B对FeCoCrNiSiBx高熵合金激光熔覆层组织和硬度的影响

采用激光熔覆制备了FeCoCrNiSiB_x高熵合金熔覆层,利用光学显微镜、扫描电镜、X射线衍射仪和显微硬度计研究微量硼元素(摩尔比x=0、0.02、0.04、0.06、0.08)对FeCoCrNiSiB_x高熵合金熔覆层组织和硬度的影响。结果表明:无B高熵合金涂层组织主要为胞状晶。B的添加会促进枝晶的生成,逐渐形成鱼骨状树枝晶,但过量的B会破坏枝晶完整性,形成蠕虫状晶。此外,高熵合金熔覆层组织为FCC和BCC双相结构,B元素的添加会形成大量0.1~2.6 μm的Cr₂B第二相,有助于提高熔覆层硬度,其中x=0.06时激光熔覆层的硬度最高,约为537 HV0.2。     

First-principles study on the dissolution and diffusion behavior of hydrogen in carbide precipitates

To understand the hydrogen (H) behavior in the carbide precipitates, the dissolution and diffusion properties of interstitial H in the transition metal carbide (TMC; TM = Hf, Nb, Ta, Ti, V, and Zr) were studied by first-principles calculations. In these carbides, it can be seen that H tends to occupy the trigonal site (tri2-site) surrounded by three transition metal atoms and one carbon atom rather than the face center (fc-site) and the body center (bc-site) which with the larger space. We found that the bonding interaction between H atom and the nearest-neighbor (1NN) carbon atom is the dominant influence on the stability of H dissolution. Besides, we obtained the temperature-dependent solubility and diffusion coefficients of H in TMC and pure vanadium through Sievert's law and transition state theory. Compared with pure vanadium, H shows the worse solubility in TMC, and it is more difficult for hydrogen to migrate in TMC, but segregate toward the interface. Furthermore, it is interesting to note that, the diffusion barrier and the H solution energy show a linear relationship for transition metal carbides in the same period. These results can help us deepen the understanding of H behavior in vanadium alloys strengthened by carbide precipitates, and furtherly providing the theoretical guidance for the design of alloys with excellent performance.     

Hydrogen storage properties of Mg98.5Gd1Zn0.5 and Mg98.5Gd0.5Y0.5Zn0.5 alloys containing LPSO phases

In this work, the as-cast Mg-rich Mg_98.5Gd₁Zn_0.5 and Mg_98.5Gd_0.5Y_0.5Zn_0.5 alloys are prepared by the semi-continuous casting method, and their hydrogen storage performance and catalytic mechanisms are investigated by experimental and first-principles calculations approaches. The results show that the LPSO phases decompose and in-situ form the RE(Gd/Y)H_x(x = 2,3) nano-hydrides upon hydrogenation. These nano-hydrides not only serve as the in-situ catalysts to promote the hydrogen ab/desorption of Mg matrix, but also present the pinning effect to inhibit the growth of Mg/MgH₂ grains during hydrogenation and dehydrogenation. Comparatively, the two alloys exhibit the similar hydrogen absorption kinetics, while the hydrogen desorption kinetics of Mg_98.5Gd₁Zn_0.5 is superior to that of Mg_98.5Gd_0.5Y_0.5Zn_0.5. The first-principles calculations reveal that the GdH₂ and YH₂ hydrides exhibit different catalytic effects on weakening the bond strength of H–H within H₂ and Mg–H within MgH₂, which interprets well the differences in the hydrogen ab/desorption kinetics between Mg_98.5Gd₁Zn_0.5 and Mg_98.5Gd_0.5Y_0.5Zn_0.5 alloys.     

Heterostructured thin LaFeO3/g-C3N4 films for efficient photoelectrochemical hydrogen evolution

The deposition of LaFeO₃ at the surface of a graphitic carbon nitride (g-C₃N₄) film via magnetron sputtering followed by oxidation for photoelectrochemical (PEC) water splitting is reported. The LaFeO₃/g-C₃N₄ film was investigated by various characterization techniques including SEM, XRD, Raman spectroscopy, XPS and photo-electrochemical measurements. Our results show that the hydrogen production rate of a g-C₃N₄ film covered by a LaFeO₃ film, exhibiting both a thickness of ca. 50 nm, is of 10.8 μmol h⁻¹ cm⁻² under visible light irradiation. This value is ca. 70% higher than that measured for pure LaFeO₃ and g-C₃N₄ films and confirms the effective separation of electron-hole pairs at the interface of LaFeO₃/g-C₃N₄ films. Moreover, the LaFeO₃/g-C₃N₄ films were demonstrated to be stable and retained a high activity (ca. 70%) after the third reuse.     

Facile synthesis of carbon self-doped g-C3N4 for enhanced photocatalytic hydrogen evolution

Graphite carbon nitride (g-C₃N₄) is an appealing metal-free photocatalyst for hydrogen evolution, but the potential has been limited by its poor visible-light absorption and unsatisfactory separation of photo-induced carriers. Herein, a facile one-pot strategy to fabricate carbon self-doped g-C₃N₄ composite through the calcination of dicyanamide and trace amounts of dimethylformamide is presented. The as-obtained carbon self-doped catalyst is investigated by X-ray photoelectron spectroscopy (XPS), confirming the substitution of carbon atoms in original sites of bridging nitrogen. We demonstrate that the as-prepared materials display remarkably improved visible-light absorption and optimized electronic structure under the premise of principally maintaining the tri-s-triazine based crystal framework and surface properties. Furthermore, the carbon doped g-C₃N₄ composite simultaneously weakens the transportation barrier of charge carriers, suppresses charge recombination and raises the separated efficiency of photoinduced holes and electrons on account of the extension of pi conjugated system. As a result, carbon self-doped g-C₃N₄ exhibits 4.3 times greater photocurrent density and 5.2 times higher hydrogen evolution rate compared with its bulk counterpart under visible light irradiation.     

Effect of carriers on deposition morphologies and catalytic performances of NiCo2O4

In this study, NiCo₂O₄ with different morphologies were fabricated using carriers by homogeneous coprecipitation combined with a sintering method. The phase and microstructure were characterized by XRD, SEM, EDS, TEM and BET, and the catalytic performances were investigated by NaBH₄ hydrolysis experiments. These studies revealed that the deposition morphology of NiCo₂O₄ can be adjusted by using different kinds of carrier templates, and the supported NiCo₂O₄ samples presented the pine-needle-like, network-like, ball-cactus-like and dandelion-like morphologies respectively. The optimal catalytic activity, durability and stability make the network-like NiCo₂O₄ an appropriate catalyst for hydrogen generation of NaBH₄ hydrolysis. It was found that the network-like NiCo₂O₄ is the most reusable and durable catalyst for ten consecutive cycles and 100% hydrogen generation conversion rate without obvious decrease among these morphologies.     

Femtosecond laser micro-milling dental glass ceramics: An experimental analysis and COMSOL finite element simulation

Dental glass ceramic materials are widely used in all-ceramic restoration technology. In order to effectively solve the problems existing in the process of traditional diamond cutter milling dental glass ceramic materials, such as severe needle loss, large tool wear and general milling efficiency, a new method of ultrafast laser milling dental glass ceramics is proposed. In this paper, 1030 nm femtosecond laser with pulse width of 600fs was used to micro-mill dental glass ceramics. Confocal laser microscopy was used to measure the milling depth and surface roughness of single-layer milling under selected laser processing parameters. The pre-layered milling software was developed to control the z-axis lifting and to compensate the focal length synchronously. Scanning electron microscope (SEM), Raman spectrometer and Vickers micro-hardness tester were used to characterize the dental glass ceramics after femtosecond laser milling. The results showed that under the specific laser processing parameters, the infrared femtosecond laser milling system can achieve a good processing morphology without changing the surface composition and surface hardness of dental glass ceramics. This new dental glass ceramics processing method based on ultrafast laser technique indicated a new direction for further chair processing of dental all-ceramic restoration technology.     

Weatherability of hybrid organic–inorganic silica protective coatings on glass

Currently, there is a growing interest in the application of silicon-based technologies for the development of advanced hybrid organic–inorganic coatings with strong weatherability. In this study, the sol–gel process is used to prepare such coatings on glass and their resistance to weathering effects is assessed afterwards. Various sols were prepared by mixing a silica-based inorganic matrix (tetraethyl orthosilicate) with different quantities of silica alkoxides functionalised with various organic groups. Subsequently, the sols were dip-coated onto glass samples at low temperatures without any heat treatment. The coatings prepared were analysed before and after three model ageing tests simulating various weathering parameters. After ageing, the best performing coatings showed good overall homogeneity and transparency (optical microscopy, SEM), improved water repellency and adhesion to the glass substrate (static contact angle measurements, cross-cut tape tests) and no colour or chemical composition changes (UV–VIS, FTIR). Compared with commercial hybrid silica products, the alkyl- and methacryloxy-functionalised silica coatings particularly displayed improved homogeneity, elasticity and barrier properties. Thus, these low temperature coatings, easily applicable to thin films, appear to fulfil the main requirements for the protection of the glass exposed to weathering phenomena.     

Super-tough poly(butylene terephthalate) based blends by modification with core-shell structured polyacrylic nanoparticles

Core-shell structured polyacrylic nanoparticles (named CSPN) impact modifiers consisting of a rubbery poly(n-butyl acrylate) core and a rigid poly(methyl methacrylate) shell with a size of about 352 nm were synthesized by seed emulsion polymerization. The CSPN modifier with core-shell weight ratio 80/20 was used to toughen poly(butylene terephthalate) (PBT) by melt blending. With an increase in CSPN content, the impact strength and the elongation at break of PBT/CSPN blends increased significantly compared with those of PBT; however, the tensile strength decreased. It was found that the polymerization had a very high instantaneous conversion (> 93%) and overall conversion (99%). The core-shell structure of CSPN was examined by means of transmission electron microscope. Scanning electron microscope was used to observe the morphology of CSPN particle and fractured surfaces of the blends. The dynamic mechanical analyses of PBT/CSPN blends showed two merged transition peaks of PBT matrix, with the presence of CSPN modifier, which was responsible for the improvement of PBT toughness. The results indicated that the notched impact strength of PBT/CSPN blend with a weight ratio of 80/20 was 8.61 times greater than that of pure PBT where the brittle-ductile transition point appeared.