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.     

Effects of high-pressure-modified soy 11S globulin on the gel properties and water-holding capacity of pork batter

The effects of high-pressure-modified soy 11S globulin (0.1, 200, and 400 MPa) on the gel properties, water-holding capacity, and water mobility of pork batter were investigated. The high-pressure-modified soy 11S globulin significantly increased (P < 0.05) the emulsion stability, cooking yield, hardness, springiness, chewiness, resilience, cohesiveness, the a^* and b^* values, and the G′ and G′′ values of pork batter at 80 °C, compared with those of 0.1 MPa-modified globulin. In contrast, the centrifugal loss and initial relaxation time of T_2b, T₂₁, and T₂₂ significantly decreased (P < 0.05). Meanwhile, the microstructure was denser, and the voids were smaller and more uniform compared with those of 0.1 MPa-modified globulin. In addition, the sample with 11S globulin modified at 400 MPa had the best water-holding capacity, gel structure, and gel properties among the samples. Overall, the use of high-pressure-modified soy 11S globulin improved the gel properties and water-holding capacity of pork batter, especially under 400 MPa.     

Facile preparation and strong adhesive strength of honeycomb polyurethane films with small pore diameter

With the continuous development of bionics, such as, geckos and virginia creeper with both superhydrophobic and super-adhesive, the surface wetting and super-adhesive properties of various porous materials have attracted extensive attention of the scientific and medical communities. Here, the honeycomb polyurethane (PU) porous films with strong adhesion were successfully prepared by microphase separation method and the effects of growth parameters on their microstructure and adhesive strength to ice were investigated. It was found that a high relative humidity (e.g., 100%) and a low solution concentration (e.g., 2%) facilitated the formation of ordered honeycomb PU porous films, and as-prepared PU pores with average pore diameter as small as 5 μm are better ordered and more uniform than these in related documents. Although the contact angle of water droplets on the surface of PU porous films increased from the premodification value of 85–130° to more than 160° after surface modification with polydopamine (PDA), the corresponding rolling angle remained approximately constant (180°), indicating that the surface of PU porous films has strong adhesion similar to geckos and virginia creeper. Furthermore, at lower temperature, the PU porous films exhibited the high adhesive strength of 142.13 kPa on ice, which was strongly dependent on the porous microstructures and surface compositions. The improved adhesive behavior to ice of honeycomb PU porous films modified with PDA provides new strategies for surface modification of materials and potential applications in medical domain.     

Centimeter-scale low-damage micromachining on single-crystal 4H–SiC substrates using a femtosecond laser with square-shaped Flat-Top focus spots

Femtosecond (fs) lasers have been proved to be reliable tools for high-precision and high-quality micromachining of ceramic materials. Nevertheless, fs laser processing using a single-mode beam with a Gaussian intensity distribution is difficult to obtain large-area flat and uniform processed surfaces. In this study, we utilize a customized diffractive optical element (DOE) to redistribute the laser pulse energy from Gaussian to square-shaped Flat-Top profile to realize centimeter-scale low-damage micromachining on single-crystal 4H–SiC substrates. We systematically investigated the effects of processing parameters on the changes in surface morphology and composition, and an optimal processing strategy was provided. Mechanisms of the formation of surface nanoparticles and the removal of surface micro-burrs were discussed. We also examined the distribution of subsurface defects caused by fs laser processing by removing a thin surface layer with a certain depth through chemical mechanical polishing (CMP). Our results show that laser-induced periodic surface structures (LIPSSs) covered by fine SiO₂ nanoparticles form on the fs laser-processed areas. Under optimal parameters, the redeposition of SiO₂ nanoparticles can be minimized, and the surface roughness Sa of processed areas reaches 120 ± 8 nm after the removal of a 10 μm thick surface layer. After the laser processing, micro-burrs on original surfaces are effectively removed, and thus the average profile roughness Rz of 2 mm long surface profiles decreases from 920 ± 120 nm to 286 ± 90 nm. No visible micro-pits can be found after removing ~1 μm thick surface layer from the laser-processed substrates.     

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.     

Theoretical study on a kind of cyclization mechanism of boron trichloride and hexamethyldisilazane to form the borazine ring for SiBCN ceramics precursor

Borazine rings act as a pivotal part in siliconboroncarbonitride ceramics (SiBCN) for high-temperature stability and great resistance to crystallization. A detailed investigation of the ring formation mechanism will guide the design and synthesis of SiBCN to meet application requirements under extreme conditions. Boron trichloride (BCl₃) and hexamethyldisilazane (HN(SiMe₃)₂) are common raw materials for the synthesis of precursors for SiBCN. In this paper, quantum chemical calculation was used to study the cyclization reaction mechanism between BCl₃ and HN(SiMe₃)₂ to form trichloroborazine (TCBZ) at the MP2/6-31G (d,p) level of theory. We discussed the structure properties, reaction pathways, energy barriers, reaction rates, and other aspects in detail. The results show that BCl₃ and HN(SiMe₃)₂ alternately participate in the reaction process, accompanied by the release of trimethylchlorosilane (TMCS), and that the entire reaction shows an absolute advantage in terms of energy. In the Step by step reaction, lower reaction barriers are formed due to the introduction of BCl₃ with more heat released compared to that for the introduction of HN(SiMe₃)₂. The final single-molecule cyclization and TMCS elimination steps are found to be faster compared to all previous bimolecular reactions.     

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.     

Display illumination with modulated directional backlight

Illumination is essential for modern life as colorful world is perceived by human visionary system. Display technology has been developing rapidly in recent decades, and the basic principle is related to the way that the image is illuminated and light is emanated. Traditional illumination is provided by different types of light sources, and the display image is visible in large viewing space until the emanating light decays to zero. This work proposes and demonstrates a novel illumination scheme for a display in which the displaying images are visible only in specific spatial regions. The directional backlight ensures the image propagating to specific direction while imaging visibility can be controlled to terminate abruptly at certain distance from the display screen while exerting no influence to nearby regions. The working principle for such an illumination scheme is the use of the modulated coherent directional backlight through an axicon lens. It is shown that the illumination scheme can robustly deliver carried image information to the designated viewing region. This new illumination scheme has many advantages over conventional illumination, including its usage for personal display, very lower energy consumption, as well as minimizing light hazard pollution.