Theoretical investigation of intrinsic point defects and the oxygen migration behavior in rare earth hafnates

In this work, the composition-dependent point defect types and formation energies of RE₂Hf₂O₇ (RE = La, Ce, Pr, Nd, Pm, Sm, Eu and Gd) as well as the oxygen diffusion behavior are systematically investigated by first-principles calculations. The possible defect reactions and dominant defect complexes under stoichiometric and non-stoichiometric conditions are revealed. It is found that O Frenkel pairs are the predominant defect in stoichiometric pyrochlore hafnates. Hf-RE cation anti-site defects, accompanied by RE vacancies and/or oxygen interstitials, are stable in the non-stoichiometric case of HfO₂ excess. On the other hand, RE-Hf anti-site defects together with oxygen vacancies and/or RE interstitials are preferable in the case of RE₂O₃ excess. The energy barriers for the migration along the V_O48f - V_O48f pathway of pyrochlore hafnates were calculated to be between 0.81 eV and 0.89 eV. Based on these results, a defect engineering strategy is proposed and the pyrochlore hafnates investigated here are predicted to exhibit potential oxygen ionic conductivity.     

Eco-friendly and degradable red phosphorus nanoparticles for rapid microbial sterilization under visible light

Pathogens pose a serious challenge to environmental sanitation and a threat to public health.The frequent use of chemicals for sterilization in recent years has not only caused secondary damage to the environment but also increased pathogen resistance to drugs,which further threatens public health.To address this issue,the use of non-chemical antibacterial means has become a new trend for environmental disinfection.In this study,we developed red phosphorus nanoparticles(RPNPs),a safe and degradable photosensitive material with good photocatalytic and photothermal properties.The red phosphorus nanoparticles were prepared using a template method and ultrasonication.Under the irradiation of simulated sunlight for 20 min,the RPNPs exhibited an efficiency of 99.98%in killing Staphylococcus aureus due to their excellent photocatalytic and photothermal abilities.Transmission electron microscopy and ultraviolet–visible spectroscopy revealed that the RPNPs exhibited degradability within eight weeks.Both the RPNPs and their degradation products were nontoxic to fibroblast cells.Therefore,such RPNPs are expected to be used as a new type of low-cost,efficient,degradable,biocompatible,and eco-friendly photosensitive material for environmental disinfection.     

The effect of alkali metal oxide on the properties of borosilicate fireproof glass: Structure,thermal properties,viscosity, chemical stability

The purpose of the current work was to research the effect of alkali metal oxide on the structure, thermal properties, viscosity and chemical stability in the glass system (R₂O–CaO–B₂O₃–SiO₂) systematically. Because the glass would emulsify when Li₂O was added to the glass batch, this article did not discuss Li₂O. The results showed that when the amount of Na₂O was less than 4 mol.%, there was a higher interconnectivity of borate and silicate sub-networks in glass, as more mixed Si–O–B bonds were present in glass. The glass samples exhibited excellent thermal properties and chemical stabilities. As the amount of Na₂O exceeded 4 mol.%, the interconnectivity of borate and silicate sub-networks was weakened. The thermal properties and chemical stabilities of the glass samples were reduced. The connectivity of the silicate sub-network was weakened slightly as the Na/K ratio varied, and the coefficient of thermal expansion (CTE) of the glass samples gradually increased, and the resistance to thermal shock (RTS) value gradually decreased. Moreover, the viscosity of the glass samples decreased with the ratio of Na/Si and Na/K increased.     

Deacetylated Cellulose Acetate/Polyurethane Composite Nanofiber Membranes with Highly Efficient Oil/Water Separation and Excellent Mechanical Properties

Nowadays, oil pollution has become more serious, which causes great threats both to the ecological environment and human life. In this study, a novel type of multifunctional deacetylated cellulose acetate/polyurethane (d-M_CA:M_TPU) composite nanofiber membranes for oil/water separation are successfully fabricated by electrospinning, which show super-amphiphilicity in air, super-hydrophilicity in oil, and oleophobicity in water. All the d-M_CA:M_TPU composite nanofiber membranes with different mass ratios can be used as water-removing, oil-removing, and emulsion separation substance only by gravity driving force. The highest separation flux for water and oil reaches up to 37 000 and 74 000 L m⁻² h⁻¹, respectively, and all the separation efficiencies are more than 99%. They have outstanding comprehensive mechanics performance, which can be controlled by simply adjusting the mass ratios. They show excellent antifouling and self-cleaning ability, endowing powerful cyclic stability and reusability. Those results show that d-M_CA:M_TPU composite nanofiber membranes have great application prospects in oil/water separation.     

Toughness and R-curve behaviour of laminated Si3N4/SiCw ceramics

Laminated Si₃N₄/SiC_w ceramics were successfully prepared by tape casting and hot-pressing. Its mechanical properties were measured and the impact resistance was discussed. The toughness of the laminated Si₃N₄/SiC_w ceramics was 13.5 MPa m^1/2, which was almost 1.6 times that of Si₃N₄/SiC_w composite ceramics, namely 8.5 MPa m^1/2. Moreover, the indentation strength of laminated Si₃N₄/SiC_w ceramics was not sensitive to increasing indentation loads and exhibited a rising R-curve behaviour, indicating that the laminated Si₃N₄/SiC_w ceramics had excellent impact resistance. The improved toughness and impact resistance of laminated Si₃N₄/SiC_w ceramics was attributed to the residual stress caused by a thermal expansion coefficient mismatch between the different layers, resulting in crack deflection and bridging of SiC whiskers in the interface layer, thus consuming a large amount of fracture work.     

Nacre-Inspired,Liquid Metal-Based Ultrasensitive Electronic Skin by Spatially Regulated Cracking Strategy

The realization of liquid metal-based wearable systems will be a milestone toward high-performance, integrated electronic skin. However, despite the revolutionary progress achieved in many other components of electronic skin, liquid metal-based flexible sensors still suffer from poor sensitivity due to the insufficient resistance change of liquid metal to deformation. Herein, a nacre-inspired architecture composed of a biphasic pattern (liquid metal with Cr/Cu underlayer) as “bricks” and strain-sensitive Ag film as “mortar” is developed, which breaks the long-standing sensitivity bottleneck of liquid metal-based electronic skin. With 2 orders of magnitude of sensitivity amplification while maintaining wide (>85%) working range, for the first time, liquid metal-based strain sensors rival the state-of-art counterparts. This liquid metal composite features spatially regulated cracking behavior. On the one hand, hard Cr cells locally modulate the strain distribution, which avoids premature cut-through cracks and prolongs the defect propagation in the adjacent Ag film. On the other hand, the separated liquid metal cells prevent unfavorable continuous liquid-metal paths and create crack-free regions during strain. Demonstrated in diverse scenarios, the proposed design concept may spark more applications of ultrasensitive liquid metal-based electronic skins, and reveals a pathway for sensor development via crack engineering.     

Maximum likelihood-based adaptive differential evolution identification algorithm for multivariable systems in the state-space form

Parameter estimation plays an important role in the field of system control. This article is concerned with the parameter estimation methods for multivariable systems in the state-space form. For the sake of solving the identification complexity caused by a large number of parameters in multivariable systems, we decompose the original multivariable system into some subsystems containing fewer parameters and study identification algorithms to estimate the parameters of each subsystem. By taking the maximum likelihood criterion function as the fitness function of the differential evolution algorithm, we present a maximum likelihood-based differential evolution (ML-DE) algorithm for parameter estimation. To improve the parameter estimation accuracy, we introduce the adaptive mutation factor and the adaptive crossover factor into the ML-DE algorithm and propose a maximum likelihood-based adaptive differential evolution algorithm. The simulation study indicates the efficiency of the proposed algorithms.     

Synthesis of Ionic Ultramicroporous Polymers for Selective Separation of Acetylene from Ethylene

The design of highly stable and efficient porous materials is essential for developing breakthrough hydrocarbon separation methods based on physisorption to replace currently used energy-intensive distillation/absorption technologies. Efforts to develop advanced porous materials such as zeolites, coordination frameworks, and organic polymers have met with limited success. Here, a new class of ionic ultramicroporous polymers (IUPs) with high-density inorganic anions and narrowly distributed ultramicroporosity is reported, which are synthesized by a facile free-radical polymerization using branched and amphiphilic ionic compounds as reactive monomers. A covalent and ionic dual-crosslinking strategy is proposed to manipulate the pore structure of amorphous polymers at the ultramicroporous scale. The IUPs exhibit exceptional selectivity (286.1–474.4) for separating acetylene from ethylene along with high thermal and water stability, collaboratively demonstrated by gas adsorption isotherms and experimental breakthrough curves. Modeling studies unveil the specific binding sites for acetylene capture as well as the interconnected ultramicroporosity for size sieving. The porosity-engineering protocol used in this work can also be extended to the design of other ultramicroporous materials for the challenging separation of other key gas constituents.