Mossbauer spectroscopy study of Fe-57 in R3Fe29-xTx (R=Y, Ce, Nd, Sm, Gd, Tb and Dy; T=V and Cr)

Fe-57 Mossbauer spectra for the Fe atoms in the R3Fe29-xTx (R=Y, Ce, Nd, Sm, Gd, Tb, Dy; T=V, Cr) compounds were collected at 4.2 K. The analysis of Mossbauer spectra was based on the results of magnetization and neutron powder diffraction measurements. The average Fe magnetic moments at 4.2 K, deduced from our data, are in accord with magnetization measurements. The average hyperfine field of Tb3Fe29-xCrx (x=1.0, 1.5, 2.0, and 3.0) decreases with increasing Cr concentration, which is also in accordance with the variation of the average Fe magnetic moment in the Tb3Fe29-xCrx compounds.

Crystallographic and magnetic properties of hydride R3Fe29-xTxHy (R=Y, Ce, Nd, Sm, Gd, Tb and Dy; T=V and Cr)

The crystallographic and intrinsic magnetic properties of hydride R3Fe29-xTxHy (R=Y, Ce, Nd, Sm, Gd, Tb, and Dy; T=V and Cr) have been investigated. The lattice constants and the unit cell volume of R3Fe29-xTxHy decrease with increasing R atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Regular anisotropic expansions, mainly along the a- and b-axis rather than along the c-axis, are observed for all the compounds upon hydrogenation. Hydrogenation leads to an increase in Curie temperature. First-order magnetization processes (FOMP) occur in magnetic fields of around 1.5 T and 4.0 T at 4.2 K for Nd3Fe24.5Cr4.5H5.0 and Tb(3)Fc(27.0)Cr(2.0)H(2.8), and around 1.4 T at room temperature for Gd3Fe28.0Cr1.0H4.2 Abnormal crystallographic and magnetic properties of Ce3Fe29-xTxHy suggest that the Ce ion is non-triply ionized.

Hydrogenation and anisotropic expansions in R3Fe29-xTx (R = Y, Ce, Nd, Sm, Gd, Tb and Dy; T = V and Cr)

A systematic study of the phase formation, structure and magnetic properties of the R3Fe29-xTx compounds (R=Y, Ce, Nd, Sm, Gd, Tb, and Dy; T=V and Cr) has been performed upon hydrogenation. The lattice constants and the unit cell volume of R3Fe29-xTxHy decrease with increasing R atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Regular anisotropic expansions mainly along the a- and b-axis rather than along the c-axis are observed for all of the compounds upon hydrogenation. Hydrogenation leads to an increase in the Curie temperature and a corresponding increase in the saturation magnetization at room temperature for each compound. First order magnetization processes (FOMP) occur in the external magnetic fields for Nd3Fe24.5Cr4.5H5.0, Tb3Fe27.0Cr2.0H2.8, and Gd3Fe28.0Cr1.0H4.2 compounds.

Structural and magnetic properties of hydrides R3Fe29-xVxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy)

A systematic investigation of crystallographic and intrinsic magnetic properties of the hydrides R3Fe29 - xVxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed in this work. The lattice constants a, b, and c and the unit cell volume of R3Fe29 - xVxHy decrease with increasing rare-earth atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Hydrogenation results in regular anisotropic expansions along the a-, b-, and c-axes in this series of hydrides. Abnormal crystallographic and magnetic properties of Ce3Fe27.5V1.5H6.5, like Ce3Fe27.5V1.5, suggest that the Ce ion is non-triply ionized. Hydrogenation leads to the increase in both Curie temperature for all the compounds and in the saturation magnetization at 4.2 K and RT for R3Fe29 - xVx with R = Y, Ce, Nd, Sm, Gd, and Dy, except for Tb. Hydrogenation also leads to a decrease in the anisotropy field at 4.2 K and RT for R3Fe29 - xVx with R = Y, Ce, Nd, Gd, Tb, and Dy, except for Sm. The Ce3Fe27.5V1.5 and Gd3Fe28.4V0.6 show the larger storage of hydrogen with y = 6.5 and 6.9 in these hydrides. (C) 1998 Elsevier Science B.V. All rights reserved.

Crystallographic and magnetic properties of the hydrides R3Fe29-xCrxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy)

A systematic study of the structural and intrinsic magnetic properties of the hydrides R3Fe29-xCrxHy (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed. Hydrogenation lends to a relative volume expansion of the unit cell and a decrease in x-ray density for each compound. Anisotropic expansions mainly along the n- and b-axes rather than along the c-axis for all of the compounds upon hydrogenation are observed. The lattice constants and the unit-cell volume of R3Fe29-xCrx and R3Fe29-xCrxHy decrease with increasing R atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Hydrogenation results in an increase in the Curie temperature and a corresponding increase in the saturation magnetization at room temperature for each compound. After hydrogenation a decrease of 0.34 mu(B)/Fe in the average Fe atomic magnetic moment and a slight increase in the anisotropy field for Y3Fe27.2Cr1.8 are achieved at 4.2 K. First-order magnetization processes (FOMP) occur in magnetic fields of around 1.5 T and 4.0 T at 4.2 K for Nd3Fe24.5Cr4.5H5.0 and TD3Fe27.0Cr2.0H2.8, and around 1.4 T at room temperature for Gd3Fe28.0Cr1.0H4.2. The abnormal crystallographic and magnetic properties of Ce3Fe25.0Cr4.0 and Ce3Fe25.0Cr4.0H5.4 suggest that the Ce ion non-triply ionized.

Crystallographic and magnetic properties of nitride R3Fe29-xCrxN4 (R = Y, Ca, Nd, Sm, Gd, Tb, and Dy)

A systematic investigation of crystallographic and magnetic properties of nitride R3Fe29-xCrxN4 (R=Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed. The lattice constants and unit cell volume decrease with increasing rare earth atomic number from Nd to Dy, reflecting the lanthanide contraction. After nitrogenation the relative volume expansion of each nitride is around between 5% and 7%. The nitrogenation results in a good improvement in the Curie temperature, the saturation magnetization and anisotropy fields at 4.2 K, and room temperature for R3Fe29-xCrxN4. Magnetohistory effects of R3Fe29-xCrxN4 and R3Fe29-xCrx (R=Nd and Sm) are observed in a low field of 0.04 T. First order magnetization process occurs in Sm3Fe24.0Cr5.0N4 in magnetic fields of 2.8 T at 4.2 K. After nitrogenation, the easy magnetization direction of Sm3Fe24.0Cr5.0 is changed from the easy-cone structure to the uniaxial. The good intrinsic magnetic properties of Sm3Fe24.0Cr5.0N4 make this compound a hopeful candidate for new high-performance hard magnets. (C) 1998 American Institute of Physics.

Crystallographic and magnetic properties of R3Fe29-xVxN4 (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy)

A systematic investigation of crystallographic and magnetic properties of nitride R3Fe29-xVxN4 (R = Y, Ce, Nd, Sm, Gd, Tb, and Dy) has been performed. Nitrogenation leads to a relative volume expansion of about 6%. The lattice constants and unit cell volume decrease with increasing rare-earth atomic number from Nd to Dy, reflecting the lanthanide contraction. On average, the Curie temperature increases due to the nitrogenation to about 200 K compared with its parent compound. Generally speaking, nitrogenation also results in a remarkable improvement of the saturation magnetization and anisotropy fields at 4.2 K and room temperature for R3Fe29-xVxN4 compared with their parent compounds. The transition temperature indicates the spin reorientations of R3Fe29-xVxN4 for R = Nd and Sm are at around 375 and 370 K which are higher than that of R3Fe29-xVx, for R = Nd and Sm 145 and 140 K, respectively. The magnetohistory effects of R3Fe29-xVxN4 (R = Ce, Nd, and Sm) are observed in low fields of 0.04 T. After nitrogenation the easy magnetization direction of Sm3Fe26.7V2.3 is changed from an easy-cone structure to the b-axis. As a preliminary result, a maximum remanence B-r of 0.94 T, an intrinsic coercivity mu(0)H(C) of 0.75 T, and a maximum energy product (B H)(max) of 108.5 kJ m(-3) for the nitride magnet Sm3Fe26.7V2.3N4 are achieved by ball-milling at 293 K.

Enhanced fiber Bragg grating sensor demodulation technique using cascade wavelength division multiplex couplers

An enhanced technique for interrogating fiber Bragg grating wavelength shift using cascade wavelength division multiplexer (WDM) couplers was proposed and demonstrated. Three WDM couplers which show a linear filter function over the expected wavelength range are employed and cascaded to track Bragg wavelength shifts. Compared with single WDM demodulator. sharper spectral slope is obtained and considerable linear filter range is kept. The static and dynamic strain sensor demodulation experiments demonstrated that the simple passive technique improves the sensitivity approximately two times and keeps 5nm linear demodulation range based on our devices. The cascade WDM coupler demodulation system has high scan rate which can be used to monitor fast vibration.

稀土(Er, Nd, Yb, Pr, Ho, Sm)有机/无机杂化材料的制备及发光性能研究

目前，国内外对于铕和铽等稀土配合物的可见区发光和应用都有大量研究，但对具有近红外发光（800-1700 nm）性能的稀土配合物的研究还处于起步阶段。由于稀土的近红外发光在光纤通讯、激光系统及诊断学等方面应用具有特殊的优点，越来越引起人们的兴趣和重视。 稀土近红外发光配合物的致命弱点是其光、热和化学稳定性较差，从而限制了其在很多领域的实际应用。而溶胶－凝胶材料和介孔材料具有良好的光、热和化学稳定性，能改善客体分子的结构环境和化学微环境，从而能有效提高客体分子的发光性能。因此，本论文将具有优良近红外发光性能的稀土配合物分别与上述两种基质复合，从实验和理论研究稀土近红外发光杂化材料的性能和应用价值，制备出具有良好稳定性的高效稀土近红外发光杂化材料，以期为光纤通讯、激光等领域提供潜在的候选材料。围绕这一宗旨，开展了如下工作： 通过原位技术分别得到了掺杂和嫁接[Ln(dbm)3phen]化合物（Ln = Er, Nd, Yb）的杂化凝胶材料，Ln-D-P gel和Xerogel-Ln。通过对其近红外发光性能的研究，表明材料中配体能很好的保护稀土离子，并将能量有效的传递给稀土离子。采用Judd-Ofelt理论对所得部分材料进行了光谱分析，基于实验数据和理论分析表明其具有潜在的光放大和激光应用价值。 选择了两种含全氟化烷基链的β-二酮配体Hhfth和Htfnb，通过功能化的phen-Si配体，将三元配合物[Ln(hfth)3phen] (Ln = Er, Nd, Yb, Sm)和[Pr(tfnb)3phen]成功共价嫁接到介孔MCM-41和SBA-15杂化材料中，得到的衍生材料Ln(hfth)3phen–MCM-41、Pr(tfnb)3phen–MCM-41和Ln(hfth)3phen–SBA-15、Pr(tfnb)3phen–SBA-15都保持了高度有序的介孔p6mm结构，并展现出稀土离子特征的近红外发射。所得稀土配合物功能化的材料的发射光谱能完全覆盖对光通讯极具应用价值的1300-1600nm区域。 通过对Er(dbm)3phen–M41(X, Y) (X = 1~14, Y = 3, 6, 12, 18, 24 h)材料系统的比较研究，选择了X = 12, Y = 6作为合成目标材料的优化参数，通过功能化的phen-Si配体将[Ln(dbm)3phen]配合物共价嫁接于有序介孔MCM-41和SBA-15中(Ln = Er, Nd, Yb)，所得两类材料Ln(dbm)3phenM41和Ln(dbm)3phenS15都保持了很好的介孔有序性，并具有良好的近红外发光性能。通过对Ln(dbm)3phenM41和Ln(dbm)3phenS15两类材料发光行为的比较，以及两类材料中稀土离子的含量及孔结构的分析，推出以SBA-15为载体得到的材料在相对发光强度和荧光寿命上，均比以MCM-41为载体的材料有所提高。 通过对8－羟基喹啉配体进行改性，合成了具有双功能的配体Q-Si，继而合成了共价嫁接8－羟基喹啉衍生物的介孔杂化材料Q–SBA-15，其形貌均一，并具有高度有序的介孔p6mm结构。通过配体交换反应，得到了嫁接稀土喹啉配合物的具有近红外发光性能的介孔杂化材料LnQ3–SBA-15 (Ln = Er, Nd, Yb)，其仍然保持高度有序的介孔结构，且外形呈现与母体材料Q–SBA-15相似的弯曲圆柱状。激发配体的吸收，LnQ3–SBA-15材料都分别展现出相应稀土离子特征的近红外发射，并详细分析和讨论了所得介孔杂化材料的近红外发光性能。

溶胶-凝胶软石印法制备稀土发光薄膜及其图案化

利用溶胶-凝胶法合成了一系列稀土离子掺杂的发光薄膜，包括三元氧磷灰石稀土硅酸盐Ca2RS（SiO4）6O2（R＝YGd）体系，YVO4体系，LaPO4体系以及钒磷酸盐形成的固熔体体系1并研究了稀土离子Eu3+，Tb3+，Dy3+，Sm3+，Er3+和类汞离子Pb2＋在这些薄膜中的发光性质和能量传递性质。同时利用软石印法结合毛细管微模板技术实现了发光薄膜的图案化。SEM以及AFM结果表明，利用溶胶一凝胶法制备的发光薄膜表面致密均匀，无开裂。通过增加镀膜溶液的粘度、镀膜的次数可以有效的控制薄膜的厚度，使其达到理想的范围。由此可见溶胶一凝胶法是一种比较理想的制备发光薄膜的方法。在三元氧磷灰石稀土硅酸盐Ca2R8（SiO4）6O2（R＝YGd）体系中，稀土离子Eu3+，Tb3+在Ca2Y8（SiO4）6O2基质中占据低刘·称性格位6h（Cs）和4f（C3），并以其特征的红光发射（5Do-7F2）和绿光发射（5D4-7F5）为主。Eu3+，Tb3+发光的最佳浓度分别为Y3+的10mol％和6mol％，Ca2Y8（51O4）6O2:Eu3＋薄膜样品的发光强度和寿命随着烧结温度的升高而增加，Ca2Y8（SiO4）6O2:Tb3+薄膜样品的发光强度和寿命在800℃时最大，随后又随烧结温度的升高有所下降，Pb2＋可以敏化Ca2Gd8（SiO4 ）6O2中Gd3+的基质晶格，通过Pb2＋→Gd3十→（Gd3＋）n→A3＋形式传递和转移能量。在YVO4体系中，利用Pechini溶胶一凝胶法以无机盐为主要原料，柠檬酸为络合剂，利用聚乙二醇调节镀膜溶液的粘度，制备了YvO4:A（A＝Eu3＋ Dy3＋，Sm3＋，Er3＋）纳米发光薄膜。结合软石印法，通过简单工艺实现了发光薄膜图案化烧结过程中图案化薄膜有一定程度的收缩，存在一定的缺陷。得到的条纹在紫外灯下发出明亮的红光。掺杂的稀土离子在YVO4薄膜中显示它们特征发射，同时VO43-和稀土离子之间存在能量传递。Dy3＋，Sm3＋，Er3十发光的最佳浓度皆为Y3+的2mol％，这三者的发光淬灭是由交叉驰豫引起的。在LaPO4发光薄膜中，Etl3+以591nm的5Do-7Fl跃迁发射为主，呈现红橙光；Tb3＋以543nm的5D4-7F5发射为主，属于绿光发射。Ce3＋则由其特有的5d-4f双峰发射组成。Tb3＋和Eu3+掺杂的样品发光强度和荧光寿命随烧结温度的升局而增加。Tb3+和Eu3+的寿命曲线符合指数衰减，但Tb3十在LaPO4:Ce，Tb薄膜中，所得的寿命曲线不符合单指数衰减。Ce3+和Tb3+之间存在吸收能量传递。通过计算得到能量传递效率可以达到95％以上。XRD结果表明，从x＝0到x＝1 YVxP1-xO4:Eu3+薄膜形成了一系列具有错石结构的固熔体。在YVxP1-xO4:Eu3+（0≤x≤1）系列薄膜中，随着x值的增加，Eu3+的发光强度和红橙比逐渐增大。除x＝0，其它的Eu3+的红橙比都大于1，说明在发射光谱中，以Eu3+禁戒5Do一7F2电偶极跃迁为主，Etls十在基质中处于低对称性格位。当x＝0时，即Y0.98Eu0.l2PO4薄膜中，Eu3+，仍处于D2d低对称性格位，但5D0一7FI橙光发射却比SD0一7F2红光发射强。x对Y0.98Eu0.02VxP1-xO4（0≤x≤l）薄膜寿命曲线有很大的影响，当0≤x≤0.5时，Eu3+5 D0-7F2发射呈单指数衰减；当x≥0.6时，Eu3+5D0-7F2发射的衰减曲线比较复杂，不能用单指数拟合。YVxP1-xO4:A3＋（0≤x≤1，A＝Er，Sm）薄膜中，由于存在VO43-A3+，以及VO43-（VO43-）n-A3+（n≥1）形式的能量传递，同时由于浓度淬灭，VO43-的蓝光发射在0.1≤x≤1范围内，随x的增加而减弱，当x＝1时，VO43-的蓝光发射被完全淬灭，而A3+发光强度随x的增加而增加。在RVO4:A3+（R＝Y，La，Gd，A＝Eu，Sm，Er）纳米发光薄膜中，R对稀土离子发光性质的影响主要是由于基质晶体结构的不同。A3+在YVO4和GdVO4中属于D2d对称性，在YVO4和GdVO4薄膜中A3+的光谱性质基本相同，而LaVO4属于单斜晶系，具有独居石结构。A3+在LaVO4中属于C1对称性。C1对称性比D2d对称性低，A3+的发光光谱中谱线的位置以及谱线的劈裂数目都略有不同。由于Gd3+和发光离子之间的能量传递，A3+在GdVO4基质中的发光最强。

镍-金属氢化物电池新型负极材料研究

贮氢合金是镍一金属氢化物电池的核心材料，其综合性能的改善是提高镍一金属氢化物电池性能的关键。本研究以探索镍一金属氢化物电池新型负极材料为目的，以非ABS型贮氢合金为研究对象，采用X射线衍射、Rietveld分析、恒电流充／放电、P-C-T曲线及线性微极化等方法，从基础和潜在应用等方面详细研究了非ABS型合金的结构与电化学性能。对La-Ni体系中非ABS型二元合金的结构和电化学性能的研究表明，LaNi_(228)具有最优异的高倍率充电性能；La_2Ni_7合金电极的高倍率放电性能最佳；La_7Ni_3在低温条件下表现出较好的放电性能。然而，所有得到的La-Ni合金电极容量远低于其理论容量。因此，必须通过进一步研究，如元素取代、热处理、表面处理等来提高其电化学容量。对RENi_3（RE＝La，Ce，Pr，Nd，Sm，Gd，Th，Dy，Ho，Er，Y）研究表明：YNi_3合金因其具有最大的晶胞体积，最小的密度，而表现出最好的高倍率充／放电性能及低温放电性能，但其高温放电性能需要进一步提高，以满足实际应用的要求。用Al、Mn、Ti、Fe、Sn、Si、Cr、M。、Cu和Co十种元素取代Ni进行了大量的配方筛选工作。得到了大量的实验数据，并发现LaNi_(3.7)Al_(0.3)合金电极电化学放电容量最高，达290.8mAh／g；LaNi_(3.7)Mo_(0.3)合金电极的高倍率放电性能最好，在以4200mA/g的电流密度下进行放电时，其放电容量仍达到145.8mA/g；而I镍一金属氢化物电池新型负极材料研究镍一金属氢化物电池新型负极材料的研究Al的取代会使合金电极性能对温度不敏感。以我们的实验为基础，进一步进行合金配方的微调，具有可能开发出具有实用价值的贮氢合金的潜力。在Ar保护下用真空电弧炉熔炼合成了四种Lal一xMg：（NICoAI）3．6体系贮氢合金，制成姐卜Ni电池负极，通过恒电流充／放电方法研究了其电化学性能。结果表明：Lal一xMg：（NiCoAI）3．6体系金属氢化物电极较容易活化，室温下具有优异的高倍率放电性能，在以4200mA／g电流放电时，La卜汉gx（NICoAI）36合金电极的放电容量是ABS型合金电极的3倍，达152hah／g，显示出良好的动力学特性。R，入1兮Ni（R：raree田劝，Ca，Y）型合金因能吸引／释放1．8一1．87％质量的HZ而被认为是种很有希望的贮氢合金。但其吸／放氢平台过高，循环寿命短。如何提高Rh厦g剑19循环稳定性是这类合金能否成功商业化的关键。研究发现，Co能够显著提高ABS型合金电极的循环寿命，但其价格太贵。人们发现Al在提高电极寿命方面与C。有类似的作用，但Al元素的添加因其在碱性电解质的作用下在电极表面易生成致密的氧化膜而不利于氢的扩散，进而对高倍率放电性能不利。入物在提高电极表面活性，改善其高倍率放电性方面作用明显。本工作在前面的基础上用Al和MO联合取代Ni，以期待同时改善La一Mg一Ni一Co合金的循环稳定性和高倍率放电性能。详细研究了La07Mg03Ni切一（A105Mo05）x（x：o，0．2，0．4，0．6，0．8）系列贮氢合金的晶体结构和电化学性能。X射线衍射及Rietveld分析发现：所有La07Mg03Ni4D一x（A105Mo05）x合金均为包含PuNi3结构的六方LaZMgNig相、CaCus结构的LaNis主相及L匆Ni7，LaN儿和LaNi杂相的多相结构。合金中La（La，Mg）剑19相及LaNis相的晶格参数及晶胞体积均随合金中Al和Mo含量的增加而增大。用电化学方法测得的RC一T曲线显示：Al和'fo部分取代Ni降低了氢的平台压力。随合金中Al和Mo含量的增加，电极的电化学容量从329．7（x＝0）、徽橇毓孺鑫盆一11瀚加至365．物A吨（＝0．6）后又降低到351．3毗吨（x＝0．8）。当以1200m刀g的电流密度进行放电时，其I｛RD从62．0％沁0）增加到82．1％沁0．8）。线性微极化结果显示：Al和Mo的添加增大了合金表面的交换电流密度，因而也改善了合金电极的高倍率放电性能。另外，Al和M。取代合金中的Ni增大了氢在电极合金中的扩散系数（D），改善了La07Mgo3Ni4。一x（Alo5M。。5）x（X＝o，0．2，0．4，0．6，0．8）合金电极的低温放电性能（LTD）。