An Atomistic Study of Interfacial Diffusion in Lamellar TiAl Alloys

In this paper we investigate self-diffusion of Ti and Al along interfaces present in the lamellar L1₀ TiAl by atomistic computer modeling. The interactions between the atoms are described by central-force many-body potentials. The approach adopted is similar to that used in earlier atomistic modeling of bulk diffusion in TiAl [1, 2]. Both the formation and migration of vacancies is examined. The interfaces studied are the three types of –interfaces: ordinary twin, pseudotwin and 120° rotational fault. For the latter two interfaces the diffusion was investigated not only for the stoichiometric case but also when the interfaces possess a surplus of titanium in the form of a layer with the composition and structure of Ti₃Al, as was found in an earlier Monte Carlo study of titanium segregation to these interfaces. The calculations suggest that the diffusivity along –interfaces is higher than in the bulk. However, the difference between bulk and interfacial diffusivity is not as drastic as it may be encountered in grain boundaries. At the same time the above mentioned surplus of Ti appears to affect the interfacial diffusion only marginally.     

Line Defects Separating Distinct Interfacial Structures: Topological Character and Diffusive Flux Considerations

A rigorous crystallographic framework for the characterisation ofinterfacial defects which separate (i) crystallographicallyequivalent and (ii) distinct interfacial structures is described. Forthis purpose, the Volterra approach for characterising line defectsis adapted for bicrystalline media. Defects in the distinct categoryare described in interfaces of materials with the L1₂(A₃B) structure. The diffusive flux of materialassociated with the motion of such defects is determined and comparedwith fluxes for defects separating equivalent structures. This isdone by modifying a recently developed equation which defines thediffusive flux in terms of the defect's topological parameters. It isshown that grain boundary dislocations in the distinct category within-plane Burgers vectors may not be glissile but may requirediffusive flux for their motion.     

On Perpendicular and Tilted Chains in Lamellar Crystals

Chain tilt and surface disorder were investigated in end-deuterated long n-alkane C₁₂D₂₅C₁₉₂H₃₈₄C₁₂HD₂₄ crystallized from solution and in n-alkane C₁₆₂H₃₂₆ crystallized from melt. Small-angle X-ray scattering and infrared spectroscopy were employed. Extended-chain crystals of C₁₂D₂₅C₁₉₂H₃₈₄C₁₂HD₂₄ as-grown from solution have the molecular axis perpendicular to the lamellar surface, but when heated, around 90°C, they start tilting relative to the layer normal. The tilt increases gradually to reach 35° just below the melting point. C₁₆₂H₃₂₆ crystallized from the melt at small supercoolings has chains tilted at 35° at the outset, as found previously for all melt-crystallized long alkanes and polyethylene. However, for the first time in long alkanes, it is found that when molten C₁₆₂H₃₂₆ is supercooled to ΔT≥10 K, crystals with perpendicular chains form. At still larger ΔT, the chains are once-folded, with a mixed population of tilted and perpendicular chain crystals. The use of Davydov splitting of the CH₂ and CD₂ bending vibration of the end-labelled alkane C₁₂D₂₅C₁₉₂H₃₈₄C₁₂HD₂₄ allows independent IR probing of molecular disorder at the deuterated surface and in the hydrogenous crystal interior. The initially small CD₂ splitting and the presence of an additional singlet component indicate a rough surface in as-grown crystals, with considerable longitudinal interchain disorder. It is estimated that about 10% of chains are displaced by up to a dozen C-atoms. The increase in splitting and decrease in absorbance of the singlet, which occur on annealing at progressively higher temperatures, are evidence of steady improvement in translational surface order, occurring simultaneously with increasing chain tilt angle. From the above evidence, it is concluded that the absence of tilt in as-grown crystals is not the result of high surface order, as in the case of shorter odd n-alkanes, but rather of a high frozen-in longitudinal disorder with chain ends or folds protruding out of or sunken beneath the crystal surface. It is also concluded that chain tilt only becomes necessary as the crystal surface becomes translationally more ordered and the crystal–amorphous interface sharpens. The effect of chain tilt on the Davydov splitting is addressed briefly.     

Nanoparticle Microreactor: Application to Synthesis Of Titania by Thermal Decomposition of Titanium Tetraisopropoxide

The nanoparticle microreactor (NPMR) is a new concept that we have introduced to describe a very small-scale system capable of converting an aerosol precursor to solid particles. The liquid precursor of about 1 µl is injected by a syringe through a septum into a tubular evaporator of 1.0 cm³ in volume with stopcocks at both ends. The evaporator has been preheated by a heating tape to a temperature sufficiently high for vaporization to occur in half a minute. By opening the stopcocks, the vaporized precursor is transported by a carrier gas stream into a quartz tube which is mounted along the axis of a tubular furnace. The nanoparticle aggregates produced in the reactor are sampled by deposition on an electron micrograph grid at the reactor exit. The NPMR was applied first to the synthesis of TiO₂ particles by thermal decomposition of titanium tetraisopropoxide (TTIP) in a nitrogen carrier gas, with TTIP concentrations varying from 1.0 to 7.0 mol% or 2.35×10^–6 to 1.65×10^–5 in TiO₂ volume loading, and decomposition temperatures from 300°C to 1000°C. Studies were made with a 2 mm reaction tube and a 4 mm tube with sheath gas. With the 2 mm tube, a considerable fraction of the TTIP precursor was consumed at the wall by surface reaction, resulting in very small particles. With the 4 mm tube, the primary particle size was comparable to that reported in the literature for steady flow experiments using a 22.2 mm tube. Primary particle sizes ranged from 200 to 400 nm. Depending on TTIP concentration and reactor temperature, the particles exhibited a bimodal size distribution, probably due to a two-stage nucleation. A fourfold increase in the gas flow rate had little effect on particle size, indicating that particle growth ended early, within one-fourth the tube length. Residence time in the reactor was between 0.35 and 1.4 s, and total run time about 1 min. The NPMR has potential for rapid assembly of large databases and is adaptable to combinatorial discovery of nanoparticles with novel properties. Design requirements for an ideal aerosol microreactor are discussed briefly.     

Lamellar pattern formation in small-world media

Numerical and analytical techniques are used to investigate the effects of quenched disorder of small-world networks on the phase ordering dynamics of lamellar patterns as modeled by the Swift-Hohenberg equation. Morphologies for small and large values of the network randomness are quite different. It is found that addition of shortcuts to an underlying regular lattice makes the growth of domains evolving from random initial conditions much slower at late times. As the randomness increases, the evolution is eventually frozen.     

Interfacial Stress,Interfacial Energy,and Phase Equilibria in Binary Alloys

A simple model is presented in order to explore the influence of interfacial stress, interfacial energy, and surface stress on the characteristics of phase equilibria in stressed, two-phase binary alloys. Two different system geometries are employed: concentric spheres and thin plates. The conditions for thermodynamic equilibrium are solved and equations of state for each geometry are obtained in terms of the phase fraction, alloy composition, system dimension, and several dimensionless materials parameters. Elastic stress introduces new equilibrium states that are further modified by the interfacial quantities. Those conditions for which interfacial quantities can induce significant changes in the equilibrium phase fraction and phase compositions are identified.     

Application of Lamellar Clustering Theory to Isotactic Polypropylene and Direct Observation of Lamellar Cluster Morphology by Electron Microscopy

In this work the lamellar cluster model was found to be applicable to the explanation of the mechanical yield behavior in polypropylene materials. According to the lamellar clustering theory, a spherulite is composed of radiating arms, each arm is composed of lamellar clusters, and each lamellar cluster is an aggregate of structural units of the cluster, including several crystalline lamellae and amorphous layers. The intercluster links capable of supporting external force play a role in the destruction of lamellar clusters at the yield point. These morphological features were directly confirmed from TEM observation on two-dimensional polypropylene spherulites that were crystallized from mixtures of isotactic polypropylene and atactic polypropylene, with the latter being removed later by a solvent. In addition, the structural parameters, such as the distance between intercrystalline links and the lamellar cluster thickness, which were determined by applying the mechanical yielding data to the lamellar cluster theory, were confirmed to be in agreement with the quantitative estimations from the TEM images of the polypropylene spherulites.     

界面水与催化

水的催化反应在界面进行,对新能源开发和环境保护等领域具有至关重要的作用.理解催化反应中材料界面水分子的结构、物性和分子机制,对于解决清洁能源、污水处理等关系国计民生的重大问题具有关键意义.由于水的复杂性,对于水分子在催化反应中的作用至今仍存在很大争议.界面水分子在催化反应中作为反应物、催化剂、溶剂,或是兼而有之,一直是科学界争论的热点话题.近年来,随着原位实验技术和计算机能力的快速提高,人们已经能够在原子尺度对催化反应中的界面水分子行为进行实时观测和理论模拟,为解析水在催化反应中的作用提供了实验依据和理论基础.本文简述当前催化反应中界面水研究面临的巨大机遇和挑战,以及现有实验和理论方法的最新进展和所遇到的困难,为设计优化与水应用相关的高效催化剂提供可行的思路.     

Defects and diffusion in MnO

Diffusional transport of manganese through MnO scales has been studied at temperatures from 900–1200°C by means of a novel diffusion/evaporation method and by the two-stage oxidation (Rosenburg) method. In the phase field of Mn_1?vO near the MnO₃O₄ phase boundary the manganese self-diffusion coefficient and the concentration of defects is concluded to be proportional to . The concentration of defects increases with decreasing temperature at constant partial pressure of oxygen. In this non-stoichiometry range Mn_1?yO has properties similar to wüstite, Fe_1?yO, and it is concluded that the important cation defects are defect clusters. The results may be explained assuming that the defect clusters consist of four vacancies on octahedral sites and one interstitial on a tetrahedral site. Values for the concentration of defects, the self-diffusion of manganese ions and of the defects have been calculated. For the phase field near the M/MnO phase boundary it is concluded that Mn-interstitials predominate.     

Lamellar structure and nanomechanical properties of quasicrystalline Al-Cu-Fe alloys

The kinetics of structural phase transformations in quasicrystal-forming Al-Cu-Fe alloys with compositions in the region of stability of the icosahedral (i) phase has been investigated. It has been shown that, depending on the development of metastable transformations i → pentagonal phases P1 and P2, a homogeneous lamellar structure (i + P1 + P2) or a polygrain i-phase is formed in the alloys. The P-h diagrams obtained upon nanoindentation, atomic force microscopy, and scanning electron microscopy of indentations have demonstrated signs of elasto-plastic deformation of the alloys with lamellar and polygrain icosahedral structures. It has been found that, in contrast to the polygrain icosahedral alloys with a normal size effect of nanoindentation, the alloys with a lamellar structure are characterized by a nonmonotonic dependence of the hardness (H) on the maximum load (P _max) and exhibit the effect of strain hardening in the range of loads 50 mN ≤ P _max < 500 mN. The strain hardening is considered as the result of resistance exerted by boundaries of the lamellar structure to the development of plastic deformation.     

Defects in metals

Recent study of defects in metals using Mössbauer spectroscopy is presented. Vacancy and interstitial atoms are focussed as defects in metals. General remarks for the study of defects are presented first and then, as examples of the study,¹¹⁹Sb and⁵⁷Co Mössbauer measurements to monitor the trapping and detrapping process of quenched-in vacancies in Au are discussed with the aid of the complementary techniques which are resistivity measurement, computer simulation and positron lifetime measurement. Detailed results from these complementary techniques are described. Recent theoretical calculations for defect-associated states are also presented briefly.     

辛烷基苯酚聚氧乙烯醚与正癸醇层状液晶的有序性及层状结构

研究了层状液晶的层状结构及有序性,用偏振光显微镜法确定了辛烷基苯酚聚氧乙烯醚(TritonX 100)与正癸醇体系25℃时层状液晶的区域,绘制了部分相图,并用核磁共振氢谱法(2H NMR)进一步验证;用自旋标记电子自旋共振法测定了层状液晶分子排列的有序参数,研究结果显示,不同组分TritonX 100 /n C10H21OH/H2O体系层状液晶的超精细偶合常数基本相同,表明层状液晶中的微极性是一致的.而有序参数随着TritonX 100含量的增加而增加,随着层状液晶中水含量的增加而减少;用小角度X射线衍射方法测定了层状液晶的层间距离,并计算了水分子在层状液晶中的渗透率,其渗透率约为50%.     

Lattice Location of 181Ta and 111Cd Probes in Hafnium and Zirconium Aluminides Studied by Perturbed Angular Correlation

The perturbed angular correlation technique was applied to study the lattice location of the ¹¹¹In/¹¹¹Cd and ¹⁸¹Hf/¹⁸¹Ta probe atoms in hafnium and zirconium aluminides. Compounds of different stoichiometries and crystallographic structures were the subject of investigation. According to the expectation, in all investigated compounds ¹⁸¹Hf/¹⁸¹Ta probes occupy the Hf(Zr) crystallographic sites. The ¹¹¹In/¹¹¹Cd probes are placed at the sites of all constituent metals—aluminum, hafnium and zirconium, depending on the crystallographic structure of compound, concentration of the constituent metals and temperature of the sample.     

Lamellar changes during heat treatment in isotactic polystyrene crystals

In the present investigation, the melting and thickening processes in lamellar crystals of isotactic polystyrene have been studied by transmission electron microscopy. It is shown that under properly chosen experimental conditions for the polymer, one can continuously follow the physical changes involved during the thickening as well as melting of lamellar crystals on heat treatment. The study of crystals grown at different temperatures reveals that melting of a single lamella starts at various areas. A commonly observed feature is the preferential melting of elastically bent parts of a lamella. It is indicated that the occurrence of melting in the various parts is due to a structural variation along the surface of lamellae resulting in a hindrance of the lamellar thickening process. At particular temperatures, melting of lamellar crystals is followed by recrystallization. The occurrence of a solid-stage thickening process is the major process so far observed during slow heat treatments. Considerable change in surface structure of the crystals grown at different temperatures is clearly reflected during the heat treatment. The rates of heating have marked influence on the resulting morphology of the crystalline superstructures.     

Interfacial Roughening in Field Theory

In the rough phase, the width of interfaces separating different phases of statistical systems increases logarithmically with the system size. This phenomenon is commonly described in terms of the capillary wave model, which deals with fluctuating, infinitely thin membranes, requiring ad hoc cut-offs in momentum space. We investigate the interface roughening in a unified approach, which does not rely on joining different models, namely in the framework of the Landau-Ginzburg model, that is renormalized field theory, in the one-loop approximation. The interface profile and width are calculated analytically, resulting in finite expressions with definite coefficients. They are valid in the scaling region and depend on the known renormalized coupling constant.     

薄膜异质结及二维材料中的磁斯格明子

磁斯格明子因具有拓扑稳定、移动速度快、尺寸小、驱动电流密度低等优异性质引起了人们的广泛关注。它被视作未来超高密度磁存储和逻辑功能器件的理想信息载体。基于磁斯格明子的自旋电子学器件具有非易失、高读写速度、高存储密度以及低功耗的优势,从而能满足人们对高性能器件的要求。此外,拓扑性与磁性的结合使得磁斯格明子成为研究拓扑磁性物理的良好平台。文章简要介绍了磁斯格明子的发展概况及其拓扑物理性质,并着重讨论薄膜异质结及二维材料中磁斯格明子的研究进展,为今后进一步探索磁斯格明子相关研究领域抛砖引玉。     

Interfacial properties in solid-stabilized emulsions

We prepared concentrated monodisperse oil-in-water emulsions stabilized by solid particles. The osmotic resistance, , of the emulsions was measured for different oil volume fractions above the random close packing ( ). The dimensionless osmotic resistance, /(/R) ( being the interfacial tension and R being the undeformed drop radius), was always substantially higher than the corresponding values obtained for surfactant-stabilized emulsions. It can be concluded that droplet deformation in solid-stabilized emulsions is not controlled by the capillary pressure, /R, of the non-deformed droplets but rather by 0/R, 0 being a parameter characterizing the rigidity of the droplets surfaces. The data can be interpreted considering that the interfacial layers are elastic at small deformations and exhibit plasticity at intermediate deformations. 0 corresponds to the surface yield stress, i.e. the transition between elastic and plastic regimes. We discuss the origin of the surface behavior considering the strong lateral interactions that exist between the adsorbed solid particles. We propose an independent measurement of 0 based on the critical bulk stress that produces droplet fragmentation in dilute emulsions submitted to shear. Finally, the bulk shear elastic modulus was measured as a function of and confirms many of the features revealed by the osmotic resistance.