Preparation of a Superhydrophilic Thin Film on Glass Substrate Surfaces with Titanium Alkoxide Solution

Thin films of anatase titanium dioxide (TiO₂) were prepared on slide glass substrate surfaces by a titanium alkoxide hydrolysis operation, and the hydrophilicity and the transparency of their films were examined. The contact angles of water and the transmittances of visible light for their substrates changed with the duration of tetraethyl orthotitanate (TEOT) hydrolysis operations. They were influenced by the thickness of the films and the size of the deposited particles on the silicon dioxide-coated slide glass substrate surfaces. The contact angles also changed with the irradiating duration of ultraviolet light. When acetylacetone was added to a TEOT solution, the contact angles on the thin films became larger and the transparency was better during the same duration of TEOT hydrolysis operations. On addition of acetylacetone, nucleation of TiO₂ particles at the initial stages of TEOT hydrolysis operations was restrained and, subsequently, the supersaturations of TiO₂ in the solution became comparatively higher in the later stages of TEOT hydrolysis ones.     

Photocatalytic treatments on dental mirror surfaces using hydrolysis of titanium alkoxide

Anatase titanium dioxide (TiO₂) photocatalytic thin films were directly formed on glass slide and commercial dental mirror substrate surfaces by a hydrolysis of titanium alkoxide, and the hydrophilicity, the degree of oxidizing power and the transparency of the anatase TiO₂-coated substrate surfaces. The contact angles of water and the decomposition rates of methylene blue on the anatase TiO₂ photocatalytic thin films improved with the increasing duration of a tetraethyl orthotitanate (TEOT) hydrolysis, but they hardly changed for the longer duration. The reflectance of anatase TiO₂ photocatalytic thin films coated on glass slide substrate surfaces was higher as the duration of a TEOT hydrolysis increased. Similar tendencies concerning hydrophilicity and transparency were recognized in cases of commercial dental mirror substrate surfaces. A hydrolysis of titanium alkoxide obtained superhydrophilic and antibacterial treatments with excellent transparency on commercial dental mirror substrate surfaces.     

Anatase Titanium Dioxide Crystallization by a Hydrolysis Reaction of Titanium Alkoxide without Annealing

The crystallization of anatase titanium dioxide (TiO₂) was achieved by a hydrolysis reaction of titanium alkoxide without annealing. The hydrolysis reaction rates of tetraethyl orthotitanate were indicated by a function of the concentration of acetylacetone added. The degree of crystallinity of the product particles was influenced by the amounts of acetylacetone and seed crystals. Anatase TiO₂ was crystallized by restraining the rapid increase in supersaturation of TiO₂ and the consequent nucleation of amorphous TiO₂. The degree of crystallinity of the product particles also changed with the types of seed crystals used, and was strongly influenced by the specific surface areas of the seed crystals.     

Preparation of submicron-sized porous titanium oxide particles by the swelling process

A method to prepare submicron-sized porous titanium oxide (TiO₂) particles is studied in this work. Polystyrene (PS) template particles were prepared by emulsifier-free emulsion polymerization. The polymer templates dispersed in the aqueous solution have been used for entrapping titanium(IV) isopropoxide (TTIP), by the swelling process in a suitable solvent mixture containing a swelling solvent (good solvent or poor solvent), a TiO₂ precursor (TTIP), and a chelating agent (AcAc), within the polymer templates, followed by hydrolysis/condensation reaction of TTIP confined in PS template particles by the addition of the chelating agent. The influence of various reaction parameters, such as mixtures of different weight ratios between the PS particles and desiccative TTIP, AcAc amounts, and the swelling solvent amounts and type, on the size, bulk, and composition of the particles was investigated. Porous TiO₂ particles have been prepared by thermal decomposition of the PS templates at 500 °C.     

Influence of chelating agent and reaction time on the swelling process for preparation of porous TiO2 particles

This study aimed to describe the preparation and characterization of porous titanium oxide particles of narrow particle size distribution by a single-step swelling process of polystyrene template microspheres. In this research, different specific surface areas, porous structures and densities of porous titanium oxide particles had been synthesized with various experimental parameters. Two main parameters were tested and discussed: (1) acetylacetone amount (from 0 to 1 ml) and (2) reaction time (from 2 to 32 h). Polystyrene template particles were polymerized by emulsifier free-emulsion polymerization (a kind of polymerization method). For the swelling process to be successful, a chelating agent (acetylacetone) was added to delay the aqueous hydrolysis of titanium (IV) isopropoxide in the water phase. The influences of various reaction parameters on size, morphology, composition, specific surface area, porous structure and density of particles were investigated. The properties of particles were analyzed by scanning electron microscope, Brunauer–Emmett–Teller, Fourier transform infrared analysis, thermogravimetric analysis, powder X-ray diffraction, and specific gravity meter.     

Formation of TiO2 hollow microparticles by spraying water droplets into an organic solution of titanium tetraisopropoxide (TTIP) — Effects of TTIP concentration and TTIP-protecting additives

Hollow, spherical TiO₂ microparticles of several tens of micrometers in diameter can be prepared by spraying water into an organic phase containing titanium tetraisopropoxide (TTIP) as a titanium source. The concentration of TTIP did not affect the shell thickness. On the contrary, the shell thickness was increased with the concentration of the additives such as acetic acid and acetylacetone, having effects to protect TTIP from hydrolysis and condensation. The formation of a hollow particle was described by a simple model involving the hydrolysis of TTIP at the water–oil interface, the inward diffusion of hydrolyzed titanium hydroxide through the passage in the shell and its incorporation into the TiO₂ shell by condensation. The reduction of porosity of shell inhibits the diffusion, resulting in the formation of hollow structure. The simulation based on this model predicted that the shell thickness increased as the diffusion rate increased or the reaction rate decreased, and was independent of the outer TTIP concentration. These predictions were in qualitative agreement with the experimental results.     

赤泥硫酸铵焙烧浸出液水解制备偏钛酸的研究

采用选择性水解的方法利用赤泥硫酸铵焙烧熟料浸出液制备偏钛酸以回收钛。首先添加还原铁粉作为还原剂,将浸出液中的三价铁离子还原为二价铁离子,然后控制水解条件,将浸出液中的四价钛离子通过水解反应合成偏钛酸并对其进行分离回收。研究结果表明,浸出液中钛水解的最佳工艺条件：还原铁粉加入量为三价铁离子完全还原为二价铁离子所需铁粉的理论量、水解温度为140 ℃、水解时间为4 h、终点pH=2.0、添加晶种的含钛量占浸出液总钛含量的9%。在优化的工艺条件下,浸出液中钛的水解率达到95%;偏钛酸产物具有锐钛矿晶型且结晶度较低;产物形貌为不规则的圆形球体颗粒及块状聚集体,具有一定程度的团聚现象;偏钛酸颗粒吸附有一定量的硫酸盐,经计算水解产物组成为TiO₂·0.7H₂O·0.08SO₃。     

Anodic dissolution of spongy titanium in ethanol solution for preparation of nano-sized TiO2 powder

Nano-sized TiO₂ powder was prepared by electrochemical dissolution of spongy titanium in an ethanol solution following direct hydrolysis of the electrolyte solution. Characterization of the electrochemical product revealed that Ti(OEt)₄ was formed by anodic dissolution of spongy titanium in ethanol solution. X-ray diffraction and transmission electron microscope were, respectively, used to investigate the structure of TiO₂. This study showed that nano-sized TiO₂ prepared by this method has a structural and thermal stability with a narrow size distribution of 5-10 nm. The optimum electrochemical operating conditions established were a temperature of 333-343 K, current density of 400 A m⁻² and faradaic efficiency of 86%. Experiments showed that this process might be recommended as a promising technique for synthesis of nano-sized powder.     

Photocatalysts prepared from layered clays and titanium hydrate for degradation of organic pollutants in water

Reaction between titanium hydrate sol of strong acidity and four smectite clays were utilized to create composite nanostructures of titanium dioxide (TiO₂) and silicate nanoparticles. The acidic sol solution reacts with the clay platelets and leaches out part of the magnesium or aluminum in the clay, while the sol particles hydrolyze further, yielding larger precursors of TiO₂ nanoparticles and condense on the fragmentised pieces of the leached silicate. Moreover, introducing PEO surfactants into the synthesis can significantly increase the porosity and surface area of the composite solids. The TiO₂ in the product are crystal grains of several nanometres in size. They disperse on silicate plates or are separated by silicate fragments and voids such that they are accessible to organic molecules. The mechanism of the synthesis reaction is distinguishingly different from conventional pillaring process. The composite solids provide highly effective photocatalysts for the degradation of phenol and synthetic dyes in aqueous solution.     

PET/纳米二氧化钛共混体系研究

研究了纳米二氧化钛加入方式、加入量及偶联剂表面修饰对二氧化钛在PET中的分散效果及对PET/纳米二氧化钛体系抗紫外性能及结晶性能的影响。研究发现 :添加纳米二氧化钛可明显提高PET的抗紫外性能。在实验条件下 ,经偶联剂处理过的二氧化钛质量分数为 0 .5 %时 ,共混体系抗紫外效果最佳。钛酸酯偶联剂能改善纳米二氧化钛在PET基体中的分散性。不同二氧化钛添加量及其分散状态 ,影响PET的结晶速率。     

Synthesis of titanium oxide particles in supercritical CO2: Effect of operational variables in the characteristics of the final product

A new chemical precursor is proposed for the synthesis of TiO₂ anatase nanoparticles in supercritical CO₂: the organometallic diisopropoxititanium bis(acetylacetonate) (DIPBAT). DIPBAT thermohydrolysis in supercritical carbon dioxide (SC-CO₂) has been studied in the range 10.0–20.0 MPa and 200–300 °C, and compared with that of titanium tetraisopropoxide (TTIP). The proposed reaction mechanism is a thermohydrolysis, where the hydrolysis of acetylacetonate groups is the limiting step of the reaction rate. The addition of water directly to the reaction favours the growth of formed particles, whereas ethanol offers better results as hydrolysing reactant, leading to smaller particles. Experiments have been performed first in a batch process and secondly in a semi-continuous one, varying the residence time in the reactor from 30 s to 2 min. The effect of operational variables in the final product and their influence in the different steps of the process have been studied. Results have shown that product crystallinity is related with temperature, and temperatures higher than 250 °C are necessary to obtain well-crystallized TiO₂ anatase. In the same sense, area Brunauer–Emmett–Teller (BET) is connected with crystallinity, and amorphous product, Ti(OH)₄, shows the highest surface area. Particle size and particle size distribution (PSD) are controlled by instantaneously supersaturation degree, and precursor concentration together with pressure are the main responsible of particle size control. Operational conditions influence solubility of species, mass transfer, chemical reaction and nucleation and particle growth and they mark the final characteristics of the product and its application. In such a way, good crystallized TiO₂ anatase particles of about 200 nm in diameter have been obtained working at 300 °C, 20.0 MPa and residence time of 2 min, with a reaction medium composed by CO₂/ethanol (80/20, v/v). Such particles present good optical properties and specific surface area BET of around 150 m²/g. At lower working temperatures the obtained particles present worse crystallinity; however, their specific surface area increases to 350 m²/g and they are suitable as support of metal clusters in heterogeneous catalysis.     

Synthesis and characterization of Au/TiO2 core-shell structure nanoparticles

Au/TiO₂ core-shell structure nanoparticles were synthesized by sol-gel process, and the morphology and crystallinity of TiO₂ shell were investigated by TEM and UV-vis absorption spectrometer. Au/TiO₂ core-shell structure nanoparticles could be prepared by the hydrolysis of TOAA (titanium oxide acethylacetonate) in gold sol ethanol solution with water. The thickness of TiO₂ shell on the surface of gold particles was about 1 nm. To investigate the crystallinity of TiO, shell, UV light with 254 nm and radioactive ray of⁶⁰Co were irradiated on the TiO₂-coated gold sol ethanol solution. The surface plasmon band of gold nanoparticles appeared only when the radioactive ray was irradiated on the TiO₂-coated gold sol ethanol solution. From these results, it was found that the TiO, shell was amorphous and the MUA (mercaptoundecanoic acid) layer on the Au particle for its dispersion in ethanol did not act as an obstacle to disturb the movement of electrons onto the surface of Au particles.     

钛液水解工艺对偏钛酸性能的影响

采用外加晶种常压水解法制备偏钛酸,使用激光粒度仪分析偏钛酸的粒度分布,通过沉降高度和洗涤时间判断偏钛酸的过滤性能。考察了晶种加入量、变灰点时间、钛液浓度、二次沸腾保温时间对偏钛酸粒度分布及其过滤性能的影响。结果表明：晶种加入量、钛液浓度和二次沸腾保温时间对偏钛酸性能有显著影响,晶种加入量越大、钛液浓度越低、水解速度就越快,变灰时间越短,得到的偏钛酸的粒度分布也越宽,过滤性能越差。延长二次沸腾保温时间可以使偏钛酸粒度分布更窄,粒子更均匀。     

Isothermal crystallization kinetics and morphology of PP/TiO2 nanocomposites using titanium n‐butoxide precursor

This study investigates the influence of the addition of TiO₂, obtained by hydrolysis–condensation reaction of titanium dioxide precursors, on the kinetics of polypropylene (PP) isothermal crystallization. The dispersion of nanoparticle and its relation to the degree of crystallinity by XRD was also investigated. The results indicated that the addition of the TiO₂ increased the degree of crystallinity of PP and its crystallization temperature. Likewise, the nucleation and crystal growth processes were also affected, as indicated by the TEM morphology, the Avrami kinetic model, and the optical microscopy, in which a nucleation effect was detected. POLYM. COMPOS. 36:517–526, 2015. © 2014 Society of Plastics Engineers     

Effects of NH3·H2O pretreatment on the fabrication of uniform titania nanocoating in an aqueous solution

An investigation is reported of the TiO₂ nanocoating on the ZnS-based phosphor via a sol-gel method in an aqueous solution using titanium diethanolamine complex as the precursor. The pretreatment of ZnS phosphors with NH₃·H₂O is important to the coating process. When NH₃·H₂O was added into the ZnS phosphor suspension, OH⁻ promoted the hydrolysis of Zn²⁺ on the surface of ZnS phosphors, which resulted in the formation of Zn-OH. Zn-OH reacted with the hydrolysis product of titanium diethanolamine complex, thus the titania coatings were obtained. The coating morphology was strongly dependant on the pH of the pretreated ZnS phosphor suspension and the weight ratio of ZnS to TiO₂.     

Reaction synthesis of several titanium oxides through electrical wire explosion in air and in water

An experimental method to synthesize titanium oxide (Ti–O) through electrical wire explosion was performed. In this study, one experiment was conducted in air atmosphere, and the other with the wire fully dipped in distilled water. In air atmosphere, TiO₂ in anatase and rutile phases with ultrafine spherical particles was recovered. In distilled water, conversely, nanosized Ti–O material was recovered from an unknown phase, possibly a special phase of TiO₂ or a different type of titanium oxide such as Ti_nO or Ti_nO_2n−1. Recovered powders were analyzed using Scanning Electron Microscopy (SEM), High-resolution Transition Electron Microscopy (HR-TEM) and X-ray Diffraction (XRD) techniques.     

Flame synthesis of titania particles from titanium tetraisopropoxide in premixed flames

An experimental investigation of flame synthesis of titania particles was conducted in premixed flames. The titanium precursor and silicon dopant used in this study were titanium tetraisopropoxide (TTIP) and hexamethyldisiloxane (HMDS), respectively. The objective of this study was to investigate the influence of flame condition, TTIP concentration, and HMDS on the phase composition and particle morphology of titania synthesized in flames. It was found that the anatase content of titania particles made in flames was appreciably increased by the increase of oxygen concentration in the oxidizer. The increase of flame temperature results in the decrease of anatase content. A significant increase in rutile content of titania particles was observed by increasing the particle residence time at high temperatures. The doping of HMDS in flames inhibits the transformation of anatase to rutile phase and, therefore, reduces the rutile content of product particles. Under the flame doped with low concentrations of HMDS, titania particles with SiO₂ particle agglomerates attached were produced. Further increase of the HMDS concentration up to the Si to Ti molar ratio equal to 0.375 results in the formation of a large amount of SiO₂ agglomerates in the product.     

The Effect of Chelating Agent on the Catalytic and Structural Properties of Sm2Zr2O7 as a Methane Combustion Catalyst

The Sm₂Zr₂O₇ of pyrochlore structure was studied as a catalyst for high temperature combustion. It was prepared by the sol-gel method with and without acetylacetone as a chelating agent. The order of crystallinity and the surface area were improved when acetylacetone was used. The catalytic activity of CH₄ combustion was also enhanced and superior to that of Mn-substituted hexaaluminate above 550 °C.     

Low-temperature solution combustion synthesis of high performance LiNi0.5Mn1.5O4

High-voltage LiNi_0.5Mn_1.5O₄ spinels were synthesized by a low temperature solution combustion method at 400 °C, 600 °C and 800 °C for 3 h. The phase composition, structural disordering, micro-morphologies and electrochemical properties of the products were investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and constant current charge–discharge test. XRD analysis indicated that single phase LiNi_0.5Mn_1.5O₄ powders with disordered Fd-3m structures were obtained by the method at 400 °C, 600 °C and 800 °C. The crystallinity increased with increasing preparation temperatures. XRD and FTIR data indicated that the degree of structural disordering in the product prepared at 800 °C was the largest and in the product prepared at 600 °C was the least. SEM investigation demonstrated that the particle size and the crystal perfection of the products were increased with increasing temperatures. The particles of the product prepared at 600 °C with ~200 nm in size are well developed and homogeneously distributed. Charge/discharge curves and cycling performance tests at different current density indicated that the product prepared at 600 °C had the largest specific capacity and the best cycling performance, due to its high purity, high crystallinity, small particle size as well as moderate amount of Mn³⁺ ions.     

Anodically nanostructured titanium oxides for implant applications

The formation of various nanostructures of titanium oxide by anodization of titanium in different electrolytes was studied in order to reveal factors that influence on the cell attachment and proliferation on the surface of anodically prepared titanium implant. We found that the morphology of titanium oxide is dramatically changed upon electrochemical conditions. Emphasizing that there is a competitive reaction between F⁻ ions and PO₄³⁻ and it provides the different levels of incorporation of anions in the formed oxide, the mechanism of nanostructured titanium oxides in terms of different anodizing conditions was described. Titanium oxides containing enriched F⁻ ions stimulate cell attachment, whereas high proliferation levels of cells are observed in phosphate incorporated titanium oxides. The map of cell attachment and proliferation vs. anodic conditions was depicted.