Crystal symmetry and the reversibility of martensitic transformations

Martensitic transformations are diffusionless, solid-to-solid phase transitions, and have been observed in metals, alloys, ceramics and proteins. They are characterized by a rapid change of crystal structure, accompanied by the development of a rich microstructure. Martensitic transformations can be irreversible, as seen in steels upon quenching, or they can be reversible, such as those observed in shape-memory alloys. In the latter case, the microstructures formed on cooling are easily manipulated by loads and disappear upon reheating. Here, using mathematical theory and numerical simulation, we explain these sharp differences in behaviour on the basis of the change in crystal symmetry during the transition. We find that a necessary condition for reversibility is that the symmetry groups of the parent and product phases be included in a common finite symmetry group. In these cases, the energy barrier to lattice-invariant shear is generically higher than that pertaining to the phase change and, consequently, transformations of this type can occur with virtually no plasticity. Irreversibility is inevitable in all other martensitic transformations, where the energy barrier to plastic deformation (via lattice-invariant shears, as in twinning or slip) is no higher than the barrier to the phase change itself. Various experimental observations confirm the importance of the symmetry of the stable states in determining the macroscopic reversibility of martensitic transformations.     

First-principles exploration of the stabilization mechanism of long-period stacking ordered structures in high performance Al alloys

Long-period stacking ordered(LPSO) structures, like 9 R, 12 R, 15 R and 18 R phases etc., play a key role in improving the mechanical properties of Al alloys. In the present study the Gaussian-Like distribution(GLD)model was utilized to investigate the effects of solute atoms(Cu, Fe, Ga, Ge, Li, Mg, Sc, Si, Sn, Sr, Ti, Y, Zn) on these phase stabilizations in Al alloys by first-principles calculations. The interaction energies between solute atoms and these phases were strictly calculated. The results suggested that the solute segregations showed different characteristics in these phase structures, and solute atoms(Ga, Ge, Si, Sn, Sr, Y) tended to segregate to the stacking fault(SF) planes of them, and Sr atom was the easiest to promote the stabilization of 15 R phase compared to other structures. High solute concentrations promoted the stabilizations of these phases, while high temperature inhibited their stabilizations. In the light of the degrees of reducing the intrinsic stacking fault energies(ISFEs), the solute atoms can be ranked by:(a) For 9 R and 12 R phases, Sr Y Sn Sc;(b) For15 R and 18 R phases, Sr Y Sc Sn. Thus, it may be concluded that Sr and Y atoms are hopeful to become the underlying candidates for exploring and exploiting high-performance Al alloys with LPSO structures.     

中子辐照对锆合金显微组织的影响研究进展

作为反应堆的第一道安全屏障,锆合金包壳材料的显微组织一直是国内外的研究热点。针对目前国内外在中子辐照对锆合金显微组织的影响研究领域现状进行了综述,总结了现有研究的不足并提出了对未来研究方向的建议:采用微观分析手段,针对不同中子注量下锆合金包壳的第二相、氢化物和氧化膜展开研究,获得其在实际使用工况下的演变规律,为我国锆合金包壳材料的优化改进提供支撑。     

调制结构的对称性

定义一种新的对称性,以恢复调制结构失去的对称元素.按照赝对称性的概念,用包含对称算子和原子坐标的解析表达式说明了在一维调制结构的四维描述中的对称操作.在某些限制下,推广三维点群的概念,导出四维空间点群.提出四维超空间群的概念,并举例加以说明.还较详尽地推导了Bravais格子和系统消光规律,并给出它们的完整的表格,以利于空间群的确定.     

Effect of long-period stacking ordered phase on microstructure, mechanical property and corrosion resistance of Mg alloys: A review

Magnesium alloys containing long period stacking ordered (LPSO) phase have been received a great deal of attention in the last decade owing to their excellent comprehensive properties of mechanical strength and corrosion resistance. In this paper, some fundamental aspects of LPSO containing Mg alloys have been reviewed, including: (1) microstructural characterization, formation conditions and the associated phase transformation of LPSO phases in Mg alloys; (2) deformation mechanism of LPSO phases and their influence on the deformation mechanism of the Mg matrix; (3) effect of LPSO structure on the mechanical performance such as tensile strength, creep resistance, fracture toughness and fatigue strength; (4) corrosion behavior of LPSO containing Mg alloys and their possible applications as the biomaterials. Moreover, some remaining unsolved issues of the LPSO containing Mg alloys and the future target about how to further improve their service properties have been also described.     

Ni-Hf非晶合金及其团簇式成分解析

Ni-Hf是一类重要的二元非晶形成体系,但其非晶形成能力较弱,最佳非晶成分尚不明确.本文利用团簇加连接原子模型,首先解析了二元深共晶点Ni65Hf35对应共晶相Ni7Hf3和Ni10Hf7的团簇结构,获得了可代表各自结构特征的主团簇;随后依据非晶合金的通用团簇式[团簇]（连接原子）1或3,设计出若干可能具有高非晶形成能力的合金成分.实验结果表明,急冷甩带后只有Ni71.43Hf28.57和Ni68.75Hf31.25两个成分点形成完全非晶,其中后者成分由团簇成分式[Ni-Ni7Hf5]Ni3描述,并具有最高的热稳定性（877K）和最低的液相线温度Tl（1482K）,被认为是Ni-Hf系中高非晶形成能力的成分点,其位于Ni65Hf35共晶点的富Ni侧,靠近共晶相Ni7Hf3.     

Experimental measurement of the photonic properties of icosahedral quasicrystals

Quasicrystalline structures may have optical bandgap properties-frequency ranges in which the propagation of light is forbidden-that make them well-suited to the scientific and technological applications for which photonic crystals are normally considered. Such quasicrystals can be constructed from two or more types of dielectric material arranged in a quasiperiodic pattern whose rotational symmetry is forbidden for periodic crystals (such as five-fold symmetry in the plane and icosahedral symmetry in three dimensions). Because quasicrystals have higher point group symmetry than ordinary crystals, their gap centre frequencies are closer and the gaps widths are more uniform-optimal conditions for forming a complete bandgap that is more closely spherically symmetric. Although previous studies have focused on one-dimensional and two-dimensional quasicrystals, where exact (one-dimensional) or approximate (two-dimensional) band structures can be calculated numerically, analogous calculations for the three-dimensional case are computationally challenging and have not yet been performed. Here we circumvent the computational problem by doing an experiment. Using stereolithography, we construct a photonic quasicrystal with centimetre-scale cells and perform microwave transmission measurements. We show that three-dimensional icosahedral quasicrystals exhibit sizeable stop gaps and, despite their quasiperiodicity, yield uncomplicated spectra that allow us to experimentally determine the faces of their effective Brillouin zones. Our studies confirm that they are excellent candidates for photonic bandgap materials.     

Hexagonal nanoporous germanium through surfactant-driven self-assembly of Zintl clusters

Surfactant templating is a method that has successfully been used to produce nanoporous inorganic structures from a wide range of oxide-based material. Co-assembly of inorganic precursor molecules with amphiphilic organic molecules is followed first by inorganic condensation to produce rigid amorphous frameworks and then, by template removal, to produce mesoporous solids. A range of periodic surfactant/semiconductor and surfactant/metal composites have also been produced by similar methods, but for virtually all the non-oxide semiconducting phases, the surfactant unfortunately cannot be removed to generate porous materials. Here we show that it is possible to use surfactant-driven self-organization of soluble Zintl clusters to produce periodic, nanoporous versions of classic semiconductors such as amorphous Ge or Ge/Si alloys. Specifically, we use derivatives of the anionic Ge9(4-) cluster, a compound whose use in the synthesis of nanoscale materials is established. Moreover, because of the small size, high surface area, and flexible chemistry of these materials, we can tune optical properties in these nanoporous semiconductors through quantum confinement, by adsorption of surface species, or by altering the elemental composition of the inorganic framework. Because the semiconductor surface is exposed and accessible in these materials, they have the potential to interact with a range of species in ways that could eventually lead to new types of sensors or other novel nanostructured devices.     

Initial corrosion observed on the atomic scale

Corrosion destroys more than three per cent of the world's GDP. Recently, the electrochemical decomposition of metal alloys has been more productively harnessed to produce porous materials with diverse technological potential. High-resolution insight into structure formation during electrocorrosion is a prerequisite for an atomistic understanding and control of such electrochemical surface processes. Here we report atomic-scale observations of the initial stages of corrosion of a Cu3Au111 single crystal alloy within a sulphuric acid solution. We monitor, by in situ X-ray diffraction with picometre-scale resolution, the structure and chemical composition of the electrolyte/alloy interface as the material decomposes. We reveal the microscopic structural changes associated with a general passivation phenomenon of which the origin has been hitherto unclear. We observe the formation of a gold-enriched single-crystal layer that is two to three monolayers thick, and has an unexpected inverted (CBA-) stacking sequence. At higher potentials, we find that this protective passivation layer dewets and pure gold islands are formed; such structures form the templates for the growth of nanoporous metals. Our experiments are carried out on a model single-crystal system. However, the insights should equally apply within a crystalline grain of an associated polycrystalline electrode fabricated from many other alloys exhibiting a large difference in the standard potential of their constituents, such as stainless steel (see ref. 5 for example) or alloys used for marine applications, such as CuZn or CuAl.     

铝合金的组织结构对磁性能的影响

本文讨论了铝合金的组织结构对磁化率及磁性特征的影响。合金组织中的固溶体及化合物相具有的磁性特征和磁化率值以及它们在组织中的相对数量,是决定合金磁化率的主要因素。通常,铝固溶体具有顺磁性,抗磁性的溶质原子铜、锌等及类似锂、镁的顺磁性元素均能降低铝的顺磁磁化率值。铜与铝及其它元素形成的二元或多元化合物,大多具有抗磁性。合金的磁化率值随着抗磁性化合物数量的增多而降低。当化合物相的数量达到一定程度的情况下,合金的磁化率值可能接近或达到零值。此外,铝固溶体的晶粒大小及铝合金中常见的氧化夹杂物对合金磁化率值也会产生一定的影响。     

Amplification of chirality in two-dimensional enantiomorphous lattices

The concept of chirality dates back to 1848, when Pasteur manually separated left-handed from right-handed sodium ammonium tartrate crystals. Crystallization is still an important means for separating chiral molecules into their two different mirror-image isomers (enantiomers), yet remains poorly understood. For example, there are no firm rules to predict whether a particular pair of chiral partners will follow the behaviour of the vast majority of chiral molecules and crystallize together as racemic crystals, or as separate enantiomers. A somewhat simpler and more tractable version of this phenomenon is crystallization in two dimensions, such as the formation of surface structures by adsorbed molecules. The relatively simple spatial molecular arrangement of these systems makes it easier to study the effects of specific chiral interactions; moreover, chiral assembly and recognition processes can be observed directly and with molecular resolution using scanning tunnelling microscopy. The enantioseparation of chiral molecules in two dimensions is expected to occur more readily because planar confinement excludes some bulk crystal symmetry elements and enhances chiral interactions; however, many surface structures have been found to be racemic. Here we show that the chiral hydrocarbon heptahelicene on a Cu111 surface does not undergo two-dimensional spontaneous resolution into enantiomers, but still shows enantiomorphism on a mesoscopic length scale that is readily amplified. That is, we observe formation of racemic heptahelicene domains with non-superimposable mirror-like lattice structures, with a small excess of one of the heptahelicene enantiomers suppressing the formation of one domain type. Similar to the induction of homochirality in achiral enantiomorphous monolayers by a chiral modifier, a small enantiomeric excess suffices to ensure that the entire molecular monolayer consists of domains having only one of two possible, non-superimposable, mirror-like lattice structures.     

Extended surface chirality from supramolecular assemblies of adsorbed chiral molecules

The increasing demand of the chemical and pharmaceutical industries for enantiomerically pure compounds has spurred the development of a range of so-called 'chiral technologies' (ref. 1), which aim to exert the ultimate control over a chemical reaction by directing its enantioselectivity. Heterogeneous enantioselective catalysis is particularly attractive because it allows the production and ready separation of large quantities of chiral product while using only small quantities of catalyst. Heterogeneous enantioselectivity is usually induced by adsorbing chiral molecules onto catalytically active surfaces. A mimic of one such catalyst is formed by adsorbing (R,R)-tartaric acid molecules on Cu(110) surfaces: this generates a variety of surface phases, of which only one is potentially catalytically active, and leaves the question of how adsorbed chiral molecules give rise to enantioselectivity. Here we show that the active phase consists of extended supramolecular assemblies of adsorbed (R,R)-tartaric acid, which destroy existing symmetry elements of the underlying metal and directly bestow chirality to the modified surface. The adsorbed assemblies create chiral 'channels' exposing bare metal atoms, and it is these chiral spaces that we believe to be responsible for imparting enantioselectivity, by forcing the orientation of reactant molecules docking onto catalytically active metal sites. Our findings demonstrate that it is possible to sustain a single chiral domain across an extended surface--provided that reflection domains of opposite handedness are removed by a rigid and chiral local adsorption geometry, and that inequivalent rotation domains are removed by successful matching of the rotational symmetry of the adsorbed molecule with that of the underlying metal surface.     

单核和双核过渡金属羰基化合物及双核过渡金属羰基夹心化合物的理论研究

用量子化学理论方法研究了一系列过渡金属羰基化合物及第一长周期双核过渡金属羰基夹心化合物.根据理论研究结果,对一些早期有关过渡金属羰基化合物的实验结论提出了质疑,对一些同族过渡金属元素原子形成的羰基化合物的结构和成键规律进行了探讨;对第一长周期过渡金属双核羰基夹心化合物进行的理论研究表明,不饱和程度较高的V2 (CO)n...     

Parity-time synthetic photonic lattices

The development of new artificial structures and materials is today one of the major research challenges in optics. In most studies so far, the design of such structures has been based on the judicious manipulation of their refractive index properties. Recently, the prospect of simultaneously using gain and loss was suggested as a new way of achieving optical behaviour that is at present unattainable with standard arrangements. What facilitated these quests is the recently developed notion of 'parity-time symmetry' in optical systems, which allows a controlled interplay between gain and loss. Here we report the experimental observation of light transport in large-scale temporal lattices that are parity-time symmetric. In addition, we demonstrate that periodic structures respecting this symmetry can act as unidirectional invisible media when operated near their exceptional points. Our experimental results represent a step in the application of concepts from parity-time symmetry to a new generation of multifunctional optical devices and networks.     

Quasicrystalline valence bands in decagonal AlNiCo

Quasicrystals are metallic alloys that possess perfect long-range structural order, in spite of the fact that their rotational symmetries are incompatible with long-range periodicity. The exotic structural properties of this class of materials are accompanied by physical properties that are unexpected for metallic alloys. Considerable progress in resolving the geometric structures of quasicrystals has been made using X-ray and neutron diffraction, and concepts such as the quasi-unit-cell model have provided theoretical insights. But the basic properties of the valence electronic states--whether they are extended as in periodic crystals or localized as in amorphous materials--are still largely unresolved. Here we investigate the electronic bandstructure of quasicrystals through angle-resolved photoemission experiments on decagonal Al71.8Ni14.8Co13.4. We find that the s-p and d states exhibit band-like behaviour with the symmetry of the quasiperiodic lattice, and that the Fermi level is crossed by dispersing d-bands. The observation of free-electron-like bands, distributed in momentum space according to the surface diffraction pattern, suggests that the electronic states are not dominated by localization.     

La-Mg-Ni/Co储氢合金中的相结构

应用真空电弧熔炼方法制备La-Mg-Ni/Co5：19和2：7型储氢合金.应用X射线衍射系统研究这两类合金的相结构,并测定各相的原子占位.研究表明：5：19型的（La1-xMgx）5Co19合金是由Pr5Co19,LaCo5和LaSb3V3种类型结构组成;在2：7型的（La1-xMgx）2Ni7合金中,除了（La0.85Mg0.15）2Ni7合金只含LaNi5类型相结构外,其他合金均含有LaNi5类型相结构及LaNi3或La2Ni7类型相之一.应用尝试法确定合金中各相的晶胞参数和体积的变化规律,并利用Rietveld全谱拟合分析方法测定了（La0.95Mg0.05）2Ni7合金的相结构及相含量.研究表明：两种储氢合金相结构中主相与晶界相的点阵常数之间存在良好的共格性.Mg原子同时部分取代La和Ni原子,随着Mg含量的增加,晶胞内空隙变大.由于吸收的H原子将占据这些空位,所以空位空间的增加有助于容纳更多的H.这暗示Mg原子的占位导致的晶体畸变与储氢合金储氢能力相关,同时由于Mg原子与H原子之间强的亲和力,以及主相与晶界相之间的共格关系,可以使得H原子更容易进人合金中,并形成稳定的相结构.     

基于第一性原理的镁合金合金相及固溶体研究进展

镁合金作为轻质的金属材料,具有广阔的应用前景,发展先进镁合金已成为当前的研究重点之一。第一性原理计算为开发和设计新型镁合金提供了一种经济高效的方法。基于第一性原理方法,综述了镁合金合金相及固溶体的研究现状,主要对晶体结构、弹性常数、弹性模量及广义层错能等的第一性原理研究进行了介绍,讨论了合金元素以及相结构对镁合金力学性能的影响。阐明第一性原理计算方法在镁合金研究中的重要作用,为新型镁合金成分设计及开发高性能镁合金提供参考。     

Anomalous properties in ferroelectrics induced by atomic ordering.

Complex insulating perovskite alloys are of considerable technological interest because of their large dielectric and piezoelectric responses. Examples of such alloys include (Ba1-xSrx)TiO3, which has emerged as a leading candidate dielectric material for the memory-cell capacitors in dynamic random access memories; and Pb(Zr1-xTix)O3 (PZT), which is widely used in transducers and actuators. The rich variety of structural phases that these alloys can exhibit, and the challenge of relating their anomalous properties to the microscopic structure, make them attractive from a fundamental point of view. Theoretical investigations of modifications to the atomic ordering of these alloys suggest the existence of further unexpected structural properties and hold promise for the development of new functional materials with improved electromechanical properties. Here we report ab initio calculations that show that a certain class of atomic rearrangement should lead simultaneously to large electromechanical responses and to unusual structural phases in a given class of perovskite alloys. Our simulations also reveal the microscopic mechanism responsible for these anomalies.     

关于晶体制约定理的一个严格证明

关于晶体制约定理,有必要研究和提出更加严格和完美的证明。不存在C5轴等价于不能够用相互之间无任何空隙的五边形填充满所有的空间。以这一观点为基础,本文利用纯粹的数学方法严格地证明了不存在晶体的C 5和C n (n≥7)对称轴,而允许存在1,2,3,4以及6重转动对称轴,从而证明了晶体的转动对称轴只能够存在C1, C2, C3, C4和C6。