Mg_(32)(Al,Zn)_(49)合金准晶结构及向晶体转化过程的研究

我们通过用电子衍射和高分辨电子显微术对Mg_(32)(Al,Z_n)_(49)合金准晶I相及相应晶体R相结构的研究对比,提出了此合金准晶I相的双三十面体原子团基本结构单元的随机准垛结构模型。进一步,用此随机准垛结构模型分析了合金处于准晶态与晶态之间过渡状态的内部结构,研究了准晶I相到晶体R相的转化过程。最后,对准晶态的结构特性进行了探讨。     

晶体的五次旋转对称

晶体结构的两大特征——长程平移有序和长程取向有序分开时,可能产生5次或其它非经典轴次旋转对称.5次旋转对称与准周期点阵有关.     

准晶体的晶胞构成及准晶格的推导

本文从结晶化学原理及二十面体相出发,提出了八次对称准晶体中可能存在的两种配位多面体形式——三角十六面体及带帽反棱柱。推导了该类准晶体的一维及二维准晶格。运用传统结晶学中定义Bravais晶胞的原则定义了准晶体中五次、十次、八次、十二次对称准晶体的四种二维准晶胞。本文作者认为准晶体实际上是具无公度平移周期的晶体,该类晶体的无公度平移对称,是通过放大或缩小这两种具分数维特征的对称操作来实现的。     

蝮蛇毒素R3晶型0.28 nm分辨率结构

蝮蛇毒素(agkistrodotoxin)是从江浙蝮蛇毒液中提取的一种磷脂酶A2型的突触前神经毒素,在碱性的条件下培养出了该毒素新晶型(R3)晶体,用X射线晶体学分子置换方法测定了该晶体0.28nm分辨率结构。经初步修正后模型晶体学R因子降到0.23,立体化学合理,对蝮蛇毒素R3晶型与其它晶型进行了结构比较,结果表明,蝮蛇毒素分子界面识别部位的一个独特疏水区在各种晶型晶体堆积中均起主要作用,对该疏水区可能的生物学功能进行了讨论。     

准晶体的结构化学

介绍准晶体的历史、结构、对称性和性质,介绍Mg32(Al,Zn)49的晶体结构和对称性,同时讨论纳米准晶颗粒的制备方法及其应用。     

准晶介绍

什么是准晶？为什么谢赫特曼在1982年4月的发现会被如此的不相信，而且需要花费2年半的时间才能在科学文献中找到它？为什么5重对称性的首次被发现会引起如此的大惊小怪？我们说晶体有这种对称性实际意味着什么？在我们回答上述问题之前，让我们先回顾一下其的某些背景。几个世纪以来，晶体都只被看作是有平坦的表面（小平面（facets...     

阶梯模冷却Mg_(68)Zn_(29)Y_3合金的组织及准晶相的形成

采用五层阶梯形模具冷却方法在Mg68Zn29Y3合金中制备了二十面体准晶相(I相)。通过扫描电镜、能谱分析仪和透射电子显微分析技术,观察了合金凝固组织和准晶相的形貌,并确定了准晶相成分及结构。结果表明:Mg68Zn29Y3三元合金在普通凝固-阶梯模冷却过程中,冷却速度对准晶相形貌、数量、大小和分布存在较为显著的影响;随着冷速的降低,准晶相的生长方式由细小弥散演变为粗大碎化,准晶晶粒尺寸由20μm逐渐长大至100μm以上;准晶相通过包晶反应形核、长大;合金凝固组织为MgZn+α-Mg+Zn60Mg30Y10。     

合成氨装置101D堵塞物中晶体定性分析

基于Boentgen、Laue与Ewald、W.H.Bragg及W.L.Bragg、Friedrich和Knipping等前辈X射线及其晶体学的研究与发现,X射线晶体结构分析已成为研究原子或离子在晶体点阵中结合、鉴定晶体化合物空间结构的可靠方法.Debye-Scherrer粉晶X射线衍射法(XRPD)在合成氨装置101D工况技术分析中,比较有意义的实际应用是解决由不同单质或化合物组成的复杂混合堵塞物中晶体的鉴定问题.采用XRPD定性分析了合成氨装置101D堵塞物样品中的主要晶体成分.实验结果表明:本法对合成氨装置101D工况技术分析具有重要的意义.     

MB25镁合金中的准晶体与晶体相的研究

利用透射电子显微术（ＴＥＭ）及能谱仪微区成分分析（ＥＤＳ）技术，对含有稀土元素的铸态Ｍｇ－Ｚｎ－Ｚｒ－Ｙ系高强镁合金ＭＢ２５中的稀土相鉴定发现，在铸态合金的晶界上存在准晶相，其电子衍射谱显示出５－３－２次对称的特点，为二十面体准晶相。在与准晶相连区域发现一种ＭｇＺｎ＿２型的Ｌａｖｅｓ相，其点阵常数为ａ＝０．５４２ｎｍ，Ｃ＝０．８７３ｎｍ。     

SAPO-5分子筛的可控合成及晶化过程探索

在非醋酸体系下分别通过动态和静态水热晶化方法合成了SAPO-5分子筛, 并考察了转速、 晶化时间及凝胶体系水硅比对SAPO-5分子筛晶相及形貌的影响, 采用X射线衍射(XRD)和扫描电子显微镜(SEM)技术研究了静态、 动态水热条件下SAPO-5分子筛的晶化过程. 结果表明, 静态水热条件下晶化6 h得到的SAPO-5分子筛为球状、 六边形柱状聚集晶体; 而在20 r/min转速下晶化2和6 h得到的SAPO-5分子筛分别为分散的凹面柱状晶体(凹面直径约6~8 μm)及均一分散的球状晶体(直径为16 μm); 在60 r/min转速下晶化3 h即可得到高度分散的六边形柱状晶体(六边形直径约5~8 μm); 提高转速至100和140 r/min时仅需晶化1 h即可得到六边形柱状晶体. 通过考察体系水硅比(H₂O/Si摩尔比)的影响, 确定最佳的水硅比为70, 此条件下所得晶相为纯相且分子筛的分散度最好. 综上可知, 相较于静态晶化, 动态晶化不仅从形貌上改善了晶体的分散度, 通过缩短晶化时间、 降低晶化转速也提高了SAPO-5分子筛的晶化效率. 本文采用较小的水硅比(H₂O/Si摩尔比为70)、 较低的模板剂用量在非醋酸体系下合成了SAPO-5分子筛, 为SAPO-5分子筛的合成提供了一条更简单、 经济的路线.     

Why are quasicrystals quasiperiodic?

In the past two decades significant progress has been made in the search for stable quasicrystals, the determination of their structures and the understanding of their physical properties. Now, quasiperiodic ordering states are not only known for intermetallic compounds, but also for mesoscopic systems such as ABC-star terpolymers, liquid crystals or different kinds of colloids. However, in spite of all these achievements fundamental questions concerning quasicrystal formation, growth and stability are still not fully answered. This tutorial review introduces the research in these fields and addresses some of the open questions concerning the origin of quasiperiodicity.     

Atomic structure of quasicrystals

The 2011 Nobel Prize in chemistry has been awarded to Dan Shechtman for his discovery of quasicrystals. The discovery has indeed been a breakthrough in crystallography and solid state physics and chemistry. After a brief introduction to the subject, we review some of the recent advances in the understanding of the atomic structure of icosahedral quasicrystals and in particular for the binary Cd?CYb type quasicrystal. Thanks to a combined analysis of periodic approximant, high quality synchrotron data, and the superspace approach, a detailed insight in the crystal chemistry of this binary quasicrystal has been achieved.     

Toward the discovery of new soft quasicrystals: From a numerical study viewpoint

This is a progress review of an emerging research front: soft quasicrystals including liquid crystalline dendrons, nanoparticles, mesoporous silica, colloids, ABC star and linear terpolymers, and even water and silicon. As an aid to readers, we explain the basics of quasicrystals developed in solid‐state physics: orders in quasicrystals, higher dimensional crystallography, approximants, phason randomness, and the origin of quasicrystal formation. Then we review some numerical studies from early to recent ones. Our main purpose is to elucidate how to construct quasicrystalline structures: The introduction of additional components or a new length‐scale is the key to discover new quasicrystals. As a case study, we describe our recent studies on ABC star terpolymer systems and present the results of simulations of dodecagonal polymeric quasicrystals. In the case of dodecagonal quasicrystals, one easily finds that the key is to search square‐triangle tiling structures with changing components. Application to photonic quasicrystals is reviewed as well. Our hope is that this review will contribute furthering quasicrystal chemistry. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

��There is no such animal (??? ??? ???)����Lessons of a discovery

The discovery of quasicrystals by Dan Shechtman in the early 1980s was a conspicuous event in materials science not only because it led to the production of a plethora of new materials but also because it signified the demise of a dogma in the science of condensed phase materials concerning symmetry restrictions. Having the discovery recognized was not easy and it required stamina on Shechtman??s part. The story of the quasicrystal discovery offers a set of lessons that might be useful to remember in similar situations.     

Dimension of the Gibbs function topological manifold: 3. Configuration entropy determined by the isotopic composition of binary quasicrystals

Even though the graph representation of thermodynamic states rules out the existence of stable binary quasicrystals, Tsai’s research team was able to discover two such systems in 2000. Our previous article showed that in terms of isotopic composition, Tsai’s two quasicrystals, as well as several other ones that have been discovered since 2000, are pseudobinary. Such systems owe their stability to high configuration entropy, which is determined by their isotopic composition. In this article, we shall use the basic methods of statistical thermodynamics to show that configuration entropy for systems without symmetry (including translational symmetry) is always higher than the entropy of their symmetrical counterparts. Thermodynamic calculations for a model of a 1-D binary Fibonacci quasicrystal, \(\hbox {AB}_{\uptau }\), indicate that the internal energy of this system is the same as the internal energy of its approximant, \(\hbox {AB}_{\mathrm{t}}(t\approx \uptau \)), i.e., the crystalline counterpart of the quasicrystal. We shall show that assuming Element A in both systems is composed of two isotopes, the configuration entropy corresponding to a single atom of the quasicrystal is about 20 % higher than the entropy of its crystalline approximant. This article also includes calculations of the configuration entropies of the few pseudobinary quasicrystals that have been synthesised so far. These entropies are exceptionally high, most often amounting to about 1.5 \(k_{\mathrm{B}}\), due to a large number of isotopic components of these quasicrystals. It in unknown whether such a high value is sufficient to ensure the stability of the quasicrystalline phase compared to the crystalline phase, as the number of configurations of the approximant required for calculations is astronomical.     

Electrical and thermal transport properties of icosahedral and decagonal quasicrystals

Electrical and thermal transport properties of quasicrystals are reviewed on the examples of i-Ag-In-Yb and i-Al-Cu-Fe icosahedral phases and d-Al-Co-Ni decagonal phase. Using samples of single-grain morphology and high structural quality, and performing the measurements along well-defined crystallographic directions, the following basic questions in the context of physical properties of quasicrystals are addressed, both experimentally and theoretically: (1) are the unusual transport properties of quasicrystals introduced by the quasiperiodicity of the structure or are they a consequence of complex local atomic order with no direct relationship to the quasiperiodicity; (2) what is the role of the electronic structure of quasicrystals in their electronic transport properties, especially the pseudogap in the electronic density of states in the vicinity of the Fermi energy; (3) what is the anisotropy of the transport coefficients along different crystallographic directions for icosahedral and decagonal quasicrystals and (4) what are the true intrinsic properties of quasicrystalline phases?     

DEDUCTION OF QUASILATTICE WITH FIVE-FOLD SYMMETRY AND PARTICLE FRACTAL STRUCTURE MODEL

In the structure of quasicrystal, the coordination icosahedron has long ordering but no translation ordering. The author dealt with the building principle ofquasicrystal and thought that two principles played a certain role in the quasicrystal structure, i.e. the icosahedron principle and the golden mean principle. We obtained the most simple.structure model of quasicrystals, and could explain all details of the high-resolution electron microscopic image of the A1-Mn quasicrystal based on the two principles. The author's model has the characteristic of fractal structure, therefore, we call it the particle fractal structure madeh The author has made a systematic deduction of quasicrystal point group, forms, possible type of quasicrystal lattice.     

Crystal-quasicrystal interfaces on Al-Pd-Mn

Two decades after their discovery, quasicrystals continue to fascinate our imagination. Even though there remain many outstanding questions about the basic structure, our focus has lately been shifting beyond the basic structural aspects, towards the search for interesting physical properties and technological applications. In this regard, undoubtedly, thin film growth on quasicrystal surfaces promises to be a very fertile ground. Despite their true long-range orientational order, quasicrystals possess forbidden fivefold or tenfold point-group symmetries and lack translational periodic order. Therefore, the interface between a quasicrystal and a crystal is of immense scientific interest, because it can metastabilize previously unknown structures with unique properties and potentially disclose structural mysteries of quasicrystalline surfaces. In our studies, we used various electron probes and observed that binary Al alloys exist as commensurate single crystals on the fivefold- and threefold-symmetry surfaces of the Al-Pd-Mn alloy. Thus, epitaxial growth conditions, like lattice and chemical matching observed in crystals are apparently satisfied on a local scale. We have also grown Al films at different temperatures on quasicrystal surfaces, and found that above RT Al readily diffuses into the bulk quasicrystal leading to a huge increase of its Debye temperature, implying that the quasicrystalline structure contains vacancies, which are filled with the additional Al. For thin films grown at RT, epitaxy locks the Al atoms to a strained quasicrystalline lattice, whereas for thicker films, excess strain energy cannot be supported and the structure relaxes to the bulk stable face-centered cubic phase by breaking into multi-twinned domains. The crystal-quasicrystal transformations also present an opportunity to investigate the electronic structure in a comparative way. We highlight a relevant result on the filling of the Mn 3d band in Al-Pd-Mn upon quasicrystal formation that gives rise to the pseudo gap.     

Mackay,Anti-Mackay,Double-Mackay,Pseudo-Mackay,and Related Icosahedral Shell Clusters

Mackay introduced two important crystallographic concepts in a short paper published 40 years ago. One is the icosahedral shell structure (iss) consisting of concentric icosahedra displaying fivefold rotational symmetry. The number of atoms contained within these icosahedral shells and subshells agrees well with the magic numbers in rare gas clusters, (C₆₀) _N molecules, and some metal clusters determined by mass spectroscopy or simulated on energy considerations. The cluster of 55 atoms within the second icosahedral shell occurs frequently and has been called Mackay icosahedron, or simply MI, which occurs not only in various clusters, but also in intermetallic compounds and quasicrystals. The second concept is the hierarchic icosahedral structures caused by the presence of a stacking fault in the fcc packing of the successive triangular faces in the iss. For instance, a fault occurs after the ABC layers resulting an ABCB packing. This is, in fact, a hierarchic icosahedral structure of a core icosahedron connected to 12 outer icosahedra by vertex sharing, or an icosahedron of icosahedra (double MI. Contrary to Mackay's iss, a faulted hierarchic icosahedral shell is, in fact, a twinlike face capping of the underlying triangles; it is, therefore, called an anti-Mackay cluster. The hierarchic icosahedral structure in an Al-Mn-Pd icosahedral quasicrystal has a core of body-centered cube rather than an icosahedron and, therefore, is called a pseudo-Mackay cluster. The hierarchic icosahedral structures have been studied separately in the past in the fields of clusters, nanoparticles, intermetallic compounds, and quasicrystals, but the underlying geometry should be the same. In the following a unified geometrical analysis is presented.