Oxygen diffusion mechanisms during high‐temperature oxidation of ZrB2‐SiC

Oxygen diffusion mechanisms during oxidation of ZrB₂‐30 vol% SiC were explored at temperatures of 1500°C and 1650°C using an ¹⁸O tracer technique. Double oxidation experiments in ¹⁶O₂ and ¹⁸O₂ were performed using a modified resistive heating system. A combination of scanning electron microscopy, energy‐dispersive spectroscopy, and time‐of‐flight secondary ion mass spectrometry was used to characterize the borosilicate and ZrO₂ oxidation products. Oxygen exchange with the borosilicate network was observed to occur quickly at the oxygen‐borosilicate surface at both 1500°C and 1650°C, while evidence of oxygen permeation was only observed at 1650°C for short time (<1 min) exposures. At longer times, >5‐9 min, complete oxygen exchange throughout both the borosilicate glass and ZrO₂ was observed at both temperatures preventing identification of the oxygen transport mechanisms, but demonstrating that oxygen transport is rapid in both oxide phases.     

The effect of Al2O3 on the high‐temperature oxidation resistance of Si‐B‐C ceramic under air atmosphere

Si‐B‐C ceramics were prepared through reaction sintering, and the influence of Al₂O₃ addition on the high‐temperature (1100‐1300°C) oxidation behavior of the material under air atmosphere was studied. The erosion behavior and mechanism are determined from the measurement of weigh changes, microstructure observations, and characterization of the generated oxides on postexposure specimens. Results show that Al₂O₃ is enriched in the oxidized layer, inhibiting the volatilization of B₂O₃ and impeding the crystallization ability of oxide (cristobalite). Narrower erosion layer and less weigh change are observed with Al₂O₃. Low‐frequency Raman results reveals that with the increase in Al₂O₃, the bending vibrations of the BO₄ units and B‐O‐B stretching of the metaborate ring relative intensity are enhanced. Furthermore, high‐frequency Raman results shows that the relative proportion of high‐dimensional vibration modes Q³ and Q⁴ which result in a higher viscosity of melt and a greater resistance of oxygen diffusion are positively correlated with Al₂O₃.     

High‐temperature tensile strength and fracture behavior of ZrB2‐SiC‐graphite composite

The tensile behavior of ZrB₂‐SiC‐graphite composite was investigated from room temperature to 1800°C. Results showed that tensile strength was 134.18 MPa at room temperature, decreasing to 50.34 MPa at 1800°C. A brittle‐ductile transition temperature (1300°C) of ZrB₂‐SiC‐graphite composite was deduced from experimental results. Furthermore, the effect of temperature on the fracture behavior of ZrB₂‐SiC‐graphite composite was further discussed by microstructure observations, which showed that tensile strength was controlled by the relaxation of thermal residual stress below 1300°C, and was affected by the plastic flow during 1300°C and 1400°C. At higher temperature, the tensile strength was dominated by the changes of microstructures.     

Establishing microstructure-mechanical property correlation in ZrB2-based ultra-high temperature ceramic composites

The current work focuses on enhancing the flexural strength and fracture toughness of zirconium diboride (ZrB₂) reinforced with silicon carbide (SiC) and carbon nanotubes (CNT). The flexural strength has shown to increase by ~ 1.2 times from 322.8 MPa (for ZrB₂) to 390.7 MPa and fracture toughness up to 3 times from 3.2 MPam^0.5 (for ZrB₂) to 9.5 MPam^0.5 with the synergistic addition of both SiC and CNT in ZrB₂ matrix through energy dissipating mechanisms such as deflection, branching and strong interfacial bonding evidenced from the transmission electron microscopy (TEM). A modified fractal model is used to evaluate the fracture toughness and delineate the contribution of residual stresses, and reinforcements (SiC and CNT) in enhancing the fracture toughness. Interfacial bonding, in terms of a debonding factor, was also evaluated by theoretically predicting the elastic modulus and then correlated with the microstructure along with other mechanical properties of ZrB₂-SiC-CNT composites.     

ZrB_2-SiC复合陶瓷发热体的电性能与发热体表面温度之间关系的研究

按照ZrB2和SiC的质量比为7525配料,混料、烘干、热压烧结后,经线切割加工成ZrB2-SiC复合陶瓷直型发热体,研究了发热体的物相组成、微观形貌及在空气和氩气气氛下发热温度随电流电压的变化规律。结果表明,ZrB2-SiC复合陶瓷由均匀分布在ZrB2基体晶界处的SiC颗粒和尺寸小于10μm的等轴状基体ZrB2颗粒组成;在空气和氩气气氛下,ZrB2-SiC复合陶瓷发热体的温度均随电流、电压及加热时间的延长呈稳步增大趋势,同时空气气氛下发热体的电阻随温度升高而增大,并呈现线性变化;在空气和氩气气氛下,ZrB2-SiC复合陶瓷发热体表面温度分别达到1800和2200℃。同时,与铬酸镧和氧化锆发热体相比,其电压、电阻变化较小,电流较大。     

High-temperature phase and microstructure evolution of polymer-derived SiZrCN and SiZrBCN ceramic nanocomposites

A zirconium and a zirconium/boron containing single-source precursor were synthesized via chemical modification of a commercially available polysilazane (Durazane 1800) with tetrakis (dimethylamido) zirconium (IV) (TDMAZ) as well as with both TDMAZ and borane dimethyl sulfide complex, respectively. The polymer-to-ceramic transformation of the precursors into SiZrCN and SiZrBCN ceramics as well as the thermal evolution of their phase composition and microstructure was studied. The pyrolysis of the precursors led to the formation of amorphous SiZrCN and SiZrBCN ceramics. Interestingly, the as prepared SiZrBCN ceramic was single-phasic and fully featureless; whereas SiZrCN exhibited the presence of nano-sized ZrO₂ particles; however, only very localized in close proximity to internal surfaces. Heat treatment at higher temperatures induced crystallization processes in both prepared ceramics. Thus, at temperatures beyond 1500°C, cubic ZrC_xN_y, β-Si₃N₄ as well as β-SiC were generated. It was shown that the incorporation of B into SiZrCN suppressed the crystallization of ZrC_xN_y and, in addition, impeded the reaction of SiN_x with C, resulting in an improved thermal stability of SiZrBCN compared to SiZrCN ceramic. Moreover boron was shown to be mainly located in the sp²-hybridized “free” carbon present in SiZrBCN, forming a turbostratic BCN phase which has been unequivocally detected by means of high-resolution transmission electron microscopy (HRTEM) and energy-dispersive X-ray spectroscopy (EDS).     

多孔陶瓷粒子电极电催化氧化降解2-氨基吡啶

采用以CuO-ZnO/多孔陶瓷粒子电极构建的三维电催化氧化反应器降解2-氨基吡啶,考察了初始pH值、槽电压、电解质投加量和曝气流速对降解效果的影响和反应的电流效率,并通过检测2-氨基吡啶降解过程中几种含氮产物,分析了2-氨基吡啶的降解过程。结果表明：酸性条件和碱性条件比中性条件更有利于2-氨基吡啶的降解,在初始pH值为8.4、槽电压为15 V、支持电解质用量为30 g/L、曝气流速为40 L/h的条件下,处理150 min,2-氨基吡啶和COD的去除率可分别达到83.98%和74.44%,粒子电极可以显著提高电流效率。2-氨基吡啶降解过程分析表明：在电催化条件下,N2和NO3?-N是2-氨基吡啶主要含氮矿化产物,且2-氨基吡啶的开环转化和矿化可以同步进行。     

Microstructure,mechanical behavior and oxidation resistance of disorderly assembled ZrB2-based short fibrous monolithic ceramics

Axially aligned fibrous monolithic ceramics present non-catastrophic fracture behavior via crack deflection and delamination along cell boundaries. However, severe in-plane anisotropy and time-consuming preparation procedures prevent their extensive promotion. The introduction of high content of weak phase components with poor oxidation resistance in weak interface destroys the excellent oxidation resistance of ceramic matrix. In this work, ZrB₂-based short fibrous monolithic (SFM) ceramics with in-plane isotropic mechanical properties and excellent oxidation resistance were easily prepared by hot pressing randomly assembled short ceramic fibers. The microstructure and mechanical behavior of ZrB₂-based SFM ceramics densified at various temperatures were systematically investigated. The mechanical properties of ZrB₂-based SFM ceramics slightly improved with the increase of sintering temperature. ZrB₂-based SFM ceramics exhibited excellent oxidation resistance and remained intact without macroscopic cracks after ablation for 615 s in oxyacetylene flame with maximum temperatures exceeding 2150 °C. The oxidation behavior was analyzed in detail.     

Carbothermal synthesis of zirconium diboride (ZrB2) whiskers

Abstract

In the present investigation, carbothermal synthesis technique is used for the production of ZrB₂ whiskers. The synthesis is carried out by heating the mixture of ZrB₂, H₃BO₃ and carbon black over the temperature range of 1300 to 1700°C in argon atmosphere. Different elements such as Ni, Co and Fe are tested for their role as catalysts. The synthesised powder contains ZrB₂ as the major phase with minor phases of ZrC and B₄C. Whisker yield is found to be low at lower temperatures (<1500°C) and then increases with the pyrolysis temperature. The Ni addition seems more effective as a catalyst than Co or Fe. Shorter length whiskers are found in the case of Co catalyst, whereas use of Fe catalyst shows whisker with rod shape and a special bird's nest type whiskers. The electron microscope study of whisker reveals the presence of various defects.     

Effect of moisture on the oxidation behavior of ZrB2

Oxidation studies of ZrB₂ were performed under wet air and dry air conditions at 1200°C, 1400°C, and 1500°C for 1, 4, and 10 h. Compared to dry air, the presence of water vapor was found to enhance the oxidation kinetics by a factor of 7 to 30, depending on the temperature. Thermodynamic calculations suggested that water vapor promoted the formation of additional volatile species such as boric acid (HBO₂), in addition to boria (B₂O₃) produced in dry air, which increased the evaporation rate of B₂O₃. Compared to dry air, the presence of water vapor leads to more rapid evaporation of boria and the transition from parabolic oxidation kinetic behavior (ie, rate controlled by diffusion through boria) to linear (ie, underlying ZrB₂ is directly exposed to the oxidizing environment) at shorter times and lower temperatures.     

微弧氧化陶瓷膜的性能研究

微弧氧化是一种新兴的金属材料表面陶瓷化处理技术。利用微弧氧化技术在纯铝和LY12铝合金表面制得陶瓷膜，推导出膜层厚度的计算公式，研究了陶瓷膜的硬度、耐蚀性、孔隙率、电绝缘性和热稳定性。结果表明，微弧氧化陶瓷膜层各项性能优异，具有很好的应用前景。     

High temperature anti‐oxidation behavior of in situ and ex situ nanostructured C/SiC/ZrB2‐SiC gradient coatings: Thermodynamical evolution,microstructural characterization,and residual stress analysis

Nanostructured C/SiC/ZrB₂–SiC oxidation protective gradient coating was prepared by a two‐step reactive melt infiltration method. In order to reduce production cost, ZrB₂ phase was synthesized by the in situ reactive that included low‐cost ZrO₂ and B₂O₃ powders as raw materials. High‐temperature oxidation behavior of coatings was evaluated by isothermal oxidation test at 1773 K in air for 10 hours. Thermodynamical behavior of the coatings at various temperatures during oxidation test and coating process was predicted by HSC Chemistry 6.0 software. Compressive residual stresses of 36.9 MPa and 41 MPa were calculated for in situ and ex situ coatings by Williamson‐Hall method. After 10 hours of isothermal oxidation at 1773K, in situ and ex situ coatings showed 12.84% and 15.69% of weight losses with oxidation rates of 1.87 × 10^?2 g cm^?3 h^?1 and 0.91 × 10^?2 g cm^?3 h^?1, respectively. These results indicated that the oxidation protection ability of the coating produced by the in situ method was very close to ex situ coating.     

Electrolytic oxidation of trichloroethylene using a ceramic anode

Trichloroethylene (TCE) was transformed to CO₂, CO, Cl^– and ClO₃^– at the anode of a two-chambered electrolytic cell. The working electrode was constructed from Ebonex^®, an electrically conductive ceramic (Ti₄O₇). Under our experimental conditions (anode potential E_a = 2.5 to 4.3 V vs SSCE), the disappearance of TCE was first order in TCE concentration. The transformation rate was independent of pH in the range 1.6 < pH < 11. TCE oxidation occurred only on the anodic surface and was limited by mass transport at high potentials (E_a > 4.0V). The maximum (transport-limited), surface-area-normalized rate constant was about 0.002 43cms^–1. Carbon-containing products included CO₂ primarily with traces of CO. At neutral and alkaline pHs, the only chlorine-containing products were Cl^– and ClO₃^–. Hydroxyl radicals were detected in the anodic compartment using a spin trap (4-POBN). A kinetic model was successfully correlated with experimental results.     

ZrB2–SiC多层陶瓷的抗氧化性

用传统陶瓷的流延工艺制备ZrB2–SiC多层陶瓷。用Archimedes法测定ZrB2–SiC多层陶瓷的相对密度。用扫描电子显微镜观察其显微结构,并进行循环抗氧化性能评价。结果表明：ZrB2–SiC多层陶瓷在1 950℃烧结的致密度达到99.7%,材料的抗氧化过程主要可分为两个阶段：第一阶段低熔点相的挥发,出现质量损失;第二阶段氧化层的形成,降低进一步氧化速率。抗氧化性能较ZrB2–SiC复相陶瓷有很大提高。     

Intermediate temperature oxidative strength degradation of a SiC/SiNC composite with a polymer‐derived matrix

The article describes an experimental investigation of oxidative degradation in mechanical performance of a SiC fiber‐reinforced composite with a SiCN matrix produced by polymer infiltration and pyrolysis. Tensile stress rupture and retained strength tests were performed at 800°C in dry air and in water vapor. Fracture surfaces were examined to determine the degree of fiber pull‐out and constituent oxidation and to measure radii of representative fiber fracture mirrors. The results indicate that degradation in tows adjacent to cut surfaces occurs equally rapidly in water vapor with or without application of stress; regions in the composite interior and near as‐processed (uncut) surfaces appear far less affected. Similar effects are evident but less pronounced in dry air. Although oxidation of fiber coatings is observed in some cases, collectively the results suggest that fiber degradation is the main mechanism leading to reduced composite strength.     

Preparation of polysiloxane phosphonic acid doped polybenzimidazole high‐temperature proton‐exchange membrane

Polysiloxane phosphonic acid doped polybenzimidazole (PBI) high‐temperature membranes were fabricated in this study. Polysiloxane phosphonic acid instead of phosphoric acid was used as a proton conductor to prevent acid from leaking. The membrane samples with different amounts of PBI were prepared and characterized with respect to the structure, thermal properties, oxidative stability, proton conductivity, and mechanical properties. The Fourier transform infrared results show that hydrogen bonds formed between PBI and polysiloxane phosphonic acid. Thermal analysis confirmed that the temperature at which membrane experienced 10% weight loss was above 230°C. None of the membrane samples broke into pieces after Fenton reagent testing. The proton conductivity of the membrane samples with 5% PBI was up to 0.034 S/cm at 140°C under nominally anhydrous conditions. The tensile strength of the membrane samples with 10% PBI was 18.3 MPa. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42956.     

Electrochemical oxidation of 1,4‐dioxane at boron‐doped diamond electrode

BACKGROUND: The electrochemical oxidation of 1,4‐dioxane at a boron doped diamond (BDD) surface on a niobium substrate anode was studied because (i) 1,4 dioxane is a resistant contaminant in waste‐waters and ground‐waters which needs to be removed/oxidized and (ii) most of the currently applied techniques for removal/oxidation require chemicals. RESULTS: Results show that in the potential region supporting electrolyte stability 1,4‐dioxane can be oxidized directly. Adhesive products, which cause electrode fouling, are also formed during oxidation in this potential region. The BDD anode can be restored to its initial activity by simple anodic treatment in the potential region of electrolyte decomposition. In this region, oxidation reactions leading to complete oxidation of 1,4‐dioxane, can take place due to electro‐generated hydroxyl radicals. Therefore, dioxane can only be effectively oxidized at these potentials. The effect of current density on the oxidation of 1,4‐dioxane has been investigated. The experimental results have also been compared with a theoretical chemical oxygen demand (COD)–instantaneous current efficiency (ICE) model. At a current density above 32 mA cm^?2, the oxidation process is completely controlled by mass transfer and no intermediates are formed. 92% of the COD can be removed with a total consumption of 7 Ah L^?1. CONCLUSIONS: Results show that dioxane can be effectively and completely oxidized at a BDD anode. Copyright © 2010 Society of Chemical Industry     

Experimental investigation on high strain rate compressive response of a ZrB2-SiC-G ceramic

The dynamic compression tests were conducted on a ZrB₂-SiC-graphite (ZrB₂-SiC-G) ceramic from the strain rate of 904–3136 s^–1 using the split Hopkinson pressure bar. The effects of strain rate on the compressive strength, critical strain, stress–strain relation, and fracture pattern were discussed from the experimental results. The results showed that the dynamic compressive response of this ZrB₂-SiC-G ceramic was obviously related to the strain rate at higher strain rates. At the strain rate of 3136 s^–1, the dynamic compressive strength, critical strain, and toughness of the ZrB₂-SiC-G ceramic increased to 1747 MPa, 0.0423, and 69.48 × 10⁶ J/m³, respectively. As the strain rate increased, the dynamic compressive strength and critical strain increased linearly, and the damage became more significant. Moreover, the energy absorption of the ZrB₂-SiC-G ceramic linearly increased with the strain rate, causing the ZrB₂-SiC-G ceramic fractured into numerous smaller fragments at higher strain rates.