A corrosion-resistance superhydrophobic TiO2 film

Applied Surface Science 258 (2012) 7460–7464Contents lists available at SciVerse ScienceDirectApplied SurfaceSciencej o u r n a l h o m e p a g e :w w w.e l s e v i e r.c o m /l o c a t e /a p s u scA corrosion-resistance superhydrophobic TiO 2filmYawei Hu a ,b ,Siya Huang a ,Shan Liu a ,Wei Pan a ,∗a State Key Laboratory of New Ceramics and Fine Processing,Tsinghua University,Beijing 100084,PR ChinabCollege of Chemistry and Chemical Engineering,Shaanxi University of Science and Technology,Xi’an,Shaanxi 710021,PR Chinaa r t i c l ei n f oArticle history:Received 21December 2011Received in revised form 8April 2012Accepted 9April 2012Available online 20 April 2012Keywords:TiO 2filmSuperhydrophobicity Corrosion-resistancea b s t r a c tA superhydrophobic TiO 2film with water contact angle greater than 170◦on Hastelloy substrate was fab-ricated through simply dip-coating method from TiO 2precursor solution containing TiO 2nanoparticles with the average diameter 25nm,followed by heat-treatment and modification with fluoroalkylsilane (FAS)molecules.The as-obtained sample was characterized by scanning electron microscopy (SEM),X-ray diffractometer (XRD),X-ray photoelectron spectroscopy (XPS),and water contact angle measurement respectively.Moreover,the dynamic light scattering (DLS)size distribution of TiO 2aggregated particles in the TiO 2precursor solution containing P25particles was evaluated by Laser Particle Sizer.It is found that the TiO 2nanoparticles in TiO 2precursor solution play a crucial role to form high superhydrophobicity.Simultaneously,the superhydrophobic TiO 2film still showed great superhydrophobicity after corroded with strong acid or alkali solutions and protected the substrate from corrosion which should be critical to the potential application in industry.© 2012 Elsevier B.V. All rights reserved.1.IntroductionSuperhydrophobic surface with a water contact angle greater than 150◦has aroused considerable interest in recent years because of the important applications in numerous aspects such as self-cleaning surfaces,non-contaminated materials,corrosion-resistant films,microfluidic devices,and other important industrial pro-cesses [1–4].As is well known,superhydrophobicity of the solid surface is not only governed by the chemical composition but also by the geometrical microstructure of the surface.It is demonstrated that superhydrophobic surface can be fabricated via either creating micro-nanostructured hydrophobic surface or chemically modify-ing the micro-nanostructured surface with low surface free energy materials,or both [5–7].Up to now,a large number of superhy-drophobic surfaces have been generated [8–13].However,very few have achieved the extremely high contact angle (greater than 170◦).Since the extremely high contact angle is very interesting and has the wealth of potential practical application,such as the reducing-friction materials in turbulent flows,efforts have been made to investigate and exploit the superhydrophobic materials with water contact angles greater than 170◦[14].At the same time,extensive researches have recently been con-ducted to realize superhydrophobicity on various metal substrate [15–17].In order to protect metals from corrosion,organic coatings have been widely used in the industry [18–20].Many inorganic∗Corresponding author.Tel.:+861062772858;fax:+861062771160.E-mail address:panw@ (W.Pan).film are also very attractive because they are more resistant to oxidation and corrosion than metals in high temperature environ-ments or corrosive conditions [21–23],such as TiO 2films which are frequently used as protective coatings [24–26].Therefore,it is practically significant to create superhydrophobic TiO 2film with water contact angle greater than 170◦on metal substrates,espe-cially considering the corrosion-resistance in the application.Until now,there have been some reports of TiO 2superhydrophobic films through various process [27].However,few of publications on TiO 2superhydrophobic films with the water contact angles greater than 170◦has been reported,in contrast to the huge number of litera-tures on TiO 2superhydrophobic films.Herein,we report a simple method for preparation of a corrosion-resistance superhydropho-bic TiO 2film on Hastelloy substrate with water contact angle 173.7◦which consists of fabricating a micro-nanostructured TiO 2film and modifying the resultant film with fluoroalkylsilane molecules.Significantly,the superhydrophobic TiO 2film still showed great superhydrophobicity after corroded with strong acid or alkali solu-tion which indicated the good corrosion-resistance property,and the superhydrophobic TiO 2film protected the metal substrate from corrosion.2.Experimental details2.1.Pretreatment of the substrates and preparation of TiO 2superhydrophobic filmIn our experiment,the Hastelloy (mainly containing Ni:56%;Cr:22%;Mo:13%;W:3%;Fe:3%and Co:3%)is used as the substrate,and0169-4332/$–see front matter © 2012 Elsevier B.V. All rights reserved./10.1016/j.apsusc.2012.04.061Y.Hu et al./Applied Surface Science258 (2012) 7460–74647461all reagents are analytical grade and used without further purifica-tion.Specific process of preparation is as follows.2.1.1.Pretreatment of HastelloyThe Hastelloy substrates,with a size of10mm×20mm×2mm were mechanically polished by metallographic abrasive paper and ultrasonically cleaned in acetone,alcohol and deionized water for 30min,respectively.Then the Hastelloy substrates were immersed in1:1HCl aqueous for1h,washed with water,and blown dry. 2.1.2.Preparation of TiO2precursorTiO2precursor was prepared through a typical controlled hydrolysis process modified from the reported method[28].First, 8.2mL tetra-n-butyl titanate was dissolved in5.8mL ethanol.The other5.8mL ethanol was mixedwith0.4mL water and0.25mL68% aqueous solution of nitric acid,and0.9g TiO2nanoparticles with the average diameter25nm(P25,containing80%anatase and20% rutile)were added and ultrasonically dispersed,then the mixturewas added dropwise to the former solution under ice-cooled con-dition with vigorous stirring.0.5g poly(ethylene glycol)(PEG)was added to the solution as soon as the0◦C mixing wasfinished.The container was sealed with stirring to dissolve PEG completely under atmosphere,and then the TiO2sol solution was stirred another24h.2.1.3.Process of TiO2filmThe Hastelloy pre-treated was immersed in TiO2sol for5min, and withdrawn with the rate of3mm s−1.After drying naturally in the ambience,such an operation is repeated two times.Then the specimen was sintered at450◦C for60min with a heating rate 5◦C min−1.2.1.4.Surface modificationThe prepared specimen was placed into a 1.0wt%ethanol solution of CF3(CF2)7CH2CH2Si(OCH3)3(FAS-17),which had been hydrolyzed by the addition of a threefold molar excess of water. The specimen was left in this solution for1h,washed with ethanol, and blown dry,finally placed in an oven at140◦C for1h.2.2.Measurement and characterizationThe TiO2gel was obtained from the TiO2precursor TiO2precur-sor heated at80◦C for20h.The thermal property of the TiO2gel was characterized by thermogravimetric analysis(TG)operating in atmosphere at a heating rate of10◦C min−1from room tem-perature to800◦C.The phases and the crystallographic structures of the TiO2films were characterized by an X-ray diffractometer (XRD)with Cu K␣radiation( =0.154nm)at a scan rate of8◦min−1 ranging from20◦to90◦.Dynamic light scattering(DLS)size distri-bution of TiO2aggregated particles in the TiO2precursor solution containing P25particles was measured by Laser Particle Sizer.The surface topography and structures of the TiO2films were charac-terized by afield-emission scanning electron microscope(FE-SEM) operating at15kV.The chemical composition of the TiO2film modified with FAS was analyzed on an X-ray photoelectron spec-troscope(XPS)equipped with a standard monochromatic Al K␣source(hv=1486.6eV).Water contact angles were measured with a drop shape analyzer at ambient temperature.Water droplets were dropped carefully on to the surfaces and the average value offive measurements at different positions of the sample were adopted as the contact angle.Advancing and receding contact angles were recorded while the water was added to and withdrawn from the drop,respectively.The corrosion-resistant property of the super-hydrophobic TiO2film was so good that the results could be found by eyes.The metal substrates with and without superhydrophobic TiO2films were placed into the corrosion solutions for100h,and Fig.1.The TG pattern of the TiO2gel obtained from the TiO2precursor without TiO2 P25nanoparticles.the corrosion-resistant property of metal substrates with super-hydrophobic TiO2films was evaluated by the photographs of the corrosion solutions.3.Results and discussionAccording to the TG pattern of the TiO2gel obtained from the TiO2precursor without TiO2P25nanoparticles heated at80◦C for 20h(Fig.1),the organic matter in TiO2gel is decomposed before 450◦C completely,which indicates that an annealing treatment at a temperature equal to or greater than450◦C may be required to eliminate the organism residing in the TiO2gel.The SEM images of the TiO2films prepared from the TiO2precur-sor solution containing TiO2P25nanoparticles with heat treatment at450◦C are shown in Fig.2a and b.Fig.2a presents a typical SEM image,which exhibits that the morphology of the TiO2film is composed of nanoparticles with sizes about50–200nm and the relatively small nanoparticles are aggregated to form clusters with the sizes about1␮m.As a result,the TiO2film containing TiO2 P25nanoparticles with heat treatment at450◦C shows micro-and nano-hierarchical structure.And after modified with low surface energy material FAS,the TiO2film displays excellent superhy-drophobic property with the water contact angle of173.7◦and contact angle hysteresis of less than5◦.Fig.2b displays the cross-section SEM image,from which it can be found that the thickness of TiO2film is about500nm.However,the surface morphology of TiO2film fabricated from the TiO2precursor solution without TiO2P25nanoparticles with heat treatment at450◦C shows that thefilm isflatter(Fig.2c)than that fabricated from the TiO2precursor containing P25nanoparti-cles,and its water contact angle and contact angle hysteresis after modified with FAS are only125.3◦and31.8◦,respectively,which indicate that the TiO2P25nanoparticles added into the TiO2pre-cursor solution have an important influence on formation of great superhydrophobicity.The particle size of the TiO2precursor solution containing TiO2 P25nanoparticles was measured by the Laser Particle Sizer.The result suggests that the TiO2P25nanoparticles in the TiO2precur-sor solution obviously generate aggregation with a size range of 150–1200nm(most frequent size,1000nm)(Fig.3),which plays a crucial role in forming the micro-and nanostructured hierarchi-cal structure of TiO2surface.The hierarchical structure of surface likely leads to the efficient trapping of numerous air pockets in the TiO2film surface which makes the TiO2surface minimal contact7462Y.Hu et al./Applied Surface Science 258 (2012) 7460–7464Fig.2.SEM images of TiO 2films of (a)and (b)containing TiO 2P25nanoparticles annealed at 450◦C,(c)without TiO 2P25nanoparticles with heat treatment at 450◦C,(d)containing TiO 2P25nanoparticles with heat treatment at 650◦C.Insets are the images of spherical water droplet placed on FAS modified TiO 2films.with the water and contributes greatly to the superhydrophobicity as often discussed in literature [29].For comparison,the SEM image of TiO 2film fabricated from the TiO 2precursor solution containing TiO 2P25nanoparticles with heat treatment at 650◦C is shown in Fig.2d.It can be observed that the grain grows,the surface becomes dense,and the roughness of surface reduces.After modified with FAS,its water contact angle is about 156.7◦and the contact angle hysteresis is about 17.5◦.As is well known,superhydrophobicity of the solid surface is governed by the chemical composition and the geometrical microstructure of the surface.The growth of TiO 2grains with heat treatment at 650◦C leads to insufficient roughness on the surface for great surperhy-drophobicity to some extent.On the other hand,the phase of TiO 2film containing TiO 2nanoparticles with heat treatment at 650◦C isFig.3.DLS size distribution of TiO 2aggregated particles in the TiO 2precursor solu-tion containing P25particles.rutile phase (curve a in Fig.4).However,the XRD pattern of TiO 2film containing TiO 2nanoparticles with heat treatment at 450◦C (curve b in Fig.4)displays that the film is mainly composed of anatase phase,and comprises little amount of rutile phase.(The rutile phase comes from TiO 2P25nanoparticles because the phase of TiO 2film uncontaining TiO 2P25with heat treatment at 450◦C is pure anatase shown in Fig.4curve c.)It is well known that the anatase TiO 2surface can more easily form hydroxyls than rutile phase,which combine with FAS to achieve superhydrophobicity.Fig.5shows the X-ray photoelectron spectroscopy (XPS)data of the TiO 2superhydrophobic surface.A strong fluorine peak located at 690eV and also the peaks of C and O were observed in this case.This demonstrated that the TiO 2surface was covered by the flu-Fig.4.XRD patterns of TiO 2films.(a and b)Containing TiO 2P25nanoparticles with heat treatment at (a)650◦C and (b)450◦C respectively,(c)without TiO 2P25nanoparticles with heat treatment at 450◦C.Y.Hu et al./Applied Surface Science258 (2012) 7460–74647463Fig.5.XPS spectrum of thefluoroalkylsilanefilm on the superhydrophobic surface. oroalkylsilanefilm which greatly reduced the free energy of the surface.It is confirmed that rough structure of the surface has a profound influence on superhydrophobic property.The superhydrophobicity of a rough surface can be described by Cassie-Baxter equation[30], cosÂr=f(cosÂ+1)−1(1) whereÂandÂr are the contact angles of the smooth and rough sur-face respectively.Here,f is the fraction of area of the solid surface that is actually in contact with water;Âr andÂ(125.3◦,the TiO2sur-face fabricated from the TiO2precursor without TiO2nanoparticles with heat treatment at450◦C is assumed to be smooth TiO2sur-face)are the contact angles of the rough and the smooth TiO2film surface,respectively.According to the equation,f is calculated to 0.014when the contact angle is173.7◦,implying that only1.4%of the observed contact area beneath a water droplet actually touches with the water droplet.In other words,the water droplet is sus-pended on the air pockets trapped in the cavities of the micro-and nano-hierarchical structure of TiO2film surface.By the same way, f is up to0.193when the contact angle is156.7◦,which means that there is19.3%of the observed contact area beneath a water droplet contacting with the water droplet.Eq.(1)has been recently modified to account for the local surface roughness on the wetted area as follows[31]cosÂr=r f f cosÂ+f−1(2) where f is the fraction of the projected area of the solid surface wet-ted by water and r f is the surface roughness of the wetted area.For the surface mainly composed of FAS(Â>90◦for a smooth FAS sur-face),since r f>1for a rough surface in comparison with a smooth wetted area,rough surface can enhance the hydrophobicity. Clearly,the preparedfilm containing TiO2nanoparticles with heat treatment at450◦C(Fig.2a)mainly composed of FAS with the spe-cial hierarchical structure,consisting of microclusters and nanopar-ticles,will have even higher values of r f.Once r f reaches a certain level,air may become trapped within the interstices of the micro-clusters underneath a water droplet.Furthermore,nanoparticles would further enhance the surface hydrophobicity and lead to the high surface superhydrophobicity,which offer less contact areas with water droplet.Therefore,we can conclude that the micro-and nano-hierarchical structure would produce more much cavities to trap air to form air pockets which make the water droplet suspend on the TiO2surface to generate excellent superhydrophobicity.One may doubt that this kind of superhydrophobic TiO2film is stable because of the highly photocatalytic property of anatase TiO2which has a negative influence on the durability of the super-hydrophobicity of TiO2film[32].To release from this suspicion,the water contact angles of the superhydrophobic TiO2film that was placed in a well-lighted room for one,two and three months were measured.However,the water contact angles almost not changed, which indicates that the superhydrophobic TiO2film has quite great stability under indoor conditions.To evaluate the corrosion-resistance property of the super-hydrophobic TiO2film on substrate,the samples were placed into extremely rigorous environment,25%HCl,10%HNO3,50% H2SO4,15%CH3COOH,5mol L−1NaOH and25%CH3CH2OH solu-tion,respectively.In this test,the samples prepared with the same method were immersed into the different corrosive solutions for 100h respectively,then washed with water and dried,followed the water contact angles were measured.The result shows that the water contact angles of TiO2films are still as high as over 170◦and contact angle hysteresis are less than10◦after eroded with H2SO4and NaOH corrosive solutions for100h respectively. Even though the wettability of TiO2film corroded with HCl cor-rosive solution is worst,its water contact angle is still154.3◦and contact angle hysteresis is27.2◦(Table1).However,the hydropho-bic TiO2film(without P25TiO2nanoparticles)with water contact angle of125.3◦has a high contact angle hysteresis of64.5◦after eroded with HCl corrosive solution which will limit the applica-tion of TiO2film as self-cleaning material(Table2).In our work, the corrosion-resistance test of the superhydrophobic TiO2film is completely different from the literatures reported in which only the acid solutions of pH1–2or alkali solutions of pH13–14were used[33–35].The concentrations of acid corrosive solutions in our work are30–1000times more than ones reported in literatures. And the concentration of alkali corrosive solution is increased to 5–50times as against ones reported in literatures.Since the acid corrosions of Hastelloy are more easily than the other solutions,the anti-acid-corrosive property of Hastelloy covered with and without superhydrophobic TiO2film was studied simply.In this test,the samples prepared with the same method were immersed into the different acid corrosive solutions for 100h respectively,then washed with water and dried,followed the water contact angles were measured.After the bare Hastelloy substrates were placed into25%HCl,50%H2SO4and10%HNO3 corrosive solution for100h,respectively,the colors of the corro-sive solutions exhibited dark green,light green and colorless in turn(Fig.6),which means that the substrate was corroded most severely in25%HCl solution.However,to the substrate with the superhydrophobic TiO2film,the colors of HCl,H2SO4and HNO3Table1Water contact angle data of TiO2film with equilibrium contact angle173.7◦after immersed in different corrosion solutions for100h.Corrosion solution Equilibrium contact angle(◦)Advancing contact angle(◦)Receding contact angle(◦)Contact angle hysteresis(◦)Before corrosion173.7176.2171.5 4.7HCl(25%)154.3169.5142.327.2HNO3(10%)164.3171.4158.113.3H2SO4(50%)171.5176.2167.09.2CH3COOH(15%)161.9170.6154.116.5NaOH(5mol/L)172.6176.6168.38.3CH3CH2OH(25%)158.1168.6148.819.87464Y.Hu et al./Applied Surface Science 258 (2012) 7460–7464Table 2Water contact angle data of TiO 2film (without P25TiO 2nanoparticles)with equilibrium contact angle 125.3◦after immersed in different corrosion solutions for 100h.Corrosion solutionEquilibrium contact angle (◦)Advancing contact angle (◦)Receding contact angle (◦)Contact angle hysteresis (◦)Before corrosion 125.3142.5110.731.8HCl (25%)100.4136.772.264.5HNO 3(10%)114.7138.392.545.8H 2SO 4(50%)116.3136.596.440.1CH 3COOH (15%)115.6137.795.342.4NaOH (5mol/L)120.0138.1102.535.6CH 3CH 2OH (25%)108.1130.678.652.0Fig.6.Photo images of corrosion solutions,(a)25%HCl,(c)50%H 2SO 4,(e)10%HNO 3after the bare Hastelloy substrate was immersed for 100h,respectively;(b)25%HCl,(d)50%H 2SO 4and (f)10%HNO 3after the Hastelloy substrate with superhydrophobic TiO 2film was immersed for 100h,respectively.corrosive solutions were colorless which illuminated that the substrates nearly were not corroded.The result powerfully proved that the TiO 2superhydrophobic film,as a barrier,effectively protected the metal substrate from corrosion.4.ConclusionsIn summary,we have succeeded in fabricating superhydropho-bic TiO 2film on metal by a simple two-step method,which consists of dip-coating TiO 2film from TiO 2sol solution contain-ing TiO 2nanoparticles with the average diameter 25nm which has been rare reported,and modifying with fluoroalkylsilane CF 3(CF 2)7CH 2CH 2Si(OCH 3)3molecules.This superhydrophobic TiO 2film exhibits high superhydrophobicity with water contact angle of 173.7◦and corrosion-resistance property.This corrosion-resistance 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