Influence of annealing temperature on structure and photocatalytic activity of TiO2 thin films prepared by DC reactive magnetron sputtering method

Transparent TiO₂ thin films were successfully prepared on high purity silica substrates by DC reactive magnetron sputtering method and annealed at different temperatures. The effects of the annealing temperature （300-600 ℃） on crystalline structure, morphology, and photocatalytic activity of the TiO₂ thin films were discussed. The photocatalytic activity of the films was evaluated by photodegradation of methylene blue solution. With increasing annealing temperature, the photocatalytic activity of the TiO₂ thin films gradually increased because of the improvement of crystallization of anatase TiO₂ thin films. At 500 ℃, the TiO₂ thin film shows the highest photocatalytic activity due to the improvement of crystallization of anatase TiO₂ thin films. When the annealing temperature increases to 600 ℃, the photocatalytic activity of thin film decreases owing to the formation of rutile phase and the decrease of surface area.     

Sol-Gel Preparation of TiO2/SiO2 Nanocomposites and Their Application in Self- cleaning Textiles

The present study involves the preparation of TiO2/SiO2 nanocrystals and their application in self-clcaning wool-polyester fabrics. The TiO2/SiO2 nanocrystals were successfully synthesized and deposited onto wool-polyester fabrics using the low-temperature sol-gel technique. The as-prepared nanoeomposites and the nanocomposites coated samples were characterized by X-ray diffraction （XRD） and scanning electron microscopy （SEM）, respectively. The XRD and SEM results showed that the single-phase anatase nanocrystallites were formed and loaded on the fabric surface successfully. The photocatalytic activities of TiO2 -coated and TiO2/SiO2-coated wool-polyester fabrics were measured by studying photodegradation of methylene blue dye. Comparison of the photocatalytic activity of the coated samples reveals superiority of TiO2/SiO2 modified sample with respect to that of pure TiO2 modified sample. Our observations indicate that by applying this technique to the fabrics, self-cleaning materials can be designed for practical application.     

Microstructure and properties of hydrophobic films derived from Fe-W amorphous alloy

Amorphous metals are totally different from crystalline metals in regard to atom arrangement. Amorphous metals do not have grain boundaries and weak spots that crystalline materials contain, making them more resistant to wear and corrosion. In this study, amorphous Fe-W alloy films were first prepared by an electroplating method and were then made hydrophobic by modification with a water repellent (heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysilane. Hierarchical micro-nano structures can be obtained by slightly oxidizing the as-deposited alloy, accompanied by phase transformation from amorphous to crystalline during heat treatment. The micro-nano structures can trap air to form an extremely thin cushion of air between the water and the film, which is critical to producing hydrophobicity in the film. Results show that the average values of capacitance, roughness factor, and impedance for specific surface areas of a 600℃ heat-treated sample are greater than those of a sample treated at 500℃. Importantly, the coating can be fabricated on various metal substrates to act as a corrosion retardant.     

Preparation and magnetic properties of CoFe2O4/TiO2 composite films

Using （Ti（OC4H9）4） and metal chlorates as starting materials, CoFe2O4/TiO2 composite films were prepared by sol-gel method. The effects of heat treatment temperature and pH of the precursor on microstructure and magnetic properties were studied. The phase structure of the samples was examined by X-ray diffraction. The microstructure was examined by scanning electron microscope, atomic force microscope and polarized microscope. The magnetic property was measured by vibrating sample magnetometer. The results show that the crystals of different phases grow up independently. CoFe2O4 is uniformly embedded into the TiO2 matrix in the prepared composite films, and the growth of composite films is dependent on the heat treatment temperatures and PH of the precursor. The average size of CoFe2O4 crystal is 19 nm in Nanocomposite film prepared when the heat treatment temperature is 800℃ and the pH of the precursor is between 2 and 3. The magnetism of the composite films is enhanced as the heat treatment temperature increases.     

Preparation and magnetic properties of CoFe_2O_4/TiO_2 composite films

Using (Ti(OC_4H_9)_4) and metal chlorates as starting materials, CoFe_2O_4/TiO_2 composite films were pre-pared by sol-gel method. The effects of heat treatment temperature and pH of the precursor on micro-structure and magnetic properties were studied. The phase structure of the samples was examined by X-ray diffraction. The microstructure was examined by scanning electron microscope, atomic force microscope and polarized microscope. The magnetic property was measured by vibrating sample magnetometer. The results show that the crystals of different phases grow up independently. CoFe_2O_4 is uniformly embedded into the TiO_2 matrix in the prepared composite films, and the growth of com-posite films is dependent on the heat treatment temperatures and PH of the precursor. The average size of CoFe_2O_4 crystal is 19 nm in Nanocomposite film prepared when the heat treatment temperature is 800℃ and the pH of the precursor is between 2 and 3. The magnetism of the composite films is en-hanced as the heat treatment temperature increases.     

Preparation of TiO2 Coated on Fabrics and Their Photocatalytic Reactivity

Nanoscale titanium dioxide functional films were prepared on the surface of the cotton woven fabric and the polyester knitted fabric at room temperature by Radio Frequency （RF） magnetron sputtering process. The surface microstructure and morphology were characterized by scanning electron microscope （SEM） and X-ray diffraction （XRD）. Photocatalytic property of two treated fabrics was tested in solar and ultraviolet （UV） radiation respectively, and their photocatalytic activity was compared. The results showed that the nanoscale titanium dioxide deposited on the surface of the treated fabrics was at different anastasia phase. The treated fabrics have excellent photocatalytic property, and after 30 launderings, the photocatalytic activity still maintained at a high level. Also, it indicated that the photocatalytic activity of the treated fabrics in UV radiation was higher than in solar radiation, but the effect wasn＇t very distinct. And at the same experimental magnetron sputtering parameters, the cotton coated with the nanoscale titanium dioxide showed better performance than the polyester fabric coated with the nanoscale titanium dioxide in terms of the photocatalytic property.     

Synthesis and Characterization of Titania and Rare Earth Doped Titania Nanoparticles by Sol-gel Process

Titania sol has been prepared by the sol-gel process with Ti（OC4H9）4, as precursor. TiO2 gel was obtained through hydrolysis and condensation process. Rare earth such as La2O3, CeO2 and Gd2O3 were introduced into the nanostructure TiO2. After TiO2 and rare earth doped TiO2 powders were calcined at 400℃, 500℃, 600℃, 700℃ and 800℃ respectively, the characteristic analyses of the TiO2 samples were studied by UV-VIS, XRD and TEM etc. It was found that there are some stringer absorption peaks at 200 - 325 nm. The rare earth doping can increase the phase transition temperature convertin8 anatase phase into rutile phase, can decrease the grain size of TiO2particles and can improve the ann-UV capacity of the coating fabrics.     

Fabrication and Photocatalytic Characteristics of TiO2 Films on Silicon Substrates

Silicon ( 111 ) and Silicon (100) have been employed for fabrication of TiO2 films by metal organic chemical vapor deposition (MOCVD). Titanium (Ⅳ) isopropoxide (Ti[O (C3H7)4 ])was used as a precursor. The as-deposited TiO2 films have been characterized with Field emission scanning electron microscopy (FE-SEM), X ray diffraction (XRD) and atomic force microscopy (AFM). The photocatalytic properties were investigated by decomposition of aqueous orange Ⅱ. The crystalline and structural properties of TiO2 film had crucial influences on the photodegradation efficiency. For MOCVD in-situ deposited films on Si substrates, thephotoactivities varied following a shape of “M”: At lower (350 ℃ ) middle (500 ℃) and higher (800 ℃) temperature of deposition, relative lower photodegradation activities have been observed. At 400 ℃ and 700 ℃ of deposition, relative higher efficiencies of degradation have been obtained, because one predominant crystallite orientation could be obtained as deposition at those two temperatures, especially a single anatase crystalline TiO2 film could be obtained at 700 ℃ growth.     

Photocatalytic oxidation of gaseous benzene over nanosized TiO2 prepared by solvothermal method

Nanosized TiO2 particles were prepared by solvothermal method using tetrabutyl titanate as precursor,ethanol and water as solvents,and a facile immobilization method of nanosized TiO2 particles on woven glass fabric was developed. The samples obtained under various preparation conditions were charac-terized by means of thermo gravimetric analysis(TG) and differential scanning calorimetry(DSC) ,X-ray diffraction(XRD) ,transmission electron microscopy(TEM) ,high resolution-transmission electron mi-croscopy(HR-TEM) ,and Brunauer-Emmett-Teller(BET) . The results show that the cube-shape of TiO2 prepared by solvothermal method has good crystallinity of(101) surface,higher thermal stability and large specific surface area. Scanning electron microscopy(SEM) images confirmed that the immobi-lized TiO2 film was uniformly distributed and clung to the substrate firmly. The photocatalytic activity of the catalysts was tested using photocatalytic oxidation of gaseous benzene. The results show that the TiO2 calcined after solvothermal treatment suffers from lower specific surface area,and hence de-creases its photocatalytic activity. The photocatalytic activities of the TiO2 by solvothermal treatment with or without calcination in degradation 400 mg/m3 benzene are 3.7 and 4.1 times as high as catalyst without solvothermal treatment,respectively.     

Preparation and characterization of SiO2 non-catalytic nucleation coating for the solidification of undercooled melt

SiO2 non-catalytic nucleation films were coated onto a ceramic substrate and the inner surface of a ceramic crucible by the Sol-Gel method. The surface morphology of the coatings was characterized with an atomic force microscope and a scanning electronic microscope. The non-catalytic effect of the coating on the heterogeneous nucleation of metal melts was tested through measuring the nucleation undercooling. Investigation results indicated that the prepared coating could act as a baffle-wall to prevent the metal melt from nucleating heterogeneously on the inner surface of the crystalline crucible. The tiny holes with a diameter below 2 μm and heaves on the coating surface have no evident effect on the undercooling of metal melts. For a poly-layer coating, the super-layer can cover the cracks in the sub-layers, which prevents the cracks in the coating from spreading in the direction vertical to the coating layers and thus eliminates the effect of cracks on the coating.     

热处理温度对TiO2薄膜光催化活性影响的研究

 采用溶胶-凝胶法及浸渍提拉法,在普通玻璃载玻片上制得了TiO₂薄膜,通过差热分析仪及X射线衍射仪分析了热处理温度对TiO₂的晶型、晶粒大小、孔隙率及薄膜的光催化活性的影响,结果表明存在一个最佳的热处理温度范围,在这一温度范围内薄膜的光催化活性最好.     

Band structur e design of semiconduc tors for enhanced photocatalytic activity: The case of TiO2

General strategies are proposed by passivated co-doping in present paper to improve the photocatalytic activity of semiconductors for degradation of environmental pollutants.The ideal band gap of semiconductors for enhancement of photocatalytic activity can be lowered to match with visible light absorption and the location of the Conduction Band(CB) should be raised to meet the reducing capacity.Then we apply the strategy to anatase TiO2.It is predicted that nonmetal–metal co-doping TiO2can modify the catalyst band edges by raising the valence band(VB) edge signifcantly and making the CB edge increased 0.24 eV.Therefore,the band gap for co-doping system should be narrowed to about2.72 eV.(N,Ta) is predicted to be the target donor–acceptor combination with the band gap of 2.71 eV,which red-shifts the TiO2absorption edge to 457.6 nm in visible range.The band engineering principle will be ft to other wide-band-gap semiconductors for enhanced photocatalytic activity.     

Bionic titania coating carbon multi-layer material derived from natural leaf and its superior photocatalytic performance

Bionic titania coating carbon multi-layer material was fabricated by employing canna leaves as substrate and carbon precursor. Titania nanocrystals were assembled and coated on the natural films. The carbonation treatment under pure N_2 atmosphere yielded the ultrathin multi-film hybrid material. The carbon layer was coated with small anatase titania crystallite(8–10 nm) and possessed a highly specific surface area of 248.3 m~2 g~(-1). Examination using UV–visible spectrophotometer(UV–vis) showed that the band gap of the multi-layer material was reduced to 2.75 eV, and the hydrogen production by photocatalytic splitting of water under visible light irradiation was about 302 μmol g~(-1) after six hour.     

纳米TiO2/玻璃膜的制备及其光催化性能

以钛醇盐为原料, 采用溶胶-凝胶法制备了纳米TiO2/玻璃薄膜. XRD、AFM和厚度分析表明,纳米TiO2/玻璃薄膜中TiO2为锐钛矿型结构, 粒径为纳米级, 三层膜的总厚度为200#nm.通过调节热处理温度, 能有效控制薄膜中粒子的大小.UV-VIS吸收光谱表明,TiO2/玻璃薄膜可以有效地降解罗丹明B染料废水,其光催化活性随TiO2粒径的减小而增大,受膜厚增加的影响不大.     

Oxygen-rich carbon-nitrogen quantum dots as cocatalysts for enhanced photocatalytic H2 production activity of TiO2 nanofibers

We developed an one-step hydrothermal method to synthesize carbon-nitrogen quantum dots(CNQDs) with oxygen-rich functional groups.The sample was characterized by TEM,AFM,FT-IR,XPS,UV-vis absorption and PL spectra.The 0/C and N/C atomic ratio of typical CNQDs with diameters of 3-6 nm are ca.0.4 and 0.2,respectively.Without noble metal cocatalyst,the photocatalytic H_2 production rate of CNQDs/TiO_2 nanofibers(NFs)(112.4 μmol h~(-1) g~(-1)) is 1.8 times higher than that of TiO_2 NFs.The good absorption of light contributes to the enhanced photocatalytic H_2 performance.The CNQDs could be promising in biomedical imaging,optical data recording storage and photo/electrocatalysis,etc.     

一步法合成耐久性水基超疏水TiO2/DTMS涂层

为制备具有优异自清洁功能的耐久性水基超疏水涂层，以十二烷基三甲氧基硅烷(n-dodecyltrimethoxysilane, DTMS)为有机改性物，通过一步法在纳米TiO₂表面嫁接长链烷基官能团得到超疏水TiO₂/DTMS涂层。分析了TiO₂涂层及TiO₂/DTMS涂层的表面润湿性、形貌和化学组成，并对所得超疏水TiO₂/DTMS涂层的自清洁性能、机械及化学稳定性进行了测试。结果表明：超疏水TiO₂/DTMS涂层表面水接触角(water contact angle, WCA)达到159°；以亚甲基蓝粉末作模拟污染物，涂覆有超疏水TiO₂/DTMS涂层的玻璃具有优异的自清洁性能；经机械磨损(10 min)、酸碱液(pH=1、3、5、7、9、11、13)浸泡、高低温(−20、30、60、90、120、150 ℃)处理后超疏水TiO₂/DTMS涂层的WCA仍大于150°，表明其具有优异的机械和化学稳定性，可用于室外防污，如建筑物外墙、玻璃、太阳能电池板等。     

An in vitro evaluation of novel NHA/zircon plasma coating on 316L stainless steel dental implant

The surface characteristics of an implant that influence the speed and strength of osseointegration include crystal structure and bioactivity. The aim of this study was to evaluate the bioactivity of a novel natural hydroxyapatite/zircon(NHA/zircon) nanobiocomposite coating on 316L stainless steel(SS) dental implants soaking in simulated body fluid. A novel NHA/zircon nanobiocomposite was fabricated with 0(control),5, 10, and 15 wt% of zircon in NHA using ball mill for 1 h. The composite mixture was coated on SS implants using a plasma spray method.Scanning electron microscopy(SEM) was used to evaluate surface morphology, and X-ray diffraction(XRD) was used to analyze phase composition and crystallinity(Xc). Further, calcium ion release was measured to evaluate the coated nanobiocomposite samples. The prepared NHA/zircon coating had a nanoscale morphological structure with a mean crystallite size of 30–40 nm in diameter and a bone-like composition,which is similar to that of the biological apatite of a bone. For the prepared NHA powder, high bioactivity was observed owing to the formation of apatite crystals on its surface. Both minimum crystallinity(Xc=41.1%) and maximum bioactivity occurred in the sample containing 10 wt% of zircon because of minimum Xcand maximum biodegradation of the coating sample.     

Fabrication and character ization of electrospun TiO2/CuS micro–nano-scaled composite fibers

A process to fabricate a kind of novel micro–nano scaled TiO2/CuS composite fibers by electrospinning technique and chemical precipitation method was developed in the present study. The microstructures and photoelectronic properties of the fibers were characterize d using SEM, FT-IR, UV–vis and fluorescence spectroscopy. The results revealed that the TiO2 portion in the composite fibers was a mixture rutile and anatase phases while TiO2 and CuS had been fully composite. The fibers had smooth surface with a diameter of 50–300 nm. Comparing with pure TiO2 fiber, the TiO2/CuS micro–nano-scaled composite fibers exhibited a strong absorption in the visible light region and the efficiency of photo-induced charge separation were enhanced. This composite system is of widely potential applications in the areas such as solar cells, supercapacity, photocatalysis, etc.     

Structure evolution of Y2O3 nanoparticle/Fe composite during mechanical milling and annealing

Fe-25 wt% Y2O3composite powders have been fabricated by mechanical milling(MM) Fe powders of 100 μm in diameter and Y2O3nanoparticles in an argon atmosphere for the milling periods of4,8,12,24,36,and 48 h,respectively.The features of these powders were characterized by using X-ray diffraction(XRD),scanning electron microscopy(SEM),electron probe micro analyzer(EPMA) and transmission electron microscopy(TEM).The experimental results showed that the mean particle size and crystalline size of MM powders decreased with the milling time increasing.All the elements distributed homogenously inside the powders after 48 h of MM.The lattice constant of the matrix α-Fe kept constant with the milling time,and no solid solution took place during MM process.After 8 h of MM,the α-Fe in each powder became nanocrystalline.After 48 h of MM,Y2O3changes from nanostructure into amorphous structure,and the crystalline size of α-Fe further decreased to 10 nm.The Y2O3in the powders mechanically milled for 48 h kept the amorphous structure after being annealed at 400 1C,and starts to crystallize when the powders are annealed at 600 1C.The amorphous Y2O3contains a small amount of Fe,and crystalline FeYO3appears at 800 1C.     

Properties of garnet-type Li6La3ZrTaO12 solid electrolyte films fabricated by aerosol deposition method

The garnet-type Li_6La_3ZrTaO_(12)(LLZT) solid electrolyte films were fabricated by aerosol deposition(AD)method.Ball-milled LLZT powder with a cubic garnet structure and a particle size of 1-2 urn was used as raw material and deposited directly on a SUS316L or a glass substrate via impact consolidation.As-deposited LLZT film has a cubic garnet structure but contains Li_2CO_3 and La_2Zr_2O_7 phases.SEM observation revealed that the film consists of LLZT particles fractured into submicron size.The impurity phase formation during AD process was caused by the local heating by the collision between LLZT particles and deposition surface and reaction with CO_2.The Li~+ ion conductivity of LLZT film was estimated to be 0.24 × 10~(-5)S cm~(-1) at room temperature.Electronic conductivity of LLZT film was confirmed to be around 10~(-12) S cm~(-1),indicating the dominant Li~+ ion conduction of LLZT film.