Fabrication of tungsten oxide photoanode by doctor blade technique and investigation on its photocatalytic operation mechanism

WO₃ is a potential material candidate for construction of photoanode for solar driven water splitting. In this work, μm-thick porous WO₃ photoanode is prepared by depositing a stable ink made of WO₃ nanoparticles and Aristoflex velvet polymer in water using the doctor blade technique, followed by a sintering in air. The nature of WO₃ nanoparticles, its loading mass on F-doped tin oxide electrode as well as sintering temperature are examined in order to optimize the photocatalytic activity of the resultant WO₃ photoanode. The operation of WO₃ photoanode is investigated by varying the light illumination direction and light incident intensity as well as changing the nature of the electrolyte. Dissolved tungsten in electrolyte is quantified by ICP-MS providing insights into the influences of electrolyte nature and operating conditions to the corrosion of WO₃. It is proposed that the H₂O₂ and OH^. radical generated as by-products of the photo-driven water oxidation on the photoanode surface are harmful species that accelerate the dissolution of WO₃.     

Highly efficient two-stage ring-opening of epichlorohydrin with carboxylic acid in a microreaction system

Ring-opening of epoxides with carboxylic acids has been widely used to prepare many high value intermediates in the polymer and pharmaceutical industries. Most of conventional processes proceeded in batch stirred reactors. As such they always suffer from low productivity and selectivity. Here we developed an advanced technology to perform the ring-opening reaction of epichlorohydrin with neodecanoic acid (NDA) for continuous production of 3-chloro-2-hydroxypropyl neodecanoate in a more efficient and safer way. A microreaction system where a microreactor connected to a stirred reactor was established. When the conversion of NDA rapidly reaching around 90% in a microreactor at 110°C, the reaction solution was transferred to a stirred reactor at 90°C. This two-stage operating mode can reduce the reaction time and improve the selectivity through free switching of temperature in the consecutive two reactors, thus substantially reducing the consumption of energy and materials.     

Homotopy continuation enhanced branch and bound algorithms for strongly nonconvex mixed-integer nonlinear optimization

Large-scale strongly nonlinear and nonconvex mixed-integer nonlinear programming (MINLP) models frequently appear in optimization-based process synthesis, integration, intensification, and process control. However, they are usually difficult to solve by existing algorithms within acceptable time. In this study, we propose two robust homotopy continuation enhanced branch and bound (HCBB) algorithms (denoted as HCBB-FP and HCBB-RB) where the homotopy continuation method is employed to gradually approach the optimum of the NLP subproblem at a node from the solution at its parent node. A variable step length is adapted to effectively balance feasibility and computational efficiency. The computational results from solving four existing process synthesis problems demonstrate that the proposed HCBB algorithms can find the same optimal solution from different initial points, while the existing MINLP algorithms fail or find much worse solutions. In addition, HCBB-RB is superior to HCBB-FP due to much lower computational effort required for the same locally optimal solution.     

Effect of ultrasonic waveforms on gas–liquid mass transfer in microreactors

This study aims to investigate the effect of ultrasonic waveforms on the gas–liquid mass transfer process. For a given load power (P), continuous rectangular wave yielded stronger bubble oscillation and higher mass transfer coefficient (k_La) than continuous triangular and sinusoidal wave. For pulsed ultrasound, the k_La decreased monotonically with decreasing duty ratio (D), resulting in weak enhancement at low D (≤33%). For a given average load power (P_A), concentrating the P for a shorter period resulted in a higher k_La due to stronger cavitation behavior. For a given P_A and D, decreasing the pulse period (T) led to an increase in k_La, which reached a constant high level when the T fell below a critical value. By optimizing the D and T, a k_La equivalent to 92% of that under continuous ultrasound was obtained under pulsed ultrasound at a D of 67%, saving 33% in power consumption.     

Energy storage performance of 0.55Bi0.5Na0.5TiO3-0.45SrTiO3 ceramics doped with lanthanide elements (Ln = La,Nd, Dy,Sm) using a viscous polymer processing route

Lead-free bismuth sodium titanate-strontium titanate (NBT-ST) dielectric ceramic materials have been extensively investigated energy storage materials because of their relaxor characteristics. In this study, four different lanthanide elements were introduced into the ferroelectric NBT-ST ceramic to improve their relaxor properties. The introduction of the lanthanide resulted in an increase in disorder at location A within the perovskite lattice and improved relaxor characteristics, leading to a stored energy density of more than 3.5 J/cm³. In particular, an ultrahigh recoverable stored energy density of 4.94 J/cm³ and efficiency of 88.45% were achieved at 440 kV/cm when the NBT-ST ceramic was modified with neodymium. The modified ceramic also exhibited good thermal stability in the range of 30–120 °C, as well as a fast discharge time of ～153 ns, indicating that Nd-incorporated NBT-ST is a promising candidate for electrical energy storage ceramic.     

A three-dimensional surface measurement system implemented with Gaussian process based adaptive sampling

Self-adaptive surface measurements that can reduce data redundancy and improve time efficiency are in high demand in many fields of science and technology. For this purpose, a system implemented with Gaussian process (GP) adaptive sampling is developed. The non-parametric GP model is applied to reconstruct the topography and guide the subsequent sampling position, which is determined from the inference uncertainty estimation. A criterion is proposed to terminate the GP adaptive measurement automatically without any prior model or data of the topography. Experiments on typical surfaces validate the intelligence, adaptability, and high accuracy of the GP method along with the stabilization of the automatic iteration termination. Compared with traditional raster sampling, data redundancy is reduced and the time efficiency is improved without sacrificing the surface reconstruction accuracy. The proposed method can be implemented in other systems with similar measurement principles, thus benefitting surface characterizations.     

New insights into microstructural changes during transient liquid phase bonding of GTD-111 superalloy

The effects of joining temperature (T_J) and time (t_J) on microstructure of the transient liquid phase (TLP) bonding of GTD-111 superalloy were investigated. The bonding process was applied using BNi-3 filler at temperatures of 1080, 1120, and 1160 °C for isothermal solidification time of 195, 135, and 90 min, respectively. Homogenization heat treatment was also applied to all of the joints. The results show that intermetallic and eutectic compounds such as Ni-rich borides, Ni−B−Si ternary compound and eutectic-γ continuously are formed in the joint region during cooling. By increasing t_J, intermetallic phases are firstly reduced and eventually eliminated and isothermal solidification is completed as well. With the increase of the holding time at all of the three bonding temperatures, the thickness of the athermally solidified zone (ASZ) and the volume fraction of precipitates in the bonding area decrease and the width of the diffusion affected zone (DAZ) increases. Similar results are also obtained by increasing T_J from 1080 to 1160 °C at t_J=90 min. Furthermore, increasing the T_J from 1080 to 1160 °C leads to the faster elimination of intermetallic phases from the ASZ. However, these phases are again observed in the joint region at 1180 °C. It is observed that by increasing the bonding temperature, the bonding width and the rate of dissolution of the base metal increase. Based on these results, increasing the homogenization time from 180 to 300 min leads to the elimination of boride precipitates in the DAZ and a high uniformity of the concentration of alloying elements in the joint region and the base metal.     

The cold sintering process: A review on processing features,densification mechanisms and perspectives

Since its first introduction in 2016, cold sintering process (CSP) has gained worldwide interest from the scientific community as green and innovative fabrication route due to the dramatic reduction of processing time, energy, and costs. Cold sintering resembles the geological formation of rocks where a ceramic powder is densified with the aid of a liquid phase under an intense external pressure and limited heating conditions (below 350 °C). Up to date, tens of different materials, including composites, have been successfully processed through CSP and extraordinary results in terms of densification, microstructure and final properties have been achieved. In the present review, processing features and variables, possible densification mechanisms and issues also for the realization of ceramic-based composites are explored. Advantages with respect to existing techniques are analysed and current challenges are described to lay the ground for new processing opportunities to be faced in the near future.     

Effects of water and carbon dioxide pressure on the adhesion of Na2SiO3 and K2SiO3 binders on silica sand surface: Comparison of experimental data and molecular dynamics simulation

In this study, the effects of different water amounts, CO₂ blowing pressures, Na₂O:SiO₂ and K₂O:SiO₂ ratios were studied on the bonding strength of Na₂SiO₃ and K₂SiO₃ binders. It was concluded that the increase in water content had an adverse effect on the bonding strength of CO₂-hardened Na₂SiO₃ sand. The blowing pressure did not have a linear relationship with the bonding strength, but it was closely related to the diffusion coefficient of CO₂. Based on scanning electron microscopic results, it was inferred that the low strength was caused by the formation of lamellar crystals after the adhesive was hardened. It was found that the low strength was caused by the formation of lamellar crystals after the adhesive was hardened. Based on molecular dynamics simulations, different pressures and water contents had a great influence on the diffusion coefficient of CO₂ in the silicate binder system. This research provides an important theoretical background to improve the technology of CO₂-hardened Na₂SiO₃- and K₂SiO₃-bonded sands during the casting process.     

The spheroidization process of micron-scaled α-Al2O3 powder in hydrothermal method

Understanding the spheroidization process of micron-scaled α-Al₂O₃ powder in hydrothermal method is of great importance but still not completely revealed. The results demonstrated that SO₄^2? played a significant role in the formation of spherical powder, while the bubble generated from the reaction of urea didn't work in the spheroidization process. The spheroidization process was summed up as two steps. The first was that SO₄^2? limited the hydrolysis of Al³⁺ and reacted with Al³⁺ and OH^- to form Al₄(OH)₁₀SO₄, which nucleated and agglomerated into granular precipitates. The second was Ostwald ripening, which gave the spherical precursors a double-layered structure. When the spherical precursors obtained 120 °C were sintered at 1200 °C, α-Al₂O₃ were got and the spherical morphology still maintained with a large number of nano-sized pores. We anticipate the spherical α-Al₂O₃ with nano-sized pores can be applied in adsorption and filtration industries.