还原扩散法制备钐铁氮磁性材料的组织结构与性能研究

研究了还原扩散法制备Sm2Fe17Nx(x≈3)磁性材料的组织结构与性能。用DTA方法测定了Sm2Fe17Nx的热稳定性,用VSM测定了本实验所制Sm2Fe17Nx磁体的磁滞回线和退磁曲线;用TEM及高分辨电镜分析了渗氮前后Sm2Fe17合金及Sm2Fe17Nx结构。结果表明:Sm2Fe17Nx的分解温度为841 K,用还原扩散法制备的Sm2Fe17Nx磁粉做成粘结磁体后各向异性不是很强烈,性能偏低。Sm2Fe17Nx磁粉磁性的好差与渗氮层的厚度有密切的关系,渗氮后的Sm2Fe17Nx确实有体积膨胀的现象,而且属非晶结构。     

稀土氧化镱对La-Mg-Ni系A2B7型储氢合金电极性能的影响

研究了分别添加纳米和微米级稀土氧化物Yb2O3(%,质量分数)后对La-Mg-Ni系A2B7型储氢合金电极电化学性能的影响。研究结果表明,添加Yb2O3能有效抑制合金电极表面La(OH)3和Mg(OH)2析出,随Yb2O3含量增加,La-Mg-Ni系A2B7型储氢合金电极的循环稳定性提高,但电极放电容量有所降低,电极动力学反应极化增加;Yb2O3粉末颗粒尺寸和团聚状态对合金电极性能影响比较明显,添加纳米级/微米级Yb2O3后均降低了合金电极放电容量,其中微米级Yb2O3对合金电极循环稳定性的改善效果更为明显。合金电极的循环稳定性与其放电过程的截止电位(-0.8～-0.6 V,相对Hg/HgO电极)有关,随截止电位减小,合金腐蚀倾向增加,电极循环寿命变差;Yb2O3在截止电位区间发生的电化学氧化-还原反应与储氢合金电极循环稳定性关系密切。     

用N2O-C2H2火焰原子吸收光谱法测定膨胀合金中硅

采用N₂O-C₂H₂火焰原子吸收光谱法测定膨胀合金中硅.建立了硅的最佳测定条件,并在样品测定中对干扰因素进行了综合考虑.实验表明:该方法具有灵敏度高、选择性好,操作简便、容易掌握、分析周期短等优点.其相对标准偏差均小于1.0%(n=6).标准加入回收率均为97.0%~99.0%(n=6)范围内.可以作为检测膨胀合金中硅含量的一种手段.     

硼对La17Fe76B7型储氢合金结构和电化学性能的影响

采用中频感应熔炼-快淬方法制备了La17Fe3Mn5Al2Ni73-xBx(x=0,1,3,5)储氢合金。结构分析表明,不含B的合金为双相结构,主相为LaNi5相,第二相为La2Ni7相,含B合金均由LaNi5相、La2Ni7相和La3Ni13B2相组成,且随着B含量的增加,LaNi5相和La2Ni7相减少,La3Ni13B2相逐渐增加。电化学测试表明,随着B含量的增加,合金的活化性能、最大放电容量不同程度下降,而循环稳定性有所改善。合金电极的倍率放电能力(HRD)随着B含量的增加呈先增大后减小的趋势,表明适量的B有利于提高合金的高倍率放电性能。合金电极的交换电流密度(I0)随着B含量的增加先增大后减小,而氢在合金中的扩散系数(D)则逐渐增大,表明合金的高倍率放电性能主要取决于合金表面的电荷转移能力。     

用N2O-C2H2原子吸收光谱法测定铜银合金中铁

提出用N2O-C2H2火焰原子吸收光谱法测试镉镍电池材料铜银合金中铁含量．方法具有良好的灵敏度,干扰少,重现性好．铁含量在0．1～30．0mg／L范围内与吸收值呈良好的线性关系．在测试铁含量为6．26mg／L（测定次数n=10）时,其相对标准偏差小于1．0％．标准回收率在97．0%-99．0％（n=6）范围内,适用于镉镍电池材料铜银合金中铁含量的质量控制分析和样品系统分析,结果令人满意．     

助熔剂对Ca0.98Bi2Ta2O9:0.02Pr3+发光性能的影响

采用传统高温固相反应法制备了Pr3+离子掺杂的铋层结构铁电氧化物Ca0.98Pr0.02Bi2Ta2O9(CBTO:Pr3+)荧光粉。利用X射线衍射、荧光光谱等研究了分别添加四种不同助熔剂(H3BO3,NH4F,CaCl2或CaF2)对CBTO:Pr3+粉体的晶体结构、发光强度的影响。结果表明,与未加助熔剂的样品相比,H3BO3,NH4F,CaCl2或CaF2的添加量为5%(摩尔分数)时,CBTO:Pr3+的发光强度分别提高了63%,43%,43%和29%;助熔剂的添加量为10%时,发光强度分别提高了186%,10%,13%和31%。随着H3BO3添加量的增加,CBTO:Pr3+的发光强度先增强后降低,在添加量为10%时,发光强度最大。样品温度特性测试表明CBTO:Pr3+粉体的热稳定性需要进一步改善。     

氮原子与卤代甲烷反应的直接氢抽提过程研究

利用B3LYP理论研究了N(~4S)+CH_3X(X = H, F, Cl)反应体系的直接氢抽提过 程,分别得到了各反应物、产物和过渡态的优化构型和谐振频率。同时应用了6- 31G(d), 6-311+G(d,p)和6-311+ + G(2d,2p)基组,考察其大小对反应体系中各物 种构型及能量的影响。理论计算表明,随着基组的增加,反应势垒逐渐降低,反应 吸热减少。对比取代甲烷的情形,结果表明反应过程中卤素原子具有典型的诱导效 应,降低了抽提势垒。     

混合稀土储氢合金中氧和氮的测定

研究了混合稀土储氢合金中氧和氮的测定方法。针对稀土金属高温易挥发、分解的特点,选择适宜的加热温度,使用镍浴,选择高温座坩埚进行试验：选择出了合适的助熔剂的预处理方法。方法已用于实际样品。对含氧0．43％、含氮0.018％的试样,分析精密度为氧4．3％,氮5.9％,加标回收率氧为93％～104％,氮为92％～110％。     

热碱处理对La-Mg-Ni系A2B7型储氢合金电极性能的影响

用真空感应熔炼和热处理制备了La0.64Gd0.2Mg0.16Ni3.1Co0.3Al0.1合金,利用SEM,EDS能谱分析、振动样品磁力计、XPS、ICP和电化学方法,研究了热碱处理时间(0~60 min)对合金颗粒表面的微观形貌、表面元素组成及状态、体相化学成分以及电化学性能的影响。研究表明:热碱处理使合金表面的Mg,Al,La和Ni元素发生不同程度的溶解析出或氧化,随处理时间增加,合金饱和磁化强度呈先增大后减小的趋势。当处理时间为15 min时,合金表面可形成较多的富Ni层,其饱和磁化强度达到最大值0.808 emu·g-1;当大于15 min时,随时间延长,富Ni层被氧化的倾向逐渐增大,同时表面形成稀土氧化物,导致合金饱和磁化强度逐渐减小。电化学性能测试表明:随热碱处理时间的增加,合金电极最大放电容量(Cmax)、循环稳定性(S100)及大电流放电特性(HRD900)均呈先增加后减小的规律。经15 min热碱处理的合金电极性能最佳,循环寿命S100由未处理时的83.67%提高到热碱处理后的93.09%。合金电极性能随热碱处理时间的变化规律与合金表面形成富镍层及其后续氧化倾向以及析出稀土氧化物关系密切。     

制备NdNi5的还原扩散过程

将CaH_2、Nd_2O_3和Ni粉混匀,并在氢气氛下加热到1000℃恒温4小时后,产物经洗涤,真空干燥得到NdNi_5。本文在确定NdNi_5制备条件的同时,对还原扩散过程进行探讨。实验结果表明在制备NdNi_5的还原扩散过程中起还原Nd_2O_3作用的除CaH_2以外还有金属Ca。反应扩散不只是在Nd和Ni之间进行,在1000℃扩散初期Ca亦参与这种扩散。形成中间产物Nd_(1-x)Ca_xNi_5。随着时间的增加Ca逐渐被Nd所取代,最后得到NdNi_5。     

Microwave-assisted synthesis of cyclopentyltrisilanol (c-C5H9)7Si7O9(OH)3

Microwave-assisted synthesis of cyclopentyltrisilanol by the hydrolytic condensation of the cyclopentyltrichlorosilane in aqueous acetone has been successfully performed. The reaction under microwave irradiation is considerably shorter in time in comparison to the traditional procedure and may be utilized for preparation of Si-containing building blocks for nanocomposite materials.     

Phosphides with Zr2Fe12P7-type structure

Twenty-six ternary phosphides Ln₂T₁₂P₇ (Ln = lanthanoid, T = Fe, Co, Ni) were prepared for the first time by reaction of the elemental components in liquid tin or by reaction of the components in evacuated silica tubes. The analysis of their powder patterns indicates their isotypism with Zr₂Fe₁₂P₇. Their lattice constants are reported. Gd₂Ni₁₂As₇ also crystallizes with that structure.     

Preparation and Structure of Cerium Titanates Ce2TiO5, Ce2TiO7, and Ce4Ti9O24

Compounds Ce₂TiO₅, Ce₂Ti₂O₇, and Ce₄Ti₉O₂₄ were prepared by heating appropriate mixtures of solids containing Ce⁴⁺ and Ti³⁺ or Ti which were placed in a platinum-silica-ampoule combination at T = 1250°C (3d) under vacuum. The new compounds were characterized by powder patterns. We obtained Ce₂TiO₅ which is isotypic to La₂TiO₅ and crystallizes in the Y₂TiO₅-type (space group Pnma) with a = 10.877(6) Å, b = 3.893(1) Å, c = 11.389(8) Å, Z = 4. Ce₂Ti₂O₇ is isotypic to La₂Ti₂O₇ and crystallizes in the monoclinic Ca₂Nb₂O₇ type (space group P 2₁) with a = 7.776(6) Å, b = 5.515(4) Å, c = 12.999(6) Å, β = 98.36(5), Z = 4. The compound Ce₄Ti₉O₂₄ crystallizes orthorhombic with a = 14.082(4) Å, b = 35.419(8) Å, c = 14.516(4) Å, Z = 16. The new cerium titanate Ce₄Ti₉O₂₄ is isotypic to Nd₄Ti₉O₂₄ (space group Fddd (No. 70)) which represents a novel type of structure.     

Ternary lanthanoid iron phosphides with YCo5P3 and Zr2Fe12P7-type structures

The new compounds YFe₅P₃ and LnFe₅P₃ (Ln = Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were prepared by reaction of the elemental components in a tin flux. They have YCo₅P₃-type structure. A structure refinement of GdFe₅P₃ from single-crystal X-ray data resulted in a conventional residual of R = 0.063 for 29 variable parameters and 693 unique structure factors. Crystals of the new compound Ce₂Fe₁₂P₇ were also prepared by the tin flux technique. Their Zr₂Fe₁₂P₇-type structure was refined to R = 0.029 for 23 variables and 1365 F values. The coordination polyhedra of the two and some other closely related structure types are discussed. The thermal parameters of the transition metal atoms in such structures increase with increasing coordination number.     

Dy3+离子掺杂的全色荧光粉Ca9La(PO4)7的制备及发光特性

采用高温固相法合成了Ca₉La(PO₄)₇:Dy³⁺发光材料. 荧光粉的晶体结构和微观尺寸由X射线粉末衍射(XRD)仪和扫描电子显微镜(SEM)测定. 光致激发和发射光谱发光揭示了材料的光学特性. 实验结果显示: Ca₉La(PO₄)₇:Dy³⁺能够有效吸收紫外-可见光(300-460 nm)而被激发, 呈现一系列的吸收峰. 样品在350 nm近紫外光激发下, 有较强的蓝光(481 nm)和黄光(573 nm)两个窄带发射, 混合成优质的白光发射, 该白光色坐标在国际照明委员会(CIE)色品图中分布在无色点D65 (0.313, 0329)周围. 随着掺杂Dy³⁺离子的摩尔分数的增加, 两种发射均发生浓度猝灭现象, Dy³⁺离子的最佳掺杂为0.05(摩尔分数), 电偶极-电偶极相互作用是主要的猝灭机理.     

TiO_2包覆Co_9S_8的制备及其电化学储氢性能

目前,寻找新型能源成为解决能源和环境问题的关键,氢能以其高效能、无污染等优点成为研究重点。其中,开发具有高储氢量和优异循环稳定性的新材料是利用氢能的重要研究方向。近些年,Co_9S_8凭借其优良的电化学储氢性能和较高的储氢容量成为目前研究热点,但其抗粉化性能仍有待于进一步提高。本文采用溶胶凝胶法和煅烧法得到了不同质量分数TiO_2包覆Co_9S_8的电极材料,利用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)和电化学测试系统分析包覆材料组成与性能,研究不同质量分数的TiO_2对材料电化学储氢性能的影响。结果表明,当TiO_2质量分数为3%时,产物的储氢性能和循环稳定性最好,最大储氢容量(质量分数)为2.03%,且经过30次充放电后,其放电容量仍能保持在60%。     

Preparation and Crystal Structure of K2Ag12Te7

 Single crystals of K₂Ag₁₂Te₇ (a = 11.460(2), c = 4.660(1) ?; V = 530.01 ?³; space group: P6₃/m; Z = 1) were synthesized under hydrothermal conditions at 250°C in concentrated aqueous KOH solution from elementary silver and tellurium. The crystal structure is characterized by trigonal prismatic KTe₆ polyhedra, connected via two common faces to KTe₃ rods parallel to [001]. These rods are combined by two crystallographically independent Ag atoms, each coordinated to four Te and three Ag atoms (Ag–Te and Ag–Ag < 3.1 ?) to a framework of the formula (K₂Ag₁₂Te₆)^2 + and with channels parallel to the sixfold axis. These channels are statistically occupied by one further Te atom per unit cell, distributed over two independent positions.     

High-pressure syntheses of TaS3, NbS3, TaSe3, and NbSe3 with NbSe3-type crystal structure

Transition metal trichalcogenides TaSe₃, TaS₃, NbSe₃ and NbS₃ were prepared under the reaction conditions of 2 GPa, 700°C, 30 min. NbSe₃ is exactly the same as that obtained in the usual sealed-tube method. The other products are modifications of each usual phase. They have crystal structures very similar to that of NbSe₃. The lattice parameters are a = 10.02Å, b = 3.48 Å, c = 15.56 Å, β = 109.6° for TaSe₃, a = 9.52 Å, b = 3.35 Å, c = 14.92 Å, β = 110.0° for TaS₃, and a = 9.68 Å, b = 3.37 Å, c = 14.83 Å, β = 109.9° for NbS₃. In spite of the similarity in their crystal structures, these high-pressure phases show a variety of electrical transport properties. TaSe₃ is a superconductor having T_c at 1.9 K. TaS₃ is a semiconductor with two transitions at 200 and 250 K. NbS₃ is a semiconductor with E_a = 180 MeV.     

Electrical conductivity of Th3P4-type EnLn2S4

Electrical conductivity measurements of Th₃P₄-type EuLn₂S₄ (Ln = LaGd) compounds have been made as functions of temperature and sulfur vapor pressure. These compounds are all p-type semiconductors, and their conductivities at room temperature have almost the same values for the specimens from EuLa₂S₄ to EuNd₂S₄ but increase on going from EnNd₂S₄ to EuGd₂S₄. In addition, the conductivity of EuGd₂S₄ is sensitive to sulfur vapor pressure and obeys the relationship . The mechanism of electrical transport in these compounds is discussed.     

Preparation and structure of NaSr0.5Al2B2O7 and NaCa0.5Al2B2O7

Two compounds NaSr_0.5Al₂B₂O₇ and NaCa_0.5Al₂B₂O₇, have been found to crystallize into a new structure type by Rietveld refinement from X-ray powder diffraction data. Their structure belongs to hexagonal space group P6₃/m, with lattice parameters of , for NaSr_0.5Al₂B₂O₇ and , for NaCa_0.5Al₂B₂O₇, respectively. The structure is built up by [Al₂B₂O₇]²⁻ double layer and Na⁺/Ca²⁺ or Na⁺/Sr²⁺ ions alternatively stacking along the c-axis. The sites in the inter-double layer are fully occupied jointly by Na and Ca or Sr, but the intra-double layer sites are only half occupied solely by Na. A mechanism of the transition of the structure from CaAl₂B₂O₇ to present structure type by replacing only 1% Ca by Na (2%) as observed by Chang and Keszler (Mater. Res. Bull. 33 (1998) 299) is also proposed.