Recent study on counterion-mediated attraction between colloidal particles

Recent experimental results were reviewed. The 1D- and 2D-USAXS studies gave higher orders of Bragg diffraction for single crystals of colloidal silica particles, allowing more accurate determinations of the lattice constant, lattice symmetry, and direction. The closest interparticle spacing thus determined was confirmed to be smaller than the average spacing. The most closely packed planes ((110) planes for bcc) of negatively charged particles were found to be parallel to the likewise negatively charged capillary surface, inconsistently with the accepted double layer interaction theory but consistently with a recent experimental finding of positive adsorption. Shaking caused disruption of the single crystals but newly formed microcrystals retained the lattice constant and the preference of the (110) planes. The liquid-solid-liquid transition, a re-entrant phase transition, was found for silica particles and latex particles at given particle volume fraction and salt concentration, when the charge density of particles was varied. It was demonstrated that the purely repulsive Yukawa potential and the concept of renormalized charge cannot account for the re-entrant behavior. The Monte-Carlo simulation using the Sogami potential, which contains short-range repulsion and long-range attraction, was found to account for the fcc–bcc transition, which was earlier claimed to be explainable only by the Yukawa potential. Furthermore, the homogeneous-inhomogeneous phase transition and void formation could be accounted for by the simulation using the Sogami potential; the Yukawa potential could not reproduce the experiments. Attention was drawn to the experimental conditions in direct measurements of interparticle forces; only short interparticle distance and low charge density particles were covered, which make it practically impossible to detect the long-range counterion-mediated attraction. It is hoped that, by technical improvements, these shortcomings may be made up and quantitative argument become possible on the attraction.     

Topochemical 3D polymerization of C60 under high pressure at elevated temperatures

Fullerene C60 monomer crystals were compressed to a face-centered cubic (fcc) phase with a lattice parameter of a = 11.93(5) A and a micro-Vickers hardness of 4500 kg/mm2 using high-pressure and high-temperature conditions of 15 GPa at 500-600 degrees C. The hardness is compatible with that of cubic boron nitride (c-BN), suggesting the formation of a 3D C60 polymer. The single-crystal X-ray structural analysis revealed that each C60 molecule in the polymer was linked to the 12 nearest neighbors by [2+2] cycloaddition between the common pentagon-hexagon (56) edges. However, ab initio geometry optimization and molecular dynamics calculations suggested that the 3D polymer should have a rhombohedral structure with the space group of R containing [3+3] cycloaddition between the pentagons of C60 molecules within the plane perpendicular to the 3-fold axis. The higher apparent symmetry of fcc was observed as an averaged structure of different orientations of the rhombohedral structure. The R structure can be derived by only a slight rotation of each C60 unit in the (111) plane of the fcc structure. The band-structure calculation suggested that the 3D polymer (R) was a semiconductor; the activation energy for the electrical conductivity was experimentally determined to be 0.25 eV at 550 K.     

Doped colloidal photonic crystal structure with refractive index chirping to the [111] crystallographic axis

A three-dimensionally ordered array of close-packed colloidal spheres, a photonic crystal structure in which the refractive index of the medium interstitial lattice in a colloidal crystal spatially changes in the [111] crystallographic axis, is demonstrated. The colloidal photonic crystal structure with refractive index chirping was produced by infiltration of a monomer and organic dopants with a high refractive index into a silica opal, followed by interfacial gel polymerization. The resulting photonic crystal structure has a gradually varying stop band at each different (111) plane in the face-centered cubic (fcc) crystal structure at a normal incidence. This novel structure exhibited optical characteristics that have band-gap broadening by the superposition of stop bands at each plane of the crystal with different dielectric functions. Moreover, the refractive index perturbation in the [111] fcc opal also showed a defect state within a pseudo-photonic band gap. This new type of photonic crystal structure should be useful for the band-gap engineering of photonic-band-gap materials.     

Three-dimensional crystallographic determination of the body-centered-cubic morphologies of shear-aligned block copolymer systems

The texture of ordered phases of block copolymer melts and gels is highly sensitive to shear. In the body-centered-cubic phase of a block copolymer system [polystyrene–poly(ethylene butylene)–polystyrene] mixed with oil, we show how a given textures can be controlled with the application of a specific shear rate and amplitude. The low-amplitude shear texture is dominated by {001} planes perpendicular to the shear gradient and by the [110] axis parallel to the flow direction, that is, the {001}/[110] slip system. Detailed crystallographic studies show that both intermediate-amplitude oscillatory shear and large-amplitude oscillatory shear lead to twin structures with {112} planes sharing neighboring twins and [111] axes parallel to the shear flow. At an intermediate shear amplitude, the ve shear plane, defined by the shear flow direction (v) and shear vorticity direction (e), is parallel to the {112} twin planes. At a high shear amplitude, the orientation is rotated 90°, and this makes the ve shear plane parallel to the {110} crystallographic planes. The crystalline slip system is accordingly ({112 }/[111] + {11 2}/[111]) under intermediate-amplitude shear and ({11 0}/[111] + {1 10}/[111]) under large-amplitude shear. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3095–3101, 2004     

Epitaxial growth of isotactic polypropylene on oriented polyethylene from solution

Oriented polyethylene (PE) films with surfaces bounded by the (100) plane were prepared. On the film surfaces, isotactic polypropylene (iPP) was crystallized epitaxially from solution as quadrits with their sides parallel and perpendicular to the polyethylene chain axis. In the through wide-angle x-ray diffraction pattern (taken with incident x-rays normal to the polyethylene film surface), the 111 iPP reflections was observed on the meridian (Parallel to the polyethylene chain axis). In the edge patterns (taken with x-rays incident on the edge of the polyethylene film), 040 and 060 reflections were observed on the equator. From the diffraction patterns, the following lattice coincidence was observed between polyethylene and isotactic polypropylene: (010)iPP//(100) PE, [101]iPP//[001] PE. The Small-angle x-ray scattering patterns showed that edge-on isotactic polypropylene lamellae 9 nm thick were arranged with their long axes inclined at an angle of 40° from the polyethylene axis. Molecular chains were oriented within the lamellae normal to the surfaces.     

Sm0.88Dy0.12Fe2合金的易磁化方向研究

运用穆斯堡尔效应，对Ｓｍ０．８８Ｄｙ０．１２Ｆｅ２合金的易磁化方向的变化进行了研究。结果表明；随着温度的升高，其易磁化方向从「１１０」渐变地转向「１１１」，在１５３至２１３Ｋ温度范围内，「１１０」和「１１１」两者共存，而并非由「１１０」其一温度突变至「１１１」。     

Influence of channeling effects on ion distribution and damage profiles during high energy ion implantation in Si

Nitrogen implantation has been performed in silicon [001] crystals in carefully controlled alignment conditions. The channeling effects are clearly evident when implanting in [001] and [011] directions at energies ranging from 0.6 to 1.4 MeV. Both ion distribution and damage profiles are strongly influenced by channeling effects during ion implantation. The angular region around the [001] direction has been also investigated by implanting at small angles with respect to the axis. The same kind of study has been performed by implanting at different angles with respect to the planar (011) direction. The ion distributions (investigated by SIMS) show a strong dependence upon the alignment conditions. Moreover in high energy ion implantation, the lattice damage is located deep inside the crystal, leaving the surface layer almost unperturbed. The channeling effects on the damage production have been investigated by double crystal diffraction (DCD) in the low-dose regime and by RBS-channeling experiments (after implantation at doses greater than 1 × 10¹⁵ cm^–2) and for different ion alignment conditions.A big increase in the ion ranges and a strong reduction in the lattice damage is evident when implanting along major crystal axes. No saturatíon of the lattice damage and of the channelled component of the beam has been detected if the implantation is performed parallel to the [011] axis.     

Photochromism of spiropyran nanocrystals embedded in sol-gel matrices

Spectroscopic and kinetic properties of a new photochromic medium, consisting of nanocrystals of spyropyran molecules (1,3-dihydro-1,3,3,5',6',pentamethyl-spiro[2H-indole-2,2'-[2H]pyrano [3,2-b]pyridinium] iodide) embedded in an organo-silicate sol-gel film, are presented and compared to microcrystals obtained by slow evaporation of a solvent. High photoconversion efficiencies for both kinds of crystals have been observed. In microcrystals, the photomerocyanine form absorbs at 570 nm with a fading rate of 5 h, in nanocrystals the photomerocyanine form absorbs at 535 nm with a fading rate of 41 h. Therefore, the crystalline structure of nanocrystals is different from the microcrystal one.     

Piezoreflectance spectra of 1s Z12 exciton in CuBr

We have investigated the piezoreflectance spectra (deltaR/R) of the 1s Z12 exciton in single crystals of copper bromide CuBr at the temperature of 95 K with linearly polarized light. The spectra were successively studied with the pressure p along the [001] and [111] axis and the wave vector k of the incident light parallel to the [110] direction. The shear deformation potentials b and d of the 1s Z12 exciton were deduced from the stress-induced shift and splitting. The results are compared with those obtained in other works.     

Magnetische Mikroanalyse von Permalloy mit Hilfe von Elektronenstrahlen

Zusammenfassung Mit Hilfe der Elektronenbeugung ließ sich belegen, daß die am leichtesten zu magnetisierende Kristallachse von Permalloy (42 Gew.-% Ni) längs der [111]-Richtung des kubisch-flächenzentrierten Gitters liegt. Dieses Verfahren mit einem feinen Elektronenbündel ist ein Beispiel für eine magnetische Mikroanalyse, wie sie für eine Fe-Ni-Legierung bequem ausgeführt werden konnte.

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Summary It was verified in terms of electron diffraction that the easy-magnetization axis of permalloy [42% (w/w) Ni] lies along the [111] direction of the cubic facecentred lattice. This procedure with a fine electron flux demonstrated a magnetic microanalysis performed successfully for a Fe-Ni alloy.

     

Synthesis and Single Crystal Structure of RbEr_2Cu_3Se_5

1 INTRODUCTION Halide fluxes are excellent media for growing single crystals of chalcogenides[1~3]. It is well known that during the single crystal growth via flux methods, occasional inclusion of the flux elements in the structure leads to the formation of new phases[4~9]. Several rare earth chalcogenides have been prepared through such reactive halid flux methods[4~9]. Thus we used RbCl as reactive flux to explore a new quaternary selenide by the reaction of ErCuSe precursor with Rb…     

Defect models of the three trigonal Ti3+ centers in LiF:Ti3+ and LiF:Ti3+:Mg2+ crystals

The EPR g factors of the trigonal Ti3+ center A in LiF:Ti3+ and two additional trigonal Ti3+ centers B and C in LiF:Ti3+:Mg2+ crystals are calculated from the third-order perturbation formulas based on the cluster approach. From the calculations and by considering the Ti3+ displacement along 111 axis obtained by ENDOR experiment, the defect models for the three Ti3+ centers are suggested. For center A, there are two possible models: (i) [Ti3+F3-O3(2-)] cluster and (ii) [Ti3+F6-] cluster with the Ti3+ off-center caused by a neighboring Li+ vacancy (VLi+) at <111> axis. The latter seems the more likely. The defect models of centers B and C are the [Ti3+F3-O(3)2-] clusters associated with a neighboring: Mg2+ ion at the Li+ site along 111 axis in the vicinity of three F- ions and three O2- ions, respectively. The reasonableness of these models is discussed.     

Atomic force microscopy of the three-dimensional crystal of membrane protein, OmpC porin

Three-dimensional microcrystals of OmpC osmoporin were air-dried slowly and imaged in air with an atomic force microscope (AFM). The overall structural features in AFM images are in good agreement with the X-ray diffraction data of these OmpC osmoporin crystals: monoclinic P2₁ with the unit cell constants a=117.6 Å, b=110 Å, c=298.4 Å, β=97°. Such a good correspondence between X-ray diffraction and AFM data suggests that the slow and mild air-drying of these crystals did not induce any significant alterations in the crystal lattices as expected upon crystal dehydration. At the (100) crystal face, individual trimeric protein–detergent complexes were resolved. These results show the potential for studying the molecular structure of microcrystals of integral membrane proteins. This study also suggests that the crystal grew in a fashion of rapid two-dimensional expansion along the bc plane followed by a slow deposition along the a axis, perhaps as a rate-limiting nucleation process. Thus, AFM imaging of air-dried crystals would also be of considerable use in the early stages of a project to grow large three-dimensional crystals of membrane proteins suitable for high-resolution X-ray diffraction studies.     

Structural changes on hot-rolling of polyethylene. I. Crystallite orientation and lamellar deformation

The crystallite orientation and lamellar deformation produced by hot-rolling in polyethylene have been investigated. In the lightly rolled stage, the [110]^* axis of polyethylene crystals orientates in the plane perpendicular to the rolling direction and the c axis becomes aligned with the rolling direction. In the heavily rolled stage the a, b, and c axes coincide with the macroscopic directions in the sample. These orientational changes are interpreted in terms of a slip mechanism. Small-angle x-ray scattering (SAXS) investigations of hot-rolled polyethylene show the following. (1) There are two kinds of lamellar structures; one in which inclined lamellae give a four-point diagram in the SAXS photograph and another in which lamellar normals are oriented around the rolling direction even at the lightly rolled stage. The latter structure is attributed to the mechanism of unfolding and recrystallization. (2) The chain-fold length in the original structure remains unchanged in the lamellae up to a roll ratio of four although the apparent long period decreases. This is explained by inclination of polymer chains in the lamellae. Further rolling aligns the polymer chains with the rolling direction and the fold length decreases.     

Crystal‐Facet Engineering of Ferric Giniite by Using Ionic‐Liquid Precursors and Their Enhanced Photocatalytic Performances under Visible‐Light Irradiation

In the work presented here, well‐dispersed ferric giniite microcrystals with controlled sizes and shapes are solvothermally synthesized from ionic‐liquid precursors by using 1‐n‐butyl‐3‐methylimidazolium dihydrogenphosphate ([Bmim][H₂PO₄]) as phosphate source. The success of this synthesis relies on the concentration and composition of the ionic‐liquid precursors. By adjusting the molar ratios of Fe(NO₃)₃ ? 9H₂O to [Bmim][H₂PO₄] as well as the composition of ionic‐liquid precursors, we obtained uniform microstructures such as bipyramids exposing {111} facets, plates exposing {001} facets, hollow spheres, tetragonal hexadecahedron exposing {441} and {111} facets, and truncated bipyamids with carved {001} facets. The crystalline structure of the ferric giniite microcrystals is disclosed by various characterization techniques. It was revealed that [Bmim][H₂PO₄] played an important role in stabilizing the {111} facets of ferric giniite crystals, leading to the different morphologies in the presence of ionic‐liquid precursors with different compositions. Furthermore, since these ferric giniite crystals were characterized by different facets, they could serve as model Fenton‐like catalysts to uncover the correlation between the surface and the catalytic performance for the photodegradation of organic dyes under visible‐light irradiation. Our measurements indicate that the photocatalytic activity of as‐prepared Fenton‐like catalysts is highly dependent on the exposed facets, and the surface area has essentially no obvious effect on the photocatalytic degradation of organic dyes in the present study. It is highly expected that these findings are useful in understanding the photocatalytic activity of Fenton‐like catalysts with different morphologies, and suggest a promising new strategy for crystal‐facet engineering of photocatalysts for wastewater treatment based on heterogeneous Fenton‐like process.     

Observation of Asymmetric Oxidation Catalysis with B20 Chiral Crystals**

The study of heterogeneous reactions for enantiomeric processes based on inorganic crystals has been resurgent in recent years. However, the question remains how homochirality develops in nature and chemical reactions. Here, the successful growth of B20 group PdGa single crystals with different chiral lattices enabled us to achieve enantioselective recognition of 3,4-dihydroxyphenylalanine (DOPA) based on a new mechanism, namely orbital angular momentum (OAM) polarization. The orbital textures of PdGa crystals indicate large OAM polarization near the Fermi level and carrying opposite signs. A positive or negative magnetization in the [111] direction is expected depending on the chiral lattice of PdGa crystals. Due to this, the adsorption energies of PdGa crystals and DOPA molecules differ depending on how well the O-2p orbital of DOPA pairs with the Pd-4d orbital of PdGa. The results provide one possible explanation for how chirality arises in nature by providing an enantioselective route with pure inorganic crystals.     

Novel Zn1-xMnxSe (x = 0.1-0.4) one-dimensional nanostructures: nanowires, zigzagged nanobelts, and toothed nanosaws

Novel Zn1-xMnxSe one-dimensional nanostructures-straight nanowires (x = 0.1 and 0.3), zigzagged nanobelts (x = 0.4), and toothed nanosaws (x = 0.4)-were synthesized using the chemical vapor deposition method. They all consisted of single-crystalline wurtzite ZnSe crystals, irrespective of the Mn content. In particular, the nanosaws have a unique structure in which double-sided teeth are rooted in the nanowire core and bent so as to align as two parallel rows. The long axis is parallel to the [010] direction, and all of the teeth have the [0001] growth direction. The X-ray diffraction pattern confirms the formation of wurtzite ZnSe crystal and the decrease of the lattice constant owing to Mn doping. The Mn2+ emission at 2.1 eV (appeared below 100 K), originating from the d-d (4T1 --> 6A1) transition, proves the effective substitution of Mn2+ ions at the tetrahedral coordinate sites.     

Mechanical Effects of Elastic Crystals Driven by Natural Sunlight and Force

Flexible crystals that can capture solar energy and convert it into mechanical energy are promising for a wide range of applications such as information storage and actuators, but obtaining them remains a challenge. Herein, an elastic crystal of a barbiturate derivative was found to be an excellent candidate, demonstrating plastic bending behavior under natural sunlight irradiation. ¹H NMR and high-resolution mass spectrum data of microcrystals before and after light irradiation demonstrated that light-induced [2+2] cycloaddition was the driving force for the photomechanical effects. Interestingly, the crystals retained elastic bending even after light irradiation. This is the first report of flexible crystals that can be driven by natural sunlight and that have both photomechanical properties and elasticity. Furthermore, regulation of the passive light output direction of the crystals and transport of objects by applying mechanical forces and light was demonstrated.     

叶状Cu(OH)2的合成及其向带有纳米孔的CuO的转化

通过乳液界面反应法, 利用以Span80(sorbitan monooleate)作为稳定剂的乳液体系控制合成了叶状Cu(OH)2单晶. 通过热处理, 可以得到表面有纳米孔的CuO, 且保持了原有的叶状形貌. 通过X射线衍射(XRD)、Fourier红外光谱(FTIR)、扫描电镜(SEM)和透射电镜(TEM)观测了其形貌和结构特征. 实验结果表明, 叶状Cu(OH)2为单晶, 且沿[111]晶面定向生长. 孔的形成是由于相转变过程中Cu(OH)2失去H2O分子所致. 通过观测不同反应时间产物的形貌, 深入探讨了叶状Cu(OH)2纳米结构的组装机理. 整个组装过程是由能量高的颗粒状纳米粒子通过端部取向连接定向生长而得到能量相对较低的叶状结构. 并且得到的CuO的紫外光谱相对于其块体材料发生了蓝移, 显示出比较大的禁带宽度.     

One-dimensional corrugation of the h-BN monolayer on Fe(110)

We report on a new nanopatterned structure represented by a single atomic layer of hexagonal boron nitride (h-BN) forming long periodic waves on the Fe(110) surface. The growth process and the structure of this system are characterized by X-ray absorption (XAS), core-level photoemission spectroscopy (CL PES), low-energy electron microscopy (LEEM), microbeam low-energy electron diffraction (μLEED), and scanning tunneling microscopy (STM). The h-BN monolayer on Fe(110) is periodically corrugated in a wavy fashion with an astonishing degree of long-range order, periodicity of 2.6 nm, and the corrugation amplitude of ～0.8 ?. The wavy pattern results from a strong chemical bonding between h-BN and Fe in combination with a lattice mismatch in either [111] or [111] direction of the Fe(110) surface. Two primary orientations of h-BN on Fe(110) can be observed corresponding to the possible directions of lattice match between h-BN and Fe(110), with approximately equal area of the boron nitride domains of each orientation.