高能球磨法制备Nb_3Al超导体

利用高能球磨法制备Nb_3Al超导体,先通过高能球磨法获得Nb(Al)固溶体,然后在不超过1000℃的温度下烧结将Nb(Al)固溶体转变为Nb_3Al超导相,对其成相反应过程展开研究.研究发现高能球磨法能够获得Nb(Al)固溶体,球磨3小时为宜,时间较短不能完全形成固溶体,时间较长使原料粉末非晶化.在烧结过程中,研究了原料组分、烧结温度及时间对制得超导相性能的影响,最终获得初始原料的化学计量比为Nb∶Al=74∶26、烧结温度为900℃、烧结时间为1小时制得的Nb_3Al超导体的Tc最高,达到15.6K.由于Nb_3Al相中的Al含量偏低,导致其Tc偏低.     

机械合金化法制备Nb_3Al_(1-x)Si_x

采用机械合金化法制备了一系列的Nb_3Al_(1-x)Si_x(x=0~0.2)多晶样品,利用高能球磨机获得Nb(Al,Si)固溶体,然后在900℃的温度下烧结将固溶体转变为超导相.XRD测试结果表明,经3小时高能球磨后Al和Si固溶到Nb中形成Nb(Al,Si)固溶体,烧结后的样品具有较好的单相性,为A15型晶体结构,并且晶格随掺杂量的增加逐渐减小.磁性测量结果表明,纯样Nb3Al的Tc约为14K,随掺Si量的增加Tc逐渐减小.结合EDX分析,所有Nb_3Al_(1-x)Si_x样品的超导电性来源于A15相,但由于随掺杂量的增加样品中Al的含量逐渐减少导致了Tc逐渐减小.     

钡铁氧体前驱体高能球磨过程的红外拟合光谱分析

高能球磨法是材料制备过程中常用的方法,通过物料在高速运转的过程中进行磨合而产生晶体空位缺陷,实现元素的掺杂,进而发生化学吸附或化学反应,合成产生新的物相,对于后续合成材料的性能有很大影响。钡铁氧体具有良好的磁性能,被用于功能材料制备的诸多领域。采用高能球磨法制备钡铁氧体前驱体,利用XRD,SEM和FTIR检测方法考察不同高能球磨时间下钡铁氧体前驱体物相、微观形貌及官能团的变化规律,并通过红外二阶导数光谱、拟合平滑光谱计算法,定量分析高能球磨过程中物相的变化规律。XRD及SEM检测结果表明,随球磨时间增加,钡铁氧体前驱体各物相的衍射峰宽度变宽,粉末细化,晶格逐渐发生畸变,产生晶体空位缺陷,从而使Ba溶入Fe₂O₃晶格中生成Ba_xFe_2-xO₃的固溶体,且产生吸附“团聚”现象;当球磨时间大于40 h时,发生“纳米尺寸效应”,生成有磁性的Fe₃O₄及Ba_xFe_3-xO₄固溶体。红外光谱分析结果显示,随着球磨时间的增加,BaCO₃和α-Fe₂O₃的特征峰均存在峰强减小、峰位发生明显移动的规律,表明随着球磨时间增加,BaCO₃和α-Fe₂O₃颗粒粒度变小,且发生化学吸附。通过红外光谱的平滑拟合光谱和二阶导数光谱计算可知,随球磨时间的增加,各吸收峰面积均明显减小。相对于球磨0 h,在球磨10,20和40 h后,波数473 cm-1的Fe—O键振动吸收峰的峰面积分别减少48.84%,65.97%和93.54%;而在波数540 cm-1处的Fe—O键吸收峰的峰面积则分别减少37.11%,51.76%和82.85%;同理,在波数856 cm-1处的O—C—O键的面内弯曲振动吸收峰的峰面积分别减少30.62%,44.71%和67.10%;在波数1 446 cm-1处的C—O键不对称伸缩振动峰的峰面积则分别减少0.03%,27.63%和57.90%。从定量分析的角度考察了钡铁氧体前驱体高能球磨过程中物相的变化规律并精准确定反应产物含量变化的百分比,对于后续材料的合成与性能随钡铁氧体前驱体物相不同而发生变化的研究有重要的指导意义。     

非晶FeMoSiB合金机械晶化的动力学机制

 研究了非晶(Fe_0.99Mo_0.01)₇₈Si₉B₁₃（FMSB）合金的机械晶化过程和机制,并讨论了局域高压的作用。结果表明：非晶FMSB合金的晶化过程及其产物与球磨强度和球磨时间有密切关系,在低能球磨FMSB非晶过程中,晶化相只有α-Fe(Mo,Si)固溶体,而在高能球磨过程中,除了α-Fe(Mo,Si)固溶体结晶相之外,还分别有(Fe,Mo)₃B和Fe₂B相析出。其晶化机制可归因于由碰撞引起的局域高压和局域高温共同作用的结果。实验结果还表明,机械球磨不仅对非晶FMSB的常压热晶化温度有重要影响,而且对其热晶化结果亦有重要影响。     

机械合金化Cu＿（1－x）Sn＿x系的穆斯堡尔研究

利用机械合金化方法获得了几种铜－锡合金，特别是熔融法不易获得的，Ｘ射线衍射结果显示球磨使各样品纳米化，并形成包含确定合金相的固溶体，穆斯堡尔谱表明，各固溶体中除包含合金相外，还存在富锡相及富铜相，提出在机械合金化过程中，首先铜和锡纳米化，然后两种原子相互扩散形成包含合金相、富α－锡相和富ｆｃｃ铜相的固溶体。     

球磨法对不同基质上转换发光的影响

分别利用高温固相法和高能球磨法,在反应温度为1 100℃、反应时间为2 h的条件下合成了以Y2O3、La2O3、LiTaO3为基质的双掺和三掺Tm3+、Er3+、Yb3+发光粉。XRD测试结果表明,高能球磨法制备的Y2O3、La2O3、LiTaO3材料的相纯度高于高温固相法。用980 nm红外激光分别对两种合成方法制得的样品粉末进行发光性质的检测,结果表明高能球磨法制得样品的发光强度高于高温固相法样品。不同基质样品的上转换发光性质表现为:Tm3+、Yb3+掺杂呈蓝光;Er3+、Yb3+掺杂呈黄光;Tm3+、Er3+、Yb3+三掺样品的发光减弱,颜色可调。     

高能球磨条件下TiO2相变的实验研究

 采用高能球磨法处理二氧化钛（TiO₂）与双氰胺粉末混合物,对不同球磨时间和球磨转速条件下TiO₂的相变进行了研究。利用X射线衍射仪对回收产物的相组成进行表征。结果表明,在700 r/min的高速球磨条件下,TiO₂发生了由锐钛矿相向金红石相和Srilankite高压相的转变,随着球磨时间的增加,Srilankite高压相和金红石相的含量逐步增加并逐渐趋于平衡;进一步提高球磨转速至1 000 r/min,锐钛矿相向Srilankite高压相的转变占主导,更易于形成Srilankite高压相,Srilankite高压相的质量分数可增加至47.8%。     

机械合金化Cu1-xSnx系的穆斯堡尔研究

利用机械合金化方法获得了几种铜－锡合金，特别是熔融法不易获得的η-Cu₆Sn₅，Ｘ射线衍射结果显示球磨使各样品纳米化，并形成包含确定合金相的固溶体，穆斯堡尔谱表明，各固溶体中除包含合金相外，还存在富锡相及富铜相，提出在机械合金化过程中，首先铜和锡纳米化，然后两种原子相互扩散形成包含合金相、富α－锡相和富ｆｃｃ铜相的固溶体。 关键词：     

球磨法对不同基质上转换发光的影响

分别利用高温固相法和高能球磨法,在反应温度为1 100 ℃、反应时间为2 h的条件下合成了以Y₂O₃、La₂O₃、LiTaO₃为基质的双掺和三掺Tm³⁺、Er³⁺、Yb³⁺发光粉。XRD测试结果表明,高能球磨法制备的Y₂O₃、La₂O₃、LiTaO₃材料的相纯度高于高温固相法。用980 nm红外激光分别对两种合成方法制得的样品粉末进行发光性质的检测,结果表明高能球磨法制得样品的发光强度高于高温固相法样品。不同基质样品的上转换发光性质表现为：Tm³⁺、Yb³⁺掺杂呈蓝光;Er³⁺、Yb³⁺掺杂呈黄光;Tm³⁺、Er³⁺、Yb³⁺三掺样品的发光减弱,颜色可调。     

非晶态Sm-Fe和Sm-Co薄膜的低温磁性

研究了非晶态Sm-Fe和Sm-Co薄膜在1.5—300K的磁性。发现Sm-Fe薄膜中Fe原子磁矩取向存在分散性,Sm-Co薄膜中Co原子有效磁矩随Sm含量的变化与Nd-Co非晶薄膜很相似。决定了Sm-Fe薄膜具有散铁磁结构,Sm-Co薄膜为共线铁磁性结构。Sm原子磁矩≈0。报道了这两个非晶合金系列的矫顽力H_c与成份和温度的依赖关系。发现Sm-Fe薄膜的H_c较高于Sm-Co的值;前者随Sm含量增加而急剧上升,并随温度升高而陡降;后者的H_c在Sm含量≈43at％有极大值,并以指数形式随温度升高而减小。发现低温范围内磁化强度随温度变化与自旋波激发和Stoner激发都有关系。 关键词：     

Formation of NI80P20 solid solution phase under pressure

A Ni-P solid solution phase was obtained by quenching of melts under a pressure of 4.5 GPa. This was considered as a metastable high pressure phase. Despite the lack of thermodynamic parameters for Ni₈₀, P₂₀ alloy under pressure, the degree of undercooling, nucleation frequency and crystal growth velocity were calculated. We conclude that metastable phases with the same composition as the melting phase, such as supersaturated solid solution phase and amorphous phase, are easily prepared by high-pressure quenching.     

An ion momentum as a novel parameter for the preparation of the magnetostrictive thin film

The Sm-Fe system known as Giant magnetostrictive (GM) thin films was prepared by d.c. magnetron sputtering process. The present study has shown the importance of the energetic incidence ions onto the depositing film surface for the magnetostrictive properties. The effect of ion bombardment on the magnetostrictive characteristics of GM films was quantitatively discussed. The new parameter, ion momentum, was proposed for the design of GM films.     

Poly(vinylidene fluoride) Crystallization Behavior and Membrane Structure Formation Via Thermally Induced Phase Separation with Benzophenone Diluent

Microporous poly(vinylidene fluoride) (PVDF) membranes were prepared by thermally induced phase separation (TIPS) at different quenching temperatures with benzophenone as the diluent. The crystallization behavior and crystal structure of PVDF in PVDF/benzophenone systems were investigated by differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD). The different PVDF concentrations had a remarkable effect on PVDF crystallization behavior and resulted in different membrane structures. Spherulitic structures were vague when the PVDF/benzophenone solution was quenched to ?8°C; however, discernable spherulitic structures were obtained when quenched to 34 and 49°C. Additionally, two phase separation mechanisms (solid–solid (S–S) and solid–liquid (S–L) phase separation) were observed during membrane preparation. It was revealed by scanning electron microscopy (SEM) that microporous membranes had more discernable spherulitic structures formed by S–L phase separation than by S–S phase separation, which induced macrovoids and irregular pores on the fracture surfaces of membranes.     

Ti1-xCexO2体系纳米粉体的制备及其结构表征

 采用溶胶凝胶法制备了纳米Ti_1-xCe_xO₂系列样品。利用X射线衍射（XRD）、透射电子显微镜（TEM）、高分辨电子显微镜（HRTEM）对纳米Ti_1-xCe_xO₂系列样品颗粒尺寸、形貌以及固溶区范围和物相组成进行了研究；同时，采用Rietveld结构精修的方法研究了Ce的不同掺杂量对TiO₂晶体结构的影响。实验结果表明，Ce掺杂TiO₂能够形成Ti_1-xCe_xO₂固溶体，Ti_1-xCe_xO₂的固溶区范围在x=0～0.06之间，Ti_1-xCe_xO₂的晶粒度为5～10 nm，平均颗粒粒度约35 nm，且粒度均匀。     

强磁场下Sm-Fe薄膜不同晶态组织演化及磁性能调控

针对Sm-Fe薄膜的不同晶态组织演化和磁性能调控问题,采用分子束气相沉积方法制备Sm-Fe薄膜时,通过改变Sm含量、膜厚和强磁场来调节薄膜的晶态和磁性能.结果表明,Sm含量可以调节Sm-Fe薄膜的晶态组织演化,而晶态组织的演化和强磁场对磁性能有显著影响.Sm-Fe薄膜在Sm原子比为5.8%时是体心立方晶态组织,在Sm含量为33.0%时为非晶态组织,而膜厚和强磁场不会影响薄膜的晶态组织.非晶态薄膜的表面粗糙度和表面颗粒尺寸都比晶态薄膜的小,施加6 T强磁场会使表面颗粒尺寸增大,而表面粗糙度降低.非晶态薄膜的饱和磁化强度M_s比晶态薄膜的M_s(1466 emu/cm~3,1 emu/cm~3=4π×10-10T)低约47.6%,施加6 T强磁场使非晶态和晶态薄膜的M_s均降低约50%.Sm-Fe薄膜的矫顽力H_c在6—130 Oe(1 Oe=103/(4π)A/m)之间,其中,非晶态薄膜的H_c比晶态薄膜的H_c大.施加6 T强磁场使晶态薄膜的H_c增大,而使非晶态薄膜的H_c减小,最高可以减少95%.结果表明含量和强磁场可以用于调控Sm-Fe薄膜的晶态和磁性能.     

Effect of alloy formation processes in the Co-Cu system on the magnetic and magnetoresistance properties of multilayer Co/Cu films with ultrathin Co layers prepared by DC magnetron sputtering

This paper reports on a study of multilayer Co/Cu films with an effective thickness of the Co layer of ～3.5 Å, which were prepared by magnetron sputtering. The samples prepared have been found to have a metastable multiphase structure. An analysis of the data obtained by structural and, primarily, by magnetic methods has revealed that the main phases are the Co/Cu supersaturated solid solution (alloy) with a Co concentration of about 30 at %, the superparamagnetic phase, and the paramagnetic phase, which is accounted for by the presence of small (a few atoms at most) Co clusters embedded in the Cu matrix. A clearly pronounced maximum in the temperature dependences of the low-field magnetoresistance has been found, which is associated with the temperature of the magnetic phase transition of the supersaturated Co-Cu alloy.     

急冷Al-Si合金超导电性的研究

本文研究了热处理对急冷Al-11.3at％Si合金的微观结构及超导电性的影响,结构分析表明,液态淬火的样品由两相组成:过饱和α-Al(Si)固溶体晶体相和Al,Si原子按统计分布的非晶相,经100℃/50小时热处理后,α-Al(Si)固溶体贫化,非晶相中析出Si的小颗粒,经200℃/100小时热处理的样品已趋向平衡态结构,测量了样品的临界温度,在研究磁场中的超导-正常转变时发现了反常的磁阻效应,它可以用样品中存在两个超导相的模型予以解释。 关键词：     

The Role of Intermolecular Interactions in Solid State Fluorescent Conjugated Polymer Chemosensors

A functionalized fluorescent conjugated polymer, tolylterpyridine poly(p-phenyleneethynylene-thienyleneethynylene (ttp-PPETE), was designed and synthesized to detect trace amounts of toxic transition metal pollutants in ground water. Photophysical studies in tetrahydrofuran (THF) successfully demonstrated this polymer as a selective and sensitive chemosensor for Ni²⁺ and Co²⁺ in aqueous solution. Solid state composites of these chemosensors have now been prepared which can be modified to provide for inexpensive and portable field based chemical detection. A solid composite of ttp-PPETE, blended with poly (methyl methacrylate) shows UV–vis absorption and fluorescence emission spectra which are red- shifted when compared to solution phase spectra, suggesting an increase in conjugation in the solid state. An additional absorption peak, not present in solution, is also observed in the solid state. The presence of this new peak provides evidence of interacting FCP chains in the solid state. Concentration dependent experiments were done on the solid composite showing red-shifted emission peaks accompanied by a significant reduction in the fluorescent quantum yield. These observations are consistent with the formation of aggregated polymer species in the solid state. Intermolecular interactions of this type can be manipulated in the design of sensitive and selective solid state fluorescent conjugated polymer sensors.     

Phase transition in multiferroic YMnO3 and its solid solution YMn(0.93)Fe(0.07)O3

Ceramics of YMnO₃ and its Fe substituted YMn_(0.93)Fe_(0.07)O₃ solid solution were synthesized by solid state reaction of the oxides at 1200 °C. Hexagonal phase was identified in both cases by X-ray powder diffraction. Rietveld refinement of cell parameters showed an increase of the parameter values for the solid solution. Dielectric permittivity measurements versus temperature showed a phase transition at 655 °C for yttrium manganite, however, for the solid solution no phase transition was detected on heating up to 700 °C. Dielectric loss measurements showed higher slope changes and better defined local maxima for the solid solution than for the pure phase.