Bi_(3.15)Nd_(0.15)Ti_3O_(12)纳米棒的拉曼和紫外吸收光谱研究

以Bi(NO3)3.5H2O,Nd(NO3)3.6H2O和Ti(OC4H9)4为原料,加入聚乙烯醇(PVA-124),采用水热法在200℃经48 h合成了铋层状钙钛矿结构掺钕钛酸铋(Bi3.15Nd0.85Ti3O12,BNdT)纳米棒,纳米棒直径约10~200 nm,长度达十几微米。利用Raman散射研究了掺钕对钛酸铋晶格结构的影响。掺钕钛酸铋和钛酸铋的Raman光谱表明,Nd取代了类钙钛矿层中A位的Bi,掺Nd改善了BTO的对称性和减小了TiO6八面体的畸变。利用UV-vis光谱研究了BNdT纳米棒的光吸收特性,BNdT纳米棒存在A(400 nm),B(275 nm),C(210 nm),D(196 nm)四个吸收带,分别对应于电子从Bi3+的基态1S0到激发态3P1,3P2,1P1的跃迁和电子从阴离子团TiO6八面体到带正电的Bi3+离子的跃迁。BNdT的带隙为4.3 eV,大的带隙归因于纳米结构的量子尺寸效应。     

钛酸钡铅纳米晶的结构和Raman光谱研究

以醋酸钡、醋酸铅和钛酸丁酯为原料,醋酸和甲醇为溶剂,采用溶胶-凝胶工艺制备了不同晶粒大小的掺铅(5mol%)钛酸钡(BPT)纳米晶。用XRD、TEM和Raman研究了BPT样品的晶粒大小、结构及其相变特性。结果表明BPT纳米晶最低晶化温度为550℃,高于650℃热处理的纳米晶BPT在常温下为四方相。随着晶粒尺寸的减小,BPT纳米晶由四方相向立方相过渡。     

纳米二氧化钛材料的相变和声子限制效应(英文)

拉曼光谱用于研究二氧化钛材料的相变和声子限制效应。化学溶液方法制备了TiO2纳米晶材料。其平均粒度为 6 8- 2 7 9nm。最低频率 1 5 2cm- 1 Eg 模随粒度减小出现蓝移和加宽。在声子限制模型下 ,理论上对不同粒度的TiO2 纳米晶 (6 8,1 0 3和 2 7 9nm)的频移和线宽进行计算 ,结果与实验吻合得很好。研究了TiO2 纳米晶锐钛矿 -金红石相变 ,其相变温度为 6 5 0 - 6 90℃ ,比体块TiO2 的相变温度 1 0 0 0℃低 ,表明了相变的尺寸效应     

钛酸铅单晶纳米棒的生长机制和声子特性研究

采用改进熔盐法经一步反应合成了直径50-80nm,长度为1-5μm的单晶PbTiO3纳米棒。纳米棒沿(100)晶向生长,其形成可以用Ostwald成熟机制来解释。PbTiO3纳米棒晶格结构为四方(a=b=3.926,c=3.963),与单晶相比四方性明显下降。通过变温拉曼测试发现其铁电-顺电相变温度为440℃,低于单晶(490℃)。相变过程中“软模”E(1TO)的软化行为(从67 cm-1到56 cm-1)比单晶显著减弱,表明钛酸铅纳米棒中铁电性的弱化。     

不同尺寸锐钛矿结构TiO2纳米晶的高压相变研究

本文利用溶胶-凝胶法合成出5.6 nm、8.6 nm和19.4 nm三种尺寸的锐钛矿结构TiO2纳米晶, 并利用金刚石对顶砧压机结合Raman光谱技术研究了尺寸效应对其在23 GPa高压下结构相变的影响。结果发现, 对于5.6 nm和8.6 nm的样品, 加压到23.2 GPa和22.5 GPa的压力时没有发生结构相变, 而是转变为无定型结构, 卸除压力后, 依然保持为无定型; 而19.4 nm的样品在约11.3 GPa时逐渐转变为单斜斜锆石结构, 在卸压后转变为α-PbO2结构。相对于块材, 尺寸越小, 相变压力越大。基于吉布斯自由能理论, 尺寸减小引起的表面能增大被认为是相变压力变大的主要原因。     

纳米多晶体的热力学函数及其在相变热力学中的应用

以往关于纳米材料热力学的研究，绝大多数以界面的热力学函数表征整体纳米材料的热力学性质，这种近似处理，对于尺寸超过几十纳米的较粗纳米材料，在相变热力学中对特征转变温度和临界尺寸等重要参量的预测，将导致很大误差. 应用“界面膨胀模型”和普适状态方程，研究了纳米晶界的热力学特性，进一步发展了纳米晶整体材料热力学函数的计算模型，给出了单相纳米多晶体的焓、熵和吉布斯自由能随界面过剩体积、温度，以及晶粒尺寸发生变化的明确表达式. 以Co纳米晶为例，分析了界面与整体纳米多晶体热力学函数的差异，确定了相变温度与晶粒尺寸的依赖关系，以及一定温度下可能发生相变的临界尺寸. 关键词： 纳米多晶体 热力学函数 相变热力学     

纳米BaTiO3陶瓷的Raman光谱研究

高压能增加陶瓷烧结的致密驱动力和抑制陶瓷晶粒的长大。用高压辅助烧结的方法得到了晶粒尺寸约为60和30 nm的致密纳米BaTiO3陶瓷。BaTiO3陶瓷的晶体结构随温度的变化由变温Raman光谱来研究。在温度范围-190℃到200℃内,与粗晶的BaTiO3陶瓷相比,纳米BaTiO3陶瓷Raman散射结果表明,随着晶粒尺寸的减小,Raman峰的强度变弱,相变越来越弥散,出现了相变峰的消失;而且随着温度的升高,在纳米BaTiO3陶瓷甚至在30 nm BaTiO3陶瓷中都有与粗晶相同的从三方相到正交相到四方相到立方相的连续相变。变温Raman散射也表明,当晶粒大小减小到纳米尺寸时,纳米BaTiO3陶瓷表现出与粗晶不同的新颖性质。在一定的温度范围内,存在多种铁电相的共存。     

Bi12TiO20纳米粉体的制备及其光吸收特性研究

以钛酸四丁酯和硝酸铋为原料 ,利用化学溶液分解法制备了Bi12 TiO2 0 纳米多晶粉体 .采用XRD和TEM对其结构和形貌进行了表征 .结合热重 差热 (TG DTA)分析 ,探讨了Bi12 TiO2 0 晶相的形成机理 .通过UV Vis漫反射谱的测定 ,研究了Bi12 TiO2 0 纳米晶粉体的光吸收特性 .结果显示 ,从组成为化学计量比的前驱液中可以很容易制得纯Bi12 TiO2 0 纳米晶粉体 ,该Bi12 TiO2 0 纳米晶粉体呈现了在很宽的波长范围内 (5 6 0～ 385nm )对光的吸收的特性 .     

反钙钛矿结构GaCMn_3纳米晶的磁热效应和临界行为研究

我们通过高能球磨的方法,制备出平均晶粒尺寸为45纳米(nm)的GaCMn_3纳米晶样品,并研究了其磁热和铁磁-顺磁相变的临界行为.在磁场变化2T时,相比于块体GaCMn_3,虽然纳米晶GaCMn_3的磁熵变(-ΔSM)减小了,但是其相对磁制冷能力(RCP)却增强了.通过Kouvel-Fisher方法,我们确定了GaCMn_3纳米晶铁磁-顺磁相变的临界指数β=0.463和γ=1.161,根据Widom标度理论,得出第三个临界指数δ=3.51.这些临界指数和平均场模型的临界指数(β=0.5,γ=1.0,andδ=3.0)很接近,表明GaCMn_3纳米晶中的铁磁耦合是长程的.     

不同粒径纳米晶硫化锌的高压结构相变研究

 应用原位能量色散X射线散射和金刚石对顶砧技术，对纳米晶ZnS进行了高压结构相变研究。初始相为纤锌矿结构的10 nm和3 nm硫化锌分别在16.0 GPa和16.7 GPa时转变为岩盐矿结构，相变压力均高于纤锌矿结构的体材料硫化锌。该相变为一可逆的结构相变。应用大型科学计算软件Materials Studio（MS）计算了纳米晶ZnS的状态方程，根据Birch-Murnaghan方程拟合了纳米晶ZnS的零压体模量，得到的零压体模量高于相应体材料的零压体模量，表明纳米晶ZnS较难压缩。     

Infrared studies of the role of monoclinic structure in the deformation of polyethylene

The transformation from the orthorhombic to the monoclinic structure has been observed by means of infrared spectroscopy in shaken preparations of single crystals of polyethylene, mixed crystals of polyethylene and perdeuteropolyethylene, and physical mixtures of single crystals of these two polymers. Annealing of such shaken samples results in the conversion of the monoclinic back to the orthorhombic structure, but with an accompanying change from the (110) folding characteristic of single crystals to (200) folding. The monoclinic structure thus appears to be an intermediate state in the fold-plane transformation which can occur upon deformation. Both unannealed and annealed physical mixtures give evidence of ciliary penetration.     

IrTi合金晶格动力学的第一性原理研究

利用密度泛函理论的平面波赝势方法研究了IrTi合金的晶格动力学行为. 声子谱计算表明四方(L1₀)结构动力学不稳定,通过冷冻不稳定声子模式, 发现IrTi会发生从四方(L1₀)到正交的结构相变.进一步分析软模对应的原子振动, 得到了具有正交对称性,空间群为Cmmm,相对于四方(L1₀)相能量更低、更稳定的结构. 这种正交新相(Cmmm)弹性稳定和动力学稳定,而且其结构参数与实验上观察到的低温结构有限的晶格参数相符合,表明IrTi合金的低温相是正交结构(Cmmm). 从理论上肯定了IrTi合金立方到四方再到正交的相变机制, 解决了实验上关于相变机制和低温相结构形式的争议.     

Cu掺杂对TiNi合金马氏体相变路径影响的第一性原理研究

不同浓度的Cu元素掺杂会极大地影响TiNi二元合金的物理性质和相变行为.为了解释其中的物理机制,本文通过第一性原理计算,对TiNi和Ti_(50)Ni_(25)Cu_(25)的相变机制和相稳定性进行了计算和讨论.通过计算Cu掺杂前后立方相到正交相、再到单斜相过程中的相变路径和相变势垒,解释了Cu掺杂对二元合金TiNi相变过程的影响.计算结果表明:TiNi合金的正交相和单斜相之间存在一个大小为1.6meV的相变势垒;而对于Ti_(50)Ni_(25)Cu_(25),这两个相之间的相变势垒大小至少为10.3meV,如此大的一个相变势垒意味着Ti_(50)Ni_(25)Cu_(25)合金的正交相很难跨过势垒相变到单斜相.     

Ferromagnetism and magnetostructural coupling in V-doped MnNiGe alloys

The magnetostructural coupling between magnetic and structure transitions plays an important role in the multifunctional applications of magentocaloric materials. In this work, ferromagnetism and magnetostructural transformation are achieved in nonmagnetic V-doped MnNiGe alloys. With simultaneously reducing the transformation temperature and converting antiferromagnetic martensite to ferromagnetic state, the magnetostructural transformation between ferromagnetic orthorhombic phase and paramagnetic hexagonal phase is established in a temperature region as large as 130 K. The magnetic-field-induced magnetostructural transformation is accompanied by considerable magnetocaloric effect.     

Phase transformations and structural characteristics of AL–Cu–Co(–Si) decagonal phase

The phase transformations and structural characteristics of the Al-Cu-Co-Si alloy have been studied by neutron diffraction and high-resolution electron microscopy. The Al₆₅Cu_17.5Co_17.5 decagonal phase is stable in the temperature range between 973 K and 1350 K. At the low-temperature end, it relaxes to a microcrystalline approximant structure. At the high-temperature end, it melts directly into liquid. Two distinct orthorhombic phases are identified in the Al₆₃Cu_17.5Co_17.5Si₂ microcrystalline structure. They are composed of several structure units that can also construct the Penrose tiling. Because of lack of units, a single orthorhombic phase cannot undergo the transformation towards the high-temperature decagonal phase. An analysis of the orientation relationships between the CsCl and orthorhombic phases leads to the definition of Penrose tiling-like subnetworks inside the orthorhombic unit cells so that these orthorhombic phases can be regarded as the periodic patchworks of quasiperiodic subnetworks.     

A 20-resolved hadox study of BaTiO3

The fine structure of YBaCu₃O₇ is examined: Twin organization, planar defects, and structural phase co-existence are discussed in the context of the tetragonal to orthorhombic transformation. Heterogeneous nucleation of an insulating phase at the twin boundary and sub-grain boundaries is demonstrated. On the basis of the morphological observations, the transformation is classified as martensitic. Considering the role of twin in relieving the martensitic transformation strain, by producing a low strain energy habit plane, the feasibility of the formation of a twinless structure is discussed.     

Laser Melting Solidification Process of Y-Ba-Cu-O Superconductors

Y-Ba-Cu-O orthorhombic superconducting phase direct crystallization from the 123 composition of liquid were realized by continuous wave CO2 laser using non equilibrium phase transformation of scanning laser melting solidification method. The transformation temperature 92 K of superconducting phase were measured. The characteristic peaks of YBa2Cu3O7 superconductors were shown by X-ray diffraction patterns. The sample of magnetization loop at 77 K and structure change were given.     

Pressure induced phase transition in MnTe2

Energy dispersive high-pressure powder X-ray experiments have been performed for MnTe₂ up to a pressure of 20 GPa. MnTe₂ undergoes a discontinuous transformation from the cubic pyrite type structure to the orthorhombic marcasite type structure at 7.0±0.5 GPa upon increasing pressure. The transformation is accompanied by a large reduction in the specific volume (ΔV/V=0.18) which probably reflects different magnetic properties of the two modifications of MnTe₂.     

Laser Melting Solidification Process of Y BaCu O Superconductors

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Spectroscopic study of phase transformations between orthorhombic and tetragonal C60 polymers

We present a detailed study of transformations between the orthorhombic and tetragonal polymeric states of C₆₀. The transformations are characterised by Raman spectroscopy and X-ray diffraction. We show that the transformation from the orthorhombic (O) phase to the tetragonal (T) phase is very fast and our results indicate that the transformation goes via an intermediate dimer (D) state in a two-stage process, O↦D and, D↦T transformations, where the second process is slower than the first. On the other hand, the transformation from the tetragonal to the orthorhombic phase is significantly slower, indicating a high-energy threshold to break the polymer bonds at the temperatures used. The results also support earlier suggestions that the tetragonal phase contains disordered dimers that can be viewed as lattice defects in the formation of higher polymers.