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Identification number: DOI : 10.1016/j.apsusc.2014.10.096
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http://dx.doi.org/10.1016/j.apsusc.2014.10.096
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Eprints ID: 12279
To cite this version:
Duguet, Thomas and Bessaguet, Camille and Aufray, Maëlenn and Esvan,
Jérôme and Charvillat, Cédric and Vahlas, Constantin and Lacaze-Dufaure,
Corinne Toward a computational and experimental model of a poly-epoxy
surface. (2015) Applied Surface Science, vol. 324 . pp. 605-611. ISSN
01694332
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Toward
a
computational
and
experimental
model
of
a
poly-epoxy
surface
Thomas
Duguet
∗,
Camille
Bessaguet,
Maëlenn
Aufray,
Jérôme
Esvan,
Cédric
Charvillat,
Constantin
Vahlas,
Corinne
Lacaze-Dufaure
CIRIMAT,CNRS–UniversitédeToulouse,4,alléeEmileMonso,BP-44362,31030ToulouseCedex4,France
Keywords: Epoxy Amine Surfacescience AFM XPS DFT
a
b
s
t
r
a
c
t
Amodelpoly-epoxysurfaceformedbythereactionofDGEBAandEDAisstudiedbythecombination ofexperimentsandDFTcalculations.Aspecialsynthesisprotocolispresentedleadingtotheformation ofasurfacethatissmooth(Sa<1nm),chemicallyhomogeneous,andthatpresentsalow-defectdensity (0.21mm−2),asshownbyAFMcharacterizations.Then,XPSisusedforthedeterminationoftheelemental andfunctionalgroups’surfacecomposition.DFTallowstheidentificationandassignmentofindividual bondscontributionstotheexperimental1score-levelpeaks.Overall,wedemonstratethatsuchamodel sampleisperfectlysuitableforauseasatemplateforthestudyofpoly-epoxysurfacefunctionalization.
1. Introduction
Poly-epoxypolymersarewidelyimplementedinthreefamilies ofapplications:adhesives,paints,andcompositematerials[1].The latters,suchasepoxy/Cfiberscompositesareincreasinglyfoundin awealthofdevicesandpartsinthefieldsofleisure(skis,rackets, boats,golfclubs,etc.),ortransports,aeronauticsandspace(cars, aircrafts,satellites,etc.),tonamebutafew.Thesecomposite mate-rialspossessstiffnessandYoung’smodulusthatcomparewellwith metallicalloysbutwithamuchlowerchemicalreactivityand den-sity.Therefore,theyallowmassreductionandalargeincreaseof partsdurability.
Replacementofmetallic or ceramicparts bypolymersoften requiressurfacefunctionalizationinordertoacquireoptical, elec-trical,magnetic,biomedical,esthetic,orchemicalproperties.The maindrawbackwhenitcomestocoatortograftthesurfaceof polymer-basedcompositescomesfromtheverylowsurfaceenergy of such materialsoncepolymerized.This leadstoa poor wett-abilityrenderingpaintingorgluingdifficult,andresultinginpoor adhesion.Thesurfaceenergy ofpoly-ether etherketone (PEEK) orpoly-epoxyisapproximately40–50mJ/m2 tobecomparedto
∗ Correspondingauthor.Tel.:+330534323439.
E-mailaddress:thomas.duguet@ensiacet.fr(T.Duguet).
approximately500mJ/m2foraluminum.Moreover,thepolar
com-ponent(duetoHbonding)isaslowas6–7mJ/m2whichinhibits
theuseofsimplefunctionalizationprotocols[2–4].Hence,alarge number ofparticularprotocolshasbeendescribed orpatented, wheretheincreaseofreactivityandroughnessissought.A selec-tion amongst the wealth of publications can be foundin Refs.
[5–16].
Such protocols or methods that have been used until now remainempiricaldespitetheresultingimprovementofthetargeted properties and/or the extension of thedurability of the mate-rial. Therefore,the needexists toaccess thebasicmechanisms whichcontrolthesurfacefunctionalizationofpolymersandto con-trolthemsoastoachieve satisfactoryfunctionalpropertiesand adhesion.Bysubscribinginthis perspective,ourapproachaims atdescribingthenucleationandgrowthofmetallicthinfilmson polymersurfaces,by usinganintegrated methodwhereallthe elementarymechanismsaretakenintoaccount.Thefirststepin this frame–objectof thepresent study–is toobtaina model ofthepolymersurface,bothexperimentalandtheoretical,atthe atomic/molecular level. Such a model will serve as a template forfurthersurfacetreatments,includingpretreatments, molecu-largrafting,orapplicationoffilmsandcoatings.Itisworthnoting that,totheauthors’knowledge,nosuchatheoreticalsurfacemodel exists,mostlikelybecauseofstructuraldisorderandalackof exper-imentalinputs.
Regardingourobjectives,specificationsofsuchanexperimental modelpolymersurfaceinclude:
•A100%polymerizationaftercuringtobecomparablewith calcu-lations,wheretotalpolymerizationisassumed.
•Alowsurfacearithmeticroughness,namelyRa<1nmtomake
surethatwecanobservenano-islandsornano-clustersofagiven thinfilm.Otherwise,theywouldbehinderedbyroughness. •Averylowdefectdensitytoavoidheterogeneousnucleationat
defects.
•Chemical homogeneityto make surethat calculationmodels wherehomogeneityisassumedarerepresentativeofthetracked chemicalreactivity.Alsotomakesurethatchemicalcomposition isindependentontheanalyzedsurfaceareacorrespondingtoa givenprobesize.
Ourexperimentalapproachisbasedonthemethoddescribed in [17,18] for forming model poly-epoxy surfaces. It consists in the polymerization of the poly-epoxy in an Ar gloves box at ambient temperature for at least 24h, followed by a post-curingatelevatedtemperature(polymer-dependent).Guetal.[17]
synthesizesamplesfromastoichiometricmixtureofDGEBA+ 1,3-di(aminomethyl)-cyclohexane,withasmallamountoftoluenefor decreasingviscosityandfavoringanhomogeneousstirring(7min). Samplesarethenstoredfor24hatambienttemperature,and post-curedfor2hat130◦Cinanairfurnace.Characterizationsofthe
freesurfacesareperformedbyatomicforcemicroscopy(AFM)in Tapping®mode.Surfaceroughnessandphasecontrastare
deter-mined.ItisshownthatsamplessynthesizedinanArgloveboxshow alowersurfaceroughnessthanthosepreparedinambient condi-tions,andthattheyarehomogeneousincomposition.Kansowet al.[18]useasimilarmethodwiththeaimofcharacterizingthe for-mationofAl,Cu,Ag,andAufilmsbyphysicalvapourdeposition. DGEBAreactswithdiethylenetriamineinlowexcessat55◦Cunder
controlledatmosphere,beforeitisleftfor48hatambient temper-ature.Atthisstep,polymerizationrateisabout75%.Completionis achievedbypostcuringfor1hat120◦C.Surfaceroughnessisabout
1nm.
Theoretically, our greatest challenge is to circumvent the descriptionof thedisordered/amorphous structure andto limit thenumberofatoms.Tothatend,westartwithasmall macro-moleculemadefromthereactionofbisphenolAdiglycidylether (DGEBA)withethylenediamine(EDA) (61atoms).Even for this moderately complex system, the analysis of the experimental core-levelXPSspectrum isnot trivialand canleadtoincorrect conclusions.Thehelpofaccuratetheoreticaltoolsisthusneeded anddensity-functionaltheory(DFT)isusuallyusedforcomputing XPScore-levelshiftsinthecaseofsmallorganicorinorganic sys-tems.Theapplicationofthistheoreticalmethodtolargesystems, e.g.polymers,isachallengebutitisestablishedthatexperimental spectraaredirectlyrelatedtotheelectronicstatesobtainedfrom calculationsonsmallermodelmolecules.Forinstance,Endoetal. presentedacomprehensiveanalysisoftheXPSC1sspectrafor poly-mersusingthenegativeoftheenergyofmolecularorbitals[19,20]. Morerecently,theyusedthe‘transitionstate’theory[21]forthe calculationofthecoreelectronbindingenergies[22,23]. Follow-ingthisworkandinafirstapproach,wecomputethemolecular orbitalsenergiesonmodelmoleculesaspreliminaryinputforthe assignmentofexperimentalXPSspectraoftheinvestigated poly-mer.
WecomplementtheseresultsinthedifferentDGEBA+EDA sys-tembyimplementingamoredetaileddescriptionofsurfacesby AFMandXPScharacterizationscomplementedbyDFTcalculations. Thepaperisorganizedasfollows.Experimentalandcomputational
detailsaregiveninSection2,followedbyresultsinSection3. Con-clusionsandperspectivesarepresentedinSection4.
2. Experimentalandcomputationaldetails
2.1. Synthesis
We use a stoichiometric mixture of DGEBA (DER 332, Dow Chemicals, n=0.03) and EDA (analytical grade, purity>99.5%, SigmaAldrich).ThemassofDGEBA(mDGEBA)isfixedto5g.The
massofEDAmEDAisthusdeterminedfollowingEq.(1).
mDAE=fDGEBA
fDAE
×MDAE×mDGEBA MDGEBA
=0.43g (1) where MDGEBA is themolar mass(348.52g/mol) ofthis DGEBA
and fDGEBA is its functionality (2), and MEDA is themolar mass
(60.10g/mol)andfDAEisthefunctionality(4)oftheEDA.Weassume
thatnoetherificationoccurs.
Themixtureisthenmechanicallystirred(inanArglovebox whenspecified)for7minbeforeitispouredintodifferentmolds ordepositedasathindropletonaluminumfoil.Polymerizationis thenallowedfor48hatambienttemperature,followedbyapost curingof2hat140◦C.Forroughnesscomparison,weconsiderthe
followingpoly-epoxysurfacesformed:
-Atfreesurfaces,surfacesref.eitherepoxyAirorepoxyArgon.
-Attheinterfacewitha1cm×1cm×0.2cmsiliconemold,itself moldedonaSiwaferfortransferringatomicflatness.Interfaces ref.SiOSi/epoxyAirorSiOSi/epoxyArgon.
-Attheinterfacewitha1cm×1cm×0.2cmsiliconemold,itself molded on polystyrene (PS). Interfaces ref. SiOPS/epoxyAir or
SiOPS/epoxyArgon.
-Bymechanicalpolishinguptoa¼mmwithdiamondpaste. Sur-facesref.polishedAir.
Interfaces formedin the same molds but in air or Ar show different roughnesses (shown hereafter). This is the reason whySiOSi/epoxyAir andSiOSi/epoxyArgon,andSiOPS/epoxyAir and
SiOPS/epoxyArgonaredifferentiated.
2.2. Bulkcharacterizations
Differentialscanningcalorimetry(DSC)isusedforthe determi-nationoftheglasstransitiontemperature(Tg)ofthepoly-epoxy
underinvestigation.WeuseaDSC204PhoenixSeries(NETZSCH) coupledwithaTASC414/4controller.Theapparatusiscalibrated againstmeltingtemperaturesofIn,Hg,Sn,Bi,andZn,applyinga +10◦/mintemperatureramp.Samplesareplacedinaluminum
cap-sules.Massismeasuredwithanaccuracyof±0.1mg.Wechooseto reporttheonsetTg-onsettemperature.
Fourier transform infrared spectroscopy, FTIR (Frontier, PerkinElmerequippedwithaNIRTGSdetector),isperformedin transmissioninthe4000–8000cm−1range.16scansarecollected
for each analysis witha resolution of 4cm−1.We monitorthe
characteristic epoxy band (combination band of the –CH2 of
theepoxy group) at 4530cm−1 withincreasing polymerization
time,andafterpostcuringtreatment.Thereferencebandisthe combinationbandofC Cwitharomatic CHat4623cm−1 [24].
Peakareasarethenusedforcalculatingtheconversionrate(XeNIR)
ofepoxygroups,followingEq.(2). XeNIR=1− Aepoxy/Areference
t=t Aepoxy/Areferencet=0 (2)whereAepoxy andAreference arethepeak areasoftheepoxyand
Fig.1.Modeldimer(1DGEBA+1EDA).
2.3. Surfacecharacterizations
Surface roughness and viscoelastic homogeneity are deter-mined by AFM (Agilent Technologies model 5500) in ambient conditions.Theformerisperformedincontactmodewithtipsof spring constantkapprox. 0.292N/m,whereas thelatteris per-formedinTapping® modewithtipsofk=25–75N/m(AppNano).
Scanningrateis2mm/s.Imagesareprocessedwiththesoftwares Gwyddionversion2.19[25]andPicoImage(AgilentTechnologies). SurfaceroughnessparametersfollowtheGeometricProduct Spec-ificationsISO25178.Saisthearithmeticroughness,Sqistheroot
meansquareroughness,andSzisthetotalroughness(maximum
peak-to-valley),determinedbyprocessingtheAFMimages. XPSanalysisisperformedusingaThermoelectronKalpha appa-ratus.PhotoemissionspectraarerecordedusingAl-Karadiation (h=1486.6eV)fromamonochromatizedsource.TheX-rayspot diameter onthe sample surface is 400mm. The pass energy is fixedat30eVfor narrowscan and170eVforsurveyscans.The spectrometerenergycalibrationwasperformedusingtheAu4f7/2
(83.9±0.1eV)and Cu2p3/2 (932.8±0.1eV)photoelectronlines.
ThebackgroundsignalisremovedusingtheShirleymethod.Atomic concentrations are determined from photoelectron peak areas usingtheatomicsensitivityfactorsreportedbyScofield[26]and takingintoaccountthetransmissionfunctionoftheanalyzer.This functionwasdeterminedatdifferentpassenergiesfromAg3dand AgMNNpeakscollectedonasilverstandard.Finally,photoelectron peaksareanalyzedanddeconvolutedusingaLorentzian/Gaussian (L/G=30)peakfitting.
2.4. Calculations
WeusedthemodelmoleculeshowninFig.1thatresultsofthe additionofoneDGEBAandoneEDAmolecule.
The geometry of the model molecule was optimized at the B3LYP/6-31G* level of theory using the Gaussian 03 software package[27].
3. Results
Bulkcharacterizationsareperformedonsamplespolymerized underambientconditions.DSCisusedforthedeterminationof
Tg-onset.Temperaturerampsaredoubledforeachsampleinorder
toensurethatthereisnophysicalagingandtoverifythat polymer-izationiscomplete.ForallsamplesTg-onset=113±1◦C.Weassume
thatTg-onsetisnotdifferentafterpolymerizationintheArglovebox
(nobulkcharacterizationforthesesamples).
Wethenmonitorthepolymerizationratewithreactionduration byfollowingthegradualdecreaseoftheepoxypeakareabyFTIR, andcalculatingtheconversionrateusingEq.(2).Resultsareshown inFig.2.
Experimentsareperformedfrom15minto11520min(8days) aftermixingofthereactants.Theconversionrateincreasesslowly in the first hours and reaches an asymptote between 24 and 48h.Themaximumconversionatambienttemperatureis84%for
t≥48h.Theonlymeanforachievingacompletepolymerization is to set the sample at a temperature above its glass transi-tion.Thepostcuringtreatment(140◦C,2h)leadstoacomplete
Fig.2.Epoxygroupconversionrateasafunctionofpolymerizationoveran8-day
periodoftime.Dashedlineindicatesthatpolymerizationiscompleteafterpost
curingat140◦Cfor2h.
polymerization(>98%,takingintoaccounttheFTIRspectrometer sensitivity)illustratedbythedashedlineinFig.2.
Thedifferentsurfacesthatweconsiderarethencharacterizedby AFMover3mm×3mmsurfaceareaimagesinordertodetermine roughnessparameters.ResultsaresummarizedinFig.3.
Roughnessofthefreesurfacesisreduced bythreeordersof magnitudewhenpolymerizationisperformedintheArglovebox. Under Ar, Sa and Sq do not exceed 1.5nm, except for sample
SiOSi/epoxyArgon,forwhichthesetwovaluesare4.9nmand6.8nm,
respectively.ThelatterisnotacceptablefortheAFMobservation of metallicnanoislands or clusters that wetarget, in therange of1–20nmindiameter[18].Inordertotransferatomicflatness tothemolds,andthentotheSiOSi/epoxysurfaces,wemold
sili-conemoldsagainstSiwaferoragainstPS.Intheseconditions,the lowestroughnessisagainobtainedwhenthesurfacesareformed underAratmosphere,andissimilarbetweenSiandPSprocesses. Somehow,atmospherealsoplaysaroleregardingroughnessatthe substrate/polymerinterface.However,aroughnessaslowasatthat ofthefreeepoxyArgonsurfaceisnotachieved,indicatingthat
mold-ingintheseconditionsisnotwellsuitedforourpurpose.Finally,the roughnessparametersofthepolishedsurfacearequitelowbutAFM imagesshowmanyscratcheswherenucleationmaypreferentially occur.Sincewewanttoavoidheterogeneousnucleationinorder tocomparenucleationwithadsorptionenergiesatthemolecular level,polishingisabandoned.
Fig.3.Roughnessparametersdeterminedbyimageprocessingon3mm×3mm
sur-facescharacterizedbyAFMincontactmode.Apolynomialofdegree2isusedin
Fig.4.AFMimagesoftheepoxyAir(aandb)andepoxyArgon(candd)surfaces.Leftcolumnshowstopographicimagesafterapolynomialofdegree2correction,andright
columnshowsdeflectionimages(orphasecontrast).
Fig.4showsaselectionofAFMimagesoftheepoxyAir(aand
b)andepoxyArgon(candd)surfaces,obtainedinTapping®mode.
Rightcolumn(Fig.4aandc)correspondstothesurfacetopography andleftcolumn(Fig.4bandd)tothedeflectionofthecantilever,i.e. tothephasecontrast.WhereasTapping®modeleadstodifferent
apparentvaluesofroughnesscomparedtocontactmode, rough-nessisagainlowerontheepoxyArgonsurface,ascanbenoticedon
thecontrastscale,ontheright-handsideoftheimages.However, bothsurfacesarequiteflatandexhibitaverylowphasecontrast. Themeasureofphasecontrastprobesthelocalviscoelastic prop-ertiesthatweassumetobeanindicationofchemicalhomogeneity inthenanometerrange.Finally,Fig.4canddischosenonpurpose inordertoillustratethepresenceofdefects,intheformofapprox. 50nm-in-diametertroughs.ThedensityshowninFig.4isnot rep-resentative(overestimated).Athoroughcountoveratotal90mm2 surfaceareagivesadefectdensityequalto0.21mm−2.
EpoxyArgonisselectedasthebestcandidateforan
experimen-talmodelsurfaceofpoly-epoxy.Thus,weinvestigateitssurface chemicalcompositionbyXPSandusetheoutputofDFT calcula-tionsforpeakidentificationsandbindingenergyassignments.A firstobservationismadeonfreesurfacesofsamplessynthesizedin siliconemolds(i.e.thatwerenotincontactwiththemold).Survey spectrashowastrongSi2pcontributionat101.8±0.1eV,whichis characteristicofsiloxanegroups[28].Itrepresentsalargeamount ofadsorbedsiliconeonthesurface(approx.8at.%).Consequently, epoxyArsamplesarenowsynthesizedonAlfoil(andsiliconeis
banishedfromtheglovebox).Thesignificantthicknessofthe poly-epoxycoupons(1mm)ensuresthatAldoesnotdiffuseuptothe freesurface,sincethemeasuredinterphasesdonotexceed300mm
[29].
TheXPSsurveyspectrumofepoxyArgon surfacespolymerized
onaluminumfoilshowneitherSinorotherelementsthantheone expectedinthepolymerorfromadsorbedmoleculesfromtheair. Atomiccompositionofthesurfaceisdeterminedby1speaksfitting, repeatedatdifferentx–ycoordinatesonthesamplesurface.We determinethefollowingsurfacecomposition:
81.5at.%C,1.8at.%N,and16.7at.%O
Theresult is slightly differentfromthebulk composition of the poly-epoxy, where the basic motif is made of 2 DGEBA (2×21C+2×4Oatoms)moleculesfor1EDA(2C+2Natoms) molecule,resultinginabulkcompositionof:81.5at.%C,3.7at.%N, and14.8at.%O.Whereasthecompositionofthesurfaceshowsa similarcarboncontent,itisricherinoxygenandpoorerin nitro-genthanthebulk.Thisisanindicationofamildsurfaceoxidation thatmayoccurinthecourseofpost-curing,whenpolymerization isnotyetcomplete(post-curingstartsat85%polymerizationrate). Itisquestioningthoughthatthecarboncontentisapparentlynot affectedaswell.
Inordertofurtherinvestigatethesurfacechemistryofthemodel poly-epoxysurface,molecularorbitalsextracteddirectlyfromDFT resultsarestudied.Table1showsthebindingenergiesof1s elec-tronsinvolvedinthedifferentbondsofthemodeldimer.Thedimer ismadeof1DGEBAand1EDAthatvirtuallybondedthrough1 epoxy/1amineprotonreaction.Therefore,thereareafew discrep-anciesbetweentheexperimentalfully-polymerizedsamplesand themodeldimer.Theyareenlightenedbythegraycoloringofthe linescorrespondingtosecondaryandprimaryamines(allshouldbe ternary)andtotheepoxygroup(nomoreepoxyringsinthe100% polymerizedsample).Thebindingenergiesshownarethe nega-tivevalueofthemolecularorbitalsenergies.Therefore,absolute valuesarenotcorrectbecause(i)XPSbindingenergiescorrespond toamulti-stepprocesswherephotoelectronsinteractwiththe cre-atedholes,withthematrixandwiththeirimagebeforeandafter extractionintovacuum,(ii)temperatureisnotconsidered,(iii)of thelimitationofKohn–Shamorbitalenergiesasreflectinginitial stateeffects[30].Nevertheless,chemicalshiftscanbeusedifone considerthelatterprocessesconstantinagivenenergydomain.
Aminimummeanchemicalshiftof0.2eVistechnically observ-ablewithourXPSapparatus.Therefore,wediscriminatephenyl groupsfrom CH3groups,andC OH&partoftheC O Cbonds
fromtheotherC O Cbonds.ThankstothesupportofDFTresults, weuse5contributionstotheC1speakdeconvolutionand2 con-tributionstotheO1speakdeconvolution.ThefinefittingoftheC 1sandO1sspectraareshowninFig.5.N1sspectrumisnotshown becauseitexhibitsonlyonecontributionforC Nbondscentered
Table1
MolecularorbitalsinvolvingO,N,andC1satomicorbitalsfromDFTcalculationsonthemodelDGEBA–EDAdimer.Correspondingelectronicbindingenergies((−1)×orbital
energy),andmeanchemicalshiftsforthegivenbond.Grayedcellsdonothaveacounterpartintheexperimentalfully-reticulatedpoly-epoxy.
Molecularorbital Bindingenergy(Hartree) Bindingenergy(eV) Meanchemicalshift(±0.1eV) Bond
O1s −19.177 521.8 +0.8 C O C
−19.170 521.6 C O C
−19.165 521.5 +0.6 Epoxy
−19.145 520.9 Ref. O H
N1s −14.324 389.8 +0.3 Secondaryamine
−14.316 389.5 Ref. Primaryamine
C1s −10.249 278.9 +2.0 C O C −10.249 278.9 C O C −10.246 278.8 C O C −10.244 278.7 C O C −10.239 278.6 +1.8 C O C −10.239 278.6 C O C −10.238 278.6 C OH −10.212 277.9 +1.0 C N −10.209 277.8 C N −10.207 277.7 C N −10.205 277.7 QuaternaryC C −10.186 277.2 +0.2 Phenyl −10.185 277.1 Phenyl −10.185 277.1 Phenyl −10.183 277.1 Phenyl −10.182 277.1 Phenyl −10.181 277.0 Phenyl −10.181 277.0 Phenyl −10.181 277.0 Phenyl −10.180 277.0 Phenyl −10.176 276.9 Phenyl −10.173 276.8 0.0 CH3 −10.173 276.8 Ref. CH3
Fig.5.XPSfinespectraofC1sandO1s.Spectraarefittedwithcontributionsderived
fromDFTcalculationsonthemodeldimer.
at399.2eV.BindingenergyscaleoftheC1sspectrumstartswith the–CH3contributionfixedat284.4eV.Then,meanchemicalshifts
extractedfromtheenergydifferencebetweenmolecularorbitalsof DFT(seeTable1)areusedforhigher-binding–energycontributions (284.4+0.2,+1.0,+1.8,+2.0eV).
Thefilledareashowstheenvelopeofthefittingcurve.Thereis anexcellentmatchingwithbothOandC1sexperimental spec-tra. Again,calculationsensurethat contributions arereal; even C N,forinstance,whichisburiedinthetailsofneighboring con-tributions.Inordertoconsolidatetheseresults,wenowdiscuss fittingwithregardstothefunctionalgroupcompositionshownin
Table2.
Experimentalatomiccompositionsinfunctionalgroupsare con-sistent.Forinstance,whereoneO1sorbitaloftheC O Cbonds showsacompositionof15.5at.%,twoC1sorbitalsoftheC O C bondsshowanapproximatelydoubledcomposition of30.5at.% (28.0 plus the contribution of C O C at 286.2eV of about 3.7 (C 1sC O C, C OH)– 1.2 (O1sC OH)=2.5at.%). Similarly, N 1sand C 1scompare wellin termsof composition inthe C N bonds(1.8vs.1.3at.%).Finally,thelastcolumnofTable2shows theexpected compositionin functional groups ina poly-epoxy wheretheDGEBA:EDAratioequals2:1.Forinstancethenumber of C 1sin phenylgroups is calculated as follows:2 DGEBA×2 phenyls/DGEBA×6Catoms=24C1s.Overall,onecanfind4C1s in–CH3,24C1sinphenyls,2C1sinC N,4C1sinC OH,4C
1sinC O C286.2eV,4C1sinC O C286.4eV,2N1sinC N,4O
1sinC OH,and4O1sinC O C.Thereforethetotalnumberof considered1sorbitalsis52.Weobservelargediscrepancies con-cerningthephenylbondsconcentrationandtheoxygenatedbonds C OHandC O Cconcentrations,a differencethatwasalready mentionedwhenconsideringtheelementalatomiccomposition. Therearetwopossibilitiesforexplainingthesedifferences:either thesurfaceisoxidizedandoxygenatedbondscontributetotheC 1sandO1ssignalsatneighboringbindingenergies,orthepolymer isorientedinsuchawaythatC O Cbondsemergeatthesurface.
Table2
ResultsoftheC,O,andN1sdeconvolutions;peakbindingenergy:BE,chemicalshiftimposedafterDFTresults;heightincountspersecond:CPS;fullwidthathalf-maximum:
FWHM;peakarea;scofieldrelativesensitivityfactor:RSF;atomicfraction:at.%;andthecompositionexpectedfromthemodelpolymerwithaDGEBA:EDAratioof2:1.
Name PeakBE(eV) Chemicalshift(eV) Height(CPS) FWHM(eV) Area(CPSeV) ScofieldRSF At.% 2DGEBA:EDAmotif(at.%)
C1s CH3 284.4 0.0 2249.74 1.06 2578.62 1 6.5 7.7
C1sphenyl 284.6 0.2 11580.87 1.3 16279.01 1 40.8 46.2
C1sC N 285.4 1.0 328.14 1.41 500.77 1 1.3 3.8
C1sC O C,C OH 286.2 1.8 1009.93 1.36 1488.52 1 3.7 C OH:7.7+C O C:7.7
C1sC O C 286.4 2.0 7147.92 1.44 11172.06 1 28.0 7.7
C1sshakeup 291.2 n/a 349.91 1.32 501.28 1 1.3 n/a
N1sC N 399.2 n/a 808.92 1.28 1195.36 1.8 1.8 3.8
O1sC OH 532.0 0.0 669.53 1.73 1255.76 2.93 1.2 7.7
O1sC O C 532.9 0.9 9494.3 1.53 15728.75 2.93 15.5 7.7
Ifweassumethatamildoxidationoccurredinthecourseof sam-plepreparation,itmaybeassignedtosub-stoichiometricgroups, suchasamines(1.3–1.8vs.3.8at.%expected)andphenyls(40.8vs. 46.2at.%expected).Inthatcasedeconvolutionmaybeimproved bysubstitutingorimplementingadditionalcontributionsthatwe arenotabletoidentifynow.
4. Conclusions
Weselectedanepoxy-aminesystemwhichpermitsitsuseas bothanexperimentalandacomputationaltemplateforfurther sur-facetreatments.DGEBAandEDAmixedinstoichiometricratioand slowlypolymerized(48h)inanArgloveboxleadtotheformation ofapoly-epoxypolymerizedata rateof85%.Total polymeriza-tionisachievedbypost-curingat120◦Cfor2h.Suchapoly-epoxy
exhibitsa glass transitiontemperature onset of 113±1◦C.
Dif-ferent substrates and atmospheres were tested and compared intermsofsurfaceroughness.Thelowestroughness(arithmetic roughness=0.2nm,peak-to-valley=1.5nm)isobtainedatthefree surfacethatpolymerizedunderAratmosphere.AFMobservations revealthat,inadditiontothehighsmoothness,thedefectdensityof thesurfaceislowenoughtoavoiddefectdrivenundesirable nuclea-tion.Additionally,phasecontrastisalmostnullwhichindicatesthat thesurfaceischemicallyhomogeneous.Atomiccompositionsfrom XPSsurveyspectraatdifferentpositionsconfirmthisresult.Fine XPSspectraoverC,O,andN1scorelevelsareanalyzedinview oftheDFTcalculationsresults.Theoreticalbindingenergy chemi-calshiftsallowanexcellentfittingoftheexperimental1sspectra. Alimitationhasbeenemphasizedconcerningthecompositionsin chemicalgroups:themaindiscrepancyconcerningamuchlarger compositioninC O Cthantheonetheoreticallyexpectedfrom theperfectpolymermodel.Inanearfuture,wewilldedicateour effortstotheimprovementof(i)thepoly-epoxynetworkmodelby allowingalargernumberofatomsandbyusingmolecular dynam-icscomputationstofreezethestructureatgiventemperatures,and (ii)ofthecore-levelbindingenergiescalculationsusingthe gener-alizedtransitionstatemethod[21]thatallowsabettertreatmentof theXPSphotoemissionprocess.Finally,theperspectivesfor exper-imentalworkwillbetheformationofthinmetallicfilmsandthe mechanisticdescriptionofnucleationandgrowth.
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