Applications of analytical electron microscopy to guide the design of boron carbide

Compositional analysis of boron carbide on nanometer length scales to examine or interpret atomic mechanisms, for example, solid-state amorphization or grain-boundary segregation, is challenging. This work reviews advancements in high-resolution microanalysis to characterize multiple generations of boron carbide. First, ζ-factor microanalysis will be introduced as a powerful (scanning) transmission electron microscopy ((S)TEM) analytical framework to accurately characterize boron carbide. Three case studies involving the application of ζ-factor microanalysis will then be presented: (1) accurate stoichiometry determination of B-doped boron carbide using ζ-factor microanalysis and electron energy loss spectroscopy, (2) normalized quantification of silicon grain-boundary segregation in Si-doped boron carbide, and (3) calibration of a scanning electron microscope X-ray energy-dispersive spectroscopy (XEDS) system to measure compositional homogeneity differences of B/Si-doped arc-melted boron carbides in the as-melted and annealed conditions. Overall, the improvement and application of advanced analytical tools have helped better understand processing–microstructure–property relationships and successfully manufacture high-performance ceramics.     

Life cycle assessment of HFC-134a production by calcium carbide acetylene route in China

HFC-134a is a widely used environment-friendly refrigerant. At present, China is the largest producer of HFC-134a in the world. The production of HFC-134a in China mainly adopts the calcium carbide acetylene route. However, the production route has high resource and energy consumption and large waste emission, and few of the studies addressed on the environmental performance of its production process. This study quantified the environmental performance of HFC-134a production by calcium carbide route via carrying out a life cycle assessment (LCA) using the CML 2001 method. And uncertainty analysis by Monte-Carlo simulation was also carried out. The results showed that electricity had the most impact on the environment, followed by steam, hydrogen fluoride and chlorine, and the impact of direct CO₂ emissions in calcium carbide production stage on the global warming effect also could not be ignored. Therefore, the clean energy (e.g., wind, solar, biomass, and natural gas) was used to replace coal-based electricity and coal-fired steam in this study, showing considerable environmental benefits. At the same time, the use of advanced production technologies could also improve environmental benefits, and the environmental impact of the global warming category could be reduced by 4.1% via using CO₂ capture and purification technology. The Chinese database of HFC-134a production established in this study provides convenience for the relevant study of scholars. For the production of HFC-134a, this study helps to better identify the specific environmental hotspots and proposes useful ways to improve the environmental benefits.     

镍基高温合金GH202高温氧化后的微观组织演变

研究了镍基高温合金GH202在800~1100 ℃高温氧化后晶粒、碳化物和强化相的演变过程。采用透射电子显微镜、扫描电子显微镜和电子背散射衍射对其微观结构进行了表征。结果表明：镍基高温合金的硬度随氧化温度的升高而降低，1100 ℃氧化100 h后，硬度降低了43.5%。800和900 ℃氧化后晶粒生长速度较慢，而经900 ℃氧化后晶界碳化物析出显著增加。在1000和1100 ℃氧化后，晶粒尺寸明显增大。氧化过程中晶界迁移是由晶界两侧自由能差决定，温度越高，晶界向曲率中心迁移越快，大量细小晶粒被吞并形成了大晶粒。大块状碳化物（MC）分解成大量的碳原子，与Cr原子结合形成少量的富Cr颗粒状M₂₃C₆。在900 ℃氧化150 h后，M₂₃C₆演化为富Ti的M₆C。随着氧化温度的升高，碳化物在γ相中回熔。在800、900和1000 ℃氧化后，γ′相逐渐长大，在1100 ℃氧化100 h后，完全溶解于γ相。     

Enhanced dielectric and piezoelectric properties in potassium sodium niobate/polyvinylidene fluoride composites using nano-silicon carbide as an additive

Piezoelectric materials are an indispensable part of modern life. Yet the existing environmental issues with conventional lead-based piezoelectrics has motivated scientist to develop novel substitutes including lead-free piezoelectric polymer composites. Following this path, the present research has focused on the fabrication of ternary composites of Polyvinylidene fluoride (PVDF)/Potassium Sodium Niobate (KNN)/nano-Silicon carbide (SiC) via hot compression molding and studying the effect of additives on the PVDF structure and the electrical properties of the composite. The obtained scanning electron micrographs and density measurements showed that the fabrication method provided dense samples. The activated polarization phenomena in the prepared samples enhanced dielectric permittivity and dielectric loss at a constant frequency with increasing KNN and SiC contents. Besides the expected dipole polarization, the presence of interfaces in the composites gave rise to the Maxwell–Wagner–Sillars effect and its corresponding polarization phenomenon. The semiconductive nature of SiC also promoted space charge polarization. However, these properties were frequency-dependent because the first two polarization mechanisms are deactivated at high frequencies. XRD patterns showed that SiC addition can alter the primary crystalline structure of PVDF and promote β-phase formation in the poled samples. Piezoelectric measurements confirmed the significant role of SiC addition to PVDF-KNN composites. The most significant increase in the piezoelectric properties was observed in PVDF-60KNN-1SiC, with a 183% increase in d₃₃ value. The PVDF-80KNN-1SiC had the highest d₃₃ value of 30.5 pC/N. It also had the best piezoelectric voltage coefficient and hence the highest figure of merit. Higher SiC contents restrict the efficiency of poling by forming a conductive path across the sample which would deteriorate the piezoelectric performance of the material. The present findings show that PVDF-KNN-SiC composites can be considered as a potential flexible piezoelectric material for future applications.     

Investigation the effect of FeNiCoCrMo HEA addition on properties of B4C ceramic prepared by spark plasma sintering

In this study, monolithic B₄C and B₄C-based ceramics incorporating FeNiCoCrMo dual-phase (FCC and BCC) high entropy alloys (HEAs) were produced by spark plasma sintering (SPS). The effect of additives on the densification behavior, mechanical properties, microstructures, and phase evaluation of the samples were investigated. X-ray analysis confirmed the existence of FCC structured HEA and depletion of BCC structured HEA, after high-temperature reaction between B₄C-HEAs. The addition of HEAs enhanced the densification behavior by liquid phase sintering. Furthermore, hardness and fracture toughness values of the samples increased with increasing HEAs content. Fracture toughness and hardness values for all composites were higher than the monolithic B₄C. A combination of the highest density (∼99.22 %) and the best mechanical properties (32.3 GPa hardness and 4.53 MPa m^1/2 fracture toughness) was achieved with 2.00 vol.% HEA addition.     

Zirconium-diboride silicon-carbide composites: A review

Zirconium diboride (ZrB₂) and silicon carbide (SiC) composites have long been of interest since it was observed that ZrB₂ improved the thermal shock resistance of SiC. However, processing of these materials can be difficult due to high and different sintering temperatures and differences in the thermodynamic stability of each material. ZrB₂–SiC composites have been processed in a variety of ways including hot-pressing, spark-plasma sintering, reactive melt infiltration, pack cementation, chemical vapor deposition, chemical vapor infiltration, stereolithography, direct ink writing, selective laser sintering, electron beam melting, and binder jet additive manufacturing. Each manufacturing method has its own pros and cons. This review serves to summarize more than 60 years of research and provide a coherent resource for the variety of methods and advancements in development of ZrB₂–SiC composites.     

Fabrication and characterization of hot-pressed B-rich boron carbide

Boron carbide has a wide solubility range owing to the substitution of B and C atoms in the crystal. In this study, boron carbides with different stoichiometric ratios were prepared using a hot-pressing sintering method, and the influences of the B/C atomic ratio on the microstructures and properties were explored in detail. X-ray diffraction analysis showed that excessive B atoms caused lattice expansion. Raman spectroscopy analysis showed disordered substitution of B atoms in the chains and icosahedra. Analysis of the densification process and microstructure evolution revealed that the addition of B promoted densification, and more stacking faults and twins occurred in B-rich boron carbide, and result in the densification mechanism gradually changes from atomic diffusion mechanism driven by thermal energy to plastic deformation mechanism dominated by the proliferation of dislocation and substructures. The introduction of chemical composition changes by dissolving excessive B into boron carbide further affected the microstructure and consequently the mechanical properties. The Vickers hardness, modulus, and sound velocity all decreased with the increase in B content. Moreover, the fracture toughness improved with increased B content. The flexural strength of the samples was optimised at the B/C stoichiometric ratio of 6.1.     

B4C–TiB2 composites fabricated by hot pressing TiC–B mixtures: The effect of B excess

Previous research have reported that B₄C–TiB₂ composites could be prepared by the reactive sintering of TiC–B powder mixtures. However, due to spontaneous oxidation of raw powders, using TiC–B powder mixtures with a B/TiC molar ratio of 6: 1 introduced an intermediate phase of C during the sintering process, which deteriorated the hardness of the composites. In this report, the effects of B excess on the phase composition, microstructure, and mechanical properties of B₄C–TiB₂ composites fabricated by reactive hot pressing TiC–B powder mixtures were investigated. XRD and Raman spectra confirmed that lattice expansion occurred in B-rich boron carbide and B_xC–TiB₂ (x > 4) composites were obtained. The increasing B content improved the hardness and fracture toughness but decreased the flexural strength of B_xC–TiB₂ (x > 4) composites. When the molar ratio of B/TiC increased from 6.6:1 to 7.8:1, the Vickers hardness and the fracture toughness of the composites were enhanced from 26.7 GPa and 4.53 MPa m^1/2 to 30.4 GPa and 5.78 MPa m^1/2, respectively. The improved hardness was attributed to the microstructural improvement, while the toughening mechanism was crack deflection, crack bridging and crack branching.     

Highly efficient chemical mechanical polishing method for SiC substrates using enhanced slurry containing bubbles of ozone gas

In this study, a highly efficient method for chemical mechanical polishing (CMP) of silicon carbide (SiC) substrates using enhanced slurry was proposed and developed. The enhanced slurry contains bubbles of ozone gas generated by ozone gas generator in pure water mixed with a conventional commercially available slurry. Therefore, the enhanced slurry has an oxidizing effect on the Si-face of SiC substrates. To confirm the effectiveness of bubbles enclosing ozone gas, both nano-indentation test and X-ray photoelectron spectroscopy (XPS) analysis were conducted. As a result, the hardness decrease of the Si-face of the SiC substrate was confirmed through the nano-indentation test, and the generation of reaction products was confirmed on Si-face of SiC substrate in the XPS analysis. According to a series of experimental results of our proposed highly efficient CMP method for SiC substrates, the removal rate can be increased when the enhanced slurry was applied, comparing with that for the not only conventional commercially available slurry but also commercially available dedicated slurry.