Physical and chemical treatments of surface for improved adhesion of PVA Coating

Mohamed Ramzi Ammar*, Gilbert. Legeay**, Alain Bulou***, Jean- Fanois.Bardeau***

*IUT de Blois, Universit Franois Rabelais, 3 place Jean Jaurs- C ! "#$3, %&$"# Blois Cede' **Centre de Trans(ert de Tec)nolo*ie du +ans - "$, rue T)als de +ilet, ,"$$$ -e +ans ***-aboratoire de .)/si0ue de l12tat Condens U+R3 C4R! 5$6, - 7venue 8 +essiaen, Universit du +aine, ,"$$$ -e +ans mohamed.ammar uni!-tours."r, glegeay #ttm-lemans.#om, alain.bulou uni!-lemans."r, $ean-"ran#ois.bardeau uni!-lemans."r,

R%&'M%( Les revtements polymres peuvent apporter des proprits intressantes aux surfaces des
dispositifs mdicaux. Des efforts significatifs sont entrepris par les chercheurs afin d'laborer des revtements plus mince, plus fiable et multi-fonctionnels n effet, les surfaces peuvent tre modifies pour amliorer la rentabilit, la longvit et la performance du dispositif.. !ependant, un certain problme d'adhrence revtement polymre"substrat est souvent rencontre. L'ob#ectif du prsent travail est de montrer $ue les traitements de surfaces peuvent amliorer fortement l'adhrence polymre"substrat. Dans notre tude, le substrat modle a t soumis % diffrents types de traitements de surfaces &chimi$ue, physi$ue et mcani$ue'. nsuite, des tests dans le milieu a$ueux sont effectus afin de caractriser l'influence de l'eau sur la stabilit de l'interface du revtement polymre"substrat.

()*+-!L +, -evtement polymre. /dhsion. *raitements de surface, Durabilit

*ntrodu#tion

During the last t0o decades, significant advances have been made in the development of biocompatible materials for biomedical applications. *he goal of actual researches is mainly devoted to the elaboration and characteri1ation of artificial materials &Ball 1997) 0hich could be in contact 0ith biological medium to improve physiologic reaction. 2o0ever, for implants, the interface bet0een the device and the human body can be critical to both performance and therapeutic effectiveness. !areful choice of materials at this interface is therefore 3ey to the success of the device. 4iocompatibility of this type can sometimes be achieved 0ith materials used in bul3 form, but surface modification, especially in the form of a coating, provides a 0ider range of design options and related performance. 5olymeric coatings, in particular, can be chemically, mechanically and physically tailored to produce the desired combination of properties and have found 0idespread use for nonthrombogenic (Frost 2005), lubricous (Thompson et al. 2005), anti-microbial (Carlson et al. 2006) and protective (Reitman et al. 2005) purposes. /lone, in combination or as carriers for active pharmaceutical ingredients, polymeric coatings continue to enable an everexpanding mar3et for implantable medical devices. /mong several choices of polymers, poly&vinyl /lcohol' &56/', a 0ater-soluble polymer, has been fre$uently explored as an implant material in biomedical applications such as drug delivery systems, dialysis membranes, 0ound dressing, artificial s3in, cardiovascular devices and surgical repairs because of its excellent mechanical strength, biocompatibility and non-toxicity (Chiellini et al. 2003) (Pereira et al. 2000) (Yamaokaet al. 1995) (Tang et al.
2007).

4eyond the bio-functional re$uirements, a successful coating must adhere to the device, be flexible and strong enough to 0ithstand the expected movement of the device, allo0 for sterilisation and be durable under the conditions of its use. 7t 0as highlighted that surface $uality strongly affects the adhesion bet0een the polymer and substrate (Cognard 2005). (any adhesion-enhancing techni$ues have been explored, such as mechanical

roughening, plasma treatment and electrochemical anodisation (Cognard 2005) (Dayss et al. 1999). +mith (Smith et al. 1999) reported recently, that they could increase the adhesive force bet0een substrate and a polymer matrix by using silane coupling agent. 7n the present study, 0e investigate the effect of coupling mechanical, chemical and physical parameters on the improved of system durability and stability. 9hat is used to characterise the durability is the extension of the test fracture after some time of exposition in humid condition (Cognard 2005).

%,-erimental

5oly&vinyl alcohol' &56/' 0ith average molecular 0eight + : ;<=== has been used. *he polymer 0as amorphous and atactic and it had degree of hydrolysis of ;< >. *his product 0as purchased from /cross )rganics, 4elgium. ?or a 0ater-soluble hydrophilic polymer, the total amount of the sorbed or the added 0ater may be extended from 1ero to infinity corresponding to its action #ust li3e a plastici1er to a solvent. 2o0ever, the addition of 0ater to 56/ ;<> is limited, no more 0ater could be further sorbed as the s0ollen polymer reaching to a state of e$uilibrium s0elling, because of acetate rest that the polymer contains. /$ueous <> 56/ solutions are prepared 0ith distilled 0ater in a covered bea3er and heating in an oven at @=A! during 8= hours.

&ur"a#e energy e""e#t

7n order to study hydrophilic"hydrophobic character effect of surfaces on polymer coatings adhesion, 0e compared results obtained from silicon substrates &about B cm B' cleaned 0ith ethanol in ultrasonic bath &C+' during < min, and others exposed, thereafter, to C6")1one radiation (Tominaga et al. 2005) during 8< min.*his process removes hydrocarbons from the surface. 2ydrophilic"hydrophobic character has been ascertained by 0ettability 0ith the contact angles measurements, global surface energy and polar and apolar components &according to )0ens-9endt model'. *hese measurements released by goniometry classical methods 0ith three li$uids techni$ue &formamide, diidomethane, 0ater' are given in table 8.

*reatment Days number before unstic3ing !ontact angle &A' 9ater drop +urface energy &mJ.m-K' Dispersive components &mJ.m-K' 5olar components &mJ.m-K'

C+ +ome hours BI L8.8 B@.< FF.@

C+ H C6 ) B L;.8 B@.B MB

/able )9 8bserved values o( contact an*le :(ro; t)ree values< and sur(ace ener*/ calculated (or silicon substrates be(ore and a(ter U=38 treat;ent +ilicon surface becomes very hydrophilic after being exposed to C6") radiation since the contact angle of 0ater drop is about BA. 7t is typically accepted that contact angle measurements smaller than D<E is a signature of a fairly flat and chemically uniform substrate (Packham 2003). Drops of the same polymeric solution are deposited on different substrates. 7nterferometry 0as used to gain accurate information on coating thic3ness &F< G F' m.

Durability test of these layers in 0ater at room temperature is follo0ed by observing the day number that film ta3es to come off completely. /ccording to *able8 results, it seems that C6"o1one treatment enhances slightly polymer coatings adhesion. 2o0ever, this durability remains insufficient, and others treatments are needed.

'se o" -rimary thin layer

7n order to enhance polymeric coating adhesion, a primer nanometric layer of 56/ on silicon substrate is deposited by spin coating process. *his techni$ue allo0s an homogenous film elaboration by a controlled parameters &rotation speed, acceleration, solution viscosity'. *hic3ness of this layer &8F= nm' has been verified by N rays reflectivity as sho0n in figure 8. N-ray reflectivity data 0as collected on a N-5ert 5hilips reflectometer 0or3ing at the energy of the !u Oa radiation &3 :=.8<M nm'

Absolute Re"le#ti!ity 1a.u.2

Reflectivit Absolue

10 1 0,1

0,01 1E-3 1E-4 1E-5 1E-6

Figure )( > curve o( a silicon deposited b/ process

1E-7 0,0 0,1 0,2 0,3

qz ( )

-1

ra/s re(lectivit/ pri;er la/er on substrate spin-coatin*

5olymeric coating of about F< m thic3ness is then deposited in the same manner as previously. 5robably adhesion mechanism bet0een polymeric coating and the primer layer is due to the interdiffusion phenomenon of polymeric chains in the interface from both side polymers according to the Pdiffusion theory of adhesionQ (Voyutskii 1977) 0hich accounted for the time and temperature dependence of the adherence bet0een miscible, soft, polymers. -ecently, it 0as sho0n that amorphous or semi-crystalline, immiscible, polymers could be stitched together by a film of copolymer having lateral chains interpenetrating in both materials 8=. Durability test in a$ueous medium has been done and results are given in *able B.

*reatments Days number before unstic3ing

C+ , +ubstrate cleaning by ultrasonic bath C6"), +ubstrate treated by C6")1one

C+ H 5L <8

C+ H C6") H 5L I8

5L , 5rimer layer

/able +( 2volution o( da/?s nu;ber be(ore pol/;eric coatin* unstic@in* in (unctions o( t)e use o( pri;er t)in la/er

*his durability test sho0s that polymeric coatings deposited on substrates strengthened 0ith a primer layer stay on more than < days. !ompared 0ith *able 8, it appears that the use of primer layer influences system durability. 7tRs certainly obvious that even the process polymeric coating affect adhesion improvement.

%""e#t o" tem-erature treatment

5erformances enhancement of adhesion by using a primer layer encouraged us to study its treatment temperature effect on adhesion. *hree types of substrates 0ere then treated in different vaccum temperatures &L=A!, I=A! and 8==A!' around the glass transition temperature &*g : I=A!'. 7n order to verify composition thin primer layer after temperature treatment, 0e study them 0ith confocal -aman scattering performed 0ith *LM=== Jobin-Svon multichannel spectrometer in simple configuration 0ith L== lines"mm grating coupled to a !!D detector is used. *he spectra 0ere collected in the bac3scattering geometry, under microscope &N8== ob#ective' using the <8M.< nm 0avelenth of /r-Or laser source 0ith 8=m9.

R ! " i"te"sit# (u$ $)

)::8 9 ++8 9
500 1000 1500 2000 2500
-1

3000

3500

% ve"u!be& (c! )
Figure +( Ra;an spectra o( pri;er la/er at roo; te;perature and ot)er treated under vaccu; untill &$$AC durin* "%) / film of polymer &thic3ness, F< m' is deposited on primer coat support. *he durability of these treatments and stability of interfacial strength are estimated by the stability of adhesion 0ith supports coated by dipping in 0ater at room temperature &*able F'. *reatment Days number before unstic3ing C+HC6") H5L &BBA!' 4 ) C+HC6") H5L &L=A!' )+ . C+HC6") H5L &I=A!' .5 3 C+HC6") H5L &8==A!' 6)37+.

/able .( 2volution o( da/?s nu;ber be(ore pol/;eric coatin* unstic@in*, in (unction o( te;perature treat;ent

?igure F sho0s the relation bet0een adhesion durability of micrometric coating according to the treatment temperature. *he results sho0 that coatingRs adhesion increases considerably 0ith the increase of annealing temperature. 7n fact, treatments at 8==A! allo0 to 3eep the polymer coating adhered to the substrates and this after more than @== days of immersion in 0ater.
'00 700 600

(u& bilit# () #s)

500 400 300 200 100 0 20 40 60 '0 100

*&e t!e"t te!+e& tu&e (,-)

Figure .( Burabilit/ test results o( substrats treated b/ U!, U=38 and .- :at various te;peratures<

Me#hani#al roughening e""e#t

7n parallel to the studies underta3en on the effect of physicochemical treatment, the couple effect of a mechanical roughening on silicon surface is estimated. 7ncrease of surface roughness is thought to increase the effective surface of contact bet0een the substrate and the polymer (Cognard 2005). -esults &*able M' indicate that mechanical roughening doesn't improve clearly system durability 0hen polymeric coating is deposited directly above or on the untreated primer layer. 7n other part analysis sho0 that the heat treatment of the primer layer associated to a mechanical roughening proves to reinforce adhesion properties since the number of days before the layer unstic3ing exceeds @8< days actually. tching tching tching tching H C+HC6") H C+HC6")H H C+HC6")H H C+HC6")H 5L &BBA!' 5L &I=A!' 5L &8==A!' 6)3 0 ) ; ) )0. )0

*reatment Days number before unstic3ing

/able 0( 2volution o( da/?s nu;ber be(ore pol/;eric coatin* unstic@in* (unctions o( pri;ar/ la/er treat;ent

9on#lusion

<

*he science of the adhesion of coatings to surfaces is a complex one that contains a degree of mystery in the sense that 0e cannot al0ays explain 0hy it 0or3s or does not 0or3. 6arious process techni$ues available to improve adhesion 0ere discussed in this article. 9hen the coater is satisfied that the surface is as clean as can be achieved, it re$uires, as 0e sho0ed, a primer thin layer to ma3e it 0or3. )ur analyses sho0 clearly that thermal treatment of nanometric primer layer associated to a mecanical etching proved true very effective to consolidate adhesion properties.

*Re"eren#es
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