Influence of passive potential on the electronic property of the passive film formed on Ti in 0.1 M HCl solution during ultrasonic cavitation

The influence of the applied passive potential on the electronic property of the passive film formed on Ti at different potentials in 0.1 M HCl solution during ultrasonic cavitation, was investigated by electrochemical impedance spectra (EIS) and Mott–Schottky plot. The influence of the applied passive potential on the structure and composition of the passive film was studied by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The results showed that the applied passive potential can obviously affect the electronic property of the passive film formed on Ti during ultrasonic cavitation. The resistance of the passive film increased, and the donor density of the passive film decreased with increasing the potential. The flat band potential moved to positive direction and the band gap of the passive film moved to negative direction with increasing potential. AES and XPS results indicated that the thickness of the passive film increased evidently with applying passive potential. The passive film was mainly composed of the mixture of TiO and TiO₂. While the TiO₂ content increased with increasing the applied passive potential, and the crystallization of the passive film increased with the increased potential.     

Investigation on ultrasonic cavitation erosion of TiMo and TiNb alloys in sulfuric acid solution

Two kinds of Ti-alloys, i.e., TiMo and TiNb alloys are manufactured in this paper, and their ultrasonic cavitation erosion behaviors in 0.1 M H₂SO₄ solution are evaluated by the mean depth erosion (MDE), SEM and white light photograph. The results show that MDE of TiMo and TiNb alloys obviously increase with increasing the cavitation erosion time, however, they evidently decrease with the increment of Mo or Nb content at each fixed cavitation erosion time, and even some large blank areas (uneroded areas) still exist on the sample surface after ultrasonic cavitation erosion for 2 h in the case of Ti10Mo and Ti20Nb samples, implying the enhanced anti-cavitation erosion property of Ti-alloy by adding Mo or Nb element. The MDE of Ti10Mo or Ti20Nb sample is lower than that of TC4 sample in the case of each cavitation erosion time, indicating the better cavitation erosion resistance of of Ti10Mo or Ti20Nb sample. The influences of Mo and Nb on the passivity of TiMo and TiNb alloys during the ultrasonic cavitation erosion are detected by potentiodynamic curves. The results display that Ti, TC4, TixMo (x = 1, 5, 10) and TixNb (x = 5, 10, 20) samples are all almost in the passive state within the potential region from 0V_SCE to 1.5V_SCE during ultrasonic cavitation erosion, and the passive current density evidently decreases with increasing Mo or Nb content, indicating the enhanced passive characteristic by adding Mo or Nb alloys during the ultrasonic cavitation erosion.     

Effect of micro-particles on cavitation erosion of Ti6Al4V alloy in sulfuric acid solution

The influences of micro-particles on ultrasonic cavitation erosion of Ti6Al4V alloy in 0.1 M H₂SO₄ solution were investigated using mass loss weight, scanning electron microscopy (SEM) and white light interferometer. Mass loss results revealed that the cavitation erosion damage obviously decreased with increasing particle size and mass concentration. Open circuit potential recorded during cavitation erosion shifted to positive direction with the decreased mass loss. Meanwhile, the mass loss sharply decreased with applying a positive potential during the entire ultrasonic cavitation erosion, and the relationship between the open circuit potential and the cavitation erosion resistance was discussed.     

Ultrasonic cavitation erosion of gas nitrided Ti–6Al–4V alloys

Ultrasonic cavitation erosion experiments were performed on Ti–6Al–4V alloys samples in annealed, nitrided and nitrided and subsequently heat treated state. The protective oxide layer formed as a result of annealing and heat treatment after nitriding is eliminated after less than 30 min cavitation time, while the nitride layer lasts up to 90 min cavitation time. Once the protective layer is removed, the cavitation process develops by grain boundary erosion, leading to the expulsion of grains from the surface. The gas nitrided Ti–6Al–4V alloy, forming a Ti_xN surface layer, proved to be a better solution to improve the cavitation erosion resistance, compared to the annealed and nitrided and heat treated state, respectively. The analysis of the mean depth of erosion rate at 165 min cavitation time showed an improvement of the cavitation erosion resistance of the nitrided samples of up to 77% higher compared to the one of the annealed samples.     

Interaction behaviors at the interface between liquid Al–Si and solid Ti–6Al–4V in ultrasonic-assisted brazing in air

Power ultrasonic vibration (20 kHz, 6 μm) was applied to assist the interaction between a liquid Al–Si alloy and solid Ti–6Al–4V substrate in air. The interaction behaviors, including breakage of the oxide film on the Ti–6Al–4V surface, chemical dissolution of solid Ti–6Al–4V, and interfacial chemical reactions, were investigated. Experimental results showed that numerous 2–20 μm diameter-sized pits formed on the Ti–6Al–4V surface. Propagation of ultrasonic waves in the liquid Al–Si alloy resulted in ultrasonic cavitation. When this cavitation occurred at or near the liquid/solid interface, many complex effects were generated at the small zones during the bubble implosion, including micro-jets, hot spots, and acoustic streaming. The breakage behavior of oxide films on the solid Ti–6Al–4V substrate, excessive chemical dissolution of solid Ti–6Al–4V into liquid Al–Si, abnormal interfacial chemical reactions at the interface, and phase transformation between the intermetallic compounds could be wholly ascribed to these ultrasonic effects. An effective bond between Al–Si and Ti–6Al–4V can be produced by ultrasonic-assisted brazing in air.     

Precise spatial control of cavitation erosion in a vessel phantom by using an ultrasonic standing wave

In atherosclerotic inducement in animal models, the conventionally used balloon injury is invasive, produces excessive vessel injuries at unpredictable locations and is inconvenient in arterioles. Fortunately, cavitation erosion, which plays an important role in therapeutic ultrasound in blood vessels, has the potential to induce atherosclerosis noninvasively at predictable sites. In this study, precise spatial control of cavitation erosion for superficial lesions in a vessel phantom was realised by using an ultrasonic standing wave (USW) with the participation of cavitation nuclei and medium-intensity ultrasound pulses. The superficial vessel erosions were restricted between adjacent pressure nodes, which were 0.87 mm apart in the USW field of 1 MHz. The erosion positions could be shifted along the vessel by nodal modulation under a submillimetre-scale accuracy without moving the ultrasound transducers. Moreover, the cavitation erosion of the proximal or distal wall could be determined by the types of cavitation nuclei and their corresponding cavitation pulses, i.e., phase-change microbubbles with cavitation pulses of 5 MHz and SonoVue microbubbles with cavitation pulses of 1 MHz. Effects of acoustic parameters of the cavitation pulses on the cavitation erosions were investigated. The flow conditions in the experiments were considered and discussed. Compared to only using travelling waves, the proposed method in this paper improves the controllability of the cavitation erosion and reduces the erosion depth, providing a more suitable approach for vessel endothelial injury while avoiding haemorrhage.     

Influence of thickness and band structure of insulating barriers on resistance and tunneling magnetoresistance properties of magnetic tunnel junctions with Al-oxide and Ti-alloyed Al-oxide barriers

We investigated the influence of insulating barrier thickness and the Ti composition dependence of the band structure of Al-oxide on the resistance and tunneling magnetoresistance (TMR) behavior of the magnetic tunnel junction (MTJ). Low resistance × area (RA) value (1.1 MΩ μm²) was achieved by decreasing the Al-oxide thickness down to 1.0 nm. However, this led to the partial oxidation of the bottom ferromagnetic (FM) electrode of the junction and non-continuous thin barriers by the occurrence of pinholes, with low TMR ratio of 8.3%. For an alternative for low RA value, we developed a new Ti-alloyed Al-oxide (TiAlO_x) that had lower band gap than Al-oxide as an insulating barrier of MTJ. As the Ti concentration increased up to 5.33 at.% Ti in Al, the RA value of the MTJs was reduced from 9.5 to 0.69 MΩ μm², owing to the band-gap reduction of TiAlO_x caused by the formation of extra bands, mainly composed of Ti-3d orbitals, within the band gap. It was analyzed that TiAlO_x has localized d states in the band gap below the conduction band. In addition, the TMR ratio increased with the Ti concentration and reached a maximum of 49% at 5.33 at.% Ti owing to the microstructural evolution of Ti–Al alloy film in the pre-oxidation state.     

The preparation and characterization of nanoparticle TiO2/Ti films and their photocatalytic activity

Nanoparticle TiO₂/Ti films were prepared by a sol–gel process using Ti(OBu)₄ as raw material, the as-prepared film samples were also characterized by TG-DTA, XRD, TEM, SEM, XPS, DRS, PL, SPS and EFISPS testing techniques. TiO₂ nanoparticles experienced two processes of phase transition, i.e. amorphous to anatase and anatase to rutile at the calcining temperature range from 450 to 700 °C. TiO₂ nanoparticles calcined at 600 °C had similar composition, structure, morphology and particle size with the internationally commercial P-25 TiO₂ particles. Thus, the conclusion that 600 °C might be the most appropriate calcining temperature during the preparation process of nanoparticle TiO₂/Ti film photocatalysts could be made by considering the main factors such as the properties of TiO₂ nanoparticles, the adhesion of nanoparticle TiO₂ film to Ti substrate, the effects of calcining temperature on Ti substrate and the surface characteristics and morphology of nanoparticle TiO₂/Ti film for the practice view. The Ti element mainly existed on the nanoparticle TiO₂/Ti(3) film calcined at 600 °C as the chemical state of Ti⁴⁺, while O element mainly existed as three kinds of chemical states, i.e. crystal lattice oxygen, hydroxyl oxygen and adsorbed oxygen with increasing band energy. Its photoluminescence (PL) spectra with a peak at about 380 nm could be observed using 260 nm excitation, possibly resulting from the electron transition from the bottom of conduction band to the top of valence band. The PL peak position was nearly the same as the onset of its diffuse reflection spectra (DRS) and surface photovoltage spectroscopy (SPS), demonstrating that the effects of the quantum size on optical property were greater than that of the Coulomb and surface polarization. The PL spectra with two peaks related to the anatase and rutile, respectively, could be observed using the excited wavelength of 310 nm. Weak PL spectra could be observed using the excited wavelength of 450 nm, resulting from surface states. In addition, during the experimental process of the photocatalytic degradation phenol, the photocatalytic activity of nanoparticle TiO₂/Ti film with three layers calcined at 600 °C was the highest.     

Oxidation of ultra-thin Ti films on Mo(100): Soft X-ray photoelectron spectroscopy study

Titanium oxide films grown on Mo(100) have been investigated by low-energy electron diffraction (LEED) and soft X-ray photoelectron spectroscopy (PES). The film was grown by Ti deposition on Mo(100) and subsequent oxidation of the film by 12 L of O₂ exposure at room temperature. As the film was annealed at 700–1000 °C, the film in which the Ti atoms were in a Ti³⁺ oxidation state was formed. As the film was annealed at 1100–1500 °C, the oxidation state of Ti in the film was converted to Ti²⁺. The valence electronic structure of the film was measured under the condition that the emission from the Mo substrate was minimized due to a Cooper minimum of the Mo 4 d photoionization cross sections (hν = 100 eV). It was found that the Ti 3 d band in normal-emission spectra was increased in intensity when the film was annealed at 1100–1500 °C. As the film was annealed at 1300 °C for 10 s and 20 s, the film-covered Mo(100) gave (2 × 2) and (4 × 1) LEED patterns, respectively. The two-dimensional band structure of the (2 × 2) system was investigated by angle-resolved PES, and it was found that the film with a (1 × 1) periodicity with respect to the Mo(100) substrate existed in the (2 × 2) system.     

Synergistic effect of ultrasonic cavitation erosion and corrosion of WC–CoCr and FeCrSiBMn coatings prepared by HVOF spraying

The high-velocity oxygen-fuel (HVOF) spraying process was used to fabricate conventional WC–10Co–4Cr coatings and FeCrSiBMn amorphous/nanocrystalline coatings. The synergistic effect of cavitation erosion and corrosion of both coatings was investigated. The results showed that the WC–10Co–4Cr coating had better cavitation erosion–corrosion resistance than the FeCrSiBMn coating in 3.5 wt.% NaCl solution. After eroded for 30 h, the volume loss rate of the WC–10Co–4Cr coating was about 2/5 that of the FeCrSiBMn coating. In the total cumulative volume loss rate under cavitation erosion–corrosion condition, the pure cavitation erosion played a key role for both coatings, and the total contribution of pure corrosion and erosion-induced corrosion of the WC–10Co–4Cr coating was larger than that of the FeCrSiBMn coating. Mechanical effect was the main factor for cavitation erosion–corrosion behavior of both coatings.     

Sonochemiluminescence observation and acoustic detection of cavitation induced by pulsed HIFU at a tissue–fluid interface

The aim of this study is to investigate the mechanism of the erosion process induced by 1.2 MHz pulsed high-intensity focused ultrasound (pulsed HIFU). By using Sonochemiluminescence (SCL) photograph, the initiation and maintenance of active cavitation were observed. In order to understand the role of both inertial cavitation and stable cavitation, a passive cavitation detection (PCD) transducer was used. Since the exposure variables of HIFU are important in the controlled ultrasound tissue erosion, the influence of pulse length (PL) and duty cycle (DC, T_on:T_off) has been examined. The results of tissue hole, SCL observation and acoustic detection revealed that the erosion was highly efficient for shorter PL. For higher DCs, the area of SCL increased with increasing PL. For lower DCs, the area of SCL increased with increasing PL from 10 to 20 μs and then kept constant. For all PLs, the intensity of SCL decreased with lower DC. For all DCs, the intensity of SCL per unit area (the ratio of SCL intensity to SCL area) also decreased with increasing PL from 10 to 80 μs, which suggested that the higher the intensity of SCL is, the higher the efficiency of tissue erosion is. At DC of 1:10, the position of the maximum pixel in SCL pictures was distant from the tissue–fluid interface with the increasing PL because of shielding effect. By the comparison of inertial cavitation dose (ICD) and the stable cavitation dose (SCD), the mechanisms associated with inertial cavitation are very likely to be the key factor of the erosion process.     

Electronic structures and effective masses of photogenerated carriers of CaZrTi2O7 photocatalyst: First-principles calculations

The band structures, density of states and effective masses of photogenerated carriers for CaZrTi₂O₇ photocatalyst were performed using first principles method with the virtual crystal approximation. The results indicated that CaZrTi₂O₇ has an indirect band gap of about 3.25 eV. The upper valence bands of CaZrTi₂O₇ are formed by O 2p states mixed with Ti 3d states, Zr 4d, 4p and 5s states, while the conduction bands are dominated by Ti 3d states, Zr 4d states and O 2p states. The calculated valence bands maximum (VBM) potential is located at 2.60 V (vs. normal hydrogen electrode (NHE)), while the conduction bands minimum (CBM) potential at ?0.65 V. Therefore, CaZrTi2O7 has the ability to split water to hydrogen and oxygen under UV light irradiation. The calculated minimum effective mass of electron in CBM is about 1.35 m₀, and the minimum effective mass of hole in VBM is about 1.23 m₀. The lighter effective masses facilitate the migration of photogenerated carriers and improve photocatalytic performance.     

Dual frequency cavitation event sensor with iodide dosimeter

The inertial cavitation activity depends on the sonication parameters. The purpose of this work is development of dual frequency inertial cavitation meter for therapeutic applications of ultrasound waves. In this study, the chemical effects of sonication parameters in dual frequency sonication (40 kHz and 1 MHz) were investigated in the progressive wave mode using iodide dosimetry. For this purpose, efficacy of different exposure parameters such as intensity, sonication duration, sonication mode, duty factor and net ultrasound energy on the inertial cavitation activity have been studied. To quantify cavitational effects, the KI dosimeter solution was sonicated and its absorbance at a wavelength of 350 nm was measured. The absorbance values in continuous sonication mode was significantly higher than the absorbance corresponding to the pulsed mode having duty factors of 20–80% (p < 0.05). Among different combination modes (1 MHz_100% + 40 kHz_100%, 1 MHz_100% + 40 kHz_80%, 1 MHz_80% + 40 kHz_100%, 1 MHz_80% + 40 kHz_80%), the continuous mode for dual frequency sonication is more effective than other combinations (p < 0.05). The absorbance for this combined dual frequency mode was about 1.8 times higher than that obtained from the algebraic summation of single frequency sonications. It is believed that the optimization of dual frequency sonication parameters at low-level intensity (<3 W/cm²) by optically assisted cavitation event sensor can be useful for ultrasonic treatments.     

Sonication effects on non-radical reactions. A sonochemistry beyond the cavitation?

The kinetics of pH-independent hydrolysis of 4-methoxyphenyl dichloroacetate were investigated under ultrasonic irradiation with an application of 10% of the maximum power of the equipment and without sonication in acetonitrile–water binary mixtures with a content of acetonitrile ranging from 0.008 to 35 wt.%. Similar kinetic investigations were performed at intensities corresponding to 10%, 20%, 30%, 40%, and 50% of the input energy in solvent mixtures containing 10 wt.% and 25 wt.% acetonitrile. In parallel, the responses of KI and terephthalic acid dosimeters at applied irradiation levels were registered under the same experimental conditions. Significant kinetic sonication effects were found at sound intensities presumably not inducing cavitation in the solution. This result provides an experimental evidence of kinetic effects of ultrasound in the absence of cavitation. A disturbing impact of cavitation on the ultrasonic acceleration of the reaction was found. The implications of these findings were discussed.     

Dependence of cavitation,chemical effect,and mechanical effect thresholds on ultrasonic frequency

Cavitation, chemical effect, and mechanical effect thresholds were investigated in wide frequency ranges from 22 to 4880 kHz. Each threshold was measured in terms of sound pressure at fundamental frequency. Broadband noise emitted from acoustic cavitation bubbles was detected by a hydrophone to determine the cavitation threshold. Potassium iodide oxidation caused by acoustic cavitation was used to quantify the chemical effect threshold. The ultrasonic erosion of aluminum foil was conducted to estimate the mechanical effect threshold. The cavitation, chemical effect, and mechanical effect thresholds increased with increasing frequency. The chemical effect threshold was close to the cavitation threshold for all frequencies. At low frequency below 98 kHz, the mechanical effect threshold was nearly equal to the cavitation threshold. However, the mechanical effect threshold was greatly higher than the cavitation threshold at high frequency. In addition, the thresholds of the second harmonic and the first ultraharmonic signals were measured to detect bubble occurrence. The threshold of the second harmonic approximated to the cavitation threshold below 1000 kHz. On the other hand, the threshold of the first ultraharmonic was higher than the cavitation threshold below 98 kHz and near to the cavitation threshold at high frequency.     

High frequency ultrasonic-assisted CO2 absorption in a high pressure water batch system

Physical absorption process is always nullified by the presence of cavitation under low frequency ultrasonic irradiation. In the present study, high frequency ultrasonic of 1.7 MHz was used for the physical absorption of CO₂ in a water batch system under elevated pressure. The parameters including ultrasonic power and initial feed pressure for the system have been varied from 0 to 18 W and 6 to 41 bar, respectively. The mass transfer coefficient has been determined via the dynamic pressure-step method. Besides, the actual ultrasonic power that transmitted to the liquid was measured based on calorimetric method prior to the absorption study. Subsequently, desorption study was conducted as a comparison with the absorption process. The mechanism for the ultrasonic assisted absorption has also been discussed. Based on the results, the mass transfer coefficient has increased with the increasing of ultrasonic power. It means that, the presence of streaming effect and the formation of liquid fountain is more favorable under high frequency ultrasonic irradiation for the absorption process. Therefore, high frequency ultrasonic irradiation is suggested to be one of the potential alternatives for the gas separation process with its promising absorption enhancement and compact design.     

Investigation of the growth and local stoichiometric point group symmetry of titania nanotubes during potentiostatic anodization of titanium in phosphate electrolytes

Potentiostatic anodization of commercially pure, 50 µm-thick titanium (Ti) foil was performed in aqueous, phosphate electrolytes at increasing experimental timeframes at a fixed applied potential for the synthesis of titania nanotube arrays (TNAs). High resolution scanning electron microscopy images, combined with energy dispersive spectroscopy and x-ray diffraction spectra reveal that anodization of the Ti foil in a 1 M NaF+0.5 M H₃PO₄ electrolyte for 4 h yields a titanate surface with pore diameters ranging between 100 and 500 nm. The presence of rods on the Ti foil surface with lengths exceeding 20 µm and containing high concentrations of phosphor on the exterior was also detected at these conditions, along with micro-sized coral reef-like titanate balls. We propose that the formation of these structures play a major role during the anodization process and impedes nanotube growth during the anodization process. High spatially resolved scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) performed along the length of a single anodized TiO₂ nanotube reveals a gradual evolution of the nanotube crystallinity, from a rutile-rich bottom to a predominantly anatase TiO₂ structure along its length.     

Effective utilization of spray pyrolyzed CeO2 as optically passive counter electrode for enhancing optical modulation of WO3

Nanocrystalline cerium oxide (CeO₂) thin films were deposited onto the fluorine doped tin oxide coated glass substrates using methanolic solution of cerium nitrate hexahydrate precursor by a simple spray pyrolysis technique. Thermal analysis of the precursor salt showed the onset of crystallization of CeO₂ at 300 °C. Therefore, cerium dioxide thin films were prepared at different deposition temperatures from 300 to 450 °C. Films were transparent (T ~ 80%), polycrystalline with cubic fluorite crystal structure and having band gap energy (Eg) in the range of 3.04–3.6 eV. The different morphological features of the film obtained at various deposition temperatures had pronounced effect on the ion storage capacity (ISC) and electrochemical stability. The larger film thickness coupled with adequate degree of porosity of CeO₂ films prepared at 400 °C showed higher ion storage capacity of 20.6 mC cm^? 2 in 0.5 M LiClO₄ + PC electrolyte. Such films were also electrochemically more stable than the other studied samples. The Ce⁴⁺/Ce³⁺ intervalancy charge transfer mechanism during the bleaching–lithiation of CeO₂ film was directly evidenced from X-ray photoelectron spectroscopy. The optically passive behavior of the CeO₂ film (prepared at 400 °C) is affirmed by its negligible transmission modulation upon Li⁺ ion insertion/extraction, irrespective of the extent of Li⁺ ion intercalation. The coloration efficiency of spray deposited tungsten oxide (WO₃) thin film is found to enhance from 47 to 53 cm² C^? 1 when CeO₂ is coupled with WO₃ as a counter electrode in electrochromic device. Hence, CeO₂ can be a good candidate for optically passive counter electrode as an ion storage layer.     

Hydrophilic polyaniline nanofibrous architecture using electrosynthesis method for supercapacitor application

An electrosynthesis process of hydrophilic polyaniline nanofiber electrode for electrochemical supercapacitor is described. The TGA–DTA study showed polyaniline thermally stable up to 323 K. Polyaniline nanofibers exhibit amorphous nature as confirmed from XRD study. Smooth interconnected fibers having diameter between 120–125 nm and length typically ranges between 400–500 nm observed from SEM and TEM analysis. Contact angle measurement indicated hydrophilic nature of polyaniline fibers. Optical study revealed the presence of direct band gap with energy 2.52 eV. The Hall effect measurement showed room temperature resistivity ∼3 × 10⁻⁴ Ω cm and Hall mobility 549.35 cm⁻²V⁻¹ s⁻¹_. The supercapacitive performance of nanofibrous polyaniline film tested in 1 M H₂SO₄ electrolyte and showed highest specific capacitance of 861 F g⁻¹ at the voltage scan rate of 10 mV/s.     

Effects of ultrasonic agitation and surfactant additive on surface roughness of Si (1 1 1) crystal plane in alkaline KOH solution

In the silicon wet etching process, the “pseudo-mask” formed by the hydrogen bubbles generated during the etching process is the reason causing high surface roughness and poor surface quality. Based upon the ultrasonic mechanical effect and wettability enhanced by isopropyl alcohol (IPA), ultrasonic agitation and IPA were used to improve surface quality of Si (1 1 1) crystal plane during silicon wet etching process. The surface roughness R_q is smaller than 15 nm when using ultrasonic agitation and R_q is smaller than 7 nm when using IPA. When the range of IPA concentration (mass fraction, wt%) is 5–20%, the ultrasonic frequency is 100 kHz and the ultrasound intensity is 30–50 W/L, the surface roughness R_q is smaller than 2 nm when combining ultrasonic agitation and IPA. The surface roughness R_q is equal to 1 nm when the mass fraction of IPA, ultrasound intensity and the ultrasonic frequency is 20%, 50 W and 100 kHz respectively. The experimental results indicated that the combination of ultrasonic agitation and IPA could obtain a lower surface roughness of Si (1 1 1) crystal plane in silicon wet etching process.