Electrochemical properties of core-shell TiC-TiO2 nanoparticle films immobilized at ITO electrode surfaces

Titanium carbide (TiC) nanoparticles are readily deposited onto tin-doped indium oxide (ITO) electrodes in the form of thin porous films. The nanoparticle deposits are electrically highly conducting and electrochemically active. In aqueous media (at pH 7) and at applied potentials positive of 0.3 V vs. SCE partial anodic surface oxidation and formation (at least in part) of novel core-shell TiC-TiO2 nanoparticles is observed. Significant thermal oxidation of TiC nanoparticles by heating in air occurs at a temperature of 250 degrees C and leads first to core-shell TiC-TiO2 nanoparticles, next at ca. 350 degrees C to TiO2 (anatase), and finally at temperatures higher than 750 degrees C to TiO2 (rutile). Electrochemically and thermally partially oxidized TiC nanoparticles still remain very active and for some redox systems electrocatalytically active. Scanning and transmission electron microscopy (SEM and TEM), temperature dependent XRD, quartz crystal microbalance, and voltammetric measurements are reported. The electrocatalytic properties of the core-shell TiC-TiO2 nanoparticulate films are surveyed for the oxidation of hydroquinone, ascorbic acid, and dopamine in aqueous buffer media. In TiC-TiO2 core-shell nanoparticle films TiO2 surface reactivity can be combined with TiC conductivity.     

ARXPS-analysis and morphology of sputtered nanocrystalline TiC/SiC coatings

ARXPS (angle resolved X-ray photoelectron spectroscopy) measurements are used to obtain informations about surfaces and grain boundaries. Data acquired from nanocrystalline carbidic hard coatings have been employed to establish structural models. Magnetron-sputtered coatings of TiC, SiC and TiC/SiC were examined. In such coatings, partly defective TiC nanocrystallites are surrounded by interfacial carbide. This excess carbon shows a binding state similar to that of doped graphite or fullerenes. X-ray amorphous SiC is found in the residue. On top of sputtered SiC coatings, less oxide and graphite is found as compared to TiC/SiC or TiC coatings.     

Alternating current electrophoretic deposition (EPD) of TiO2 nanoparticles in aqueous suspensions

TiO(2)-nanostructured coatings from aqueous suspensions have been successfully prepared by the application of alternating current (AC) instead of direct current (DC) during electrophoretic deposition (EPD). No organic additives in suspension were required for successful EPD. The quality of the AC-EPD TiO(2) coatings in terms of homogeneity and extent of microcracking, upon drying, observed by SEM, was superior to that of DC-EPD coatings made from the same type of suspensions. The main difference between AC- and DC-EPD was the suppression of bubble formation. The absence of water electrolysis at the electrodes can be explained by the particular distribution of the electric field during AC mode, which prevents the nucleation of bubbles. The preparation of TiO(2) coatings from aqueous suspension and without the aid of organic stabilizers opens the possibility for co-deposition of sensitive materials such as biomolecules and even cells for biomedical applications, given the high biocompatibility of TiO(2). The deposition of TiO(2) coatings from aqueous suspensions is also attractive from environmental and economical points of view.     

TiN和TiC涂层对碳氢燃料裂解结焦的影响

采用化学气相沉积(CVD)法,在304型不锈钢管道内壁分别沉积了TiN和TiC涂层,并采用SEM、EDS、金相显微镜和热冲击等方法对其进行了性能表征和测试。结果表明,两种涂层均匀致密,TiN涂层厚度为7.24μm,TiC涂层为11.52μm,且均具有良好的结合强度。为评价涂层抑制结焦效果,选用某碳氢燃料A,采取程序升温法进行超临界裂解实验,当反应管前后压差超过1 MPa时停止实验,结果表明,304空白管由于严重结焦,在650℃只运行了180 s;而TiC和TiN涂层管分别在780℃运行了275和1560 s。通过压差、产气组成和积炭微观形貌的综合分析表明,TiN、TiC涂层均呈现出优良的抑焦效果,且TiN涂层抑焦效果更优。     

医用多孔NiTi合金表面溶胶-凝胶法制备TiO2涂层

采用溶胶-凝胶法结合浸渍提拉工艺在多孔NiTi合金表面制备出了结构均一的锐钛矿型TiO2涂层,并在溶胶中添加聚乙二醇(PEG)作为造孔剂,进而在多孔NiTi合金表面制备出内层致密、外层多孔的TiO2复合涂层。SEM分析结果表明,TiO2涂层均匀地覆盖了多孔NiTi合金基体的外表面以及孔的内表面。Hanks溶液中的阳极极化曲线结果表明,与未处理的多孔NiTi合金相比,具有致密TiO2涂层的多孔NiTi合金其耐腐蚀性能有了显著提高。而多孔TiO2复合涂层进一步增大了多孔NiTi合金的实际表面积,提高了材料表面的生物活性。     

膨胀石墨负载锐钛矿型纳米TiO2的制备及光电催化性能

采用等体积浸渍法制备了膨胀石墨负载锐钛矿型纳米TiO2。 用X射线衍射（XRD）表征了纳米TiO2的晶型,扫描电子显微镜（SEM）研究了膨胀石墨负载纳米TiO2前后的表面形貌。 将该复合材料填充到自制的新型光电反应器中,考察了光催化、电催化及光电催化不同降解方法对主要成分是活性蓝的印染废水降解的影响,结果表明,该复合材料对印染废水具有良好的光电催化效应,以0.1 mol/L NaCl作为支持电解质经过光电协同处理后,脱色率达到99.3%,化学需氧量（COD）降低约93.1%,其效率远高于单纯光催化或者电催化的结果。     

耐环境性SiO2/SiO2-TiO2 增透膜的设计与制备

根据膜层设计理论设计出以K9玻璃为基体的耐环境性的双层增透膜, 这种增透膜在特定波长处具有超高的透过率. 以盐酸为催化剂, 分别以正硅酸乙酯和钛酸丁酯为前驱体制备了SiO2和TiO2溶胶, 将SiO2和TiO2溶胶按一定比例混合得到SiO2-TiO2复合溶胶. 通过改变复合溶胶中SiO2的含量调节复合膜的折射率, 通过改变提拉速度控制薄膜的厚度. 实验结果表明, 双层增透膜在550 nm处的透过率达到99.9%. 增透膜经较强机械摩擦后峰值透过率基本保持不变, 表明该增透膜具有优良的耐摩擦性. 进一步采用六甲基二硅氮烷对增透膜表面进行修饰, 修饰后增透膜的接触角增大至98.3°, 增透膜的疏水性及环境稳定性得到较大提高.     

Comparative study of microstructure and tribological behavior of TiC/a‐C:H and a‐C:H coatings in a sand‐dust environment

TiC/a‐C:H and a‐C:H nanocomposite coatings were prepared on AISI 440C steel substrates using magnetron sputtering process. A comparative study was made on their composition and microstructure by Raman spectroscopy and high‐resolution transmission electron microscopy (HRTEM). The tribological properties of two types of carbon‐based coatings were investigated by pin‐on‐disc tribometer under the sand‐dust conditions concerning the influence of applied load, amount of sand and sand particle sizes. The results show that these carbon‐based coatings exhibited high tribological performance with low friction coefficient and wear rate under the sand‐dust environments. However, the TiC/a‐C:H coatings exhibit relatively higher fluctuant friction coefficient as well as higher wear rate in comparison with the a‐C:H coatings under sand‐dust environments. The formation of nanocrystalline hard TiC phase distributed in amorphous carbon matrix decreased the residual stress but significantly increased the hardness and Young's modulus of TiC/a‐C:H coatings, and consequently caused a relatively higher abrasive and fatigue wear loss under the sand‐dust conditions. Copyright © 2010 John Wiley & Sons, Ltd.     

Single-walled carbon nanotube-facilitated dispersion of particulate TiO2 on ZrO2 ceramic membrane filters

We report that SWCNTs substantially improve the uniformity and coverage of TiO2 coatings on porous ZrO2 ceramic membrane filters. The ZrO2 filters were dip coated with 100 nm anatase TiO2, TiO2/SWCNT composites, a TiO2+SWCNT mixture, and a TiO2/MWCNT composite at pH 3, 5, and 8. Whereas the TiO2+SWCNT mixture and the TiO2/MWCNT composite promote better coverage and less clumping than TiO2 alone, the TiO2/SWCNT composite forms a complete uniform coating without cracking at pH 5 ( approximately 100% coverage). A combination of chemical and electrostatic effects between TiO2 and SWCNTs forming the composite as well as between the composite and the ZrO2 surface explains these observations.     

Self-organized TiO2 nanorod arrays on glass substrate for self-cleaning antireflection coatings

Herein we report the direct fabrication of TiO(2) subwavelength structures with 1-dimensional TiO(2) nanorods on glass substrate through solvothermal process to form self-cleaning antireflection coatings. TiO(2) precursor solutions with different solvent constituents create TiO(2) nanorods with much different morphologies grown on glass substrates. Apiculate TiO(2) nanorods with vertical orientation are grown on the glass substrate which is solvothermally treated in the precursor solution containing ethylene glycol. This glass substrate exhibit the highest transmittance of 70-85% in the range of 520-800 nm and negligible absorption in visible light region (400-800 nm). Furthermore, the TiO(2) nanorod arrays show high hydrophobicity and photocatalytic degradation ability which offer the glass substrate self-cleaning properties for both hydrophilic and oily contaminants.     

Dye surface coating enables visible light activation of TiO2 nanoparticles leading to degradation of neighboring biological structures

Biologically and chemically modified nanoparticles are gaining much attention as a new tool in cancer detection and treatment. Herein, we demonstrate that an alizarin red S (ARS) dye coating on TiO2 nanoparticles enables visible light activation of the nanoparticles leading to degradation of neighboring biological structures through localized production of reactive oxygen species. Successful coating of nanoparticles with dye is demonstrated through sedimentation, spectrophotometry, and gel electrophoresis techniques. Using gel electrophoresis, we demonstrate that visible light activation of dye-TiO2 nanoparticles leads to degradation of plasmid DNA in vitro. Alterations in integrity and distribution of nuclear membrane associated proteins were detected via fluorescence confocal microscopy in HeLa cells exposed to perinuclear localized ARS-TiO2 nanoparticles that were photoactivated with visible light. This study expands upon previous studies that indicated dye coatings on TiO2 nanoparticles can serve to enhance imaging, by clearly showing that dye coatings on TiO2 nanoparticles can also enhance the photoreactivity of TiO2 nanoparticles by allowing visible light activation. The findings of our study suggest a therapeutic application of dye-coated TiO2 nanoparticles in cancer research; however, at the same time they may reveal limitations on the use of dye assisted visualization of TiO2 nanoparticles in live-cell imaging.     

Morphology of RuO2-TiO2 coatings and TEM characterization of oxide sols used for their preparation

Characterization of RuO(2) and TiO(2) sols of different aging times, obtained by forced hydrolysis of appropriate chloride salts, was performed by transmission electron microscopy (TEM). The aging time of TiO(2) sols was observed to affect the size of particles as well as the crystallinity of the solid phase of the sols. The surface morphology of RuO(2)-TiO(2) coatings on titanium, obtained by the sol-gel procedure using TiO(2) sols of different aging times and RuO(2) sol of fixed aging time, was investigated by scanning tunneling microscopy (STM) at three different scan sizes. The STM data indicated uniform microdistribution of the coating material (small microroughness) and an increase in nanoroughness with the aging time of the TiO(2) sol. The observed increase in real coating surface area with increasing TiO(2) particle size confirms the earlier cyclic voltammetry results.     

Vanadium Doped Sol-Gel TiO2 Coatings

A study of the experimental conditions required to obtain vanadium doped sol-gel TiO2 coatings is presented. Tetraethyl orthotitanate was employed as the TiO2 source and VCl3, VOSO4 · H2O and VOSO4 dissolved H2SO4 where employed as vanadium sources.Dip coating has been used to produce coatings on silicon wafers, spectral carbon electrodes and titanium electrodes. Both supported and unsupported films have been studied by UV-Vis spectra, IR spectroscopy and X-ray diffraction (XRD). The measurements have been made on samples as prepared and treated thermally at temperatures between 100°C and 300°C. The thermal treatment temperatures have been established from DTA/TGA measurements.The vanadium doped sol-gel TiO2 coatings have been tested as sensors for redox potential measurements in electrochemical processes. The influence of both the thickness of films and the nature of substrate has been investigated.     

Reactive layer-by-layer deposition of poly(ethylene imine) and a precursor of TiO2: influence of the sodium chloride concentration on the film growth, interaction with hexacyanoferrate anions, and particle distribution in the film

Films prepared according to a layer-by-layer (LBL) manner find increasing importance in many applications such as coatings with dedicated optical or electronic properties, particularly when including nanomaterials. An alternative way to prepare such hybrid layer-by-layer coatings is to perform sol-gel chemistry in a layer-by-layer manner. In this article, we highlight the importance of the NaCl concentration as a parameter to control the growth as well as the properties of LBL films made from poly(ethylene imine) as the organic counterpart and titanium IV (bisammoniumlactato)dihydroxyde ([Ti(lac)(2)(OH)(2)](2-)) as the precursor of TiO(2). An increase in the sodium chloride concentration leads to the faster growth of the film and to a decrease in the number of hexacyanoferrate anions remaining in the film after a buffer rinse. This may be due to a progressive increase in the fraction of negatively charged TiO(2) as suggested by transmission electron microscopy. In the presence of 0.5 M NaCl, the fraction of TiO(2) is close to 60% in mass. As a surprising finding, the films produced from 0.15 M NaCl are not homogeneously filled with TiO(2) even if the film is produced in an LBL fashion. The increased concentration of TiO(2) at the film-solution interface could constitute a barrier for the incorporation of the negatively charged redox probe.     

Depositional characteristics of metal coating on single-crystal TiO2 nanowires

Ultralong single-crystalline TiO(2) nanowires were prepared by a simple, low-cost solvothermal process. Silver nitrate, neodymium chloride, ceric nitrate, stannic chloride hydrate, and cadmium chloride were used as metal sources and deposited by reduction on the surface of TiO(2) nanowires. The composites were subsequently characterized by transmission electron microscopy, and their coverage was compared. The nature of the coatings on the TiO(2) nanowires varies from metal to metal. A novel approach on modified one-dimensional nanostructures with metal coating was developed, which has great potential applications in catalysts, sensors, and nanoscale devices.     

Preparation and Properties of Chemically Bonded Ceramic Coatings Reinforced by GO-TiO2 composites

Russian Journal of Applied Chemistry - Graphene oxide (GO) decorated by titanium dioxide (TiO2) was fabricated and introduced into the chemically bonded ceramic coatings as a nanofiller. The...     

Large oriented arrays and continuous films of TiO(2)-based nanotubes

We report for the first time a one-step, templateless method to directly prepare large arrays of oriented TiO2-based nanotubes and continuous films. These titania nanostructures can also be easily prepared as conformal coatings on a substrate. The nanostructured films were formed on a Ti substrate seeded with TiO2 nanoparticles. SEM and TEM results suggested that a folding mechanism of sheetlike structures was involved in the formation of the nanotubes. The oriented arrays of TiO2 nanotubes, continuous films, and coatings are expected to have potentials for applications in catalysis, filtration, sensing, photovoltaic cells, and high surface area electrodes.     

Investigation of multi-layer coatings on cemented carbide cutting tools by analytical electron microscopy

Multi-layer coatings on cemented carbide substrates have been investigated by analytical electron microscopy (AEM). The samples were taken from cross-sections through the coating thus enabling a study of individual layers and interfaces. Various phenomena are shown: (1) tungsten diffusion and graphite inclusions in TiC layers, (2) oxygen impurities in Ti(C, N) coatings and (3) the occurrence of titanium oxinitrides in the interface between the Al₂O₃ and TiN-layers.Dedicated to Professor Günther Tölg on the occasion of his 60th birthday     

Sol–gel derived Ba/SrTiO3–MgF2 solar control coating stack on glass for architectural and automobile applications

Research on Chemical Intermediates - Fully dielectric solar control coatings based on alternating layers of Ba (or Sr)TiO3 and MgF2 were deposited on soda lime glass substrates. Three-layered...     

Effect of adhesive and cohesive strength on the tribological behaviour of non‐reactively sputtered TiC thin films

Titanium carbide (TiC) thin films were deposited on D9 steel substrates at room temperature (RT), 200 °C and 400 °C. A compound TiC target was sputtered to deposit films in a non‐reactive argon atmosphere. As‐deposited films were characterised for structural, chemical and mechanical properties. Nanoindentation and scratch tests were performed to evaluate the cohesive and adhesive strength of the films, respectively. Tribological properties of the films were investigated using a tribometer. An increase in nano‐hardness from 7.2 to 10.5 GPa was observed as deposition temperature was increased. The films deposited at RT and 200 °C showed poor adhesion leading to the inferior tribological performance. In contrast, films deposited at 400 °C showed better adhesion which improved the wear resistance. Tribological behaviour of TiC thin films was correlated with contact deformation modes of coatings. These modes revealed significant role of adhesive and cohesive strength associated with the coatings. Copyright © 2009 John Wiley & Sons, Ltd.