Characterization of TiO2 coatings prepared by a modified electric arc-physical vapour deposition system

TiO₂ thin coatings were prepared, on various substrates, through evaporation of metallic titanium in an oxidizing atmosphere by modified electric arc-physical vapor deposition (EA-PVD). The coatings were characterized chemically (by means of XPS and SIMS) and from the structural point of view (by means of XRD and Raman spectroscopy), in order to understand the factors which lead to homogeneous coatings with high anatase content. The type of substrate is the main parameter that influences the crystal structure of the coatings: when stainless steel is used as substrate the coatings consist essentially of rutile, while on glass substrates coatings containing mainly anatase are obtained. The photocatalytic activity of the samples upon UVA irradiation was tested by using phenol as the target molecule. Phenol in the solution can be photocatalytically and rapidly degraded through the EA-PVD anatase TiO₂ coatings.     

聚四氟乙烯表面PDA/TiO2复合薄膜的构建及其细胞响应性

聚四氟乙烯（PTFE）具有良好的生物稳定性,是一种被广泛应用的生物材料。利用聚多巴胺（PDA）化学及原位共沉积法,在PTFE基板表面沉积制备复合薄膜,以改善其表面的亲水性和细胞响应特性。研究结果显示,由PDA和TiO₂构成的薄膜可以有效地沉积与PTFE基板表面。薄膜均匀且与基板结合牢固,剪切强度可达23.5 MPa。薄膜中的TiO₂含量可以通过沉积液中的TiO₂水溶胶加入量调节。具有薄膜的PTFE表面成纤维细胞和成骨细胞响应性较之PTFE基板显著改进,1 d的细胞粘附试验和3 d的细胞增殖试验均显示涂层表面细胞数量显著高于无涂层的PTFE。这种在PTFE表面构建二氧化钛涂层的方法简单易行,在PTFE植入体表面修饰方面具有较好的应用前景。     

Non-destructive evaluation of strength and residual stress for weldments using continuous indentation technique

TiO₂ photocatalysts are attractive and promising materials due to their excellent properties such as high photocatalytic activity, stability and non-toxicity. Therefore, TiO₂ photocatalyst has applied into various fields such as environmental purifications. The major forms of TiO₂ photocatalysts are fine particles in order to obtain high surface areas. In order to fabricate commercial applications, the coating procedures using binder chemicals must be employed. However, the fine TiO₂ particles slightly scattered at the surface, since most particles are buried in binder chemicals, leading to obtaining poor photocatalytic activity. TiO₂ films can be easily formed on a metallic titanium substrate by anodization. However, the amorphous TiO₂ films with no photocatalytic activities are usually obtained in conventional anodization. We have successfully obtained the high performance photocatalytic TiO₂ films by using combined treatment of pre-nitridation and anodization. The photocatalytic TiO₂ films show the high photocatalytic activities to decompose the various volatile organic compounds such as trichloroethylene, isopropyl alcohol, acetaldehyde, and so on.     

Physical properties of chemical vapour deposited nanostructured carbon thin films

A simple thermal chemical vapour deposition technique is employed for the deposition of carbon films by pyrolysing the natural precursor “turpentine oil” on to the stainless steel (SS) and FTO coated quartz substrates at higher temperatures (700-1100 °C). In this work, we have studied the influence of substrate and deposition temperature on the evolution of structural and morphological properties of nanostructured carbon films. The films were characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), contact angle measurements, Fourier transform infrared (FTIR) and Raman spectroscopy techniques. XRD study reveals that the films are polycrystalline exhibiting hexagonal and face-centered cubic structures on SS and FTO coated glass substrates respectively. SEM images show the porous and agglomerated surface of the films. Deposited carbon films show the hydrophobic nature. FTIR study displays C-H and O-H stretching vibration modes in the films. Raman analysis shows that, high ID/IG for FTO substrate confirms the dominance of sp³ bonds with diamond phase and less for SS shows graphitization effect with dominant sp² bonds. It reveals the difference in local microstructure of carbon deposits leading to variation in contact angle and hardness, which is ascribed to difference in the packing density of carbon films, as observed also by Raman.     

Corrosion resistance of TiO2 films grown on stainless steel by atomic layer deposition

Titanium dioxide (TiO₂) films have been deposited onto stainless steel substrates using atomic layer deposition (ALD) technique. Composition analysis shows that the films shield the substrates entirely. The TiO₂ films are amorphous in structure as characterized by X-ray diffraction. The electrochemical measurements show that the equilibrium corrosion potential positively shifts from − 0.96 eV for bare stainless steel to − 0.63 eV for TiO₂ coated stainless steel, and the corrosion current density decreases from 7.0 × 10^− 7 A/cm² to 6.3 × 10^− 8 A/cm². The corrosion resistance obtained by fitting the impedance spectra also reveals that the TiO₂ films provide good protection for stainless steel against corrosion in sodium chloride solution. The above results indicate that TiO₂ films deposited by ALD are effective in protecting stainless steel from corrosion.     

TiOxNy coatings grown by atmospheric pressure metal organic chemical vapor deposition

Titanium oxynitride coatings were deposited on various substrates by an original atmospheric pressure metal organic chemical vapor deposition (MOCVD) process using titanium tetra-iso-propoxide as titanium and oxygen precursors and hydrazine as a nitrogen source. The films composition was monitored by controlling the N₂H₄ mole fraction in the initial reactive gas phase. The variation of the N content in the films results in significant changes in morphological, structural and mechanical properties. When a large excess of the nitrogen source is used the resulting film contains ca 17  at % of nitrogen and forms dense and amorphous TiO_xN_y films. Growth rates of these amorphous TiO_1.5N_0.5 coatings as high as 14 μm/h were obtained under atmospheric pressure. The influence of the deposition conditions on the morphology, the structure, the composition and the growth rate of the films is presented. For the particular conditions leading to the growth of amorphous TiO_1.5N_0.5 coatings, first studies on the mechanical properties of samples grown on stainless steel have revealed a high hardness, a low friction coefficient, and a good wear resistance in unlubricated sliding experiments against alumina which make them very attractive as protective metallurgical coatings.     

Electrochemical behaviors of TiO2−x films synthesized by plasma-based ion implantation and deposition in fibrinogen containing PBS solution

TiO_2−x films were synthesized on carbon by plasma-based ion implantation and deposition (PBII-D). Electrochemical behaviors of the prepared films were investigated in phosphate buffer solution (PBS) and fibrinogen containing PBS solution (PBS(Fn)), to probe charge transfer phenomena between TiO_2−x film and fibrinogen. Electrochemical impedance spectroscopy (EIS) as well as simulated values of equivalent circuit units including reaction resistance and electric double layer has been obtained, indicating different charge transfer rate occurred across the interfaces. The shape of Mott-Schottky spectroscopy around the rest-open potential indicates that TiO_2−x films are typical n-type semiconductor. Donor density results calculated by Mott-Schottky theory show that TiO_2−x films exhibit higher donor density in PBS(Fn) than in PBS, indicating charge transfer from fibrinogen to TiO_2−x films, and the space charge layers bend lower.     

Morphology and photocatalytic activity of highly oriented mixed phase titanium dioxide thin films

Thin TiO₂ films on quartz substrates were prepared by spin coating of undoped and metal-ion-doped Sol-Gel precursors. These films were characterised by Scanning Electron Microscopy, Laser Raman Microspectroscopy, X-ray Diffraction and UV-Vis Transmission. The photocatalytic performances of the films were assessed by the photo-degradation of methylene-blue in aqueous solution under UV irradiation. Films exhibited a high degree of orientation and a thermal stabilization of the anatase phase as a result of substrate effects. In the absence of dopants, the rutile phase formed as parallel bands in the anatase which broadened as the transformation progressed. TiO₂ films doped or co-doped with transition metals exhibited the formation of rutile in segregated clusters at temperatures under ~ 800 °C as a result of increased levels of oxygen vacancies. Photocatalytic activity of the films synthesised in this work was low as likely a result of poor TiO₂ surface contact with dye molecules in the solution. The presence of transition metal dopants appears detrimental to photocatalytic activity while the performance of mixed phase films was not observed to differ significantly from single phase material.     

Production of MgB2 superconducting coatings by electrophoresis on metal substrates

Production of MgB₂ coatings on various metallic substrates was achieved by means of the direct electrophoretic deposition technique. An inexpensive simple heat treatment in evacuated quartz tubes was developed as an alternative to inert gas flow during the process. The films were characterized by XRD, SEM and SQUID. It resulted that the procedure led to the production of uniform, dense and well-adhesive superconducting films. Stainless steel proved to be the best substrate among the investigated metals.     

SnO2@TiO2核-壳纳米线的制备及其光催化性能研究

本文通过固-液-气(VLS)生长机制,利用化学气相沉积法(CVD)制备SnO₂纳米线。利用原子层沉积(ALD)以钛酸四异丙酯为前驱体在SnO₂纳米线表面沉积不同厚度的TiO₂壳层,形成SnO₂@TiO₂核-壳纳米线结构。通过中间Al₂O₃插层,分别制备出金红石和锐钛矿两种不同晶型的TiO₂,从而制备出两种不同复合结构的SnO₂@TiO₂核-壳纳米线。实验研究该复合结构中TiO₂的厚度与晶型对紫外光下光催化降解甲基橙溶液活性的影响。     

An efficient protection of stainless steel against corrosion: Combination of a conversion layer and titanium dioxide deposit

In the present work, a novel process has been developed to improve the corrosion properties of ferritic stainless steels. Titanium oxide coatings have been deposited onto stainless steel by sol-gel process after a pre-functionalization of the substrate in a conversion bath. Gel titania was prepared by hydrolysis of a titanium butoxide through a sol-gel process. Duplex systems “conversion layer/uniform TiO₂ coating” have been prepared on stainless steels using a dipping technique and thermal post-treatments at 450 °C. The preparation of sol-gel coatings with specific chemical functions offers tailoring of their structure, texture and thickness and allows the fabrication of large coatings. The morphology and structure of the coatings were analysed using scanning electron microscopy with field effect gun (SEM-FEG), Mass spectroscopy of secondary ions (SIMS) and X-ray diffraction (XRD). The anticorrosion performances and the ageing effects of the coatings have been evaluated in neutral and aggressive media by using several normalized tests.The results show that the conversion layer was not sufficient to protect steel but sol-gel TiO₂ coatings, anchored on the metal substrate via the conversion layer, show good adhesion with the substrate and act as a very efficient protective barrier against corrosion. So, duplex layers with TiO₂ nanoparticle coatings on steels exhibit an excellent corrosion resistance due to a ceramic protective barrier on metal surface. Analysis of the data indicates that the films act as geometric blocking layers against exposure to the corrosive media and increase drastically the lifetime of the substrate.     

Evaluation of physico-chemical properties of plasma treated PS-TiO2 nanocomposite film

In this work, we use TiO₂ nanoparticles with average particle size 30 nm and polystyrene for production nanocomposite thin films. After polystyrene was dissolved in toluene, then TiO₂ nanoparticles was added to the solution with different percentage. The obtained solutions were coated on quartz substrate using spin coater. The effect of argon RF plasma (13.6 MHz, with treatment time 30-120 s) on the optical properties, crystallinity, and the surface energy of PS-TiO₂ nanocomposite has been investigated. Some characterization techniques viz., X-ray diffraction analysis (XRD), UV-visible spectroscopy and contact angle measurement were used to study the induced changes on the properties of the treated PS-TiO₂ nanocomposite. Crystalinity and optical properties remained unchanged at the same conditions. Moreover, the surface energy of treated sample varied comparing to the respective untreated samples.     

Ionic compounds lamination reaction and characteristics of photosensitive copper indium sulfide on titania nanotube arrays

This study investigates using an inorganic photosensitive CuInS₂ (CIS) coating instead of an organic dye on TiO₂ nanotube arrays (TNAs). The stoichiometric characteristics by use of various deposition parameters such as precursor concentrations (0.1 M, 0.05 M, and 0.01 M) and deposition cycles (1-60 cycles) are then analyzed in relation to the crystallinity and photosensitivity. TNAs are synthesized by anodic oxidation of Ti metal, modified by the TiO₂ film, and are subsequently annealed at 450 °C for 30 min, producing what are named T-TNAs. They show high photocatalytic efficiency and photosensitivity under UV-illumination. The photosensitive CIS coatings on the T-TNAs are processed by an ionic compounds lamination reaction (ICLR) method. The more immersion cycles and the higher the precursor concentration of copper sulfide, the more CIS peeled off as precipitates formed, which result in less indium sulfide deposition being required for reacting with the copper sulfide to reach stoichiometry. Near stoichiometric CIS can be obtained by controlling the precursor concentration and deposition cycles of the ICLR process. Good crystallinity and n-type characteristics are achieved by controlling the precursor concentrations and deposition cycles suitably to obtain a high current density. When the Cu/In ratio is adjusted for n-type characteristics, the current density reaches at least 300 μA/cm² under visible light illumination intensity of 100 mW/cm².     

Photosensitive nanostructured TiO2 grown at room temperature by novel “bottom-up” approached CBD method

The current paper incorporates with a “bottom-up” approached chemical bath deposition method to grow titanium dioxide (TiO₂) nanostructure at room temperature on glass and stainless steel substrates. The room temperature deposited TiO₂ films are heat treated at 673 K for 1 h in air and the corresponding change in structural, morphological and optical properties are studied by means of X-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), and UV-VIS-NIR spectrophotometer. The heat-treated films are utilized as a photocathode in photoelectrochemical (PEC) cell in 1 M NaOH electrolyte. The experimental results show that, the CBD method allows formation of photosensitive, anatase TiO₂ thin film, which can be potentially tuned in many functional applications with feasibility.     

Thin nanocrystalline TiO2–SnO2 sprayed films: Influence of the dopant concentration,substrate and thermal treatment on the phase composition and crystallites sizes

Thin nanocrystalline TiO₂–SnO₂ films (0–50 mol% SnO₂) are coated on quartz and stainless steel substrates by spray pyrolysis method. The synthesized films are investigated by XRD, Raman spectroscopy and XPS.The diffraction peaks of anatase phase fade while the peaks of rutile phase appear in the X-ray profiles with increasing of the treatment temperature and the content of SnO₂ in the sprayed films. It is found that SiO₂ coming from the quartz substrate stabilizes the anatase phase up to 700 °C. A more pronounced crystallization of rutile is registered with the films deposited on stainless steel substrate, which probably is caused by combined effect of SnO₂ doping and penetration of iron and chromium from the substrate inside the films.Dopant concentration (SnO₂) influences the size of the crystallites of the titania films deposited on quartz substrates The size of crystallites in the titania films decreases from 45 to 25 nm with increasing of SnO₂ amount.The SnO₂ amount does not affects substantially the size of crystallites (about 23 nm) for the films deposited on stainless steel.     

Development of a novel cathodic plasma/electrolytic deposition technique part 1: Production of titanium dioxide coatings

A new atmospheric pressure plasma electrolytic deposition process has been developed for the production of crystalline titanium dioxide films on metal substrates. The process occurs in a liquid precursor composed of titanium tetraisopropoxide and absolute ethanol. A plasma discharge is created and confined around the cathode in a superheated vapour sheath surrounded by the liquid phase, inducing the production of a nano-crystalline TiO₂ coating at the surface of the cathode. The analysis of the structure and composition of these TiO₂ coatings have been carried out by Scanning Electron Microscopy, Transmission Electron Microscopy, Raman and X-Ray Photoelectron Spectroscopies and X-Ray Diffraction. The produced crystalline titanium dioxide coatings are very adherent to the substrate and present a dendritic-like structure. We have moreover demonstrated that it is possible to adjust easily its composition by a post-processing calcination. Such characteristics make these films very interesting for photocatalysis, solar cells and gas sensing applications, and promise therefore some useful industrial benefits.     

Mutifunctional arc ion plated TiO2 photocatalytic coatings with improved wear and corrosion protection

An arc ion plating (AIP) system was used to deposit anatase TiO₂ thin films with photocatalytic and antimicrobial properties. This study aims to evaluate the properties and performance of such films, including surface hardness, adhesion, abrasive wear resistance and corrosion protection. The experimental results show that film hardness and scratch adhesion reach maximum values of 679.6 HV and 21.2 N, respectively. Film quality is strongly influenced by the degree of crystallinity, which is in turn affected by both deposition time and oxygen partial pressure. The wear resistance of the TiO₂ coatings can be closely correlated to the film adhesion, however all films impart significantly higher resistance to abrasive wear than that of the uncoated surface. On the other hand, TiO₂ coatings on stainless steel give rise to an increased (less negative) corrosion potential and decreased corrosion current in a sodium chloride solution. Overall, AIP-TiO₂ film can however provide satisfactory protection for stainless steel.     

Low temperature growth of nanocrystalline TiO2 films with Ar/O2 low-field helicon plasma

TiO₂ thin films were deposited on silicon wafer substrates by low-field (1 < B < 5 mT) helicon plasma assisted reactive sputtering in a mixture of pure argon and oxygen. The influence of the positive ion density on the substrate and the post-annealing treatment on the films density, refractive index, chemical composition and crystalline structure was analysed by reflectometry, Rutherford backscattering spectroscopy (RBS) and X-ray diffraction (XRD). Amorphous TiO₂ was obtained for ion density on the substrate below 7 × 10¹⁶ m^− 3. Increasing the ion density over 7 × 10¹⁶ m^− 3 led to the formation of nanocrystalline (~ 15 nm) rutile phase TiO₂. The post-annealing treatment of the films in air at 300 °C induced the complete crystallisation of the amorphous films to nanocrystals of anatase (~ 40 nm) while the rutile films shows no significant change meaning that they were already fully crystallised by the plasma process. All these results show an efficient process by low-field helicon plasma sputtering process to fabricate stoichiometric TiO₂ thin films with amorphous or nanocrystalline rutile structure directly from low temperature plasma processing conditions and nanocrystalline anatase structure with a moderate annealing treatment.     

Photogenerated cathodic protection of flower-like, nanostructured, N-doped TiO2 film on stainless steel

Flower-like, nanostructured, N-doped TiO₂ (N-TiO₂) films were fabricated using a low-temperature hydrothermal method. The morphology, crystalline phase, and composition of these flower-like nanostructured films were characterized systematically by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and UV-vis spectroscopy. The photoelectrochemical properties of N-TiO₂ films in 0.5 M NaCl solution were evaluated under illumination and in the dark through electrochemical measurements. Flower-like nanostructured TiO₂ films exhibited a drastically enhanced photocurrent in the UV light region and a notable absorption in the visible light region (600-700 nm). The negative shifts of the electrode potentials of 316L stainless steel coupled with N-doped TiO₂ photoanodes are 470 and 180 mV under UV and visible light irradiation, respectively. The flower-like, nanostructured, N-doped TiO₂ films were able to function effectively as photogenerated cathodic protection for metals under UV and visible light illumination. Such photogenerated cathodic protection could last a period of 5.5 h even in darkness.     

AISI430铁素体不锈钢表面制备MnCo2O4涂层特性及内应力研究

为了探究MnCo₂O₄尖晶石涂层作为固体氧化物燃料电池的金属连接体表面涂层的性能,使用溶胶-凝胶法制备出纯净的前驱体粉末,再使用电泳沉积方法制备出致密的MnCo₂O₄尖晶石涂层,利用SEM、EDS和XRD等表征手段观察分析MnCo₂O₄尖晶石涂层的相结构和微观组织形貌。采用“四探针法”测量MnCo₂O₄尖晶石涂层800℃氧化200h前后的面比电阻使用拉拔法完成不同界面粗糙度下的涂层结合强度测试,并用有限元仿真加以验证。结果显示,MnCo₂O₄尖晶石涂层结构均匀,致密度较好。相较于AISI430不锈钢基体来说,在800℃空气中氧化200h,抗氧化性提高了接近3倍。且中温面比电阻小于SOFC金属连接体规定的极限值。此外,基体表面粗糙度可以有效的增加涂层与基体的机械咬合作用,但同时也会导致应力集中,出现缺陷,从而降低了结合强度。