Fabrication and corrosion behavior of TiO2 nanotubes on AZ91D magnesium alloy

The major drawback of magnesium alloys in biomedical applications is the rapid degradation rate and the lack of biological activity. In this study, TiO₂ nanotubes were fabricated on the surface of AZ91D magnesium alloy (TiO₂-Mg) to overcome such limitations. The corrosion behavior of TiO₂-Mg nanotubes was studied in simulated body fluid solution using open circuit potentials (OCP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests. The high polarization resistance and open circuit potentials of TiO₂-Mg nanotubes indicate the formation of highly stable TiO₂ layer in simulated body fluid than that of titanium layer on magnesium alloy (Ti-Mg). TiO₂ nanotubes on AZ91D magnesium alloy (AZ91D) can effectively decrease the degradation rate of magnesium alloy, thus can be further applied in orthopedic implants.     

Nb doped TiO2 nanotubes for enhanced photoelectrochemical water-splitting

Nanostructured titanium dioxide is one of the classic materials for photoelectrochemical water splitting. In the present work we dope TiO(2) nanotube anodes. For this, various low concentration bulk-Nb-doped TiO(2) nanotube layers were grown by self-organizing anodization of Ti-Nb alloys. At Nb-contents around 0.1 at%, and after an adequate heat-treatment, a strongly increased and stable photoelectrochemical water-splitting rate is obtained.     

TiO2加入量对刚玉-尖晶石浇注料性能的影响

以板状刚玉为骨料,电熔白刚玉粉、电熔尖晶石粉、α-Al2O3微粉、纯铝酸钙水泥、金红石型TiO2为基质,按骨料、基质质量比为70:30配料,用金红石型TiO2替代≤0.044 mm电熔白刚玉细粉,其加入量(w)分别为0、2%、4%和6%,加水混匀后振动浇注成25 mm×25 mm×125 mm的试样,于室温下养护24 h后脱模,经110℃24 h烘干后,分别经1 100、1 300、1 500℃热处理3 h后,进行常温物理性能、热态抗折强度、抗热震性的研究,并利用SEM对部分试样在1 400℃下高温抗折强度试验后的断口形貌进行分析。结果表明:(1)1 300和1 500℃烧后试样基质中主要物相为刚玉、尖晶石、钛酸铝和六铝酸钙;随TiO2加入量的增加,TiO2与Al2O3反应生成的钛酸铝衍射峰强度逐渐增加。(2)加入TiO2对1 100和1 300℃烧后刚玉-尖晶石浇注料的显气孔率、体积密度和线变化率影响较小;但使1 500℃烧后浇注料的显气孔率降低,体积密度增加,体积变化从微膨胀到收缩。(3)加入2%TiO2可明显提高浇注料的常温强度,但加入量>4%时明显降低了浇注料的常温强度。(4)加入TiO2对浇注料的高...     

Zn2+ doped TiO2/C with enhanced sodium-ion storage properties

To improve the performance of anatase TiO₂ as an anode material for sodium-ion batteries, Zn²⁺-doped TiO₂/C composites are synthesized by a co-precipitation method. The results of XRD, EPR and XPS demonstrate that Zn²⁺ occupies at the Ti⁴⁺ site of TiO₂ to form a solid-solution, resulting in an expansion of lattice and an increase of Ti³⁺ content. The expansion of lattice can enhance the stability of the crystal structure of TiO₂. The increase of Ti³⁺ content can improve the conductivity of TiO₂. Therefore, Ti_0.94Zn_0.06O₂/C delivers a reversible capacity of 160 mA h g⁻¹ with a capacity retention of 96% after 100 cycles at 5 C. Even charged/discharged at 10 C, this sample still exhibits a reversible capacity of 117 mA h g⁻¹, comparing to 86 mA h g⁻¹ for TiO₂/C. The enhanced electrochemical performances can be ascribed to the improvement of the conductivity and the structural stability of TiO₂ due to Zn²⁺-doping. Therefore, Ti_0.94Zn_0.06O₂/C is an attractive anode material of sodium-ion batteries.     

Electrical properties of polyimide composite films containing TiO2 nanotubes

A study on the dielectric behavior of polyimide composite films containing different amounts of TiO₂ nanotubes (TNs) was performed. The films were prepared by casting solutions resulting from direct mixing of a poly(amic acid) and TNs onto glass plates, followed by thermal imidization. The influence of TNs content on the properties of polyimide composites was investigated. AFM and SEM analyses showed good compatibility between the filler and polymer matrix. Dynamic mechanical analysis and broadband dielectric spectroscopy were used to evidence relaxation processes into the films. The electrical properties were evaluated on the basis of dielectric constant and dielectric loss, and their variation with frequency and temperature. At moderate temperature a secondary β relaxation was observed while incorporation of TNs decreased the activation energy and facilitated the appearance of an additional β ₁ process. An α relaxation and a conductivity process were evidenced at higher temperatures. The values of dielectric constant and dissipation factor increased with TNs amount, and the maximum of σ relaxation peak shifted to higher temperatures. POLYM. COMPOS., 38:2584–2593, 2017. © 2015 Society of Plastics Engineers     

Photocatalytic properties of mesoporous TiO2 nanocomposites modified with carbon nanotubes and copper

The photocatalytic activity of mesoporous TiO₂ modified by the addition of carbon nanotubes (CNTs) and Cu is reported. Nanocomposites of carbon nanotubes (CNTs) containing varying amounts of Cu were formed by treatment with Cu²⁺ then reduced to Cu⁰ using NaBH₄ as the reducing agent. The mesoporous TiO₂, synthesized by a sol-gel method from titanium isopropoxide, was combined with the CNT/Cu nanocomposites to form the photocatalysts which were characterized by XRD, SEM, TEM, FTIR, XPS and BET surface area analysis. The photocatalytic properties of the mesoporous TiO₂ composites were studied by measuring the degradation of methyl orange (MO) which was optimal in the sample containing 20 wt% of the Cu-CNT nanocomposite. The degradation efficiency for MO was a synergistic effect of photo-degradation of TiO₂ and may be due to improvement of the electrical conductivity of the system by the presence of the CNT/Cu networks, since the photodegradation of MO and the photocatalytic activity of the photoactive systems increased with increasing copper content.     

纳米二霸化钛光催化材料研究进展

综合评述了TiO2光催化材料的掺杂改性和大比表面积气凝胶制备和性能等方面的国内外研究进展。     

One-step synthesis of nanograss-free TiO2 nanotubes using DTPA-enriched electrolytes

A single-step anodic fabrication of TiO₂ nanotubes (TNT) without a surface layer of nanograss was attained in electrolytes containing diethylenetriamine-pentaaceticacid (DTPA) as chelating agent. The role of DTPA concentration and anodization voltage on the final TNT morphology was studied. We discuss chemical aspects of the DTPA effect over the surface of TNTs as well as the physical properties of TNT samples prepared under several anodization conditions. We demonstrate that the DTPA concentration has a significant effect on the final surface morphology of TNTs, leading to a surface free of nanograss. Furthermore, we propose a mechanism that explains this phenomenon.     

Synthesis and Characterization of Rutile TiO2 Nanopowders Doped with Iron Ions

Titanium dioxide nanopowders doped with different amounts of Fe ions were prepared by coprecipitation method. Obtained materials were characterized by structural (XRD), morphological (TEM and SEM), optical (UV/vis reflection and photoluminescence, and Raman), and analytical techniques (XPS and ICP-OES). XRD analysis revealed rutile crystalline phase for doped and undoped titanium dioxide obtained in the same manner. Diameter of the particles was 5–7 nm. The presence of iron ions was confirmed by XPS and ICP-OES. Doping process moved absorption threshold of TiO₂ into visible spectrum range. Photocatalytic activity was also checked. Doped nanopowders showed normal and up-converted photoluminescence.     

The keys to avoid undesired structural defects in nanotubular TiO2 films prepared by electrochemical anodization

The effect of the viscosity of solvent mixtures based in ethylene glycol on the formation of undesired structural defects (nanograss) during the electrochemical synthesis of nanotubular TiO₂ structures is analyzed. High quality nanotubular TiO₂ films can be achieved by diminishing the viscosity of ethylene glycol-based media by increasing the water content as well as using ethanol as additive. High surface tension of water also promotes the film fracture and accumulation of agglomerates on the film surface. A previously unexplored one-step strategy consisting in the addition of ethanol to ethylene glycol/water mixtures as an alternative anodization medium is proposed. The evidence obtained indicate that this medium allows obtaining nanotubular TiO₂ films with superior structural stability against capillary forces during the film drying, avoiding the use of time consuming post-treatments such as the commonly employed supercritical CO₂ dehydrating, improving the properties of the obtained nanomaterials.     

Simple solution-combustion synthesis of Fe2TiO5 nanomaterials with enhanced lithium storage properties

The porous Fe₂TiO₅ particles are successfully synthesized through a facile one step solution combustion method. The Fe₂TiO₅ negative materials exhibit remarkable electrochemical performance with discharge capacities of 371.4?mAh g^?1 at the 100 th cycle, and display promising rate stability with discharge capacities 76.6?mAh·g^?1 at a high current density of 3.2?A?g^?1. In addition, the mechanism of electrochemistry reaction is illustrated by the CV, raman and EIS measurements, the irreversible capacity mainly causes from the irreversible lithium insertion at 1.8?V. The results indicate that the one step solution combustion synthesis of porous Fe₂TiO₅ is a promising strategy for developing low-cost and high-performance Ti-based negative materials.     

二氧化钛纳米管稳定Pickering乳液制备PS/TiO2纳米管复合微球

利用γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH-570）,对水热法制备的TiO₂纳米管进行了表面改性,并用改性的纳米管为稳定剂,采用Pickering乳液聚合法制备了聚苯乙烯/TiO₂纳米管复合微球。采用红外光谱（IR）、光学显微镜、高分辨透射电镜（HRTEM）、高分辨扫描电子显微镜（FESEM）、X射线光电子能谱（XPS）等分析手段,对改性前后TiO₂纳米管以及复合微球的结构和形貌进行了表征,用三相接触角仪测试并优化了TiO₂纳米管的表面润湿性。研究结果表明,当m_KH-570/m_TiO2=15%时,改性TiO₂纳米管表面润湿性最佳,能很好地稳定Pickering乳液聚合,聚合后可以得到壳层为致密均匀TiO₂纳米管,核为聚苯乙烯的复合微球。     

Efficient synthesis of titania nanotubes and enhanced photoresponse of Pt decorated TiO2 for water splitting

We investigated the effect of HMT (hexamethylenetetraamine) on the anodic growth of TiO₂ nanotube arrays. The tube length increases to 4.3 μm with HMT concentration increasing to 0.04 mol·L⁻¹. Adsorption of HMT on the TiO₂ surface is shown to markedly decrease the chemical dissolution rate of tube mouth, resulting in longer nanotube length. Furthermore, Pt nanoparticles were successfully deposited on the surface of TiO₂ nanotubes by ac electrodeposition method. The TiO₂/Pt composites were characterized by field emission scanning electron microscope (FESEM), X-ray photoelectron spectra (XPS), and photoelectrochemistry. An enhancement in photocurrent density has been achieved upon modification of TiO₂ nanotubes with Pt nanoparticles.     

Formation process of zirconia nanotubes and porous structures and model of oxygen bubble growth

Preparation and growth mechanism of anodization of Ti and Al has been widely concerned for two decades, but the research on anodic ZrO₂ is relatively lacking. In this paper, anodic TiO₂ and ZrO₂ nanotubes were prepared in glycerol electrolyte containing 0.35 M NH₄F and 4 vol% H₂O under different anodizing voltages. We had successfully prepared the anodic ZrO₂ nanotubes (AZNTs) with a complete top and a “bulb” at the bottom under 60 V, and with the increase of the applied anodizing voltage, the “bulb” cavity also increased. However, under the same anodizing conditions, the surface of anodic TiO₂ nanotubes (ATNTs) is a cluster of nano-tip morphology, and the bottom of the ATNTs is a conventional hemisphere shape. In addition, both AZNTs and porous anodic zirconia (PAZ) were found to coexist in the anodic ZrO₂ layer prepared at 60 V. Here, we used the oxygen bubble model and ionic current and electronic current theories to analyze the reason of the special morphology. It is confirmed that the porous anodic oxides are actually evolved from nanotubes. In other words, the structure is essentially the same.     

Characterization and mechanical properties of TiO2 nanotubes formed on titanium by anodic oxidation

The well-ordered titanium dioxide (TiO₂) nanotube array surfaces were formed at different voltages such as 20 V, 40 V, 60 V, 80 V and 100 V for 1 h on cp-Ti by anodic oxidation (AO) technique. And then, to improve crystallinity of the surface, heat treatment was applied at 450 °C for 1 h to all surfaces without any morphological changing. The surface and cross sectional morphology, elemental structure, phase composition, functional groups, roughness and thickness, wettability and mechanical results were investigated by SEM, EDX, XRD, FT-IR, AFM, contact angle measurement device and nanoindentation tester, respectively. Mainly, anatase- and rutile-TiO₂ phases were obtained at post-heat treatment whereas only, Ti phase was detected on AO surfaces at pre-heat treatment. All nanotube structures and the elements of Ti and O were uniformly distributed through the whole surface. The roughness and thickness of tube structures usually increased with increasing voltage values and measured. The roughness and thickness values were measured as 10.67–111.97 nm and 0.21–1.92 μm, respectively. TiO₂ nanotube surfaces exhibited hydrophobic behaviors with respect to plain Ti surface. Furthermore, mechanical properties such as hardness and elastic modulus of the coating produced at minimum voltage were great compared to ones at higher voltage and plain Ti surface under a Berkovich indenter due to phase structure, homogeneity and density of nanotube structures.     

Preparation of calcined hydrotalcite/TiO2-Ag composite and enhanced photocatalytic properties

A series of calcined hydrotalcite/TiO₂-Ag (HTC/TiO₂-Ag) composites with different silver (Ag) contents were successfully prepared and investigated as a catalyst for the photodegradation of phenol using UV–vis light (λ>300 nm). The Ag nanoparticles were deposited on the surface of TiO₂ (TiO₂-Ag) through photodeposition method. The TiO₂-Ag nanoparticles were supported on hydrotalcite (HT) by the co-precipitation method at variable pH (HT/TiO₂-Ag), and then calcined at 500 °C to obtain the HTC/TiO₂-Ag composites. The composites were characterized by inductively coupled plasma mass spectrometry (ICP-MS), N₂ adsorption/desorption (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), and diffuse reflectance spectra (DRS). Results show that there is an optimum silver ratio to obtain the highest photocatalytic performance in the HTC/TiO₂-Ag photocatalyst which is 2 wt%, and is assigned as HTC/TiO₂-Ag(2). The association of silver nanoparticles on TiO₂ enhanced photocatalytic activity of the bare semiconductor composite. Only 56% of phenol was photodegraded when photodegradation was performed with HTC/TiO₂, whereas ~100% was photodegraded using HTC/TiO₂-Ag(2). The data gathered from the photocatalytic degradation of phenol were successfully fitted to Langmuir-Hinshelwood model, and can be described by pseudo-first order kinetics. The results showed the HTC/TiO₂-Ag(2) as efficient photocatalyst, low cost, separable from solution by sedimentation, and reusable. The superior performance of HTC/TiO₂-Ag(2) composite photocatalyst may be attributed to the synergic catalytic effect between silver and TiO₂, dispersion of TiO₂-Ag(2) nanoparticles supported on calcined hydrotalcite, and the calcined hydrotalcite like photocatalyst.     

Effect of ZnO and TiO2 doping on the sintering behavior of Y2O3 ceramics

Full densification of Y₂O₃ is challenging and requires a very high sintering temperature (above 1700 °C). In this study, the effect of ZnO and TiO₂ dopants on its densification was investigated, showing that both dopants lowered the sintering temperature and improved the process. Moreover, ZnO promoted the grain growth, while TiO₂ inhibited it; hence, the ZnOTiO₂ co-doping and the change in the ZnO/TiO₂ ratio allowed the control of the sintered body microstructure while maintaining high densification. Since Y₂O₃ has a higher plasma erosion resistance than conventional Si-based materials, the plasma dry etching resistance of the sintered Y₂O₃ was also evaluated and found superior due to the improved densification and controlled grain size of the doped samples.     

Graphene oxide modified TiO2 nanotube arrays: enhanced visible light photoelectrochemical properties

Novel nanocomposite films, based on graphene oxide (GO) and TiO(2) nanotube arrays, were synthesized by assembling GO on the surface of self-organized TiO(2) nanotube arrays through a simple impregnation method. The composite films were characterized with field emission scanning electron microscopy, X-ray diffraction, Raman spectroscopy and UV-vis diffuse reflectance spectroscopy. The photoelectrochemical properties of the composite nanotube arrays were investigated under visible light illumination. Remarkably enhanced visible light photoelectrochemical response was observed for the GO decorated TiO(2) nanotube composite electrode compared with pristine TiO(2) nanotube arrays. The sensitizing effect of GO on the photoelectrochemical response of the TiO(2) nanotube arrays was demonstrated and about 15 times enhanced maximum photoconversion efficiency was obtained with the presence of GO. An enhanced photocatalytic activity of the TiO(2) nanotube arrays towards the degradation of methyl blue was also demonstrated after modification with GO. The results presented here demonstrate GO to be efficient for the improved utilization of visible light for TiO(2) nanotube arrays.     

TiO2 nanotubes manufactured by anodization of Ti thin films for on-chip Li-ion 2D microbatteries

The use of self-organized TiO₂ nanotube arrays electrochemically grown onto Si is investigated for the fabrication of an alternative electrode dedicated to on-chip Li-ion 2D microbatteries. Discharge/charge curves and cycling performance are studied in lithium-anode electrochemical test cells for both amorphous and crystalline titania nanotubes. At 5 μA cm⁻² amorphous TiO₂ nanotube layers onto Si deliver a maximum areal capacity of 89 μAh cm⁻² in the first reversible discharge and 56 μAh cm⁻² over 50 cycles. We demonstrate that these nanostructured thin film electrodes showing such electrochemical performances are compatible with IC technology.     

Electrochemically hydrogenated TiO2 nanotubes with improved photoelectrochemical water splitting performance

One-dimensional anodic titanium oxide (ATO) nanotube arrays hold great potential as photoanode for photoelectrochemical (PEC) water splitting. In this work, we report a facile and eco-friendly electrochemical hydrogenation method to modify the electronic and PEC properties of ATO nanotube films. The hydrogenated ATO (ATO-H) electrodes present a significantly improved photocurrent of 0.65 mA/cm² in comparison with that of pristine ATO nanotubes (0.29 mA/cm²) recorded under air mass 1.5 global illumination. The incident photon-to-current efficiency measurement suggests that the enhanced photocurrent of ATO-H nanotubes is mainly ascribed to the improved photoactivity in the UV region. We propose that the electrochemical hydrogenation induced surface oxygen vacancies contribute to the substantially enhanced electrical conductivity and photoactivity.