Mn掺杂Ni(OH)2的合成及电化学性能研究

本工作采用缓冲溶液法制备Mn掺杂Ni(OH)₂(Ni_1-xMn_x(OH)₂, x=0.1, 0.2, 0.3, 0.4), X射线衍射测试表明样品主要是β相, 有少量Mn₃O₄杂相; 循环伏安测试表明, x=0.2的材料还原峰积分面积最大、还原分支的峰电流最高; 恒流充放电测试表明, 在100 mA/g电流密度下, Ni_0.8Mn_0.2(OH)₂放电比容量最高, 其第20次循环放电比容量为271.8 mAh/g, 同等条件测试的商用β-Ni(OH)₂放电比容量为253.6 mAh/g; 在300、500 mA/g电流密度下, Ni_0.8Mn_0.2(OH)₂放电比容量仍保持最高, 分别为294.7、291.5 mAh/g, 而且Mn掺杂Ni(OH)₂的循环稳定性也优于商用β-Ni(OH)₂。Mn掺杂可改善镍电极的循环稳定性、降低镍电极成本, 具有广阔的应用前景。     

Al-Mg-Sc-Ti合金中Al3(Scx,Ti1-x)粒子的析出行为

用激冷铸造法制备Al-5.5Mg-0.25Sc-0.04Ti合金,研究了在不同温度退火后其硬度随时间的变化,并用金相显微镜(OM)和透射电镜(TEM)研究了这种合金中Al₃(Sc_x,Ti_1-x)第二相粒子的存在形式和形成机制。结果表明：用急冷铸造法制备的Al-5.5Mg-0.25Sc-0.04Ti铸态合金中Sc和Ti原子主要以固溶的形式存在于α(Al)基体中,在电镜下很难观察到这些粒子。铸态合金在较低温度(低于250℃)下退火时其硬度提高得比较慢,退火较长时间才能出现硬度的峰值;而在比较高的温度(高于350℃)退火硬度提高得非常快,很快出现峰值。但是,硬度出现峰值后继续退火则大幅度降低;在300℃退火硬度的热稳定性比较高。硬度的变化,与次生Al₃(Sc_x,Ti_1-x)粒子的析出密切相关。在较低温度下次生Al₃(Sc_x,Ti_1-x)粒子的析出不充分且粒径较小,对晶界、亚晶界和位错的钉扎作用较弱;而在过高的温度下Al₃(Sc_x,Ti_1-x)粒子发生粗化,使合金的性能降低。     

(La1-xMgx)2Ce2O7-x的合成与热物理性能

Mg对La₂Ce₂O₇的掺杂可提高其热膨胀系数、降低其热导率, 从而改善其作为热障涂层材料的性能。采用溶胶-凝胶法制备了(La_1-xMg_x)₂Ce₂O_7-x系列组成样品。X射线测试表明: 当 0≤x≤0.4时, 所有(La_1-xMg_x)₂Ce₂O_7-x 样品均与La₂Ce₂O₇具有相同的缺陷萤石结构, 且晶胞参数随x的增大而递减; 当x?0.4时, 样品中出现MgO的峰。在组成相同的情况下, 样品(La_1-xMg_x)₂Ce₂O_7-x (0≤x≤0.4)的热膨胀系数随温度升高而增大, 而热导率随温度升高而降低。在相同温度下, 不同组成样品(La_1-xMg_x)₂Ce₂O_7-x (0≤x≤0.4)的热膨胀系数随x的增大而增大; 而样品的热导率则随Mg掺杂量的增加呈先增大后减小的趋势。在此基础上, 探讨了Mg掺杂对La₂Ce₂O₇的物相、晶胞参数、热膨胀系数以及热导率的影响机理。     

Er2O3掺杂Gd2(Zr0.8Ti0.2)2O7陶瓷的物理性能

用固相反应法制备(Gd_1-xEr_x)₂(Zr_0.8Ti_0.2)₂O₇(摩尔分数x=0,0.2,0.4)陶瓷并测试其晶体结构、显微形貌和物理性能,研究了Er₂O₃掺杂的影响。结果表明,(Gd_1-xEr_x)₂(Zr_0.8Ti_0.2)₂O₇陶瓷具有立方烧绿石结构,显微结构致密,在室温至1200℃高温相的稳定性良好;Er³⁺掺杂降低了陶瓷材料的热导率和平均热膨胀系数,当x=0.2时,其1000℃的热导率最低(为1.26 W·m^-1·k^-1)。同时,Er³⁺掺杂还提高了这种材料的硬度和断裂韧性。     

电纺制备多孔Ni1-xZnxFe2O4超细纤维的结构与磁性能

采用静电纺丝技术结合后期的热处理制备了具有多孔结构的Ni_1-xZn_xFe₂O₄(x=0~0.8)超细纤维. 利用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、场发射扫描电镜(FESEM)、低温N₂吸附-脱附和振动样品磁强计(VSM)对纤维样品的晶体结构、微观形貌、孔特征和室温磁性能进行了研究. 结果表明, 550℃焙烧2?h得到的多孔Ni_1-xZn_xFe₂O₄超细纤维均为单相尖晶石结构, 平均粒径约为25~30?nm, 纤维直径主要分布在200~500?nm之间, 且具有较大的长径比; 所制备的Ni_0.5Zn_0.5Fe₂O₄多孔纤维的孔结构主要以狭缝状介孔为主, 其平均孔径约为11?nm; 随着Zn含量x由0增加0.8, Ni_1-xZn_xFe₂O₄纤维的晶格常数a线性增大, A位的红外特征振动频率单调递减, 矫顽力由13.8?kA/m逐步减小到2.3?kA/m, 比饱和磁化强度先增大后减小, 在x=0.4时达到最大值66.8?A·m²/kg. 与相近尺寸的Ni-Zn铁氧体纳米粒子相比, Ni-Zn铁氧体超细纤维由于其形状各向异性而表现出更高的矫顽力.     

硬脂酸盐熔融法合成(Y,Lu)AG:Ce荧光粉及荧光性能研究

采用硬脂酸盐熔融新方法合成了[(Y_1-xLu_x)_1-yCe_y]₃Al₅O₁₂固溶体荧光粉(x=0’0.5, y=0.005’0.03), 并通过XRD、SEM、BET和PL-PLE等方法对该荧光粉进行了表征。结果表明, 纯相石榴石在800℃的低温下即可生成, 而不经过YAM和YAP中间相。煅烧所得[(Y_1-xLu_x)_1-yCe_y]₃Al₅O₁₂ 荧光粉具有良好的均一性和分散性, 并在455 nm蓝光激发下于544 nm附近呈现最强黄光发射。粉体的发光强度随煅烧温度升高而增大, 归因于结晶度提高和表面缺陷减少。发现Ce³⁺的荧光猝灭浓度为1.5%, 猝灭机制为Ce-Ce间的交换相互作用和晶格缺陷。发现发射峰位随Ce³⁺含量增加而红移, 而最强激发峰和发射峰随Lu³⁺含量增大而蓝移, 归因于Ce³⁺离子5d激发态能级重心移动和晶体场劈裂的共同作用。     

Li/Ce/La共掺杂对CaBi2Nb2O9陶瓷晶体结构及电学性能的影响

采用固相反应法制备(Li_0.5Ce_0.25La_0.25)_xCa_1-xBi₂Nb₂O₉铋层状结构压电陶瓷, 分析多元稀土元素掺杂对CaBi₂Nb₂O₉(CBN)陶瓷晶体结构、微观形貌及电学性能的影响。Rietveld结构精修表明, 多元稀土元素进入晶格内部形成固溶体, 掺杂使晶体结构有由斜方晶系向四方晶系转变的趋势, 反位缺陷中A位的Bi ³⁺具备6s2孤对电子, 抑制这种变化趋势。SEM照片显示, 掺杂主要抑制晶粒沿垂直c轴平面生长, 这是由于稀土氧化物具备较高的熔点, 在烧结过程中不易扩散。准同型相界附近, 垂直b轴方向的a滑移面被打破, 极化方向沿a轴和b轴, 导致压电性能增强。其中, (Li_0.5Ce_0.25La_0.25)_0.17Ca_0.83Bi₂Nb₂O₉陶瓷具备最优异的性能: 居里温度为913 ℃, 压电系数高达16.4 pC/N; 经850 ℃退火2 h, 其d₃₃值为14.0 pC/N, 约为原始值的85.4%。     

Al、O含量对SiAlCO纤维高温转化为Si(Al)C纤维过程的影响

采用不同Al含量的聚铝碳硅烷(PACS)为先驱体, 通过不同的PACS纤维不熔化方法调节O引入量, 制备了具有不同Al和O含量的连续SiAlCO纤维。研究了SiAlCO纤维经高温处理转变为Si(Al)C纤维过程中, Al、O含量对SiC_xO_y相分解、β-SiC结晶生长和微观形貌的影响。结果表明: 纤维中SiC_xO_y相的分解温度区间为1300~1700℃, 与Al、O含量基本无关; 提高Al含量可减少纤维在高温下表面形成粗大SiC结晶颗粒和相互连通的气孔, 并且对1700℃以上β-SiC结晶生长的抑制作用增强, 有利于烧结致密化; 利用纤维中O元素, 以放出CO或CO₂方式脱除富余C, 但O含量过高导致气体逸出时产生较大孔洞, 不利于烧结致密化。当Al和O含量分别约为0.6wt%和9wt%时, SiAlCO纤维经高温处理后能得到具有较大β-SiC晶粒尺寸的致密化Si(Al)C纤维。     

电解质表面微结构对固体氧化物燃料电池的阴极极化电阻的影响

在固体氧化物燃料电池(SOFC)中, 电解质对阴极界面极化电阻(R_c)有着显著影响。通过测量以Sm_0.2Ce_0.8O_2-δ (SDC)为电解质、(La_0.85Sr_0.15)_0.9MnO_3-δ(LSM)和La_0.6Sr_0.4Fe_0.8Co_0.2O_3-δ(LSCF)为阴极的对称电池的交流阻抗谱, 研究SDC电解质表面微结构(晶粒大小和晶界长度)对R_c的影响。通过改变烧结温度和时间, 制备出具有不同晶粒尺寸和晶界密度的电解质。通过SEM得到微结构参数, 建立R_c与这些参数的联系。结果发现, 随着晶粒尺寸的减小、晶界密度的增加, R_c明显降低。此外, 对于LSM电极, 晶界密度的增加, 促进了阴极反应的氧离子传导。     

三元过渡金属硼化物Os1-xRuxB2的制备及其结构和性能研究

以高纯锇(Os)、钌(Ru)、硼(B)粉为原料, 在常温常压下采用机械化学法制备了三元过渡金属硼化物Os_1-xRu_xB₂粉末, 并对合成的粉末进行无压烧结使其致密化。研究了机械化学法合成Os_1-xRu_xB₂的反应过程、Ru含量对OsB₂相结构的影响、合成粉末的热稳定性及烧结后块体材料的力学性能。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对Os_1-xRu_xB₂粉末及块体的相成分、表面形貌和微观结构进行表征, 并通过维氏硬度计测得其烧结后块体材料的显微硬度。实验结果表明: 合成过程中生成了中间产物Os_1-xRu_xB_1.1, 随着球磨时间的延长有少量Os_1-xRu_xB₂生成, 球磨24 h后合成粉末的主相为Os_1-xRu_xB₂, 继续球磨到40 h, 粉末中相成分不再发生变化。当x≤0.1时, 合成粉末的主相为六方结构Os_1-xRu_xB₂; 而当x≥0.15时,合成粉末的主相为正交结构的Os_1-xRu_xB₂。经1450℃(保温1 h)热处理后的粉末中有部分六方结构的Os_1-xRu_xB₂向正交结构发生相变, 并生成了低硼化物 (Os_1-xRu_x)₂B₃。合成的OsB₂和Os_0.85Ru_0.15B₂粉末经1700℃无压烧结后颗粒呈板条状, 其致密度均为85%左右, 在0.49 N载荷下测得其硬度分别(27±2) GPa和(21±1) GPa。     

A new resource-saving,low chromium and low nickel duplex stainless steel 15Cr–xAl–2Ni–yMn

A new family of resource-saving, low Cr and low Ni duplex stainless steels, with compositions of 15Cr–xAl–2Ni–yMn (x = 1.2–2.8, y = 8–12, wt.%) has been developed by examining the effect of Al and Mn on microstructure, mechanical property and corrosion property. The results show that 15Cr–1.2Al–2.0Ni–8Mn and 15Cr–2.0Al–2.0Ni–10Mn alloys have a balanced ferrite–austenite relation and that 15Cr–2.8Al–2.0Ni–12Mn alloy has a primary ferrite phase structure. The ferrite volume fraction increases with the solution treatment temperature and Al content while decreases with Mn content. No precipitate was found after solution-treated at 750 °C for 30 min. 15Cr–1.2Al–2.0Ni–8Mn alloy has a strong strain hardening effect, and 15Cr–2.0Al–2.0Ni–10Mn alloy has a good TRIP effect. Both of the 15Cr–1.2Al–2.0Ni–8Mn and 15Cr–2.0Al–2.0Ni–10Mn alloys have excellent impact toughness at low temperature with the impact energy higher than 125 J at −40 °C. The pitting corrosions always occur in austenite phase. Among the designed alloys, 15Cr–1.2Al–2.0Ni–8Mn and 15Cr–2.0Al–2.0Ni–10Mn are found to be excellent alloys with a proper phase proportion and a better combination of superior mechanical property and good pitting corrosion resistance.     

铸造双相不锈钢点腐蚀行为研究

采用化学浸泡腐蚀试验及微观组织和化学成分分析研究了5种铸造双相不锈钢在6%Fe Cl3溶液中的点腐蚀行为,并与316L奥氏体不锈钢进行了对比。结果表明,铸造双相不锈钢的抗点腐蚀性能均优于316L的,腐蚀速率和点腐蚀深度均小于316L奥氏体不锈钢的;双相不锈钢主要耐点蚀能力合金元素在奥氏体和铁素体相内分布不均匀,铬、钼更多地分配于铁素体相内,而镍、氮则更多地分配于奥氏体相内,铁素体相的耐点蚀指数PRE(Cr%+3.3Mo%+16N%)大于奥氏体相;双相不锈钢的耐点腐蚀性能与化学成分有关,随着PRE的增加,双相不锈钢的耐点腐蚀性能提高,铜元素在铁素体内析出的富铜相导致点蚀优先在铁素体内发生和发展。     

直接热分解法制备单相Pd-Fe合金催化剂及电催化氧还原活性

以醋酸钯和醋酸亚铁为前驱体, 采用直接热分解法制备了碳载Pd₃-Fe₁(Pd₃-Fe₁/C)催化剂。用X射线衍射(XRD)、透射电镜(TEM)和X射线光电子能谱(XPS)等技术对催化剂进行了表征, 用循环伏安法和线性扫描伏安法研究了催化剂对氧的电催化还原性能。结果表明, 制备的Pd₃-Fe₁/C复合催化剂具有单相均一的合金结构, Fe进入Pd晶格改变了Pd电子结构和结构常数。电化学数据表明, Pd₃-Fe₁/C对氧还原比Pd/C催化剂有更高的电催化性能。     

Thermodynamics of duplex stainless steels

Abstract

The thermodynamic predictions of microstructures in the multicomponent alloys used for duplex stainless steels are discussed in detail in this paper. The production of the duplex ferrite–austenite microstructure by high temperature (1323–1423 K) annealing is considered. Phase diagrams are calculated for Fe–Cr–Ni ternary alloys and the more complex multicomponent systems. It is shown that there is good agreement between the predictions of the thermodynamic models and the measurements carried out on heat treated alloys. The low temperature aging behaviour of Fe–Cr–Ni ternary alloys is discussed and the limitations of activation energy approaches to the modelling of the aging process in these alloys are shown.

MST/1201     

Solidification microstructures selection of Fe–Cr–Ni and Fe–Ni alloys

The transition of solidified phases in Fe–Cr–Ni and Fe–Ni alloys was investigated from low to high growth rate ranges using a Bridgman type furnace, laser resolidification and casting into a substrate from superheated or undercooled melt. The ferrite–austenite regular eutectic growth, which is difficult to find in typical production conditions of stainless steels, was confirmed under low growth rate conditions. The transition velocity between eutectic and ferrite cell growth had a good agreement predicted by the phase selection criterion. Which of either ferrite or austenite is easier to form in the high growth range was discussed from the point of nucleation and growth. Metastable austenite formation in stable primary ferrite composition was mainly a result of growth competition between ferrite and austenite. For a binary Fe–Ni system, a planar metastable austenite in the steady state, simultaneous growth such as eutectic and banded growth between ferrite and austenite in an initial transient region are confirmed.     

Solidification microstructures selection of Fe-Cr-Ni and Fe-Ni alloys

The transition of solidified phases in Fe–Cr–Ni and Fe–Ni alloys was investigated from low to high growth rate ranges using a Bridgman type furnace, laser resolidification and casting into a substrate from superheated or undercooled melt. The ferrite-austenite regular eutectic growth, which is difficult to find in typical production conditions of stainless steels, was confirmed under low growth rate conditions. The transition velocity between eutectic and ferrite cell growth had a good agreement predicted by the phase selection criterion. Which of either ferrite or austenite is easier to form in the high growth range was discussed from the point of nucleation and growth. Metastable austenite formation in stable primary ferrite composition was mainly a result of growth competition between ferrite and austenite. For a binary Fe–Ni system, a planar metastable austenite in the steady state, simultaneous growth such as eutectic and banded growth between ferrite and austenite in an initial transient region are confirmed.     

Low temperature metal oxide film deposition and reaction kinetics in supercritical carbon dioxide

An effective method is developed for low temperature metal oxide deposition through thermal decomposition of metal diketonates in supercritical carbon dioxide (scCO₂) solvent. The rates of Al(acac)₃ (Aluminum acetyl acetonate) and Ga(acac)₃ (Gallium acetyl acetonate) thermal decomposition in scCO₂ to form conformal Al₂O₃ and Ga₂O₃ thin films on planar surfaces were investigated. The thermal decomposition reaction of Al(acac)₃ and Ga(acac)₃ was found to be initialized at  150 °C and 160 °C respectively in scCO₂ solvent, compared to  250 °C and 360 °C in analogous vacuum-based processes. By measuring the temperature dependence of the growth rates of metal oxide thin films, the apparent activation energy for the thermal decomposition of Al(acac)₃ in scCO₂ is found to be 68 ± 6 kJ/mol, in comparison with 80–100 kJ/mol observed for the corresponding vacuum-based thermal decomposition reaction. The enhanced thermal decomposition rate in scCO₂ is ascribed to the high density solvent which effectively reduces the energy of the polar transition states in the reaction pathway. Preliminary results of thin film deposition of other metal oxides including ZrO_x, FeO_x, Co₂O₃, Cr₂O₃, HfO_x from thermal decomposition of metal diketonates or fluorinated diketonates in scCO₂ are also presented.     

Evaluation of Mn substitution for Ni in alumina-forming austenitic stainless steels

There has been increasing interest in the substitution of low-cost Mn for Ni in austenitic stainless steels due to the rising price of Ni. This paper investigates the possibility of such a substitution approach for the recently developed alumina (Al₂O₃)-forming austenitic (AFA) class of heat-resistant stainless steels. Computational thermodynamic tools were utilized to predict the alloy composition range to maintain an austenitic matrix microstructure when Mn is substituted for Ni in the presence of Al, which is a strong body-centered-cubic (BCC) phase stabilizer. Phase equilibria, oxidation behavior, and creep properties of Fe–(10–14)Cr–(5–15)Mn–(4–12)Ni–(2.5–3)Al–Cu–Nb–C–B (in weight percent) based alloys were studied. The alloys based on Fe–14Cr–2.5Al–(5–9)Mn–(10–12)Ni exhibited the best balance of oxidation and creep resistance, which represents approximately 50% reduction in Ni content compared to previously developed AFA alloys. These low-Ni, high-Mn AFA alloys formed protective Al₂O₃ scales up to 973–1073 K in air and at 923 K in air with 10% water vapor. Creep-rupture lives of the alloys under a severe screening condition of 1023 K and 100 MPa were in the 7.2 × 10⁵–1.8 × 10⁶ s (200–500 h) range, which is comparable to or somewhat improved over that of type 347 stainless steel (Fe–18Cr–11Ni base).     

不锈钢表面阴极微弧电沉积氧化铝膜层的性能

以0.4 mol/L Al（NO₃）₃乙醇溶液为电解液,用阴极微弧电沉积方法在304不锈钢表面制备了80μm厚的氧化铝膜层。分析了膜层的形貌、成分和相组成,测试了膜层的抗高温氧化和电化学腐蚀性能。结果表明.电沉积膜层由γ-Al₂O₃和α-Al₂O₃组成。膜层中含有少量的Fe、Cr、Ni元素,表明膜/基界面附近的不锈钢基体在微弧放电作用下也参与氧化铝膜层的沉积和烧结过程。氧化铝膜层使不锈钢在800℃恒温氧化速率明显降低,表明其抗高温氧化性能得到提高。同时,其腐蚀电位正向移动,腐蚀电流密度降低1个数量级,表明其耐腐蚀性能得到提高。