KF对Na3AlF6-Al2O3熔盐电解阴极过程的影响

采用循环伏安法、交流阻抗法和方波伏安法等电化学测量技术,考察了KF对Na₃AlF₆-Al₂O₃熔盐电解体系的阴极过程的影响。研究结果表明：在Na₃AlF₆-Al₂O₃和Na₃AlF₆-Al₂O₃-KF电解质体系的循环伏安曲线中,还原峰随着扫描速率的增大而负移,氧化峰随着扫描速率的增大而正移,在扫描速率较低（25～100 mV·s^-1）的情况下,反应过程不可逆,反应过程相对平缓稳定;随着扫描速率的提高,电极可逆性相对提高。由于电极附近铝离子的聚合现象,使得在无KF的熔盐体系下,交流阻抗的高频区出现了感抗现象;在含KF的体系下,反应是由电化学反应过程和扩散过程共同控制的,且随着KF含量的增加,Warburg阻抗系数减小,电化学反应过程控制逐步取代扩散过程控制;反应电流也随之增大,氧化速率加快,还原和氧化过程可逆性降低。同时KF的加入抑制了铝的沉积,合金化作用比较明显,通过对阴极前波进行高斯拟合,得到不同KF含量（0、3%、5%）体系下的铝离子的电子转移数分别为1.19、1.02、0.75。     

KF对Na_3AlF_6-Al_2O_3熔盐电解阴极过程的影响

采用循环伏安法、交流阻抗法和方波伏安法等电化学测量技术,考察了KF对Na3AlF6-Al2O3熔盐电解体系的阴极过程的影响。研究结果表明:在Na3AlF6-Al2O3和Na3AlF6-Al2O3-KF电解质体系的循环伏安曲线中,还原峰随着扫描速率的增大而负移,氧化峰随着扫描速率的增大而正移,在扫描速率较低(25~100 mV·s-1)的情况下,反应过程不可逆,反应过程相对平缓稳定;随着扫描速率的提高,电极可逆性相对提高。由于电极附近铝离子的聚合现象,使得在无KF的熔盐体系下,交流阻抗的高频区出现了感抗现象;在含KF的体系下,反应是由电化学反应过程和扩散过程共同控制的,且随着KF含量的增加,Warburg阻抗系数减小,电化学反应过程控制逐步取代扩散过程控制;反应电流也随之增大,氧化速率加快,还原和氧化过程可逆性降低。同时KF的加入抑制了铝的沉积,合金化作用比较明显,通过对阴极前波进行高斯拟合,得到不同KF含量(0、3%、5%)体系下的铝离子的电子转移数分别为1.19、1.02、0.75。     

含LiF和KF的电解质熔体对铝电解阴极的渗透过程

研究了Na3AlF6-Al2O3-KF-LiF电解质体系中KF和LiF含量、电流密度和NaF/AlF3分子摩尔比对阴极石墨材料渗透过程的影响.结果表明,K和Na渗透到阴极碳块中形成石墨层间化合物,而Li在阴极表面生成Li2C2化合物;当钾盐含量为0～7％(ω)时,碱金属渗透深度可达28～40 mm:当锂盐含量为0～7％...     

Ni3Al增韧Al2O3陶瓷机理的研究

以Ａｌ２Ｏ３,Ｎｉ３Ａｌ为原料热压烧结得到高韧性复合材料,并对材料进行了机械性能测试,从Ｎｉ３Ａｌ的晶体结构、合金化、拔出现象、裂纹偏转等方面对Ｎｉ３Ａｌ增韧Ａｌ２Ｏ３陶瓷机理作了深入研究。     

过渡相Cr2O3对Al-Al2O3复合滑板微观结构及性能的影响

以板状刚玉、电熔白剐玉、工业Cr2O3微粉和金属Al粉为原料,热固性酚醛树脂为结合剂,在1 450℃保温6h埋炭烧成获得添加过渡相的Al-Al2O3复合滑板.结果表明:Cr2O3微粉在l450℃保温6h埋炭烧成后不能稳定存在,会转变为Cr3C2、Cr7C3或Al8Cr5铝铬金属间化合物,其存在状态由其添加量决定.复合滑板中(Al2OC)1-x(AlN)x、Al4O4C、Cr3C2及Cr7C3为增强相,Al8Cr5铝铬金属间化合物为塑性相.当Cr2O3微粉含量为3％(质量分数)时,复合滑板的组成为Al-Al4O4C-Al2O3;当添加Cr2O3微粉为6％、9％和12％时,复合滑板的组成为Al8Cr5-(Al2OC)1-x(AlN)x-Al2O3;当添加Cr2O3微粉为15％时,复合滑板的组成为Al8Cr5-Al2O3.当Cr2O3微粉含量为6％时,Al8Cr5-(Al2OC)1-x(AlN)x-Al2O3复合滑板物理性能最佳.在1 450℃保温6h埋炭烧成条件下,Cr2O3微粉表现为过渡相.     

Al2O3/Fe3Al复合材料的制备及性能

利用热压烧结制备了致密的Al_2O_3/Fe_3Al复合材料。测试表明,该复合材料具有良好的力学性能,其抗弯强度和断裂韧性的最大值分别为832 MPa和7.96 MPa·m~1/2。对试样进行压痕实验,采用SEM对裂纹扩展方式进行观察,结果表明,在复合材料中存在着多种增韧机制,裂纹表现出复杂的扩展方式,这将在较大程度上吸收裂纹扩展能,从而使复合材料的断裂韧性得以提高。     

添加剂对Al2O3(f)/Ti-Al原位复合材料纤维生成形式的影响

以金属钛粉、铝粉及添加剂为原料压制成预制体,通过石墨与氧化铝混合粉对预制体的覆埋实现气氛保护并进行热处理,使其原位合成氧化铝纤维增强钛铝金属间化合物复合材料。通过XRD和SEM测试,分析了材料最终晶相组成及内部显微结构,并结合DTA进行了反应的热力学研究。SEM分析显示Ti-A l-Nb2O5、Ti-A l-La2O3、Ti-A l-Kaolin三种体系配料均可合成出A l2O3(f)/Ti-A l原位复合材料,但A l2O3纤维的生成方式不同:Ti-A l-Nb2O5体系以A l、Nb2O5的铝热反应为主生成;其余两种体系主要是A l纤维被氧化形成A l2O3纤维。铝热反应迅速且放热量高,使纤维纤细,团聚性较强;缓慢氧化得到的纤维直径较粗,分散性较好。     

Al2O3-Mi3Al复合材料的机械性能研究

金属间化合物已被用来作为第二相物质增韧增强陶瓷材料。本文研究了Ni3 Al增强Al2 O3 复合材料的热压烧结与性能。含有 1 0Vol% (体积百分数 )Ni3 Al的复合材料在 1 3 50℃、2 5MPa热压 60min其相对密度达到 98%。在不同温度下测试了材料的弹性模量、抗弯强度及断裂韧性 ,并利用扫描电镜对相应试样的显微结构与增强机理进行了分析。     

γ-Al2O3和α-Al2O3与其对应的氢氧化物对合成尖晶石的影响

以γ-Al2O3(勃姆石在700℃保温4 h热处理后的产物)、α-Al2O3(Al(OH)3在1 400℃保温4 h热处理后的产物)、勃姆石、Al(OH)3为原料,与轻烧MgO按n(Al2O3):n(MgO)=1的组成配料并制备试样,研究了在800～1 600 ℃下不同氧化铝及其对应的氢氧化物对合成尖晶石的影响.结果表明:γ-Al2O3和α-Al2O3分别同与其对应的氢氧化物为原料的试样具有相似的烧结性能;且以氢氧化物为原料比以氢氧化物煅烧后所得的氧化物为原料更有利于尖晶石的生成,但不利于尖晶石的致密化.     

Na和铝电解质对振动成型TiB2惰性阴极的渗透

采用振动成型的TiB2和石墨分别作为Na和铝电解质渗透实验的阴极材料,在工业铝电解条件下电解5 h,考察了Na和铝电解质对其腐蚀渗透情况. XRD分析结果表明,振动成型TiB2阴极的基体中未发现Na或F的单质及化合物,而在石墨阴极中则有NaF和Na3AlF6等物质存在. SEM及EDS分析结果表明,Na, F, Al等元素渗透到TiB2阴极基体中的量极少,渗透到石墨中的量则较多. 可见振动成型TiB2阴极能够有效减缓Na和铝电解质的渗透,但并不能完全阻止.     

Indirect cathodic electrocatalytic degradation of dimethylphthalate with PW11O39Fe(III)(H2O) and H2O2 in neutral aqueous medium

Cyclic voltammetry and degradation of dimethylphthalate (DMP) revealed that the iron-substituted heteropolytungstate anion PW₁₁O₃₉Fe(III)(H₂O)⁴⁻ is an excellent indirect cathodic oxidative electrocatalyst in the presence of H₂O₂. PW₁₁O₃₉Fe(III)(H₂O)⁴⁻ can electrocatalyze the reduction of H₂O₂ to hydroxyl radicals via an inner-sphere electron transfer mechanism, which cause oxidative decomposition of DMP. Almost complete DMP removal and ca. 30% mineralization were obtained in less than 120 min in a mixed phosphate solution at pH 6.86 containing 0.1 mM DMP. MS analyses of the intermediates and final products suggested that glyoxal, oxalic acid and acetic acid are the main ring-opening products, besides some unstable hydroxylated aromatic intermediates. The effects of added H₂O₂ concentration, applied cathodic potential and DMP initial concentration on the degradation of DMP were also investigated. A concentration of 1.0 mM H₂O₂ and cathodic potential of −0.3 V were optimal conditions for DMP degradation in our experiments. At higher initial DMP concentrations degradation also occurred, but at a slower decay rate compared to lower initial concentrations. The present system thus represents a possible method to use PW₁₁O₃₉Fe(III)(H₂O)⁴⁻ as an indirect cathodic oxidative electrocatalyst in water and wastewater treatment.     

Calciothermic reduction of NiO by molten salt electrolysis of CaO in CaCl2 melt

Metallic nickel powders with low and uniform residual oxygen content were produced from NiO using the molten salt electrolysis of CaO in CaCl₂ melt. Suitable amount of CaO for the reduction was in the range of 0.5–3.0 mol% CaO.The electrical isolation of NiO from both electrodes could produce metallic Ni in CaCl₂ melt. Separating the metal oxides from the cathode confirmed the mechanism of calciothermic reduction that the electrolysis of dissolved CaO in CaCl₂ melt produces Ca, and that the dissolved Ca in molten CaCl₂ successfully reduces NiO to metallic Ni. An average of about 600 ppm oxygen in Ni sample was achieved directly from oxide, when NiO was detached from the cathode.     

Preparation, morphology and electrochemical characteristics of LiNi1/3Mn1/3Co1/3O2 with LiF addition

LiNi_1/3Mn_1/3Co_1/3O₂ with LiF additives was prepared by a spray dry process, and characterized by XRD, SEM, TEM, ICP, XPS, EIS and charge-discharge testing. Although some of the LiF was lost during the preparation, the remaining LiF existed on the surface of the LiNi_1/3Mn_1/3Co_1/3O₂ particles and had little influence on its structure. The LiF addition could not only promote the combine of the particles and increase the tap density of the material, but also effectively improve the cyclic performance of LiNi_1/3Mn_1/3Co_1/3O₂ at high cutoff voltages (up to 4.7 V) and at a high current density. The EIS results suggest that the LiF presence could significantly suppress the increase in the charge transfer resistance that occurred during the charged storage state or after long cycling, which should be related to the improvement on the electrochemical properties.     

成型工艺条件对铈锆铝复合载体性能的影响

采用压缩成型法对铈锆铝复合载体进行了放大制备,考察放大制备过程中造粒粉含水量、成型压力、焙烧温度等成型工艺条件对载体机械强度、吸水量、密度、织构性质及晶相的影响。结果表明,造粒粉含水量是影响颗粒成型的主要因素,含水量过高,颗粒不能成型或容易层裂;成型压力是影响载体强度、吸水量、密度等机械性能的主要影响因素,适宜的成型压力有助于获得各项机械性能均衡的载体;焙烧温度是影响载体比表面积及晶相结构的关键因素。结合生产要求确定最佳工艺条件为造粒粉含水量为15%,半成品强度(7~9)N·mm-1,焙烧温度(800~900)℃。     

Performance of solvothermally prepared Ga2O3-Al2O3 catalysts for SCR of NO with methane

The solvothermal reaction of mixtures of aluminum isopropoxide (AIP) and gallium acetylacetonate (Ga(acac)₃) directly yielded the mixed oxides of γ-Ga₂O₃-Al₂O₃. In the solvothermal synthesis, the crystal structure of mixed oxides was controlled by the initial formation of γ-Ga₂O₃ nuclei. The mixed oxides prepared in diethylenetriamine have extremely high activities for selective catalytic reduction (SCR) of NO with methane as a reducing agent. With increasing crystallite size of the spinel structure, the catalytic activity increased. The ratio of the amount of methane consumed by combustion to total methane conversion was proportional to the density of acid sites on the surface of the mixed oxides. The mixed oxide catalysts prepared in diethylenetriamine had lower densities of acid sites and showed a higher methane-efficiency for CH₄-SCR than those prepared in other solvents. These catalysts maintained their high activity even when the reaction was carried out under the severe conditions (i.e., high space velocity and low NO concentration).     

Preparation and characterization of Cr2O3-TiO2-Al2O3-V2O5 green pigment

Green pigments with high near infrared reflectance based on a Cr₂O₃-TiO₂-Al₂O₃-V₂O₅ composition have been synthesized. Cr₂O₃ was used as the host component and mixtures of TiO₂, Al₂O₃ and V₂O₅ were used as the guest components. TiO₂, Al₂O₃, and V₂O₅ were mixed into 39 different compositions. The spectral reflectance and the distribution of pigment powder were determined using a spectrophotometer and a scanning electron microscope, respectively. It was found that a pigment powder sample S9 with a Cr₂O₃-TiO₂-Al₂O₃-V₂O₅ composition of 80, 4, 14 and 2 wt%, respectively, gives a maximum near infrared solar reflectance of 82.8% compared with 49.0% for pure Cr₂O₃. The dispersion of pigment powders in a ceramic glaze was also studied. The results show that the pigment powder sample S9 is suitable for use as a coating material for ceramic-based roofs.     

Electrolytic reduction behavior of U3O8 in a molten LiCl-Li2O salt

An electrolytic reduction of U₃O₈ in a molten LiCl-Li₂O salt was investigated using the electrochemical techniques of cyclic voltammetry (CV) and chronopotentiommetry (CP). The electrolytic reduction of U₃O₈ powder exhibited a different behavior when the initial current density was higher than for 10 g U₃O₈/batch run. Two kinds of reduction mechanisms, an electro-metallothermic reduction (EMR) and a direct electrochemical reduction (DER) were adopted to explain the resultant behavior. Current efficiencies and reduction products were obtained by a series of constant current runs. Current efficiencies, evaluated for a reduction side, were estimated to be more than 75% throughout a series of constant current runs and lithium uranium oxides (lithium uranates) were detected during the U₃O₈ reduction to metallic uranium.     

Influence of CaO-ZrO2-Al2O3-SiO2 glass-ceramic frits on the technological properties of porcelain stoneware bodies

In the present work, the effect of the addition to a porcelain stoneware body of glass-ceramic frits belonging to the CaO-ZrO₂-Al₂O₃-SiO₂ (CZAS, containing 1, 3, 5, and 10 mol% of Al₂O₃) system as replacement of the “state of the art” frit belonging to CaO-ZrO₂-SiO₂ system (CZS) was evaluated. The firing process was performed in a furnace able to complete the thermal cycle in 50 min, in order to simulate the industrial process.Technological properties such as water absorption, firing shrinkage, flexural strength, and thermal expansion behaviour were measured. Aesthetical properties were also evaluated. X-ray diffraction and scanning electron microscopy studies were also carried out to analyse the microstructure and the phase compositions of the studied samples.It was found that the sample containing the CZAS frit with 5 mol% of Al₂O₃ shows, in general, the best combination of properties in term of mechanical, physical and aesthetical properties.     

Synthesis and properties of PdO/CeO2-Al2O3 catalysts for methane combustion

This study focuses on the loading of catalytic materials, e.g., palladium on the surface of supporting materials, with the aim to obtain catalysts with high activity for methane combustion. The catalyst PdO/CeO₂-Al₂O₃ was prepared by impregnation under ultrasonic condition. The effect of different activation methods on the activity of catalysts for methane catalytic combustion was tested. The properties of reaction and adsorption of oxygen species on catalyst surface were characterized by H₂-temperature programmed reduction (H₂-TPR), and O₂-temperature programmed desorption (O₂-TPD). Furthermore, the sulfur tolerance and sulfur poisoning mode were investigated. The results indicate that the catalyst PdO/CeO₂-Al₂O₃ activated with rapid activation shows higher activity for methane combustion and better sulfur tolerance. The result of sulfur content analysis shows that there is a large number of sulfur species on the catalyst’s surface after reactivation at high temperature. It proves that the activity of catalysts cannot be fully restored by high-temperature reactivation.