Small angle neutron scattering study of pore microstructure in ceria compacts

Ceria powders were prepared by gel combustion process using cerium nitrate and hitherto unexplored amino acids such as aspartic acid, arginine and valine as fuels. The powders have been characterized by X-ray and laser diffraction. Cold pressed compacts of these powders have been sintered at 1250°C for 2 h. Internal pore microstructure of the sintered compacts has been investigated by small angle neutron scattering (SANS) over a scattering wave vector q range of 0.003–0.17 nm⁻¹. The SANS profiles indicate surface fractal morphology of the pore space with fractal dimensionality lying between 2.70 and 2.76.      

Self-cleaning characteristics on a thin-film surface with nanotube arrays of anodic titanium oxide

Self-cleaning of a surface of nanotube arrays of anodic titanium oxide (ATO) is demonstrated. The ATO was prepared in fluoride ion containing sulfate electrolytes with a structure of 0.4 μm length, 100 nm pores diameter, 120 nm interpore distance, 25 nm pore wall thickness, a 8×10⁹ pores cm⁻² pore density, and 68.2% porosity. Prepared as thin films either directly from a Ti foil or on a glass substrate, these arrays have the property that water drops spread quickly over the surface of the films without irradiation. In contrast, a flat anatase TiO₂ film requires irradiation with UV light for several minutes before the contact angle decreases to zero. The observed self-cleaning behavior of the ATO thin films is due to the capillary effect of the nanochannel structure and the superhydrophilic property of the anatase TiO₂ surface inside the tube.     

Effect of sintering conditions on the properties of sol-gel-derived Li<Subscript>1.3</Subscript>Al<Subscript>0.3</Subscript>Ti<Subscript>1.7</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

Solid electrolyte Li_1.3Al_0.3Ti_1.7(PO₄)₃ was prepared by sol-gel method under different sintering conditions. The structural identification, surface morphology, electrochemical window, ionic conductivity, and activation energy of the Li_1.3Al_0.3Ti_1.7(PO₄)₃ sintered pellets were investigated by X-ray diffraction, scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. It is found that the sintering temperature and time have considerable effect on the properties of the Li_1.3Al_0.3Ti_1.7(PO₄)₃ sintered pellets. The Li_1.3Al_0.3Ti_1.7(PO₄)₃ pellet sintered at 900 °C for 2 h is denser than the pellets sintered at other conditions. Different sintering conditions result in the sintered pellet with different porosity. However, the sintering conditions have little effect on the electrochemical window of Li_1.3Al_0.3Ti_1.7(PO₄)₃. Among the Li_1.3Al_0.3Ti_1.7(PO₄)₃ pellets sintered at various conditions, the pellet sintered at 900 °C for 2 h shows the highest ionic conductivity of 3.46 × 10⁻⁴ S cm⁻¹ and the lowest activation energy of 0.2821 eV.     

Effect of porosity and pore morphology on the low-frequency dielectric response in sintered ZrO<Subscript>2</Subscript>—8 mol% Y<Subscript>2</Subscript>O<Subscript>3</Subscript> ceramic compact

Effect of porosity and pore size distribution on the low-frequency dielectric response, in the range 0.01–100 kHz, in sintered ZrO₂—8 mol% Y₂O₃ ceramic compacts have been investigated. Small-angle neutron scattering (SANS) technique has been employed to obtain the pore characteristics like pore size distribution, specific surface area etc. It has been observed that the real and the imaginary parts of the complex dielectric permittivity, for the specimens, depend not only on the porosity but also on the pore size distribution and pore morphology significantly. Unlike normal Debye relaxation process, where the loss tangent vis-à-vis the imaginary part of the dielectric constant shows a pronounced peak, in the present case the same increases at lower frequency region and an anomalous non-Debye type relaxation process manifests.     

An ab initio molecular dynamics study of ionic conductivity in hexagonal lithium lanthanum titanate oxide La0.5Li0.5TiO3

To date, the fastest lithium ion-conducting solid electrolytes known are the perovskite-type ABO₃ oxide, with A = Li, La and B = Ti, lithium lanthanum titanate (LLTO) Li_3x La_{( 2 \mathord}

Variations in the structural, optical and electrochemical properties of CeO2-TiO2 films as a function of TiO2 content

Alcohol based sols of cerium chloride (CeCl₃·7H₂O) and titanium propoxide (Ti(OPr)₄) in ethanol mixed in different mole ratios have yielded mixed oxide films on densification at 500 °C. The reversibility of the intercalation/deintercalation reactions has shown electrochemical stability of the films. Addition of TiO₂ in an equivalent mole ratio manifests in producing highly transparent films with appreciable ion storage capacity. The electrochemical studies have revealed the significant role of TiO₂ in controlling the ion storage capacity of the films, as it tends to induce the disorder. In addition, the films prepared from an aged sol are observed to exhibit a much higher ion storage capacity than the films deposited using the as-prepared sol. The X-ray photoelectron spectroscopic studies have provided information on the variation of Ce⁴⁺/Ce³⁺ ratio as a function of increased TiO₂ content in the films. This study has led to a better understanding of the increased ion storage capacity with the increased TiO₂ proportion. The transmission electron microscopic study has demonstrated the presence of CeO₂ nanograins even in films, which are amorphous to X-rays. Elucidation of the structural, optical and electrochemical features of the films has yielded information on aspects relevant to their usage in transmissive electrochromic devices. The films have been found to exhibit properties that can find application as counter electrode in electrochromic smart windows in which they are able to retain their transparency under charge insertion, high enough for practical uses. Also, the fastest coloration-bleaching kinetics for the primary electrochromic electrode (WO₃) working in combination with Ce/Ti (1:1) electrode stimulates the use of latter in electrochromic windows (ECWs).     

DC magnetron sputtered Mo-Ti oxide films for color neutral electrochromic devices

Mo-Ti oxide films with compositions ranging from MoO₃ to TiO₂ were prepared by reactive DC magnetron sputtering using a newly developed high-rate technique with interacting plasma zones. Optical and electrochemical measurements showed that an increase of the Ti content yielded increased electrochemical stability, decreased coloration efficiency, and increased potential for electrochromic coloration. The films have interesting properties for color-neutral electrochromic devices. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Metal/TiO<Subscript>2</Subscript> interfaces for memristive switches

The interfaces between metal electrodes and the oxide in TiO₂-based memristive switches play a key role in the switching as well as in the I–V characteristics of the devices in different resistance states. We demonstrate here that the work function of the metal electrode has a surprisingly minor effect in determining the electronic barrier at the interface. In contrast, Ti oxides can be readily reduced by most electrode metals. The amount of oxygen vacancies created by these chemical reactions essentially determines the electronic barrier at the device interfaces.     

Anodic TiO<Subscript>2</Subscript> nanotubes powder and its application in dye-sensitized solar cells

An increasing energy demand and environmental pollution create a pressing need for clean and sustainable energy solutions. TiO₂ semiconductor material is expected to play an important role in helping solve the energy crisis through effective utilization of solar energy based on photovoltaic devices. Dye-sensitized solar cells (DSSCs) are potentially lower cost alternative to inorganic silicon-based photovoltaic cells. In this study, we report on the fabrication of DSSCs from anodic TiO₂ nanotubes (NT) powder, produced by rapid breakdown potentiostatic anodization of Ti foil in 0.1 M HClO₄ electrolyte, as photoanode. TiO₂ NT powders with a typical NT outer diameter of approximately 40 nm, wall thickness of approximately 8–15 nm, and length of about 20–25 μm, have been synthesized. The counter electrode was made by electrodeposition of Pt from an aqueous solution of 5 mM H₂PtCl₆ onto fluorine-doped tin oxide (FTO) glass substrate. The above front-side illuminated DSSCs were compared with back-side illuminated DSSCs fabricated from anodic TiO₂ NTs that were grown on the top of Ti foil as photoanode. The highest cell efficiency was 3.54% under 100 mW/cm² light intensity (1 sun AM 1.5G light, Jsc = 14.3 mA/cm², Voc = 0.544 V, FF = 0.455). To the best of our knowledge, this is the first report on the fabrication of DSSC from anodic TiO₂ NTs powder. The TiO₂/FTO photoanodes were characterized by FE-SEM, XRD, and UV–Visible spectroscopy. The catalytic properties of Pt/FTO counter electrodes have been examined by cyclic voltammetry.     

Metal point contacts and metal-oxide tunnel barriers fabricated with an AFM

We report the fabrication of atomic point contacts and lateral tunnel junctions by using anodic oxidation of thin metal films with an atomic force microscope.In situelectrical measurements were used as feedback to control the fabrication of metal nanowires that were subsequently anodized through their cross section to form point contacts and tunnel junctions. When the conductance of an Al device is reduced below 5×10⁻⁴S it starts to decrease in discrete steps of 2e²/h. In some devices we are able to stabilize the conductance at a value near 2e²/hwhich corresponds to a single, atomic-sized conducting channel. Similar experiments on Ti devices result in a continuous decrease of the conductance and the formation of stable tunnel junctions. This continuous behavior is a result of the large series resistance and the small oxide barrier height of the Ti/TiO_xsystem.     

Selective MOCVD of titanium oxide and zirconium oxide thin films using single molecular precursors on Si(1 0 0) substrates

Titanium oxide (TiO₂) and zirconium oxide (ZrO₂) thin films have been deposited on modified Si(1 0 0) substrates selectively by metal-organic chemical vapor deposition (MOCVD) method using new single molecular precursor of [M(OⁱPr)₂(tbaoac)₂] (M=Ti, Zr; tbaoac=tertiarybutyl-acetoacetate). For changing the characteristic of the Si(1 0 0) surface, micro-contact printing (μCP) method was adapted to make self-assembled monolayers (SAMs) using an octadecyltrichlorosilane (OTS) organic molecule which has -CH₃ terminal group. The single molecular precursors were prepared using metal (Ti, Zr) isopropoxide and tert-butylacetoacetate (tbaoacH) by modifying standard synthetic procedures. Selective depositions of TiO₂ and ZrO₂ were achieved in a home-built horizontal MOCVD reactor in the temperature range of 300-500 °C and deposition pressure of 1×10⁻³-3×10⁻² Torr. N₂ gas (5 sccm) was used as a carrier gas during film depositions. TiO₂ and ZrO₂ thin films were able to deposit on the hydrophilic area selectively. The difference in surface characteristics (hydrophobic/hydrophilic) between the OTS SAMs area and the SiO₂ or Si-OH layer on the Si(1 0 0) substrate led to the site-selectivity of oxide thin film growth.     

Characterizing the Evolution of Porosity during Controlled Drug Release

Nuclear magnetic resonance (NMR) techniques have been successfully used to characterize the evolving pore structure of partially soluble pharmaceutical pellets as they absorb water and release soluble components. The restricted diffusivity of water trapped within pellets, which have been immersed in water for differing times, has been measured by pulsed field gradient NMR. These measurements have been used to calculate the surface-to-volume ratio and tortuosity of the pore structure. A one-shot Carr–Purcell–Meiboom–Gill sequence has been used to measure the spin–spin (T ₂) relaxation time of water trapped within the pellets. These data have been regularized and then analyzed by the Brownstein–Tarr model to provide a pore size distribution for the pellets as a function of increasing immersion time. It has been found that pore structure changes significantly as water enters the pellet matrix. Two pellet formulations (herein referred to as placebo and drug-loaded) were studied and showed the same trends of a decreasing surface-to-volume ratio and tortuosity with increasing immersion time. At an immersion time of 10 min, both of these parameters decreased to approximately 70% of their values compared to an immersion time of 2 min. The placebo material tested consistently had both a higher tortuosity and surface-to-volume ratio than the drug-loaded material. At an immersion time of 2 min, the tortuosity for the placebo and drug-loaded materials were about 18 and about 10, respectively, and surface-to-volume ratios of about 6 μm⁻¹ and about 5 μm⁻¹, respectively. The materials tested also show changes in their pore size distribution with immersion time. In both formulations the mean and modal pore sizes increase with immersion time. The placebo material maintains an approximately similar mean and modal pore size, about 2 μm over the timescales studied, suggesting a more symmetric pore size distribution. In the drug-loaded pellets the mean pore size is much higher than the modal pore size, their values being 6.5 and 2.1 μm after 10 min immersion time, respectively. Authors' address: Michael D. Mantle, Department of Chemical Engineering, University of Cambridge, Pembroke Street, Cambridge CB2 3RA, UK     

TiO<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript> nanoparticles synthesized using He/Ar thermal plasma and their effectiveness on low-concentration mercury vapor removal

Oxygen-vacant titanium dioxide (TiO_2−x ) nanoparticles were synthesized using thermal plasma as a heating source at various applied plasma currents and He/Ar ratios. Samples with diverse characteristics were developed and the mercury removal effectiveness was subsequently evaluated. TiO₂ nanoparticles possessing high purity and uniform particle sizes were successfully synthesized using metal titanium and O₂ as precursors and Ar as plasma gas. TiO_2−x in anatase phase with a particle size at 5–10 nm was formed at the He/Ar volume ratio of 25/75. Further increasing the He/Ar ratio elevated the plasma temperature, causing the tungsten to melt, vaporize from the cathode, and then dope into the formed TiO₂ nanoparticles. The doped W appeared to inhibit the growth of nanoparticles and decrease the crystallinity of formed anatase. The effectiveness of oxygen-vacant sites on Hg⁰ removal under the visible light circumstance was confirmed. Hg⁰ removal by the TiO_2−x nanoparticles was enhanced by increasing the O₂ concentration. However, moisture reduced Hg⁰ capture, especially when light irradiation was applied. The reduction in Hg⁰ capture may be resulted from the competitive adsorption of H₂O on the active sites of TiO_2−x with Hg⁰ and transformed Hg²⁺.     

TiO<Subscript>2</Subscript> nanotube height effect on the efficiency of dye-sensitized solar cells

Performance of dye-sensitized solar cells (DSSCs) based on TiO₂ nanotubes (NTs) filled with TiO₂ nanoparticles (NPs) was studied as a function of NT height (h). The NT height was varied in the range of 1.5–7.0 μm, while the NT diameter was kept constant at ~80 nm. The studies showed that DSSC efficiency, current density, and fill factor linearly increased with h and ranged in 1.76–6.5%, 3.62–13.2 mA/cm², and 0.66–0.76, respectively, within the h range studied. The electrochemical impedance spectroscopy was also performed to study DSSC electron transport properties. Based on both photovoltaic and electrochemical impedance spectroscopy data, the results were explained as being due to the increased dye loading that led to higher light-harvesting efficiency.     

Nano TiO2 film electrode for electrocatalytic reduction of furfural in ionic liquids

Nanoporous TiO₂ having enhanced surface area was synthesized by sol–gel method. An “environmental friendly” method for production of furfuryl alcohol was presented by electrocatalytic reduction of furfural to furfuryl alcohol in ionic liquid medium at the surface of nanoporous TiO₂ film electrode. The heterogeneous catalytic redox behaviour of a nanoporous TiO₂ film electrode surface was investigated by cyclic voltammetry (CV). It was found that the catalytic reduction of furfural by Ti(IV)/Ti(III) redox system on the nanoporous TiO₂ film surface. The electrode reaction mechanism is called catalytic (EC′) mechanism, current density can reach 38 mA/cm² and yielding an overall conversion efficiency of 61.7%.     

Synthesis and characterization of TiO2 thin films coated on metal substrate

Nanostructured titanium dioxide (TiO₂) thin films have been prepared on metal substrates using a facile layer-by-layer dip-coating method. The phase structure and morphologies of preparing samples were characterized by means of X-ray powder diffraction (XRD) and field-emission scanning electron microscopy (FESEM). The results confirm that films are highly crystalline anatase TiO₂ and free from other phases of titanium dioxide. Scanning electron microscopy (SEM) shows that the nanoparticles are sintered together to form a compact structure. The electrical properties of samples were investigated by cutternt-voltage analysis, the result indicates that a rectifying junction between the nanocrystalline TiO₂ film and metal substrate was formed. The photoelectrochemical characteristics recorded under 1.5 AM illumination indicates that the as-fabricated thin film electrode possesses the highest photocurrent density at 450 °C, which is 1.75 mA/cm² at 0 V vs. Ag/AgCl.     

<Superscript>2</Superscript>H and <Superscript>47, 49</Superscript>Ti nuclear magnetic resonance in the γ phase of titanium deuterides TiD<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Titanium deuterides TiD_1.92, TiD_1.98, and TiD_2.0 have been studied by ²H and ^{47, 49}Ti NMR in a magnetic field of 7.04 T and a temperature range of 120–500 K. At all temperatures and compositions, the ²H NMR line is a singlet described by the Gaussian function. The contribution of demagnetizing fields to the ²H NMR shift is ∼50 ppm. The titanium NMR spectra for all compositions comprise two signals due to the ⁴⁷Ti and ⁴⁹Ti isotopes. The shift between these signals depends on the deuterium content and temperature. The ^{47, 49}Ti NMR line shape, width, and shifts have been considered in the framework of second-order quadrupole effects for a tetragonal lattice distortion and random distribution of vacancies. The Knight shifts σ(²H) and K(^{47, 49}Ti) are a function of temperature with a clearly pronounced singularity at ∼300 K. The contact, orbital, and polarization contributions to the Knight shifts have been estimated from analysis of the temperature dependences of σ(²H) and K(^{47, 49}Ti).     

The NASICON solid solution Li1−x La x /3Zr2(PO4)3: optimization of the sintering process and ionic conductivity measurements

The Li_1−x La _{x /3}Zr₂(PO₄)₃ NASICON-type compounds (0 ≤ x ≤ 1) have been synthesized in powder form by a sol-gel method and sintered for ionic conductivity measurements. In order to improve the compactness of the ceramic without decomposition of the compound, several sintering processes have been tested for one member of the solid solution (x = 0.6): the use of sintering aids (ZnO, B₂O₃, TiO₂ and LiNO₃), a ball-milling of the synthesized powder, a flash heating, high isostatic pressure, and spark plasma sintering. Finally, a satisfactory compactness of 85% is obtained compared to the referenced value (63%) obtained by uniaxial and isostatic pressing. The ionic conductivity study was performed by impedance spectroscopy. It shows that, despite the formation of vacancies, the substitution Li⁺→ 1/3 La³⁺ + 2/3 □ has unfortunately no influence on the conduction for 0 ≤ x ≤ 0.7 since the ionic conductivity remains identical to the LiZr₂(PO₄)₃ one. For higher x values, the ionic conductivity strongly decreases.     

Fabrication,characterization and biocompatibility of TiO2 nanotubes via anodization of Ti6Al7Nb

Ti6Al7Nb has been used as an implant material because of its good corrosion resistance and high mechanical properties. However, the presence of aluminium (Al), which may lead to ostemalacia, anaemia and nervous system disorders, limited its wide clinical use. In this study, a titanium oxide (TiO₂) nanoporous layer was fabricated on a Ti6Al7Nb alloy using an electrochemical anodic oxidation method. The structure of the TiO₂ nanoporous layer was examined by scanning electron microscopy. The chemical compositions of the samples were analysed by X-ray photoelectron spectroscopy (XPS). Biocompatibility was evaluated by culturing rat osteoblast cells. The result showed that TiO₂ nanoporous layers comprise a mixed oxide containing TiO₂ and a small amount of nobium oxides (Nb₂O₅) and almost no elemental aluminium. The outer layer of the TiO₂ nanoporous layer comprises highly ordered nanotubes and the inner layer forms disordered nanopores. The TiO₂ nanoporous layer could support the adhesion, proliferation, differentiation and gene expression of osteoblast cells. Therefore, a TiO₂ nanoporous layer could enhance the biocompatibility of Ti6Al7Nb alloy and is as a promising candidate for Ti6Al7Nb alloy implants.     

Preparation and characterization of cerium oxide doped TiO2 nanoparticles

A mixed oxide consisting of TiO₂ as the major phase and CeO_2−y (0<y<0.5) as the dopant phase was prepared via the sol-gel reaction of Ti(i-OC₃H₇)₃ in an aqueous solution of Ce(NO₃)₃. The resulting oxide powders with different CeO_2−y contents were all composed of nano-sized spheres. The CeO_2−y phase was identified to have retarding effect on the phase transition from anatase TiO₂ to rutile TiO₂ at calcinations temperature as high as 800 °C, which would otherwise be a thorough conversion. The CeO_2−y-TiO₂ powders could apparently shift the UV-absorption band of TiO₂ toward visible range, and there was an optimal CeO_2−y content in association with the maximum absorbance. This effect is interpreted as the existence of an n-type impurity band, due to the substitution of Ti⁴⁺ for Ce^3+/4+ at the interface between the two oxides, in the gap of TiO₂. According to X-ray photoelectron spectroscopy (XPS) investigation, the Ti element mainly existed as the chemical state of Ti⁴⁺ and the Ce oxide doping did not affect the peak position of Ti 2p. The Ce 3d spectrum of CeO_2−y-doped TiO₂ sample basically denotes a mixture of Ce^3+/4+ oxidation states giving rise to a myriad of peaks.