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Optically Transparent, Super Hydrophobic Methyltrimethoxysilane Based Silica Coatings Without Silylating Reagent

Optically Transparent, Super Hydrophobic Methyltrimethoxysilane Based Silica Coatings Without Silylating Reagent

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03/28/2014

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Contentslistsavailable
 
AppliedSurface
 
Science
 journalhomepa
 
Opticallytransparent,
 
superhydrophobic
 
methyltrimethoxysilanebasedsilica
 
coatings
 
without
 
silylatingreagent
Mahendra
 
S.Kavale
a
,D.B.Mahadik
a
,V.G.Parale
a
,P.B.Wagh
b
,Satish
 
C.Gupta
b
,A.Venkateswara
 
Rao
a
,
,Harish
 
C.Barshilia
c
a
 AirGlass
 
Laboratory,Departmentof 
 
Physics,ShivajiUniversity,Kolhapur,416004,Maharashtra,India
b
 AppliedPhysicsDivision,Bhabha
 
 Atomic
 
ResearchCentre(BARC),Trombay,Mumbai400085,India
c
NationalAerospaceLaboratories,Bangalore560017,India
a
 
r
 
ticle
 
inf
 
o
 Articlehistory:
Received24
 
 January2011Receivedin
 
revisedform25
 
 July2011Accepted5
 
August
 
2011
Available online 11 August 2011
Keywords:
Sol–gel
 
processSuperhydrophobicsubstratesPMMATransparentcoatings
a
 
bs
 
tr
 
a
 
ct
The
 
superhydrophobic
 
surfaces
 
have
 
drawn
 
lot
 
of 
 
interest,in
 
both
 
academicandindustries
 
becauseof 
 
opticallytransparent,adherent
 
andself-cleaningbehavior.Surface
 
chemical
 
composition
 
andmor-phologyplays
 
an
 
important
 
role
 
in
 
determiningthe
 
superhydrophobic
 
nature
 
of 
 
coatingsurface.Such
 
concert
 
of 
 
non-wettabilitycan
 
be
 
achieved,usingsurface
 
modifyingreagents
 
or
 
co-precursormethodin
 
sol–gel
 
process.Attempts
 
have
 
been
 
made
 
to
 
increase
 
the
 
hydrophobicityandoptical
 
trans-parencyof 
 
methyltrimethoxysilane
 
(MTMS)
 
basedsilicacoatings
 
usingpolymethylmethacrylate
 
(PMMA)insteadof 
 
formal
 
routes
 
like
 
surface
 
modification
 
usingsilylatingreagents.The
 
opticallytransparent,superhydrophobic
 
uniform
 
coatings
 
were
 
obtainedbysimple
 
dipcoatingmethod.The
 
molar
 
ratio
 
of MTMS:MeOH:H
2
Owas
 
kept
 
constant
 
at
 
1:5.63:1.58,respectivelywith
 
0.5
 
M
 
NH
4
Fas
 
acatalyst
 
andtheweight
 
percent
 
of 
 
PMMA
 
variedfrom
 
1
 
to
 
8.The
 
hydrophobicityof 
 
silicacoatings
 
was
 
analyzedbyFTIRandcontact
 
angle
 
measurements.These
 
substrates
 
exhibited91%optical
 
transmittance
 
as
 
comparedtoglass
 
andwater
 
dropcontact
 
angle
 
as
 
high
 
as
 
171
 
±
1
.The
 
effect
 
of 
 
humidityon
 
hydrophobic
 
natureof 
 
coatinghas
 
been
 
studiedbyexposingthese
 
films
 
at
 
relative
 
humidityof 
 
90%at
 
constant
 
tempera-ture
 
of 
 
30
C
 
for
 
aperiodof 
 
45
 
days.The
 
micro-structural
 
studies
 
carriedout
 
bytransmission
 
electronmicroscopy(TEM).
© 2011 Elsevier B.V. All rights reserved.
1.
 
Introduction
Thewater
 
repellent
 
coatingshaveimportant
 
featurein
 
theindustriesto
 
enhancethe
 
durabilityof 
 
materials.The
 
wettabilityof 
 
the
 
surfaceis
 
acharacteristicpropertyof 
 
materialsandstronglydependson
 
boththe
 
surfacechemical
 
compositionandsurfaceroughness[1].Thesesurfacesare
 
easyto
 
clean,theyhaveself-cleaningproperties.In
 
nature,manynatural
 
speciesexhibit
 
watercontact
 
anglehigher
 
than150
suchas
 
sacredlotus
 
leaves[2],water strider’slegs,animal
 
furs
 
[3],cicadaorni’swings[4],etc.These substratesare
 
water
 
repellent
 
in
 
that
 
water
 
dropletsroll
 
off 
 
thesurfaceat
 
asmall
 
tilt
 
angle(slidingangle)
 
andherebyremovingcontaminantsfrom
 
the
 
substrates(self-cleaning).Lotusleavesare
 
one
 
of 
 
the
 
most
 
famousbecauseexam-ples
 
amongnaturallyoccurringsuperhydrophobicsurfaces.Themicrostructureof 
 
lotusleavesconsistsof 
 
acombinationof 
 
twoscalesroughness:one
 
around10
 
m
 
(roughstructure)andaround100
 
nm
 
(fine
 
structure).Thesesubstratesare
 
also
 
referredas
Correspondingauthor.Tel.:+91
 
231
 
2609228.
E-mailaddress:
avrao2012@gmail.com(A.VenkateswaraRao).
hierarchical
 
micro-
 
andnanostructures.The
 
hydrophobicityof 
 
alotus
 
leaf 
 
arisesfrom
 
the
 
epicuticularwaxsecretedbythe
 
leaf 
 
itself [5].The
 
contact
 
angleof 
 
water
 
dropwithlotus
 
leaf 
 
161
±
2.7
[6].The
 
waxhas
 
acontact
 
angleof 
 
110
,not
 
highlyhydrophobic;how-ever,the
 
lotus
 
leaf 
 
still
 
exhibitsasuperhydrophobicproperty.It
 
ispresumedthat
 
this
 
combinationof 
 
roughnessandwaxcontributeto
 
the
 
superhydrophobicityof 
 
the
 
lotus
 
leaf.The
 
rollingof 
 
waterdropletsandremoval
 
of 
 
the
 
contaminantsfrom
 
the
 
surfaceof 
 
lotusleaf 
 
is
 
referredas
 
the
 
“LotusEffect”.The
 
lotus
 
leaf 
 
thereforealwaysexhibitsaverylow
 
degreeof 
 
contamination:self-cleaning.Inspiredbythe
 
lotusleaf 
 
effect,manyeffortshavebeenmadetofabricatesuchsurfaceswith
 
binaryhydrophobicroughness.Start-ingfrom
 
apolymer
 
solution,superhydrophobiccoarsecoatingsareobtainedbyphaseseparationor
 
electro-spinning[7,8].Papillae- mimeticpolyanilineparticlesare
 
assembledin
 
the
 
presenceof perfluoroocatanesulfonicacid,whichcan
 
form
 
superhydropho-biccoatingsin
 
situ[9].Assemblingnano-particlesfollowedbya post-hydrophobicmodificationleads
 
to
 
coarsesuperhydrophobicsurfaces[10].A
 
superhydrophobiccoatingcan
 
also
 
be
 
obtainedbycontrollingcrystal
 
growthdynamicsfrom
 
melt
 
 
bymeansof 
 
electrochemistryonto
 
metallicsubstrates[12].Gener- allyin
 
sol–gel
 
processhydrophobicitycan
 
be
 
achievedbyusing
0169-4332/$
 
see
 
front
 
matter
© 2011 Elsevier B.V. All rights reserved.
 
M.S.Kavaleetal./AppliedSurfaceScience
 258 (2011) 158–162
159
silylatingreagents,whichreplacessurfacepolar
 
hydroxyl
 
dropsinto
 
non-polaralkyl
 
groups.But
 
this
 
methoddecreasesthe
 
adher-enceo
 
the
 
coatingsbecauseof 
 
the
 
highlyreactivesilylatingreagents.Here
 
we
 
havedemonstratedthe
 
without
 
use
 
of 
 
silylatingreagentssuperhydrophobicitycan
 
be
 
achievedbyusingPMMA
 
inthe
 
methyltrimethoxysilanebasedsilicacoatings,whichenhanceshydrophobicbehavior.
2.
 
Experimental
 2.1.Preparation
 
of 
 
coatingsolution
For
 
the
 
preparationof 
 
superhydrophobiccoatingthe
 
chemi-calsusedwere,methyltrimethoxysilane(Sigma–AldrichChemie,Germany),methanol
 
andToluene(S.D.Fine
 
ChemLtd.,Mumbai,India)
 
andAmmoniumFluoride(LobaChemie,India),Polymethyl-methacrylate(PMMA)(Fluka,Germany).Doubledistilledwaterwasusedin
 
the
 
preparationof 
 
catalyst.All
 
chemicalswere
 
usedas
 
receivedwithout
 
further
 
purification.Further,1
 
to
 
8
 
gof 
 
PMMAweighedanddissolvedin
 
100
 
ml
 
of 
 
Tolueneto
 
obtain1–8
 
wt%of 
 
thePMMA.
 
The
 
mixturewas
 
vigorouslystirredat
 
50
C
 
to
 
get
 
transpar-ent
 
andstablesolutionof 
 
PMMA.
 
This
 
wt%o
 
PMMA
 
addedwiththesol
 
to
 
get
 
superhydrophobiccoating.A
 
coatingsol
 
was
 
pre-paredbykeepingthe
 
molar
 
ratio
 
of 
 
MTMS:MeOH:H
2
Oconstant
 
at1:5.63:1.58,respectivelywithvariationof 
 
PMMA
 
from
 
1
 
to
 
8
 
wt%and0.5
 
M
 
NH
4
Fas
 
acatalyst.The
 
cleanedglass
 
substratesweredippedverticallyafter
 
additionof 
 
base
 
catalyst
 
in
 
the
 
sol
 
andtakenout
 
after
 
gelation.Further,theseglass
 
substrateswere
 
annealedat150
Cfor
 
3
 
h
 
to
 
removeresidual
 
solvent.
 2.2.Characterizations
The
 
water
 
dropcontact
 
anglewas
 
measuredusingstandardgoniometer(Ramehart
 
Instrument
 
Co.,USA)
 
equippedwith
 
CCDcamera.All
 
CA’s
 
weremeasuredbykeeping10
 
L
 
water
 
dropletoncoatedglasssubstrateat
 
roomtemperature.Surfacechemi-cal
 
compositionstudieswerecarriedout
 
usingFourier
 
transforminfrared(FTIR,PerkinElmer783,USA)
 
spectroscopyandmicro-structural
 
studiesof 
 
the
 
substratescoatingbytransmissionelectronmicroscopy(Philips,Tecnai,F20
 
model,Netherlands).The
 
opticaltransmittance(%)
 
of 
 
coatinganalyzedusingUV–VISspectropho-tometer(Shimadzu,UV1800.Japan).Thermal
 
conductivityandspecificheat
 
of 
 
the
 
coatingsquantifiedusingC–Tmeter
 
(TelephCompany,France).The
 
effect
 
of 
 
humidityon
 
the
 
wettingpropertiesof 
 
the
 
substrateswas
 
studiedin
 
ahumiditychamber(REMIInstru-mentationLtd.,Mumbai,India).The
 
thermal
 
stabilityof 
 
coatingswas
 
characterizedbyTGA
 
andDSCanalysisin
 
inert
 
atmosphere.
 2.3.Reaction
 
mechanism
The
 
hydrolysisandcondensationof 
 
methanol
 
dilutedMTMS
 
inpresenceof 
 
PMMA
 
andNH
4
Fis
 
as
 
shownin
 
followingchemicalreactions.HydrolysisCH
3
Si(OCH
3
)
3
+
3H
2
O
NH
4
F
CH
3
Si(OH)
3
+
3CH
3
OH(1)Water
 
Condensation(2)
OH OH OH OHCH
3
Si OH
+
 
OH
 
Si CH
3
CH
3
Si O Si CH
3
+
 
H
2
OOH
 
OH OH OH
Alcohol
 
Condensation(3)
OHOH CH
3
CH
3
CH
3
CH
3
CH
3
Si O Si CH
3
+
 
H
3
CO Si OCH
3
OH Si O Si O Si OCH
3
+
 
CH
3
OHOH OHOCH
3
OH OH OCH
3
Polymerization(4)
CH
3
CH
3
CH
3
CH
3
OH Si O Si O Si OCH
3
+
(CH
3
C )OH OH OCH
3
COOCH
3
PMMACH
3
CH
3
CH
3
CH
3
Si O Si O Si OCH
3
+
2CO
2
+
H
2
O + 1/2 H
2
CH
3
CH
3
OCH
3
The
 
expectedpolymerizationreactionbetweenthe
 
hydrolyzedMTMS
 
andPMMA
 
is
 
as
 
shownin
 
the
 
reaction(4).The
 
surface–OHgroupsare
 
replacedbythe
 
CH
3
groupsof 
 
the
 
PMMA
 
in
 
order
 
toachievethe
 
inherent
 
superhydrophobicityas
 
well
 
as
 
nanostruc-turedsilicanetworkresultedon
 
the
 
substratesurfacewith
 
releaseof 
 
two
 
moleculesof 
 
carbondioxide,water
 
andhydrogenatom.Thismechanismis
 
responsiblefor
 
the
 
gelation.
3.
 
Results
 
andDiscussion
 3.1.Contactanglemeasurements
The
 
hydrophobicnatureof 
 
the
 
surfacecan
 
be
 
quantifiedbymeasuringthe
 
contact
 
angleof 
 
water
 
droplet
 
with
 
the
 
surface.Fig.1aandb
 
showsimageof 
 
water
 
droplet
 
on
 
the
 
coatingpre-paredwith
 
MTMS
 
as
 
precursorwithout
 
PMMA
 
andwith
 
PMMA(7%)
 
respectively.The
 
water
 
dropcontact
 
anglefor
 
thesecoatingswas
 
foundto
 
be
 
increasedfrom
 
116
 
±
1
to
 
171
 
±
1
.The
 
hydroxylgroupsare
 
present
 
on
 
the
 
surfaceof 
 
the
 
coatedsubstrateare
 
mainsourcesof 
 
the
 
hydrophilicityas
 
theypromotethe
 
adsorptionof watermolecules.Theseterminal
 
hydroxyl
 
groupsinteract
 
withwater,leadingto
 
the
 
deteriorationof 
 
the
 
non-wettabilityof 
 
surfacewhetherit
 
is
 
aerogel
 
or
 
coatingsurface.The
 
increasein
 
the
 
contactangleindicatesthat
 
the
 
increasein
 
hydrophobicityof 
 
the
 
silicacoat-ings
 
whichmight
 
be
 
due
 
to
 
replacementof 
 
the
 
polar
 
–OHgroupsof thesurfacebythe
 
non
 
polar
 
–CH
3
groupsof 
 
the
 
PMMA.
 
The
 
staticcontact
 
angleis
 
governedbythe
 
forcebalanceat
 
the
 
threephaseboundaryandis
 
givenbyYoung’sequation[13].But
 
the
 
Young’sequationis
 
appliedfor
 
the
 
flat
 
surfaceandnot
 
to
 
aroughsurface.The
 
effect
 
of 
 
surfaceroughnesson
 
wettingbehavioris
 
accountedbythe
 
model
 
developedbyWenzel,whereit
 
is
 
assumedthat
 
thespacebetweenthe
 
protrusionson
 
the
 
surfaceis
 
filledbythe
 
liquid.Wenzel
 
hadmodifiedthe
 
Young’sequationas
 
in
 
the
 
following[14].cos
Â
=
 
s
 
sl
 
l
=
cos
 
Â
(5)where
sv
,
sl
and
lv
are
 
solid–vapor,solid–liquidandliquid–vaporinterfacial
 
energies,respectivelyand
Â
is
 
the
 
contact
 
angle,where
 
160
M.S.Kavaleetal./AppliedSurfaceScience
 258 (2011) 158–162
Fig.
 
1.
 
Water
 
dropcontact
 
angleimageson
 
the
 
silicacoating.(a)
 
Without
 
PMMA
 
(b)
 
withPMMA
 
(7%).
r
 
is
 
the
 
ratio
 
betweenthe
 
true
 
surfaceareaandits
 
horizontal
 
pro- jection.In
 
contrast,CassieandBaxter
 
[15]proposedan
 
equation:cos
 
Â
=
1
 
+
 f 
 
(cos
Â
+
1)
 
(6)where
 f 
 
is
 
the
 
areafractionof 
 
the
 
liquid–solidcontact
 
to
 
the
 
pro- jectedsurfacearea.The
 
Cassie–Baxtermodel
 
suggestedthat
 
thesurfacetrapsair
 
in
 
the
 
hollow
 
spacesof 
 
the
 
roughsurface,sothat
 
the
 
droplet
 
essentiallyrests
 
on
 
alayer
 
of 
 
air.de
 
Gennes[16]explainedathresholdroughness
*
for
 
air
 
trapping;
=
1
 
+
tan
2
Â
4
(7)For
 
low
 
roughness(
<
*
),the
 
solid/liquidinterfaceconfirmstothe
 
profileof 
 
the
 
solidsurfaceandthe
 
contact
 
angleis
 
givenbyWenzel’slaw.Beyondathreshold
*
(
>
*
),air
 
pocketsare
 
trappedandCassie–Baxterequationmust
 
be
 
usedto
 
evaluate
Â
*
.
 3.2.Fouriertransforminfraredspectroscopystudies
Thewettingbehaviorof 
 
superhydrophobicsurfacesis
 
governedbychemical
 
compositionof 
 
surfaceandroughnessof 
 
surface.Thecoatedmaterial
 
on
 
glasssubstratewas
 
removedandpowder
 
of material
 
exposedupto
 
100
Cfor
 
one
 
hour
 
for
 
removingthe
 
mois-ture.Then
 
coatingpowder
 
was
 
milledwith
 
potassiumbromide(KBr)
 
to
 
form
 
averyfine
 
powder.This
 
powder
 
is
 
compressedintoathin
 
pellet
 
for
 
FTIR
 
analysisin
 
transmissionmode,sinceKBris
 
transparentin
 
the
 
IR
 
region.The
 
heat
 
treatment
 
is
 
helpful
 
toremovethe
 
physicallyadsorbedwater
 
molecules.Fig.2aandb showsthe
 
Fourier
 
transforminfrared(FTIR)
 
spectraof 
 
the
 
silicacoatingpreparedwithout
 
PMMA
 
andwithPMMA
 
(7%),respec-tively.Several
 
characteristicabsorptionpeakswereobservedintherange450–4000
 
cm
1
indicatingthe
 
presenceof 
 
methyl
 
groupsinthe
 
sample.The
 
broadabsorptionpeakobservedat
 
1080
 
cm
1
whichis
 
characteristicpeakof 
 
the
 
Si–O–Si
 
bondpresent
 
in
 
bothsamples[17].The
 
absorptionbandswere
 
observedat
 
2950
 
and1400
 
cm
1
are
 
due
 
to
 
stretchingandbendingmodesof 
 
C–Hbondandthe
 
peaksobservedat
 
765
 
and1265
 
cm
1
are
 
due
 
to
 
the
 
Si–Cbonds[18].The
 
1265
 
cm
1
peakindicatesthe
 
presenceof 
 
the
 
Si–Cbonding.The
 
absorptionpeaksat
 
1600
 
and3400
 
cm
1
correspond-ingto
 
the
 
polar
 
–OHbonds,the
 
residual
 
Si–OHgroupsare
 
the
 
mainsourceof 
 
hydrophiliccharacterof 
 
coating.In
 
the
 
spectrumof 
 
with-out
 
PMMA
 
absorptionpeaksintensitiesof 
 
Si–CandC–Hbondareless
 
than
 
peaksobservedwith
 
PMMA
 
(7%)
 
coating.This
 
confirmsthat
 
numbersof 
 
Si–CH
3
groupsare
 
morein
 
the
 
coatingwith
 
PMMA(7%),whichis
 
the
 
mainreasonfor
 
shiftingthe
 
hydrophiliccharac-ter
 
to
 
superhydrophobicnatureof 
 
MTMS
 
basedsilicacoating.Alsoas
 
wt%of 
 
PMMA
 
increasespolar
 
groupslike
 
–OHare
 
replacedby–CH
3
non-polargroupsandfinallysurfacepossesssuperhydropho-biccharacter.
 3.3.Transmission
 
electron
 
microscopicstudies
Fig.3,showsthe
 
transmissionelectronmicrographof 
 
the
 
sil-icacoatingspreparedwith7%PMMA
 
in
 
MTMS
 
silicacoating.Thesilicacoatingon
 
the
 
glass
 
substrateselectedfor
 
the
 
TEM
 
analy-sis,whichshowedhighest
 
contact
 
angleof 
 
171
 
±
1
.This
 
studyrevealedthat
 
the
 
silicaparticlesformedananostructurednetworkparticlessize
 
of 
 
less
 
than
 
50
 
nm.Thesestudiesconfirmthe
 
presenceof 
 
roughnanostructuredprotrusionsandthereforethesemight
 
beresponsiblefor
 
the
 
superhydrophobicityof 
 
the
 
silicacoatingsassuggestedbythe
 
Cassie–Baxtermodel.This
 
studyrevealedthatwell
 
distributednanostructurednetworkof 
 
silicaparticleswithsize
200
 
nm.Thesestudiesconfirmthe
 
91%optical
 
transmittanceinthevisibleregionandpresenceof 
 
roughnanostructuredasperitiesandthereforethesemight
 
be
 
responsiblefor
 
the
 
superhydropho-bicityof 
 
the
 
silicacoatingsas
 
suggestedbythe
 
Cassie–Baxtermodel.
Fig.
 
2.
 
FTIR
 
spectraof 
 
the
 
superhydrophobicsilicacoatings.

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