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.     

Fabrication of crescent-shaped ceramic microparticles based on single emulsion microfluidics

Ceramic microparticles have great potentials in various fields such as materials engineering, biotechnology, microelectromechanical systems, etc. Morphology of the microparticle performs an important role on their application. To date, it remains difficult to find an effective and controllable way for fabricating nonspherical ceramic microparticles with 3D features. This work demonstrates a method that combines UV light lithography and single emulsion opaque-droplet-templated microfluidic molding to prepare the crescent-shaped ceramic microparticles. By tailoring the intensity of UV light and flow rate of fluid, the shapes of microparticles are accordingly tuned. Therefore, varieties of crescent-shaped microparticles and their variations have been fabricated. After sintering, the crescent-shaped alumina ceramic microparticles were obtained. Benefitting from the light absorption and scattering behavior of most ceramic nanoparticles, this system can serve as a general platform to produce crescent-shaped microparticles made from different materials, and hold great potentials for applications in microrobotics, structural materials in MEMS, and biotechnology.     

Solution-Synthesized Multifunctional Janus Nanotree Microswimmer

Synthetic active matters are perfect model systems for non-equilibrium thermodynamics and of great potential for novel biomedical and environmental applications. However, most applications are limited by the complicated and low-yield preparation, while a scalable synthesis for highly functional microswimmers is highly desired. In this paper, an all-solution synthesis method is developed where the gold-loaded titania-silica nanotree can be produced as a multi-functional self-propulsion microswimmer. By applying light, heat, and electric field, the Janus nanotree demonstrated multi-mode self-propulsion, including photochemical self-electrophoresis by UV and visible light radiation, thermophoresis by near-infrared light radiation, and induced-charge electrophoresis under AC electric field. Due to the scalable synthesis, the Janus nanotree is further demonstrated as a high-efficiency, low-cost, active adsorbent for water decontamination, where the toxic mercury ions can be reclaimed with enhanced efficiency.     

Dual effect synergistically triggered Ce:(Y,Tb)3(Al,Mn)5O12 transparent ceramics enabling a high color-rendering index and excellent thermal stability for white LEDs

Ce:Y₃Al₅O₁₂ transparent ceramics (TCs) with appropriate emission light proportion and high thermal stability are significant to construct white light emitting diode devices with excellent chromaticity parameters. In this work, strategies of controlling crystal-field splitting around Ce³⁺ ion and doping orange-red emitting ion, were adopted to fabricate Ce:(Y,Tb)₃(Al,Mn)₅O₁₂ TCs via vacuum sintering technique. Notably, 85.4 % of the room-temperature luminescence intensity of the TC was retained at 150 °C, and the color rendering index was as high as 79.8. Furthermore, a 12 nm red shift and a 16.2 % increase of full width at half maximum were achieved owing to the synergistic effects of Tb³⁺ and Mn²⁺ ions. By combining TCs with a 460 nm blue chip, a warm white light with a low correlated color temperature of 4155 K was acquired. Meanwhile, the action mechanism of Tb³⁺ ion and the energy transfer between Ce³⁺ and Mn²⁺ ions were verified in prepared TCs.     

Influence of CO2 inleakage on the slight-alkalization of generator internal cooling water

The slight-alkalization of generator internal cooling water (GICW) is widely used to inhibit the corrosion of hollow copper conductor and thereby ensure the safe operation of the generator. CO₂ inleakage is increasingly identified as a potential security risk for GICW system. In this paper, the influence of CO₂ inleakage on the slight-alkalization of GICW was theoretically discussed. Based on the equilibriums of the CO₂-NaOH-H₂O system, CO₂ inleakage saturation was derived to quantify the amount of the dissolved CO₂ in GICW. This parameter can be directly calculated with the measured conductivity and the [Na⁺] of GICW. The influence of CO₂ inleakage on the slight-alkalization conditioning of GICW and the measurement of its water quality parameters were then analyzed. The more severe the inleakage, the narrower the water quality operation ranges of GICW, resulting in the more difficult the slight-alkalization conditioning of GICW. The temperature calibrations of the conductivity and the pH value of GICW show non-linear correlations with the amount of CO₂ inleakage and the NaOH dosage. This study provides insights into the influence of CO₂ inleakage on the slight-alkalization of GICW, which can serve as the theoretical basis for the actual slight-alkalization when CO₂ inleakage occurs.     

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.     

Magnetically Guidable Proteinaceous Adhesive Microbots for Targeted Locoregional Therapeutics Delivery in the Highly Dynamic Environment of the Esophagus

The esophagus is a tubular-shaped muscular organ where swallowed fluids and muscular contractions constitute a highly dynamic environment. The turbulent, coordinated processes that occur through the oropharyngeal conduit can often compromise targeted administration of therapeutic drugs to a lesion, significantly reducing therapeutic efficacy. Here, magnetically guidable drug vehicles capable of strongly adhering to target sites using a bioengineered mussel adhesive protein (MAP) to achieve localized delivery of therapeutic drugs against the hydrodynamic physiological conditions are proposed. A suite of highly uniform microparticles embedded with iron oxide (IO) nanoparticles (MAP@IO MPs) is microfluidically fabricated using the genipin-mediated covalent cross-linking of bioengineered MAP. The MAP@IO MPs are successfully targeted to a specific region and prolongedly retained in the tubular-structured passageway. In particular, orally administered MAP@IO MPs are effectively captured in the esophagus in vivo in a magnetically guidable manner. Moreover, doxorubicin (DOX)-loaded MAP@IO MPs exhibit a sustainable DOX release profile, effective anticancer therapeutic activity, and excellent biocompatibility. Thus, the magnetically guidable locomotion and robust underwater adhesive properties of the proteinaceous soft microbots can provide an intelligent modular approach for targeted locoregional therapeutics delivery to a specific lesion site in dynamic fluid-associated tubular organs such as the esophagus.