Chemical durability and surface alteration of lanthanide zirconates (A2Zr2O7: A = La-Yb)

Chemical durability of lanthanide zirconates (A₂Zr₂O₇) (A = La-Yb) under near-field environments is important for evaluating their application as potential nuclear waste forms. In this work, A₂Zr₂O₇ (A = La-Yb) are synthesized by spark plasma sintering with controlled microstructure and their chemical durability are evaluated in a nitric acid solution (pH = 1). Scanning transmission electron microscopy analysis reveals an amorphous passivation film either enriched with Zr or lanthanide. The complex chemistry of the passivation films can be correlated with a transition in corrosion mechanisms from a preferential release of lanthanide in La₂Zr₂O₇ to a preferential release of Zr in Er₂Zr₂O₇ and Yb₂Zr₂O₇. These results suggest a dominant mechanism of incongruent dissolution and surface reorganization for the formation of passivation films. Strong correlations are identified between the leaching rates and cation ionic size, ionic potential, electronegativity differences between A-site cation and Zr, and bonding valence sum of oxygen, suggesting important impacts of structural and bonding characteristics in controlling chemical durability of lanthanide zirconates.     

Matrix Manipulation of Directly-Synthesized PbS Quantum Dot Inks Enabled by Coordination Engineering

The direct-synthesis of conductive PbS quantum dot (QD) ink is facile, scalable, and low-cost, boosting the future commercialization of optoelectronics based on colloidal QDs. However, manipulating the QD matrix structures still is a challenge, which limits the corresponding QD solar cell performance. Here, for the first time a coordination-engineering strategy to finely adjust the matrix thickness around the QDs is presented, in which halogen salts are introduced into the reaction to convert the excessive insulating lead iodide into soluble iodoplumbate species. As a result, the obtained QD film exhibits shrunk insulating shells, leading to higher charge carrier transport and superior surface passivation compared to the control devices. A significantly improved power-conversion efficiency from 10.52% to 12.12% can be achieved after the matrix engineering. Therefore, the work shows high significance in promoting the practical application of directly synthesized PbS QD inks in large-area low-cost optoelectronic devices.     

A novel approach for bulk micromachining of 4H-SiC by tool-based electrolytic plasma etching in HF-free aqueous solution

Bulk micromachining of single-crystal SiC has been challenging due to its extreme stability both mechanically and chemically. To address this issue, a novel tool-based electrolytic plasma etching method is proposed, with which micropatterns and micro-holes are fabricated in SiC in a hydrofluoric acid-free aqueous solution with no need for masks. The material removal is the result of the combined effects of electrolytic plasma chemistry and physics. The chemistry refers to the reaction of Si with hydroxyl radical to form various SiO_x and with H to form silanes, and the reactions of C to form volatile carbon oxides or hydrocarbons, all of which are accomplished and enhanced under the electrolytic plasma atmosphere. Besides, the local high temperature of plasma thermally promotes the evaporation or dissolution of SiO₂ in NaOH solution. The tool-based electrolytic plasma etching method provides alternative approaches for the fabrication of SiC-based MEMS and devices.     

Electrodeposition of B,Ni co-doped diamond-like carbon films on AZ91D magnesium alloy: Corrosion and wear resistance

Diamond-like carbon (DLC) possesses brilliant and excellent properties, including excellent corrosion resistance as well as outstanding wear resistance. Ni and B co-doped DLC films were deposited on AZ91D magnesium alloy by electrodeposition under mild conditions (300 V and 25°C). Uniform and dense morphology of co-doped DLC films were observed, and Ni and B were uniformly incorporated into the carbon-based films. Among all the electrodeposits, the appearance of D and G peaks near 1330 and 1570 cm⁻¹ revealed that the as-deposited films were typical DLC films. As the addition of Ni was increased to 0.05 g, the highest microindentation hardness, the lowest friction coefficient, and wear loss were achieved to be 164.5 HV, 0.3, and 0.6 × 10⁻⁵ kg/m, respectively. The amorphous carbon films fabricated at 0.05 g Ni had the lowest corrosion current density and the most positive corrosion potential, which was mainly due to the small and dense granular structure effectively hindering the penetration of corrosion media.     

Thermal transport and chemical conversion in single reacting sorbent particles

The effects of particle size and carbon dioxide concentration on chemical conversion in engineered spherical particles undergoing calcium oxide looping are investigated. Particles are thermochemically cycled in a furnace under different carbon dioxide concentrations. Changes in composition due to chemical reactions are measured using thermogravimetric analysis. Gas composition at the furnace exit is evaluated with mass spectroscopy. A numerical model of thermal transport phenomena developed previously is adapted to match the physical system investigated in the present study. The model is used to elucidate effects of reacting medium characteristics on particle temperature and reaction extent. Experimental and numerical results show that (1) an increase in particle size results in a decrease in carbonation extent, and (2) the carbonation step consists of fast and slow reaction regimes. The reaction rates in the fast and slow carbonation regimes increase with increasing carbon dioxide concentration. The effect of carbon dioxide concentration and the distinction between the fast and slow regimes become more pronounced with increasing particle size.     

Structural dependence of microwave dielectric properties in ilmenite-type Mg(Ti1-xNbx)O3 solid solutions by Rietveld refinement and Raman spectra

Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics were prepared by the conventional solid-state reaction method. The phase composition, sintering characteristics, microstructure and dielectric properties of Ti⁴⁺ replacement by Nb⁵⁺ in the formed solid solution Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics were systematically studied. The structural variations and influence of Nb⁵⁺ doping in Mg(Ti_1-xNb_x)O₃ were also systematically investigated by X-ray diffraction and Raman spectroscopy, respectively. X-ray diffraction and its Rietveld refinement results confirmed that Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics crystallised into an ilmenite-type with R-3 (148) space group. The replacement of the low valence Ti⁴⁺ by the high valence Nb⁵⁺ can improve the dielectric properties of Mg(Ti_1-xNb_x)O₃ (x = 0–0.09). This paper also studied the different sintering temperatures for Mg(Ti_1-xNb_x)O₃ (x = 0–0.09) ceramics. The obtained results proved that 1350 °C is the best sintering temperature. The permittivity and Q × f initially increased and then decreased mainly due to the effects of porosity caused by the sintering temperature and the doping amount of Nb₂O₅, respectively. Furthermore, the increased Q × f is correlated to the increase in Ti–O bond strength as confirmed by Raman spectroscopy, and the electrons generated by the oxygen vacancies will be compensated by Nb⁵⁺ to a certain extent to suppress Ti⁴⁺ to Ti³⁺, which was confirmed by XPS. The increase in τ_f from ?47 ppm/°C to ?40.1 ppm/°C is due to the increment in cell polarisability. Another reason for the increased τ_f is the reduction in the distortion degree of the [TiO₆] octahedral, which was also confirmed by Raman spectroscopy. Mg(Ti_0.95Nb_0.05)O₃ ceramics sintered at 1350 °C for 2 h possessed excellent microwave dielectric properties of ε_r = 18.12, Q × f = 163618 GHz and τ_f = ?40.1 ppm/°C.     

Performance of Al2O3 particle reinforced glass-based seals in planar solid oxide fuel cells

Glass-based materials are usually considered as excellent seals for jointing adjacent components in planar solid oxide fuel cells, but the uncontrollable crystallization in the glass may cause delamination and micro-cracks in such seals. To solve this problem, Al2O3 ceramic particles were added to a BaO–CaO–Al2O3–B2O3–SiO2 glass system to reduce negative effects caused by crystalline phase on the gas tightness and the joint strength in the seals. At an operating temperature of 750 °C, the glass-based seals with 20 wt% Al2O3 addition (GA80) exhibited extremely low leakage rates (~0.002 sccm/cm under an input gas pressure of 13.6 kPa) and higher shear strength (3.31 MPa). The Al2O3 ceramic addition and the crystalline phase BaAl2Si2O8 reinforced the glass matrix. Further thermal cycle analyses indicated that leakage rates for the GA80 seals remained at around 0.0025 sccm/cm after 10 thermal cycles, which was consistent with minor microstructural change and good interface bonding. Single cell testing with of GA80 seals was performed and the results demonstrated stable electrochemical performance through 6 thermal cycles at an open circuit voltage of 1.16–1.18 V, as well as a power density above 546 mW/cm2 at a current density of 925 mA/cm2. These results showed the high thermal cycle stability of the glass/Al2O3 composite seals in intermediate temperature planar solid oxide fuel cells.     

Optimized microwave absorption properties by tailoring the morphology of carbon coated TiC nanoparticles by N2 pressure

Increasing the dielectric loss capacity plays an important role in enhancing the electromagnetic absorption performance of materials. It remains a challenge to simultaneously introduce multiple types of dielectric losses in the material. In this work, we show that the atomic and interfacial dipole polarizations can be simultaneously enhanced by substituting N species into both carbon coating layers and bulk TiC lattices of a core-shell TiC@C material. Additionally, substitution of N species results more exposed TiC(111) facets and refines the TiC grain sizes in the bulk material, which is beneficial for enhancing the scattering of the external electromagnetic waves. The maximum reflection loss of the N substituted TiC@C material is measured as ?47.1 dB with an effective absorbing bandwidth of 4.83 GHz at 1.9 mm, which illustrates a valuable way to further tuning the electromagnetic absorption performance of this type of materials.     

特种工程胎硫化外胎质量缺陷原因分析以及解决措施

我公司使用的硫化机采用氮气定型,二次水硫化的工艺。由于特种工程胎胎体偏厚且大,成型机都比较大,生产过程中的帘布筒、钢丝、胎侧等部件都比较重且大。成型胎面使用胎面缠绕机缠绕,所以整个生产过程难度较大。特种工程胎硫化外胎的主要质量问题有:胎面皮泡、胎侧缺胶、胎侧泡、胎肩侧皮泡、子口内侧露线、子口缺胶、胎肚内缺(窝气)、胎肚露线、胎肚皮泡、胎肚串泡、子口支边、胎冠支边、子口鼓包、外胎花缺等。通过对特种工程胎硫化外胎质量缺陷原因分析,找到相应的解决措施,从而减少硫化外胎质量缺陷。     

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.