddommeTso Sacurkfacocesfenscinuoinaomlneamsmueersesimrencnmtfseo,rtBt,heewendygonrloayrmtihe
SreaTon arthesiusrrcieinapn.ttoliutiioenrehsaitnS1quaabtrs
ifhgsnpreahdeindgypnhaemniocmesnwa.ce1hrsctiomnedpeeet hey to adsorption esat ihsoon'
EP ou es bece1eTdER0On Sub Te SA kt (es
a8
I"
mo
he
A EE --n ------------
creirneenalhsgicartpoionnisofbdoror oimnsbm = 1(33C%3, dKYofoRy sKe R 1583onpdtsBe
[ iopetrusr han ta e sisorp piobn t eof DuArohrEA46A 1 HIoweri wonAA E5biS dtt
reno acl pentont of ree ren3 tand costa me.
ibothEro6 ta s mia o ioes mrg2, 0oh
ja rToovnpSotgaadeivaesleyivmyas 4. rt Eooab of ueoendoo oereSt dRo Rs THrs
oat
rare as wi mms mis sions ss ach
bnesbnshoewn iug f3 Boe renrmythe
i ohowig cae shown1.. Tfardeatdependence oF ky = 000070 .
WO=rle= DY,
61 Itisinteresting tocompareourexperimental
where ky = RTUTTMF/(DK)'"C,. Here I* is resultswith those of Joosand Van Hunsel (8).
rAneciareroett n ityomI eEeieF6i t7he 20e4I 3emelodt et w Vue1sra sn e--di--m cdoo--neomtt seeemi .Tamdans would shaso traiw ght linewiththeinversely
Vi=di=d KS",
1
29
SPREADING OF SURFACTANTS ON SUBSTRATES
ww
57
ha
7. DysonGame iFi. plots 8 cio ofcsofcme
`oachfiotsnhsectsxapunrbtesscsto.on bnIencttoemtamehsseidofenntshiietaynranagdspvriescaodsiintgy woCeflolPpFnrAesdCiicatnhedddeebfCyaTrcEtAqti.Bhan(t7oE)ng,a.wbh7een)raeeansieatwmayisxtvunaroleti.
C I.
ony or pure liquids it s suprising het the
m"eTrheicsaalmceonramtVaenaet=xpdwraeastasdis=otn,Ke'esxtcerpt bfyoaCr tohetcn[a8u] efOqfourtamhteeiroxnseuwrdfaascstaalynstomsp,yrsothveomew.devtFeoorr,betthhveeaylsiodptrfeaoairdnitenhdge
aa nd Sci. nothtei sudy ofthe spreadoifnoigl apn oempniorfiecialmneex1tpr5esnsoiton s4hosweiqnugitrheadtbtyheheex--
or0ca0dsinagndofVaanFHCu.n1s2e9lsdeomuoinosntroantedCCthlatwtahse Oa0rg.yr4.e2e5bm)ue.tntTrbhateehtyewrceceolmotseheeloytroyaa--bn1date(xaepcdteuraitlmheevnatilu1se
o i
ofe thoLeniatincmtea.th.Iaf)otnthheeesspmerseeatddhienpgeecmnopdciefrniiccciyaolnoftetxdhpeeopaneenrndats
be stphreaapdrinegsiraotnefoV, (E,q.wo[u8]l)dwboeucldomveandiesnhiaanld
For
J
+ThtmoenEetq. a[gn5]od.odthesgtrhceomreyn,tEbqet7w)e,eninththeei cexapeero:f
jFEET TET
rFiCn1s2e9d/CsCurliaapcpaenatrsatoadeiaicvteltyhahtigthhiscon Conon (05% actives) may indecd have 8
oFob. &CCoonmemmrtiondeenminsoftheesroocni. M(hLAEEOCFSac anvd eetasels tpenesionoe
Trae ck oan:
Surfcrettenc sion lh iqauidtt onr3ehi1gh surfsatcerne
30
1s
c mo
(sFiiogn 5sbu)bstrate, TFulion (1
CCl, which
3s aeady discuss describes ou exper.
AcksoWLEDGNENT] TH sri bok to GaGyCorpoor
d`meemnotanlstcroantceeintnrtahtiisosntuddeyp,efnrdoemntcheedayrcnsa,miacs "On PUbish is paper.
pC`arudoespsoerrpalttyiotunhnedbeemrhsaetvoiroodranoftatenhrdemtsshuoerfrfteahfcoteradenytcnamanomliebc-e |
REFERENCES
2 TinORSALE Kcmao.
Suolruftcioenand inefacil aofShe DoRAnNG 2 Fo C7d Chere8eW0Cr3..S 150t
vasTtliy disffseorenitnterxepsetriinmgen1t0alncooenditthaitondsewspieted,3 in Joos and Van Humes study and in our +
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