(Ti0.25Zr0.25Nb0.25Ta0.25)C高熵陶瓷的制备、力学性能及氧化行为研究

本文通过对碳化物粉末进行放电等离子烧结(SPS),成功制备了(Ti_0.25Zr_0.25Nb_0.25Ta_0.25)C高熵陶瓷(HECs),系统研究了HECs的微观结构演变、力学性能和氧化行为。结果表明,单相HECs的形成温度为1 800 ℃,低于已报道的HECs烧结温度。1 900 ℃烧结的陶瓷晶粒细小,平均晶粒尺寸约7.5 μm,元素分布均匀,相对密度高达99.2%。1 800 ℃和1 900 ℃烧结的HECs的室温显微硬度值分别为30.9 GPa和33.2 GPa,断裂韧性值分别为(4.6±0.24) MPa·m^1/2和(4.5±0.31) MPa·m^1/2,高于大多数已报道的HECs。原位高温纳米压痕试验结果表明,HECs的硬度随温度的升高而降低,当温度达到500 ℃时,1 800 ℃和1 900 ℃烧结的陶瓷硬度分别下降到21.9 GPa和22.2 GPa,具有突出的高温稳定性。此外,HECs在温度低于500 ℃时无明显氧化,当温度超过650 ℃时会发生明显氧化,氧化速率随温度升高而增加。     

Na_(0.25)K_(0.25)Bi_(2.5)Nb_2O_9-xCaTiO_3铋层状陶瓷的结构与性能

采用传统固相法制备Na_(0.25)K_(0.25)Bi_(2.5)Nb_2O_9-x mol%CaTiO_3(NKBN-CT,x=0,0.7,1.0,2.0,3.0,4.0)铋层状无铅压电陶瓷材料。本文系统研究了CaTiO_3掺杂对Na_(0.25)K_(0.25)Bi_(2.5)Nb_2O_9基陶瓷物相结构、微观结构以及电性能的影响。结果表明:所有陶瓷材料样品均为单一的铋层状结构。随着CaTiO_3掺量的增加,Curie温度T_c呈增高趋势(653~665°C),压电常数d_(33)先增大后减小;当x=1.0时,样品的电性能达到最佳值,即d_(33)=25pC/N,介电损耗tanδ=0.42%,机械品质因数Q_m=2845,T_c=659℃。退极化研究表明NKBN-CT陶瓷样品的压电性能具有良好的热稳定性,说明CaTiO_3掺杂改性Na_(0.25)K_(0.25)Bi_(2.5)Nb_2O_9基系列陶瓷具有高温领域应用的潜力。     

Nd~(3+)掺Na_(0.25)K_(0.25)Bi_(2.5)Nb_2O_9压电陶瓷的结构与性能

采用固相法制备Na_(0.25)K_(0.25)Bi_(2.5–x)Nd_xNb_2O_9(NKBN–xNd~(3+),0≤x≤0.40,x为摩尔分数)铋层状无铅压电陶瓷,研究了不同Nd~(3+)掺杂量对NKBN–x Nd陶瓷显微结构、电学性能的影响及NKBN–0.20Nd~(3+)陶瓷高温下的电导行为。结果表明:所有样品均为单一的铋层状结构;当Nd~(3+)的掺杂量x为0.02时,样品的晶粒尺寸减小并趋于均匀,致密度提高;适量的Nd~(3+)掺杂能降低样品的介电损耗,提高NKBN陶瓷的压电常数d33。NKBN–0.20Nd~(3+)陶瓷样品的电学性能最佳:压电常数d_(33)=24 p C/N,机械品质因数Q_m=2 449,tanδ=0.40%,2P_r=1.11μC/cm~2。NKBN–0.20Nd~(3+)样品的阻抗谱表明:在高温区域陶瓷的晶粒对电传导起主要作用,当温度高于600℃时,样品主要表现为本征电导,NKBN–0.20Nd~(3+)和NKBN的电导活化能分别为1.85和1.64 e V。     

Synthesis,structure, optical and magnetic properties of Nd1−xAxMn0.5Co0.5O3−δ (A = Ba,Sr and Ca; x = 0 and 0.25)

The structural, optical, and magnetic properties of polycrystalline Nd_1-xA_xMn_0.5Co_0.5O_3−δ (A = Ba, Sr and Ca; x = 0 and 0.25) perovskite oxides were investigated. The powder XRD pattern demonstrates that the unit cell volume decreases with the changing A-site dopant type. The estimated bandgap energy (Eg) from UV–vis spectroscopic for NdMn_0.5Co_0.5O_3−δ, Nd_0.75Ba_0.25Mn_0.5Co_0.5O_3−δ, Nd_0.75Sr_0.25Mn_0.5Co_0.5O_3−δ and Nd_0.75Ca_0.25Mn_0.5Co_0.5O_3−δ are 3.27, 3.82, 3.79 and 3.53 eV respectively. The substitution of divalent element alters the absorption spectrum, while the redshift optical transition was observed with an increasing ionic radius of dopant. Temperature-dependent magnetization exposes that the Curie temperature (TC) gradually decreases with the decreasing size of alkaline earth metals, and glassy nature was observed at a lower applied magnetic field. The observation of TC can be well explained by the considering of the cationic size disorder parameter in A-site than the random distribution of B-site ions.     

CVD制备MB_2(M=Ti,Zr,Hf)研究进展

MB2(M=Ti,Zr,Hf)是ⅣB族过渡金属的硼化物,化学气相淀积(CVD)是制备MB2类薄膜材料和保护涂层的最有效技术之一。对MB2类材料CVD制备的热力学进行了简要分析。阐述了反应前驱体的选择和应用。对近年来MB2类材料的CVD合成制备的最新研究报道进行了整理和总结,对MB2类材料的CVD制备发展进程进行了概括。从CVD过程的设备工艺到产物的表征,从显微结构的定性研究到晶格常数匹配的定量分析,均进行了简要的阐述。最后,对CVD工艺制备MB2类材料的发展和应用前景进行了展望。     

Er~(3+)掺杂对Na_(0.25)K_(0.25)Bi_(2.5)Nb_2O_9压电陶瓷电学和光学性能的影响

采用传统固相法制备Na0.25K0.25Bi2.5Nb2O9+x Er(NKBN–x Er,0≤x≤0.06)铋层状无铅压电陶瓷,研究了不同Er3+掺杂量对NKBN–x Er陶瓷显微结构、电学性能及上转换荧光性能的影响。结果表明:所有样品均为单一的铋层状结构;随着Er3+掺杂量x从0增加到0.06,样品的晶粒尺寸逐渐增大,Curie温度TC升高,适量的Er3+掺杂能提高陶瓷的压电性能;电导率与温度的关系在高温区域,热激活氧空位二级电离电子电导起主导作用;在980 nm激光激发下,所有样品在513~570和644~679 nm处可观察到绿光和红光发射峰,分别对应于Er3+的2H11/2→4I15/2、4S3/2→4I15/2和4F9/2→4I15/2能级跃迁。当x=0.02时,电学性能最佳:压电常数d33=22 p C/N,介电损耗tanδ=0.38%,品质因子Qm=2 324,且样品均具有良好的荧光性能,表明该组分陶瓷可作为高温应用光—电多功能材料。     

Influence of Al-substitution on structures,resistivity and magnetic properties of LaxSr(2−x)Fe(1+y)Mo(1−y)O6 (x=3y,y=0.05, 0.1, 0.15, 0.2)

Two series of single-phased La_xSr_(2−x)Fe_(1+y)Mo_(1−y)O₆ and La_xSr_(2−x)Fe_(1+0.5y)Al_0.5yMo_(1−y)O₆ (x=3y, y=0.05, 0.1, 0.15 and 0.2) double perovskites were prepared by solid-state reaction. The effects of Al-substitution on the structures, resistivity and magnetic properties of La_xSr_(2−x)Fe_(1+y)Mo_(1−y)O₆ were investigated. Although Al-replacement exhibits a negligible influence of on the B-site ordering degree, it results in the suppression of magnetisation caused by non-magnetic Al³⁺ ions. Reduction of grain sizes leads to increased resistivity, thus an optimised magnetoresistance (MR) behaviour is observed. The greatest MR extent improvement can be obtained when y is 0.15 and the MR% of the Al-doped ceramics reaches −10.5% (10 K, 1 T), which is 2 times greater than that of the undoped ceramics (−4.6%, 10 K, 1 T). Interestingly, the Curie temperature (Tc) of both Al-doped and undoped samples maintained relatively constant values of approximately 420 K and 405 K, respectively, which were different results from the data obtained for similar electron-doping systems in the literature.     

Nd^(3+)掺Na_(0.25)K_(0.25)Bi_(2.5)Nb_2O_9压电陶瓷的结构与性能EI北大核心CSCD

采用固相法制备Na_(0.25)K_(0.25)Bi_(2.5–x)Nd_xNb_2O_9(NKBN–xNd^(3+),0≤x≤0.40,x为摩尔分数)铋层状无铅压电陶瓷,研究了不同Nd^(3+)掺杂量对NKBN–x Nd陶瓷显微结构、电学性能的影响及NKBN–0.20Nd^(3+)陶瓷高温下的电导行为。结果表明:所有样品均为单一的铋层状结构;当Nd^(3+)的掺杂量x为0.02时,样品的晶粒尺寸减小并趋于均匀,致密度提高;适量的Nd^(3+)掺杂能降低样品的介电损耗,提高NKBN陶瓷的压电常数d33。NKBN–0.20Nd^(3+)陶瓷样品的电学性能最佳:压电常数d_(33)=24 p C/N,机械品质因数Q_m=2 449,tanδ=0.40%,2P_r=1.11μC/cm^2。NKBN–0.20Nd^(3+)样品的阻抗谱表明:在高温区域陶瓷的晶粒对电传导起主要作用,当温度高于600℃时,样品主要表现为本征电导,NKBN–0.20Nd^(3+)和NKBN的电导活化能分别为1.85和1.64 e V。     

Ho~(3+)掺杂Na_(0.25)K_(0.25)Bi_(2.5)Nb_2O_9陶瓷的结构、电学和上转换发光性能

采用传统固相法制备了Na_(0.25)K_(0.25)Bi_(2.5–x)Ho_xNb_2O_9(NKBN–x Ho~(3+),0.000≤x≤0.030)铋层状陶瓷,研究了Ho~(3+)掺杂对NKBN陶瓷结构、电学和上转换发光性能的影响。X射线衍射谱表明Ho~(3+)进入NKBN晶格形成了固溶体。随着Ho3+掺杂量的增加,NKBN陶瓷的晶粒尺寸降低,当x=0.020时,样品的压电和铁电性能均达到最佳:d_(33)=21.8pC/N2Pr=1.84μC/cm。(d_(33)为压电常数,Pr为剩余极化强度)所有样品在400℃均未出现明显的退极化现象,在高温下表现出良好的压电稳定性。在980 nm激光激发下,所有陶瓷样品均表现出上转换荧光发光特性,表明NKBN–x Ho~(3+)陶瓷在光电多功能材料领域具有潜在的应用价值。随着极化电压的增加,陶瓷样品的晶格结构对称性提高,上转换荧光发光强度降低。     

Ge-Ga-X(X=S,Se)系统玻璃的研究

本文研究了该系统玻璃的生成范围,观察了玻璃中晶相的形貌,并鉴定了它们的组成,进行了结构分析。认为该系统是由[GeX_4]、[GaX_4]等结构单元组成的。玻璃的红外透过范围分别为0.5—11.5和0.7—14μm,是优良的红外材料。最后讨论了它们的成分、结构和性质之间的关系。     

Ce掺杂Na_(0.25)K_(0.25)Bi_(2.5)Nb_2O_9-0.4wt%Cr_2O_3高温无铅压电陶瓷的研究

采用固相法制备了Na0.25K0.25Bi2.5Nb2O9-0.4wt%Cr2O3-xwt%CeO2(x=0.00~1.00)高温无铅压电陶瓷,研究了Ce掺杂对该系列陶瓷微观结构及电性能的影响。结果表明所有样品均为单一的铋层状结构陶瓷,适量的Ce掺杂明显改善了陶瓷的压电与铁电性能,降低了陶瓷的电导率和介电损耗。当掺杂量x=0.50时,样品具有最佳性能:d33=27 pC/N,tanδ=0.09%,kp=7.97%,Qm=2637,Tc=656℃,Ec=46 kV/cm和Pr=4.4μC/cm2,表明该材料在高温领域内具有良好的应用前景。     

Crystal Structure,Chemical Bonding and Magnetism Studies for Three Quinary Polar Intermetallic Compounds in the (Eu1?xCax)9In8(Ge1?ySny)8 (x = 0.66, y = 0.03) and the (Eu1?xCax)3In(Ge3?ySn1+y) (x = 0.66, 0.68; y = 0.13, 0.27) Phases

Three quinary polar intermetallic compounds in the (Eu_1−xCa_x)₉In₈(Ge_1−ySn_y)₈ (x = 0.66, y = 0.03) and the (Eu_1−xCa_x)₃In(Ge_3-ySn_1+y) (x = 0.66, 0.68; y = 0.13, 0.27) phases have been synthesized using the molten In-metal flux method, and the crystal structures are characterized by powder and single-crystal X-ray diffractions. Two orthorhombic structural types can be viewed as an assembly of polyanionic frameworks consisting of the In(Ge/Sn)₄ tetrahedral chains, the bridging Ge₂ dimers, either the annulene-like “12-membered rings” for the (Eu_1−xCa_x)₉In₈(Ge_1−ySn_y)₈ series or the cis-trans Ge/Sn-chains for the (Eu_1−xCa_x)₃In(Ge_3−ySn_1+y) series, and several Eu/Ca-mixed cations. The most noticeable difference between two structural types is the amount and the location of the Sn-substitution for Ge: only a partial substitution (11%) occurs at the In(Ge/Sn)₄ tetrahedron in the (Eu_1−xCa_x)₉In₈(Ge_1−ySn_y)₈ series, whereas both a complete and a partial substitution (up to 27%) are observed, respectively, at the cis-trans Ge/Sn-chain and at the In(Ge/Sn)₄ tetrahedron in the (Eu_1−xCa_x)₃In(Ge_3−ySn_1+y) series. A series of tight-binding linear muffin-tin orbital calculations is conducted to understand overall electronic structures and chemical bonding among components. Magnetic susceptibility measurement indicates a ferromagnetic ordering of Eu atoms below 5 K for Eu_1.02(1)Ca_1.98InGe_2.87(1)Sn_1.13.     

白光LED用Ca_(0.5-y)WO_4:Eu_(0.25)~(3+),Li_(0.25)~+,Sm)y~(3+)红色荧光粉的合成及发光特性

采用固相法制备了白光LED红色荧光粉Ca_(0.71)WO_4:Sm_(0.04)~(3+)Li_(0.250)~+和Ca_(0.5-y)WO_4:Eu_(0.25)~(3+),Li_(0.25)~+,Sm_y~(3+)(y=0.00,0.02,0.04,0.06),通过X射线衍射(XRD)、荧光分光光度计以及稳态/瞬态荧光光谱仪研究了荧光粉样品的物相、Sm~(3+)的掺杂量对荧光粉发光性能以及荧光寿命的影响。XRD分析表明,合成的样品均为白钨矿结构。荧光光谱表明,所合成的系列荧光粉均可以被近紫外光(393 nm)和蓝光(464 nm)有效激发,其发射主峰位于615 nm处,归属于Eu~(3+)的~5D_0→~7F_2跃迁。发光衰减曲线表明,Sm~(3+)的掺杂对荧光粉Ca_(0.5)WO_4:Eu_(0.25)~(3+),Li_(0.25)~+荧光寿命没有影响。实验结果表明,在系列Ca_(0.5-y)WO_4:Eu_(0.25)~(3+),Li_(0.25)~+,Sm~(3+)荧光粉中Sm~(3+)的最佳掺杂量为4%(摩尔分数)。     

一种制备Me_xSe_y(Me=Cu,In,Ga)的简便工艺

提出了一种制备太阳能电池靶材CIGS的中间产物Cu2Se、In2Se3和Ga2Se3的简便工艺。以高纯铜粉、铟块、镓块、硒粉为原料,根据中间产物的化学计量比配制混合粉末,先进行热分析,然后将粉末装入石英管中,在抽真空的状态下用乙炔火焰将石英管密封,分别加热到300℃、500℃、650℃和770℃,最后打破石英管取出产物研成粉末,进行XRD分析。结果表明:在升温速率为1℃·min-1、冷却方式为炉冷的条件下,300℃保温3h得到单相的Cu2Se;300℃、500℃和650℃分别保温3h,得到单相的In2Se3;300℃、500℃、650℃和770℃分别保温3h,得到Ga2Se3相和少量的GaSe相。     

AM_2O_8(A=Zr,Hf;M=Mo,W)氧化物粉体的低温 液相合成及其结构控制(英文)

立方AM2O8氧化物(A=Zr,Hf:M=Mo,W)是最有希望的一类负热膨胀材料.为开发这类材料,期望获得高质量AM2O8粉体,而传统固相合成法不能达到这一目的.低温液相合成法是一种有望合成高质量AM2O8氧化物粉体的途径.本文介绍了1998年以来低温液相合成AM2O8粉体的研究进展,首先,概述了AM2O7(OH)2·2H2O脱水的合成工艺,其后讨论了用于制备醇盐或羧酸盐前驱体的凝胶技术.着重讨论了材料结构控制问题, 并提出了进一步研究方向.     

稀土配合物[Ln(C_3H_7NO_2)_x(C_3H_4N_2)(H_2O)](ClO_4)_3(Ln=La,x=3;Ln=Pr,Nd,Sm,x=2)的合成、表征与热分析

合成了稀土高氯酸盐与咪唑、DL α 丙氨酸的4种配合物晶体。经傅里叶变换红外光谱(FTIR)、元素分析和化学分析测定后确定其组成为[Ln(C3H7NO2)x(C3H4N2)(H2O)](ClO4)3(Ln=La,x=3;Ln=Pr,Nd,Sm,x=2)。用差示扫描量热法(DSC)测定了4种配合物的热分解数据,4个配合物开始熔化分解的温度分别为502 5K,532 4K,495 7K,516 7K,配合物有较高的热稳定性。     

Chemistry of soluble β-diketiminatoalkaline-earth metal complexes with M-X bonds (M=Mg, Ca, Sr; X=OH, Halides, H)

Victor Grignard's Nobel Prize-winning preparation of organomagnesium halides (Grignard reagents) marked the formal beginning of organometallic chemistry with alkaline earth metals. Further development of this invaluable synthetic route, RX+Mg→RMgX, with the heavier alkaline earth metals (Ca and Sr) was hampered by limitations in synthetic methodologies. Moreover, the lack of suitable ligands for stabilizing the reactive target molecules, particularly with the more electropositive Ca and Sr, was another obstacle. The absence in the literature, until just recently, of fundamental alkaline earth metal complexes with M-H, M-F, and M-OH (where M is the Group 2 metal Mg, Ca, or Sr) bonds amenable for organometallic reactions is remarkable. The progress in isolating various unstable compounds of p-block elements with β-diketiminate ligands was recently applied to Group 2 chemistry. The monoanionic β-diketiminate ligands are versatile tools for addressing synthetic challenges, as amply demonstrated with alkaline earth complexes: the synthesis and structural characterization of soluble β-diketiminatocalcium hydroxide, β-diketiminatostrontium hydroxide, and β-diketiminatocalcium fluoride are just a few examples of our contribution to this area of research. To advance the chemistry beyond synthesis, we have investigated the reactivity and potential for applications of these species, for example, through the demonstration of dip coating surfaces with CaCO(3) and CaF(2) with solutions of the calcium hydroxide and calcium fluoride complexes, respectively. In this Account, we summarize some recent developments in alkaline earth metal complex chemistry, particularly of Mg, Ca, and Sr, through the utilization of β-diketiminate ligands. We focus on results generated in our laboratory but give due mention to work from other groups as well. We also highlight the closely related chemistry of the Group 12 element Zn, as well as the important chemistry developed by other groups using the complexes we have reported. Although Mg and Ca are more abundant in living organisms, no other metal has as many biological functions as Zn. Thus Zn, the nontoxic alternative to the heavier Group 12 elements Cd and Hg, occupies a unique position ripe for further exploration.     

20%BaCO_3/La_(0.8)Sr_(0.2)MO_3(M=Fe,Co,Mn)催化分解NO的研究

通过NO程序升温吸附脱附(NO-TPD)分析测试手段,研究了20%BaCO3/La0.8Sr0.2MO3(M=Fe、Co、Mn)催化分解NO的机理,解释La0.8Sr0.2MO3(M=Fe、Co、Mn)与BaCO3简单混合后催化分解NO的性能提升的原因。