添加剂对MA和MgO-MA材料性能的影响

综述了金属氧化物、稀土氧化物以及复合添加剂对镁铝尖晶石(MA)和方镁石-镁铝尖晶石(MgO-MA)材料性能的影响及其作用机理.引入的添加剂在一定温度下能与镁铝尖晶石形成固溶体,或可提高镁铝尖晶石晶体空位浓度,活化晶格,或与材料中某些杂质反应生成低熔点物相,促进了试样的烧结,从而使常温力学性能提高.有些添加剂的引入还能与材料中某些物质发生反应生成高熔点相,堵塞气孔,阻挡了熔渣的渗透,增加材料抗侵蚀性能等.本文期望能为从事MA与MgO-MA材料性能、结构设计以及合理选择添加剂提供理论基础.     

加入ZnO对含Al低碳MgO-C耐火材料抗氧化性的影响

以质量分数为70%的粒度≤3 mm和24%的粒度<0.074 mm的电熔镁砂,3%的粒度<0.15 mm的鳞片石墨,3%的粒度<0.045 mm的金属铝粉为原料,外加4%的酚醛树脂制备了含Al低碳MgO-C耐火材料。加入1%(w)的<0.045 mm的ZnO替代电熔镁砂粉,研究了加入ZnO对含Al低碳MgO-C材料抗氧化性的影响。通过对比这两种材料的显气孔率、常温耐压强度,试样基质的物相变化来探讨原位尖晶石的生成与基质中加入ZnO之间的关系,并通过对比试样中脱碳层与原始层之间出现的致密MgO层来讨论两种低碳MgO-C材料抗氧化性的差异。研究表明:加入ZnO能够在MgO-C材料基质中形成ZnAl2O4,并加速尖晶石的原位生成,使得材料中能够更快更多地形成致密的MgO层,最终提高低碳MgO-C耐火材料的抗氧化性。     

NiFe2O4隋性阳极的制备及其电解腐蚀机理

以Fe2O3和NiO为主要原料，添加2％（按质量计）MnO2，采用固相烧结工艺制备了NiFe2O4惰性阳极。用X射线衍射和扫描电子显微镜对材料的组成和微观结构进行了研究，测量了样品在冰晶石熔盐中不同电流密度下的电解腐蚀速率，并对其腐蚀机理作了初步探讨。结果表明：惰性阳极由NiO和NiFe2O4尖晶石两相组成，MnO2作为固溶体在尖晶石晶界处富集。电解腐蚀呈现出物理化学溶解过程，熔盐对试样的电解腐蚀首先要在晶界处发生反应生成更稳定的FeAl2O4相，而FeAl2O4相结构致密，冰晶石熔盐通过该相向NiFe2O4尖晶石晶粒内扩散速度减慢，从而降低了腐蚀速率。     

Synthesis and electrochemical performance of LiNi0.5Mn1.5O4 spinel compound

Spinel compound LiNi_0.5Mn_1.5O₄ was synthesized by a chemical wet method. Mn(NO₃)₂, Ni(NO₃)₂·6H₂O, NH₄HCO₃ and LiOH·H₂O were used as the starting materials. At first, Mn(NO₃)₂ and Ni(NO₃)₂·6H₂O reacted with NH₄HCO₃ to produce a precursor, then the precursor reacted with LiOH·H₂O to synthesize product LiNi_0.5Mn_1.5O₄. The product showed a single spinel phase under appropriate calcination conditions, and exhibited a high voltage plateau at about 4.6-4.8 V in the charge/discharge process. The LiNi_0.5Mn_1.5O₄ had a discharge specific capacity of 118 mAh/g at about 4.6 V and 126 mAh/g in total in the first cycle at a discharge current density of 2 mA/cm². After 50 cycles, the total discharge capacity was above 118 mAh/g.     

Oxidation behavior and electrical properties of metal interconnects with Ce-doped Ni–Mn spinel coatings

To improve the high-temperature oxidation resistance and electrical conductivity of ferritic stainless steels, protective Ce-doped NiMn₂O₄ spinel coatings were fabricated on the surface of SUS430 steel by electrophoretic deposition (EPD). The phase structure and microstructure of Ce-doped NiMn₂O₄ in both powder and coating forms were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The high-temperature oxidation of the NiMn₂O₄ spinel coating before and after Ce doping in the air at 800 °C for 168 h was studied by weight gain experiments. The area-specific resistance (ASR) of coatings was measured by a standard four-probe method. It was found that the Ce-doped NiMn₂O₄ spinel powder displayed a stable structure, high crystallinity, fine grain size, and decreased agglomeration when the Ce content was fixed at 0.05 mol?L^?1. The oxidation kinetics of NiMn₂O₄-coated SUS430 steel before and after Ce doping obeyed a parabolic law with parabolic rate constants of 4.58 × 10^?15 g² cm^?4 s^?1 and 1.83 × 10^?15 g² cm^?4 s^?1, respectively. When oxidized at 800 °C for 50 h, the ASR value of the coated samples before and after Ce doping stabilized at about 15.2 mΩ?cm² and 14.5 mΩ?cm², respectively. This work demonstrated that the Ce-doped NiMn₂O₄ spinel coating improved the high-temperature oxidation resistance and the electrical conductivity of metal interconnects.     

Thermodynamic calculation and microstructure characterization of spinel formation in MgO–Al2O3–C refractories

In this paper, by simulating the gas phase conditions inside the MgO–Al₂O₃–C refractories during continuous casting process and combining with thermodynamic analysis, as well as SEM analysis, the gas-gas and gas-solid formation of MA spinel were clarified in carbon containing refractories. Thermodynamic calculations showed that gas partial pressure of CO, O₂ and Mg could meet the formation and stable existence conditions of MA spinel in MgO–Al₂O₃–C refractories under service environment, and nitrogen could not affect the formation of MA spinel at 1550 °C in the thermodynamic condition. The formation processes of MA spinel were analyzed experimentally under embedding carbon atmosphere. The carbon-coated alumina powders in MgO–Al₂O₃–C refractories prevented the direct contact between magnesia and alumina. Mg gas was formed by carbon thermal reaction, then reacted with alumina (gas-solid) and gas containing aluminum (gas-gas) to generate MA spinel. Through gas-gas or gas-solid reaction, the formation of MA spinel was effectively controlled. By means of SEM analysis, a two-layer structure with dense outer spinel layer and loose inner layer was formed in MgO–Al₂O₃–C refractories.     

Enhancement in magnetic permeability of Ni-Co-Zn ferrites using CuO doping for RF and microwave devices

Novel soft magnetic ferrite materials will play a crucial role in next-generation trillion-dollar sensor technologies related to 5G communications and internet of things as these materials can achieve improved wireless power/signal transfer efficiency with high operation frequency. In this work, Ni_0.4Co_0.25Zn_0.35Fe₂O₄ ferrites with high permeability and low magnetic loss were prepared for RF and microwave device applications. Composition and microstructure control is crucial to obtain the desired magnetic and loss properties. CuO dopant (x = 0 wt% to 20 wt%) were employed during the synthesis of Ni_0.4Co_0.25Zn_0.35Fe₂O₄ ferrite specimens to modify the microstructures, thus improving the magnetic properties of the ferrites. High value of measured relative permeability (μ’ of 4-10) and relatively low magnetic loss tangent ( of 0.01-0.1) has been achieved at frequency range between 100 and 800 MHz. Addition of CuO, especially up to 3 wt%, can cause a significant increase in permeability. Real part of the permeability of 3.87 and 10.9 has been achieved for undoped and 3 wt% CuO doped specimens, while noticeable reduction in magnetic losses has been observed for the doped sample measured at 400 MHz. The resonance frequency of synthesized ferrites has also been shifted into GHz range, when higher concentration of CuO dopants (>5 wt%) were employed.     

ACr_2O_4尖晶石氧化物(A=Co,Zn,Mn,Cu)上二氯甲烷的催化燃烧:A位阳离子的影响

采用溶胶-凝胶法制备4种不同ACr_2O_4尖晶石氧化物(A=Co,Zn,Mn,Cu),考察A位阳离子对ACr_2O_4尖晶石氧化物的性质以及对二氯甲烷催化燃烧性能的影响,并对催化剂进行SEM、HRTEM、H_2-TPR、NH_3-TPD以及XPS等表征。结果表明,A位离子显著影响催化剂的可还原性和表面酸性,催化剂催化活性顺序为CoCr_2O_4Zn Cr_2O_4Mn Cr_2O_4CuCr_2O_4。结合表征结果,认为催化剂活性与其可还原性能和表面酸性存在密切关系。CoCr_2O_4由于具有最佳的可还原性和较高的表面酸性,具有最高的催化活性;而CuCr_2O_4由于具有最低的表面酸性导致其催化活性最低。     

Novel Fe‐based complex oxide catalysts for hydroxylation of phenol

Novel catalysts for the hydroxylation of phenol, Fe–Si–O, Fe–Mg–O and Fe–Mg–Si–O complex oxides, have been synthesized by a coprecipitation method. X‐ray diffraction studies show that MgFe₂O₄ crystallites with spinel structure are formed in Fe–Mg–Si–O and Fe–Mg–O complex oxides and the crystallite size of the metal oxide or complex oxide is reduced after addition of Si. In the hydroxylation of phenol with hydrogen peroxide, Fe‐based complex oxides exhibit high activities after a short induction period. The phenol conversion is improved when silicon is introduced into the Fe‐based complex oxides, and formation of MgFe₂O₄ crystals with spinel structure in the catalysts increases the diphenol selectivity. The addition of a little acetic acid to the reaction liquid can shorten the induction period effectively. Under the same reaction conditions, phenol conversion and diphenol selectivity over the Fe–Mg–Si–O catalyst are close to those over TS‐1, and furthermore, the reaction time is more than ten times shorter as compared to TS‐1. The reaction mechanism of the hydroxylation of phenol on the catalysts has been studied, and a free‐radical mechanism initiated by the formation of phenoxy free radicals is suggested. This revised version was published online in August 2006 with corrections to the Cover Date.     

TiO2加入量对富铝尖晶石烧结性能的影响

以α-Al2O3、分析纯的MgO及分析纯的TiO2为原料,研究了在1400℃、1500℃、1600℃保温3 h下,TiO2加入量(分别为0、1%、2%、4%)对Al2O3与MgO物质的量比为21的富铝尖晶石烧结性能的影响,并利用XRD进行物相组成分析,利用SEM和EDAX进行显微结构分析.结果表明由于TiO2与MgAl2O4的固溶作用,加入TiO2可显著改善富铝尖晶石的烧结性能;随着TiO2加入量的增加,试样的体积密度增加,显气孔率降低,特别是在1600℃烧结后的试样尤为显著.