Highly transparent yttria ceramics with Nb2O5/Ta2O5 as novel sintering additives by pressureless vacuum sintering

Highly transparent yttria ceramics were fabricated by pressureless sintering with Nb₂O₅ or Ta₂O₅ as a novel sintering additive. The optical transmittance, microstructural evolution, and thermo-mechanical properties of the samples were investigated. The optimal doping concentrations of Nb₂O₅ and Ta₂O₅ are 0.3 and 0.2 at.%, respectively, which are much lower compared to those of previously reported counterparts. The transmittance of the sample with 0.3 at.% Nb₂O₅ reaches 81.6% at 1100 nm and 72.4% at 400 nm (2 mm in thickness), similar transmittance was obtained in the sample with 0.2 at.% Ta₂O₅. The microhardness (∼7 GPa), fracture toughness (∼0.85 MPa·m^1/2), and biaxial strength (∼200 MPa) of the present samples were confirmed to be comparable or even better compared to those of previously reported transparent yttria ceramics fabricated by pressureless sintering. Furthermore, the present samples, by virtue of the low doping concentrations, possessed relatively high thermal conductivity values (>10 W/m·K), which substantially guaranteed high thermal shock resistance.     

Investigation of ammonium polyphosphate dilution with ground eggshells and lignin through the study of natural fibre composite flammability

The interactions of Calcium carbonate (e.g., eggshell powder) and Lignin with ammonium polyphosphate (APP) when used as fire retardants were investigated. Three mixing ratios - 1:3, 1:1, and 3:1, were used with natural fibre reinforced composites containing a hemp mat and an epoxy matrix manufactured using a light resin transfer moulding (L-RTM) process. The thermal decomposition of the retardant mixtures and composites was investigated using thermogravimetric analysis (TGA). The findings showed that even though the decomposition reactions of APP with eggshell powder and lignin mixtures interacted and overlapped, the same interactions could not be seen in the composites. In the composite form while the residue was affected by the retardant, the decomposition reactions were driven primarily by the hemp and epoxy. Flammability of the composites was studied by testing to 20, 35, 50, and 75 kW/m² with a cone calorimeter, and determining the critical heat flux. While the samples with eggshell powder had higher ignition times, the critical heat flux for ignition was 13 kW/m² for all sample groups except for a ratio of 1:3 APP to eggshell powder, which was 14 kW/m². The lowest burning rates (mass loss and heat release) occurred in composites containing only APP, however, the addition of eggshell powder or lignin at even a ratio of 3:1 APP to either provided a notable reduction.     

Role of catalyst supports in biocatalysis

Biocatalysis utilizes enzymes and microbial cells as catalysts for a wide range of applications in biotechnology. Immobilization of biocatalysts on various materials has several advantages, including the capacity for reuse, quick reaction termination, easy biocatalyst recovery and operational stability. The present article focuses on the use of material supports for developing immobilized biocatalysts in applications related to energy, environment and chemical synthesis. The work provides a comprehensive overview of a broad class of materials, including organic, inorganic and composites, that have been shown to be prosperous candidates to support the immobilization of enzymes and microbial cells. It also highlights the properties of nanomaterial support such as large surface area and comfort compartment for immobilization. The availability of different types of materials as catalyst support provides an opportunity to understand and develop efficient biocatalytic systems. The choice of selecting a catalyst support will mostly depend on the interaction of the material with the enzyme or microbial cell. Finally, potential challenges, future approaches in developing immobilized biocatalytic systems for various applications and novel material supports are suggested. © 2022 Society of Chemical Industry (SCI).     

Enhancing low-temperature energy harvesting by lead-free ferroelectric Ba(Zr0.1Ti0.9)O3

The energy-harvesting ability of the lead-free ferroelectric Ba(Zr,Ti)O₃ was investigated and greatly enhanced using the Kim novel electrothermodynamic cycle for low-temperature application. Ba(Zr,Ti)O₃ was synthesized with a Zr:Ti ratio of 10:90 (BZT10) by hot-press sintering, which exhibited a mix relaxor-ferroelectric behavior. For power generation using the Kim cycle with low and high temperatures of T_L = 25°C, T_H = 120°C, the most optimized temperature pattern occurred for a heating time of 12.5 s and a cooling time of 22.5 s. Under these conditions, the electric field increased during the novel isodisplacement process, and the displacement variation in the isoelectric step reached the highest value and maximized the BZT10 cycle loop area. Applying these conditions while lowering T_L to 20°C, an energy density N_D = 504 mJ/cm³ was achieved. This value is the highest obtained energy density in a practical test for lead-free ferroelectric bulk material in the BaTiO₃ family.     

Ultrafast-laser-treated poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) electrodes with enhanced conductivity and transparency for semitransparent perovskite solar cells

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is an important organic electrode for solution-processed low-cost electronic devices. However, it requires doping and post-solvent treatment to improve its conductivity, and the chemicals used for such treatments may affect the device fabrication process. In this study, we developed a novel route for exploiting ultrafast lasers (femtosecond and picosecond laser) to simultaneously enhance the conductivity and transparency of PEDOT:PSS films and fabricate patterned solution-processed electrodes for electronic devices. The conductivity of the PEDOT:PSS film was improved by three orders of magnitude (from 3.1 to 1024 S·cm^–1), and high transparency of up to 88.5% (average visible transmittance, AVT) was achieved. Raman and depth-profiling X-ray photoelectron spectroscopy revealed that the oxidation level of PEDOT was enhanced, thereby increasing the carrier concentration. The surface PSS content also decreased, which is beneficial to the carrier mobility, resulting in significantly enhanced electrical conductivity. Further, we fabricated semitransparent perovskite solar cells using the as-made PEDOT:PSS as the transparent top electrodes, and a power conversion efficiency of 7.39% was achieved with 22.63% AVT. Thus, the proposed route for synthesizing conductive and transparent electrodes is promising for vacuum and doping-free electronics.     

Fibrous ceramic membrane constructed by mullite whiskers for the treatment of oil-in-water emulsions

Ceramic membranes with high porosity and excellent separation efficiency are necessary for the efficient treatment of large-scale wastewaters. However, the conventional ceramic membranes are usually prepared by particles-packing, which inhibits the advances of separation efficiency because of the low porosity and connectivity. Here, a fibrous ceramic membrane with mullite whiskers-interlocked structure was prepared by gas-solid reaction. The effects of aluminum fluoride (AlF₃) on the formation and growth of mullite whiskers, and then the permeability and selectivity of the ceramic membranes were investigated. With the increase of AlF₃ contents, the mullite phase evolved from needle-like, rod-like to flake-like structure, thus the catalyst accelerated the growth of mullite whiskers in the diameter direction. For the ceramic membrane sintered at 1400°C, the porosity increased from 58% to 76% while the average pore sizes increased from 0.65 to 3.93 μm because of the whisker-constructed structures. For the ceramic membrane sintered at 1450°C, the emulsion flux increased stably from 295 L/(m²·h) to 992 L/(m²·h) with the increase of trans-membrane pressure, and the oil rejection exceeded 98%. Thus, this study provides a feasible strategy for the preparation of ceramic membranes with high porosity and excellent separation performances.     

Phase equilibria of hydrates from ternary mixtures of methane + ethane + propane and methane + propane + carbon dioxide

Hydrate–liquid–vapour (HLV) equilibrium of aqueous clathrates formed from gas mixtures can be complex compared to hydrates formed with single guests. Typically, pressure and temperature are controlled to obtain these data, but for multicomponent systems, it is necessary to control/report more intensive variables, namely, composition. Metastability, manifested as impractically long experimental times, has been reported to be a challenge with some multicomponent systems. We present HLV equilibrium conditions of two ternary gas mixtures: methane + ethane + propane (90:7:3 molar ratio) and methane + propane + carbon dioxide (55:5:40 molar ratio). Conditions varied in the temperature range of 275–285 K and the pressure range of 1.24–4.75 MPa. Experimental standard uncertainties were on average 0.10 K and 0.005 MPa for methane + ethane + propane and 0.19 K and 0.005 MPa for methane + propane + carbon dioxide. Our technique allowed us to bypass the limitations reported in the literature and provided fast, reproducible HLV equilibria for gas-dominated systems.     

Analysis of the kinetics of ion intercalation: Ion trapping approach to solid-state relaxation processes

This paper develops a new framework for the interpretation of impedance or capacitance spectroscopy of ion insertion processes in thin film electrodes, with a particular emphasis in electrochromic materials. The model distinguishes types of inserted ion charge regarding the energetics and kinetics properties of ion storage sites. The ion charge in a connected network of sites moves rapidly (fast sites) and is distributed according to equilibrium thermodynamic properties, while slower sites trap the ions and provide a variety of kinetic behaviors that dominate the response in the long time scale. We show that the assumption that a fraction of the intercalated ions have been immobilized at certain sites, and do not participate in diffusion, provides a suitable explanation for the observation of different capacitive components in the faradaic impedance of homogeneous systems (fast and slow charging modes). Moreover, ion trapping contributes a resistive component to the impedance, related to homogeneous charge-transfer between different types of sites (trap resistance). The model predicts an arc in the complex capacitance representation associated to the solid-state reduction step involved in the coloration by electroinsertion. The characteristic features of the relaxation in structurally disordered materials are studied in the kinetic framework of a multiple trapping scheme. We show that a wide distribution of trapping times provides a power law of frequency, which relates to the frequent observation of a constant phase element (CPE) impedance.     

Study on pH‐sensitive and thermosensitive polymer networks containing polyacetal segments

A series of pH‐sensitive and thermosensitive polymer networks were first obtained by copolymerization of telechelic poly(1,3‐dioxolane) (PDXL) with acrylic acid (AA), acrylamide (AM), and N‐isopropylacrylamide (NIPAM), respectively. The copolymerization of PDXL diacrylate (PDXLDA) with AA, AM, or NIPAM is expected to lead to polymer networks in which homopolymeric segments of the monomer are connected by polyacetal segments. As a combination of these two parts, these polymer networks can have some interesting physical properties. For example, the copolymer networks of poly(AA‐b‐DXL) showed pH sensitivity, and both the copolymer networks of poly(AM‐b‐DXL) and poly(NIPAM‐b‐DXL) showed temperature sensitivity. Moreover, because of the low ceiling temperature of polyDXL, the networks containing polyacetal segments (PDXL) can degrade by treatment with a trace of appropriate cationic initiator. The polymer networks prepared were characterized by Fourier transform infrared, differential scanning calorimetry, and swelling data. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3002–3006, 2002; DOI 10.1002/app.2329     

Synthesis and characterization of pH‐sensitive networks containing degradable poly(1,3‐dioxolane) segments

pH‐sensitive networks were obtained by radical copolymerization of telechelic poly(1,3‐dioxolane) (PDXLDA) with acrylic acid (AA). PDXLDA was synthesized by acrylation of the corresponding dihydroxylated polyacetal (polyDXL) with AA in pyridine. The copolymer networks of poly(AA‐b‐DXL) showed pH sensitivity due to —COOH groups, which are insoluble in any solvents, but can swell in water or good solvents. The swelling behavior is closely related to the solvents and is composition‐dependent. The networks containing polyDXL segments can be decrosslinked under acidic conditions due to the low ceiling temperature of polyDXL. After degradation, the linear segments of polyDXL became cycled molecules. The networks' structure, swelling behavior, and degradation were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, GC–MS analysis, and swelling data. This kind of material can be potentially used in biosystems, such as in intelligent drug‐delivery systems. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1678–1682, 2002