《材料保护》2010年第11期

醋酸锰体系中钛材电沉积MnOx阳极的析氧催化性能 过去,对钛材在醋酸锰[Mn（CH3COO）2]电解液中电沉积MnOx层作析氧催化材料研究不充分。通过X射线衍射确定了MnOx沉积层的晶型,用扫描电镜技术观察其表面形貌;以循环伏安、极化曲线和电化学阻抗等方法测试了MnOx沉积层电极的电化学性能,探讨了MnOx沉积层电极结构、形貌与电催化性能的关系。     

Ru-Co-Ce复合氧化物阳极制备及析氧性能研究

采用溶胶-凝胶法制备RuO2-Co3O4-CeO2(Ru-Co-Ce)复合氧化物电极,对制备电极的热处理温度和稀土CeO2含量进行了优化.利用SEM、XRD分析方法对电极表面形貌进行表征,通过开路电压(Eoc)、循环伏安(CV)及阳极极化曲线等手段研究电极在1.0 mol·L-1 KOH溶液中的析氧催化活性.结果表明,制备温度对电极表面形貌有很大影响(优选400℃),复合氧化物电极中适量稀土CeO2可增强电极表面致密性,使RuO2晶相衍射峰减弱,峰形宽化,提高电极活性表面积,促进活性组分RuⅢ/RuⅣ的转化,使析氧过电位降低60 mV,从而提高电极析氧反应的活性,Ce最佳比例为0.4(摩尔分数).     

稀土Nd掺杂Ti/RuO2-Co3O4电极电催化性能研究

采用热分解法在400℃下制备了稀土Nd改性Ti/RuO2-Co3O4氧化物阳极,对稀土Nd掺杂量进行优化。利用SEM、EDX及XRD等分析方法对电极表面形貌、组成及结构进行了表征,通过开路电压、循环伏安、极化曲线及强化电解寿命等电化学方法研究了电极的析氧催化活性及稳定性。结果表明:稀土Nd掺杂使表面层晶粒细化,晶型饱满,且促进活性组分RuO2向电极表面富集,增加电极催化活性中心;掺杂量为20:1时,电极析氧性能最佳,伏安电荷容量高达686mC/cm2,反应活化能低至16.76kJ/mol,掺入稀土Nd后电极基体与涂层的结合力增强,电极强化电解寿命高达158h。     

稀土Y掺杂Ti/SnO2+MnOx/PbO2电极的电化学性能研究

采用热分解和电沉积的方法制备了稀土元素Y掺杂Ti/SnO2+MnOx/PbO2耐酸阳极.用XRD、SEM表征了电极的物相和表面形貌,用CV、EIS测定了电极的电化学性能,并研究了Y掺杂对电极在强酸性溶液中使用寿命的影响.结果表明:Y以Y2O3的形式与SnO2形成半导体固溶体,使电极在高电流密度(4 A/cm2)下的预期使用寿命达到70 h;同时该电极的析氧电位高达2.1 V,且电极表面呈蘑菇状,电催化性较好,Ti/SnO2+Y2O3+MnOx/PbO2电极是一种较理想的耐酸阳极材料.     

热处理对混晶结构Ni-Mo合金镀层电化学性能的影响

对获得的非晶/纳米晶混合结构形态的镍钼合金镀层在氮气保护条件下作热处理实验,研究热处理后合金镀层的电化学性能.结果表明,非晶/纳米晶的Ni-Mo合金具有较好的析氢催化活性,与镀层中的非晶态含量及镀层的真实接触面积有关.在350℃以下热处理,镀层结构仍具有混晶结构形态,具有良好的析氢催化活性;当温度高于450℃以上时,合金镀层开始以晶态合金出现,析氢催化活性降低.     

热处理温度对Pt-Ni合金结构演变及催化性能的影响

采用置换法在石墨烯上负载的Ni颗粒上制备出石墨烯负载Pt-Ni颗粒(Pt-Ni/G),通过对Pt-Ni/G进行不同温度的热处理,研究了热处理温度对Pt-Ni合金的结构变化和对氧还原反应和析氢反应催化活性的影响。结果表明,200℃热处理条件下,原子发生短程扩散迁移,Pt-Ni合金催化剂对氧还原反应(ORR)和析氢反应(HER)具有最好的催化活性;当热处理温度达到300℃和400℃后,除了Pt和Ni的衍射峰外,还出现了Ni-P合金的衍射峰,说明Ni原子和P原子进行了长程运动,由于Ni-P化合物的存在,使Pt-Ni合金催化剂对ORR和HER的催化活性降低。     

锌电积用Pb-Ag阳极MnO2镀膜的电化学性能

锌电积用Pb-Ag阳极存在析氧过电位高、表面铅易电化学氧化溶解,造成阴极电锌品质低等突出问题,如何减少阳极的溶铅污染并提升其催化析氧活性、降低反应能耗,成为亟待解决的难题。本文在Pb-Ag阳极表面电沉积一层均匀、致密的MnO₂薄膜,采用SEM、XRD和ICP等对MnO₂催化层的表面微观形貌、晶体结构和溶液含铅量进行分析;采用CV、LSV、EIS和Tafel等对Pb-Ag/MnO₂阳极的析氧催化活性和耐腐蚀性能进行分析。结果表明：在MnSO₄-H₂SO₄溶液中,当循环速率为200 mL/min、温度为80℃时,以4 mA/cm²电沉积120 min制备的Pb-Ag/MnO₂镀膜电极具有最佳的催化析氧和耐蚀性能;PbAg阳极经优化镀膜后,50 mA/cm²时其析氧过电位由936 mV降低为648 mV,腐蚀电流密度由7.03μA/cm²降低至0.66μA/cm^2<...     

热处理对超级电容器MnO2电极电化学性能的影响

采用阳极电沉积法制备MnO2粉末,并在不同温度(200～450℃)下对MnO2热处理,通过XRD分析热处理温度对MnO2粉末物相结构的影响,采用循环伏安法、恒流充放电法测试热处理温度对MnO2电极电化学性能的影响。结果表明:随着温度的升高,MnO2由原始的γ-MnO2逐渐变为β-MnO2,MnO2电极的比容量先增加后减小;当温度为300℃时,MnO2电极的比容量达到最高,在0.5 mol/L Na2SO4溶液中循环伏安扫描速度为10 mV.s-1条件下,电极比容量为156 F.g-1,且此时电极的稳定性良好,在10000个循环充放电内MnO2电极比容量几乎无衰减。     

烧结温度对Ti/TiN_(x)/Mn_(2)O_(3)阳极涂层性能的影响EI北大核心CSCD

采用热分解工艺在Ti/TiN_(x)表面制备了Mn2O3催化层,研究了制备过程中烧结温度对Ti/TiN_(x)/Mn2O3阳极材料析氧电催化性能的影响。通过SEM、XRD、Raman、XPS等表征方法对Mn2O3催化层的表面微观形貌和晶体结构进行分析;通过Tafel、LSV、恒流极化、EIS、ECSA等电化学测试手段对阳极材料的耐腐蚀性能、析氧催化活性进行分析。结果表明:烧结温度对Ti/TiN_(x)/Mn2O3阳极材料的表面微观结构、Mn的价态、耐电化学腐蚀性能以及电催化性能具有较大的影响。当烧结温度为200℃时,阳极材料表面的Mn2O3催化层致密平整且结晶性最好。随着烧结温度的升高,Mn2O3催化层产生较多的裂纹,同时氧空位的含量逐渐减少,Mn(Ⅳ)逐渐增多,参与电化学反应的电极表面的活性位点数量大幅降低,抑制了析氧动力学。     

烧结温度对热分解制备的RuO2电容性能的影响

采用X射线衍射(XRD)、恒流充放电和电化学表面分析研究了热处理温度对Ti/RuO2电极结构和电容性能的影响。XRD分析结果表明,Ti/RuO2电极的晶化程度随制备温度的升高而逐渐提高;恒流充放电、功率-密度特性和电化学表面分析结果表明,电极的比电容随制备温度提高先增大后减小,在临界晶化温度附近300℃制备的Ti/RuO2电极拥有最高的比电容、能量密度和功率密度。     

Structural, mechanical and corrosion properties of TiOxNy/ZrOxNy multilayer coatings

Results on the deposition and characterization of TiO_xN_y/ZrO_xN_y multilayers, with bilayer periods of 20 and 400 nm, are presented. The coatings were deposited on TiNiNb alloy substrates by the pulsed magnetron sputtering method. The elemental composition, hardness, adhesion and corrosion resistance of the coatings were analyzed.As resulted from the XPS analysis, the individual layers consisted of a mixture of titanium or zirconium oxynitrides and corresponding oxides. X-ray analysis revealed that the coatings were amorphous. Only slight differences between the microhardness and adhesion values of the coatings with small and large bilayer period Λ were found. The experiments also showed that the multilayered coatings improved the corrosion resistance of the uncoated alloy and reduced the amount of ion release in artificial body fluids.     

MOCVD growth and characterizations of BxAl1−xAs and BxAl1−x−yInyAs alloys

Zinc-blende B_xAl_1−xAs and B_xAl_1−x−yIn_yAs alloys have been grown on exactly oriented (0 0 1)GaAs substrates by low pressure metalorganic chemical vapor deposition (LP-MOCVD). The influence of susceptor coating, growth temperature and gas-phase boron mole fraction on boron incorporation into AlAs has been comprehensively investigated. It has been found that boron incorporation into AlAs could be enhanced and the optimal growth temperature range of B_xAl_1−xAs alloys changed from 580 °C to 610 °C when SiC-coated graphite susceptors were replaced by the non-coated ones. In this study, the maximum boron composition x of 2.8% was achieved for the pseudomorphically strained B_xAl_1−xAs alloys. AFM measurements show that RMS roughness of B_xAl_1−xAs alloys increased sharply with the increase of gas-phase boron mole fraction. Raman spectra of B_xAl_1−xAs alloys show a linear increase of the BAs shift with boron composition x. Based on BAlAs deposition, bulk B_xAl_1−x−yIn_yAs (x = 1.9%) quaternary alloy was grown lattice-matched to GaAs successfully. Moreover, 10-period BAlAs/GaAs and BAlInAs/GaAs MQW heterostructures were also demonstrated.     

High strength and good ductility of casting Al-Cu alloy modified by PrxOy and LaxOy

A modified Al-Cu alloy with high tensile strength and ductility of about 574.0 MPa and 10.4%, respectively, was obtained by adding multiple rare earth oxides (Pr_xO_y and La_xO_y) as modifier. Compared with the unmodified Al-Cu alloy, the tensile strength and ductility of the modified sample were increased by 24.3% and 42.5%, respectively. The improvement both in the strength and ductility may attribute to the finer crystal grains and dendrites, more homogeneously distributed θ′ phase precipitates and the intermetallic compounds formed at the crystal grain boundaries as well as in the space of the dendrites.     

铸造CAD／CAE／ES／PDM／ERP一体化及集成技术研究

详细阐述了支持铸造工艺设计、工艺优化、工艺信息管理、企业管理的系统研究与应用特点,在此基础上提出了基于PDM平台的铸造CAD／CAE／ES／PDM／ERP一体化框架体系,在华铸实验室现有软件体系（华铸CAE／CAD／PDM／ERP）及应用的基础上,设计与实现了一体化系统关键点及其集成技术。最后,以若干实际案例来证明本研究一体化系统的实用性。     

Hydrothermal synthesis of superconductors Ba1−xKxBiO3 and double perovskites Ba1−xKxBi1−yNayO3

Superconductors Ba_1−xK_xBiO₃ and body-centered double perovskites Ba_1−xK_xBi_1−yNa_yO₃ have been selectively synthesized by a facile hydrothermal route. The appropriate ratio and adding sequence of initial reagents, alkalinity, reaction temperature and time are the critical factors that influence the crystal growth of the compounds. The purity and homogeneity of the crystals were detected by the ICP, SEM, EDX and TEM studies. Magnetic measurements show that the superconducting transition temperatures T_C of Ba_1−xK_xBiO₃ decrease from 22 K (for x = 0.35) to 8 K (for x = 0.55) with increasing the K doping level.     

生物医用NiTi形状记忆合金腐蚀研究进展

镍钛形状记忆合金(NiTi-SMA)具有较好的耐腐蚀和机械性能,在口腔和临床医学中有着大量而广泛的应用。NiTi-SMA腐蚀后释放Ni²⁺会引发细胞毒性和过敏反应,进一步提高NiTi-SMA的耐蚀性是目前生物医学材料领域发展的核心之一。本文对近年来国内外有关口腔医学和临床医学中常用NiTi-SMA的腐蚀研究现状进行了总结,同时也对NiTi-SMA增材制造及表面改性技术进行了评述,以期为开发高性能抗腐蚀生物医用NiTi-SMA提供一定的指导意义。     

Li掺杂Ba(Ti1/7Sn1/7Zr1/7Hf1/7Nb1/7Ga1/7Li(1/7-x))O3高熵陶瓷的制备及介电性能研究

近年来,在高熵合金基础上发展起来的高熵陶瓷逐渐引起了研究者的广泛关注,其出现为开发高性能的无机非金属材料提供了新的设计思路。本文采用固相法制备了BaMO3基钙钛矿型高熵陶瓷Ba(Ti1/7Sn1/7Zr1/7Hf1/7Nb1/7Ga1/7Li(1/7-x))O3 (x = 0, 2.3%, 5.3%, 8.3%, 11.3%),并研究了Li含量对高熵陶瓷物相结构、微观形貌及介电性能的影响。结果表明,Li含量对陶瓷结构的影响不大,陶瓷均保持立方钙钛矿结构,且无杂相产生;陶瓷的晶粒尺寸相对较均匀。当x = 0时,即B位七元等摩尔比Ba(Ti1/7Sn1/7Zr1/7Hf1/7Nb1/7Ga1/7Li1/7)O3高熵陶瓷,其介电常数达到了最大值2920 (@100 Hz),相较于已报道的不掺Li的六元高熵钙钛矿陶瓷Ba(Ti1/6Sn1/6Zr1/6Hf1/6Nb1/6Ga1/6)O3提升了近50倍。     

Ti/Mn(0.8-x)SnxIr0.2O2电极的电容性能研究

采用热分解法制备了Ti/Mn_(0.8-x)SnxIr_0.2O_2三元氧化物电极材料。通过扫描电子显微镜,X射线衍射、循环伏安和交流阻抗谱等分析了Ti/Mn_(0.8-x)Sn_xIr_0.2O_2电极材料的组织结构和电容性能。结果表明:随SnO_2含量增加,氧化物涂层中正方结构Mn_3O_4相逐渐减少,正方结构SnO_2相逐渐增加。与锰铱二元氧化物相比,SnO_2的加入可明显改善电极材料在0~0.5 V区间的电流响应,并促进氧化锰活性的发挥,但在一定程度上也抑制了氧化铱的活性。SnO_2的加入也改变了电极材料的电荷转移电阻、弛豫时间常数、以及不同频率下的电容响应速度。相比其它电极材料,Ti/Ir_0.2Mn_0.6Sn_0.2O_2电极材料在低频范围(≤1 Hz)有更好的电容响应和更高的活性,因而获得最高的比电容值。     

Thermoelectric properties of Sn1−x−yTiySbxO2 ceramics

Thermoelectric properties of Sn_1−x−yTi_y Sb_xO₂ ceramics were investigated in detail. The addition of Sb into SnO₂ matrix increased the electric conductivity, σ. The increase in the σ value should be caused by the increase in the carrier concentration. The Seebeck coefficients of all the samples were negative, which means that these samples have n-type conduction. The samples of this study have porous structure. The maximum Z value of all the samples measured in this study was 2.4 × 10⁻⁵ K⁻¹.     

Magnetic phase diagrams of the TbRh2−xPdxPdxSi2 and TbRu2−xPdxSi2 systems

The a.c. susceptibility and high field magnetization on TbRh_2−xPd_xPd_xSi₂ and TbRu_2−xPd_xSi₂ compounds were investigated up to 140 kOe. The (T,x) magnetic phase diagrams were determined. For both systems, an increase in the Pd content causes a decrease in the Néel temperature and changes the magnetization curves.