Structural investigation of copolymerization reactions in restricted dimensions

190 Pages·2000·2.4 MB·English

by  Weerasekera, Gayanga, 1969-

STRUCTURALINVESTIRGEASTTIROINCOTFEDCODIPMOELNYSMIEORNISZATIONREACTIONSIN
By
GAYANGAWEERASEKERA
OAFDTIHSESOUEFNRITTVAHETERIRSOIENDTQPOYURCIOETRFSOEEFRMNLETOONEFRTDIPSDTHAFOIOLITRNOHSPTEOAHGPREHTRDIYAEADGLURFAEUTELEFOSIFCLLHMOEONLT
UNIVERSITYOFFLORIDA
2000
ThisdissaenrtdatHiaozneilsWdeeedricaasteekdertao,mfyorptahreeinrtsl,ovSeoamnadpasluappWoerte.rasekera
ACKNOWLEDGMENTS
mfoermhbiesrgIsuwioodfuatlnhdceelDiauknerdatfnoreiRxeepnsrdeseahsriscprhoaGvyersroiuntchpeeralenadsatptpfhrieveecGieyaeotarirgosne.taoInwmdoyJuolmsdeenplthiokiren.etoDBrtu.htlaRenarknPadloylltyDhmuerearn,
ResearchLaboratoryfortheirfriendshipandhelpandformakingthePolymerGroupan
enjoyableplacetowork.
FinancialandtechnicalsupportwasgivenbyThePetroleumResearchFund
(31667-AC7),GraduateResearchAssistantshipProgramgrantedbyDevelopment
SponsoredResearchatUniversityofFlorida,KSVInstrumentsofFinland,andMicrocal
SJoafntKwamreet.ko1wforuolmdNloirktehtwoesatcekrnnowUlnievdegresiPtuylaakndDuNtatdai,aMLaeryyarDouvrsbkian,,AAnldorkemwayKiDnagtt,aa,nadnd
BdiulrlinLgavtehendseyrncfhrroomtrMoRnCexApTer,imAerngtosn.neSpNeactiiaolntahlaLnakbsotroatPoireirerseVfeorrstthreaiertheelwphaontdragnusifdearrnecde
theLBfilmsandranX-rayexperimentswithmeandtoJefferyCulpandStefanSetzwho
ran24-7synchrotronX-rayexperimentswithme.ThankstoDavidPowell,Dean
Schoenfeld,JodieJohnson,RickYostandChrisReddickforspendingtheirvaluabletime
runningmysamplestoobtainmeaningfulmassspectrometrydata.
loveandmademefeelathome.MySpecialthankstoDavidBaarda,ElizabethBaarda,
BMeutrtayliJoThDiumnmna,lB,ilMlcLearmabT,hDiorruimsalM,oaonddyD,hMaamrgmuiekraitGeuDnealwgaardod,enCahrwihstoopihnetrroRdaujcieadh,meto
GeorgiaCollege.Alsoraythanksgotomyclosefriends,JackieandDennisTissera,for
Mtmwuheyerriareblecits,ohtnePrcfrereairfvenoenredansmn,adetasdntuuhdperpSioUenrnagtin.va,lel1rwstkhiihotnaydnhskoaofvmfFeylwsoerfhairtodihawee,nnrdS.smtaeetMptthyhhaeentihUfeanuninRkvossemirtdasoefirtoByaafcrocbhfoalFarllnaeodgrSeiLmdleeaisf,rlea.CiehgiIeKrmiafnuoggsr,,teHwdtiihhrtaaoinnn,kg
thetext
f1woocrautnlundsauatclecsteooeldhi.akevIetcomagnyinvofeattahbeevrge,irmnyotstpoheeecxrip,arlaetnshdsathnwkoowyobmruuottchoheHrtseh,emiSaroblWioctveheraaaansndedksePurapapdomwreht,omtesouabpneplotiroetvmeeed.tmhae1t
financiallyduringmyundergraduatestudies.1wouldnotbeherewithouthersupport:
thankyouforhavingfaithinme.
Finally,IwouldliketothankthewonderfulstaffoftheChemistryDepartment
includingLorraineWilliams,JoeShalosky,ToddProx,JoeCarusone,LawrenceHartley,
andMichaelHcrlevich.SpecialthankstoLoriClark,DonnaBalkomandJimDeyrupat
thegraduateprogramofficeforhelpingmewithalltheproblemsthatgraduatestudents
.
TABLEOFCONTENTS
ACKNOWLEDGMENTS
LISTOFTABLES
LISTOFFIGURES
ABSTRACT
CHAPTERS
IIINITLRanOwDnUjiCfTI<uOiiiNIAngmiarBlodgettFilms ^
2CHARACTERIZATIONOFTHEIANGMUIRFILMS 39
EEEEiFSSSSSgSIEEEEE
444C555'.M.O24j234INE444R444CIS55RCIexoS.nornJJ22233s23tpnunT.-.urecnc423232II3lIoRrillMdtriuPXX2PGGVTXUuusrms--rreoo-hcs.C3erairraarwwteetnoaazcTiaddm1ditnyyoiiylseeIcXaDnnnalarrDDilDDOggilniifeiHoDDNgffPftsIIDniiffmr-lencenffVrraoOuccfcutifaaccrtiilisFrcctaedoedsrattHitderceiciiTi-onutsnTtooo.:HncircinornnFeneaoreoI.oo.gnpuRfXXfp.oogIM-A-afiLfihrrirNaaraaaMtSnrnyhtyoogIgeuTnrmDDmIsMRii-ouOffouUmiNffrnreMrr-oaarEBFccmsliNtteuiiloToodmrfnngsAe3oo1atffHttIDttAhhOfiPeeirNflaLLFWmnaaasdOnntggReSmmr'uuGOiIiRnDrrtAP-eFBZrilfIloamcdNesgGettFilms..
APPENDICES
ACDIASLTCOURLTAETDIOHNEXOAFGHOONRAILZOLNATTTAILCBE.ONDLENGTHSOFA .155
BCREFEFMMWEXOEOERPRCNREEHOEGNRALRCIUNAAEMSIZSYEECIENDNARTIGLSNSIDEATNRTTHCAUFITWPDHGICEIENHNDGMECESAECXKRDOPLCIFEIFARDSFTIITRMFBAFEFECONETARTRIMEAOLNLNITINOCGEFONLMMAPENNOGTNMEPUNRITORSCEWDHUIRCEH 11I55M79
BIOGRAPHICALSKETCH
LISTOFTABLES
Someofthesynchrotronso
Propertiesandapplications
edfromFigure2-"'
2-2Importantvaluesi edfromFigures2-o8fsomeselectedpeaksofthe
sofsomeselectedpeaksofthe
aaoobbttaaiinneeddffrroommtthheeppoowwddeerrddiiffffrraaccttiioonnooffN3HODDPP
aobtainedfromtheGET)ofl-angmuir-Blodgcnfilms
nmancedinformationofseveraldifferentGillsetups
LISTOFFIGURES
Surfacepressureve eapermoleculeisothermforalongchainorganic
Diagrams(nottoscale)showingforcesactingontheWilhelmyplate
DTreapnossfietriroinngtyapnesY-otfyLpBeLfiBlmmsu.lt.ilayerstoahydrophilicsurface
Generalmechanismfortheoxidanvepolymenzanooofpynole
SGVpeieoecmwteroatlfrtybhroieflmlmoi-annpoclleaaonyfeesrXo-amrneadyXtd-hirefafcyroarscroteuirsccpneosnd.ingintensit.ydistributionstilted
Ks.SmVat5it0aa0cthiCcedL'aingmuirtro'u"ighnusyasstuemmw.icthfaedciepppoetrenatnid-alsubryfa.v.ciebbnaultanngcpelauineits
SchematicofBrewsterAngleMicroscope .
SHyn-tVheMtiRcreopuetciertaooIf-mhoeanxoamdeercyslpyrrole...
M'Von-oNlaMyRer-sipseocttrhaeromfsmoofnJomHeDrPs/NODP.imxhrresat.2..S..T..... ...
2$IsothermscfmixturesofJI1DPandNODPardifferenttereperarures
29Hysteresisofthepolymerizedmonolayerproductof3-hccadecylpyrrole
2-10Excessareaofmixingal10“C..... -.68
22-1121DBeApieM)ndilemOnamgcNees'omoffteNmOpeDrPatureandmolefractiononcompressibilityat 69
2-13Surfacepotentialo!monomersat2fT TO
2-14Surfacedipolemomentcorrespondingtotheirsurfacepressure 71
2-15Lanwgamfueirr-Blodgetttransferof3-hexadecylpyiroleontohydrophobizedsilica
2-16Isothermsofpolymerafterreactingatfl~20mN'mand2S*C 74
22223-----111879UPPVool-lfyvyrmimoeserminstzzphaeaetcUitLuroBoanoootfffro(p5uau)0grh%3e-i3mhnieHcxxDhtalPudoreraecloyofl2fo5rp3®ymCHrsrDoolPluetaainondndN(Ob)DiPtsaplo2l5ym*eCrizationproduct—.777856
2-20IR-psrpodeuecmtiminoKfB(ra)3-bexadecylpyrroleand(b)itsmonolayerpolymenzauon
2-2212-G'PHNaCnMddRadstiapeoesfcudgtigrfefusetmreednotfccLhoeammnpigocrsaoilutusitomrnuocontfoulr1eaHyDerPpaonldymNeOriDzPed3-hexadecylpyrrole8820
31--213SLMtDArIuLcsDtpuIerecSstprueufcmtMorAfuLmDDTo1fLNmmOaatlDrniPcxe.su.s-edinthissrudy 899117
333---456MMMAAAiCLLLnHDDDQrIIIlC--rNSTTCpmOOeUNhFc--tVTssrEppHueetmFcchtto•rry'faaElt3oohAyffHlcSD3A/IWPcN1i/DVNP3a'HboDmPopaondlyNmOerDPwictohpmoaltyrmiexrDwTiIt.hmmatrixDTI.999236