Obituary: Professor Valery Privalko

Gold decoration was applied to elucidate the morphology of annealed and unannealed oriented structures produced by shearing of polyethylene single crystals of known thicknesses, and the morphology of drawn and undrawn “shish kebabs” obtained by stirrer-induced crystallization. Distinct Au periodicities were observed perpendicular and parallel to the unannealed oriented structure, revealing distinctly the presence of microfibrils and an alternation of crystalline and noncrystalline regions within a given microfibril of which the periodicity is, however, found to be much larger than the corresponding original crystal thickness. Annealing resulted in fibrils being completely replaced by lamellae standing edgewise with the Au particles decorating directly on top of the edge but concentrated mainly on the folds leaving the crystalline region almost entirely void of gold. Deformation studies revealed an unusual ductility associated with the shish kebab structure, with the kebab splitting first, then disappearing with increasing elongation, and finally, resulting in a uniform fiber. The kebab disappearance implies that it is molecularly integrated with the interkebab material and not a completely separate chain-folded lamella attached to it. Distinct Au periodicities were observed perpendicular and parallel to the drawn shish-kebab fibers similar to the sheared single crystals. Annealing experiments and the high ductility suggest that the interkebab material is not of a fully extended-chain morphology.     

Mechanical denaturation of high polymers in solutions XXIX. Stress-induced crystallization of poly(vinyl alcohol) from its aqueous solution under steady-state flow

The crystallization of poly(vinyl alcohol), derived from its aqueous solution was carried out under a steady-state flow. The effect of the rate of stirring on the crystallization and details of several phenomena observed in stirred solutions during crystallization are presented. Moreover, the structure of crystallized poly(vinyl alcohol) was studied with use of an electron microscope. Evidence is presented for a crystal morphology that includes smooth fibrils and the absence of lamellar overgrowth, i.e., no shish kebabs.     

Energy storage in heavily doped zinc sulfide crystals with laminar morphology

We have measured the optical and structural properties of zinc sulfide crystals doped with 0.8% indium and 0.1% copper. These crystals store electronic energy at low temperatures and exhibit a broad structureless thermoluminescence. Their properties are compared with those of crystals with lower dopant concentrations. The thermoluminescence of the heavily-doped crystals can be excited by their own photoluminescent emission. This results in energy storage throughout the volume of the sample, even with the primary photoexcitation at spectral regions of strong absorption. We relate the energy storage to the laminar morphology and attribute the storage to the separation of electrons at the lamina surfaces from recombination sites in the interior of the laminae.     

Electrical properties of cadmium and zinc doped CuInS2

The electrical resistivity and mobility of Cd and Zn doped CuInS₂ single crystals grown by a Bridgman technique have been investigated. Crystals annealed in Cd or Zn vapor at high temperatures (～ 800°C) exhibit degenerate behaviour while those crystals annealed at more moderate temperatures (～650°C) show ionized impurity conduction with a shallow activation energy on the order of 0.004 eV. Resistivities as low as 0.15 Ω-cm and mobilities as high as 90 cm²/v-sec have been observed.     

Stretch-Induced Shish-Kebabs in Rubbery Poly(L-Lactide)

The oriented crystallization in stretched rubbery poly(L-lactide) has been studied with the aid of in-situ rheo-Fourier transform infrared spectroscopy (FTIR) measurements and morphological observations. The oriented segments that survived after stretching are first transformed into shish structure composed of helical sequences via intra-chain conformational ordering and propagation, followed by the transverse growth of kebabs from the coiled chains in the surrounding matrix. Moreover, the formation of shish structure and kebabs shows different dependences on the stretching temperature as a result of different controlling molecular processes.     

Unexpected shish-kebab structure in a sheared polyethylene melt

Scanning electron micrographs of a solvent-extracted sheared polyethylene (PE) blend revealed, for the first time, an unexpected shish-kebab structure with multiple shish. The blend contained 2 wt % of crystallizing ultrahigh molecular weight polyethylene (UHMWPE) and 98 wt % of noncrystallizing PE matrix. The formation of multiple shish was attributed to the coil-stretch transition occurring in sections of UHMWPE chains. Synchrotron x-ray data provided clear evidence of the hypothesis that multiple shish originate from stretched chain sections and kebabs originate from coiled chain sections, following a diffusion-controlled crystallization process.     

Multimolecule glasses and crystals of isotactic polystyrene

When spreading dilute solutions of isotactic polystyrene (iPS) on water, it was observed that different concentrations produce different morphologies in the resulting amorphous films. From 10^?1 to 10^?2 wt% solutions, ribbonlike films and circular platelets of multimolecule aggregates were obtained. After isothermal crystallization of these amorphous films, lamellae, incipient spherulites, and single-molecule crystals were observed. The formation of lamellar crystals lying flat on the substrate is an indication of the absence of epitaxy by the substrate, which would require the molecular chains to be in the surface plane and thus yield lamellae normal to the substrate. The dense packing in the center of sheaflike spherulites is caused by screw-dislocation growth, and it produces structures similar to shish kebabs. It was also observed that the lamellae grown from the center develop secondary growth spirals, causing the branching and splaying of the structure typical for spherulitic growth.     

Infrared studies of single crystals of polycaprolactam

Infrared studies of the α-crystalline form of polycaprolactam (nylon 6) have confirmed the assignment of the 1288 and 1210-cm^?1 bands to a unique fold conformation. The γ-crystalline phase has a band at 1212 cm^?1 which overlaps the 1210-cm^?1 fold band in samples containing both α and γ phases. The 1288-cm^?1 band was, therefore, used to monitor regular fold content. No unique fold bands were detected in the γ form. Irregular folds present in solution-grown crystals regularize to the unique fold conformation upon annealing. Crystals which originally exhibit slight differences in regular folding as a result of different crystallization history have similar amounts of regular folds upon annealing at 220°C. Crystals grown from solutions of very dilute concentrations of polymer have different amounts of regular folding. The annealing behavior of crystals prepared from two different solution concentrations reflect the processes of regularization and long period increase.     

The polymorphic weddellite crystals in three species of Cephalocereus (Cactaceae)

Mineral inclusions in plant cells are genetically regulated, have an ecological function and are used as taxonomic characters. In Cactaceae, crystals in epidermal and cortical tissues have been reported; however, few studies have conducted chemical and morphological analyses on these crystals, and even fewer have reported non-mineral calcium to determine its systematic value. Cephalocereus apicicephalium, C. totolapensis and C. nizandensis are Cactaceae species endemic to the Isthmus of Tehuantepec, Mexico with abundant epidermal prismatic crystals. In the present study, we characterize the mineral cell inclusions, including their chemical composition and their morphology, for three species of Cephalocereus. Crystals of healthy branches of the three species were isolated and studied. The crystals were identified by X-ray diffraction (XRD), their morphology was described using a petrographic and scanning electron microscope (SEM), and their elemental composition was measured with Energy Dispersive X-ray (EDXAR). The three species synthesized weddellite with different degrees of hydration depending on the species. The optical properties of calcium oxalate crystals were different from the core, which was calcium carbonate. We observed a large diversity of predominantly spherical forms with SEM. EDXAR analysis detected different concentrations of Ca and significant amounts of elements, such as Si, Mg, Na, K, Cl, and Fe, which may be related to the edaphic environment of these cacti. The occurrence of weddellite is novel for the genus according to previous reports. The morphological diversity of the crystals may be related to their elemental composition and may be a source of phylogenetic characters.     

Advanced Mechanics and General Relativity,by J. Franklin

Ion Coulomb crystals, formed by atomic ions at low temperatures in radiofrequency and Penning ion traps, are structures that have remarkable properties and many applications. Images of Coulomb crystals are striking and reveal the crystal structure, which arises from a balance between the trapping forces acting on the ions and their mutual Coulomb repulsion. Applications of these structures range from frequency standards and quantum simulation through to measurement of the cross-sections of chemical reactions of ions.     

Ferroelastic detwinning of the high-temperature superconductor YBa2Cu3O7-δ

Crystals of YBa₂Cu₃O_7-δ (YBC) were prepared using a flux technique. The as-grown crystals were typically on the order of 200 μm × 200 μm × 50 μm, where the 50 μm dimension is in the c-direction. Ferroelastic behavior was observed by applying a uniaxial stress along the [100]_tet-direction using a specially-designed fixture which was mounted to a programmable hot/cold stage of a polarizing reflected-light microscope. Domain wall motion was observed for temperatures greater than 200°C, and complete poling was accomplished at stresses on the order of 50–100 MPa at temperatures of 350–400°C. An ionic diffusion-activated mechanism is suggested.     

氯化钾水溶液微观结构的分子动力学模拟研究

氯化钾水溶液不同于氯化钠的,其在低温下只能形成无水盐和冰.现有研究表明在氯化钠水溶液中不仅存在着水分子连续分布的区域与离子团簇,而且这二者的物质组成也与该溶液所形成晶体的分别对应.为了探寻其他溶液中是否存在此类对应关系,并考察溶液的微观结构,本文采用分子动力学方法对氯化钾水溶液进行了研究,表明了该溶液的一些性质.氯化钾水溶液中K⁺-K⁺和Cl^--Cl^-径向分布函数的特征具有一致性,峰的最大值所对应的位置都分别相同,明显不同于氯化钠水溶液的.系列时刻下瞬态图像内O到其最近离子距离中最大值的统计结果表明氯化钾水溶液中存在着一定大小的水分子连续分布的区域,其平均尺寸至少为2.26 nm;瞬态图像中K⁺与其最近邻Cl^-之间的距离主要分布在0.28 nm～0.38 nm之间,占比约为97.4%;溶液中存在着较大和较小两类离子团簇,较大团簇的平均尺寸为1.73nm,平均离子数是25.0,其内部的离子与周围离子之间具有与氯化钾晶体类似的结构;这些结果表明氯化钾水溶液中也...     

Biaxial Orientation Mechanism of Drawn Natural Rubber. II. Quantitative Analysis of the Biaxial Orientation

Natural rubber film was prepared from triple centrifuged latex. The film was uniaxially drawn at room temperature and the induced crystalline orientation was quantitatively studied by wide angle X‐ray diffraction. The intensity distribution of 200 and 120 reflections confirmed that the induced crystals have a biaxial orientation with the c‐axis parallel to the draw direction. The orientation of the a‐axis was evaluated by using an orientation function of the (200) plane. The function (F ₂₀₀) indicated that the crystalline a‐axis is parallel to the film surface depending on the draw ratio and on positions in the film. The experimental results are possible to explain by shish‐kebab‐like crystallization developed from a highly oriented fibril. The secondary crystallization grows perpendicularly to the draw direction along the a‐axis. The population of the secondary crystals is controlled by an ellipsoidal free space. The shape of the ellipsoid is changed by the fibril distribution depending on width and thickness of the sample film. In this study, the quantitative biaxial orientation is consistently explained by the shish‐kebab‐like crystallization and the ellipsoidal free space.     

Effect of heat treatment on morphology, crystalline structure and photocatalysis properties of TiO2 nanotubes on Ti substrate and freestanding membrane

Highly ordered titanium oxide (TiO₂) nanotubes were prepared by electrolytic anodization of titanium electrodes. Morphological evolution and phase transformations of TiO₂ nanotubes on a Ti substrate and that of freestanding TiO₂ membranes during the calcinations process were studied by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction microscopy. The detailed results and mechanisms on the morphology and crystalline structure were presented. Our results show that a compact layer exists between the tubular layer and Ti substrate at 600 °C, and the length of the nanotubes shortens dramatically at 750 °C. The freestanding membranes have many particles on their tubes during calcinations from 450 to 900 °C. The TiO₂ nanotubes on the Ti substrate transform to rutile crystals at 600 °C, while the freestanding TiO₂ membranes retain an anatase crystal with increasing temperature to 800 °C. The photocatalytic activity of TiO₂ nanotubes on a Ti substrate annealed at different temperatures was investigated by the degradation of methyl orange in aqueous solution under UV light irradiation. Due to the anatase crystals in the tubular layer and rutile crystals in the compact layer, TiO₂ nanotubes annealed at 450 °C with pure anatase crystals have a better photocatalytic activity than those annealed at 600 °C or 750 °C.     

Phase separated composite films of liquid crystals

Phase separation of liquid crystals from a solution with polymers has long been studied and used to prepare polymer stabilized and polymer dispersed structures. They are formed by spatially isotropic phase separation. A new mode, in which the phase separation proceeds anisotropically, has recently been discovered. Known as phase separated composite films (PSCOF), the resultant structures are made of adjacent parallel layers of liquid crystal and solidified polymer. PSCOFs have been made with nematic, ferroelectric (FLC), and antiferroelectric (AFLC) liquid crystals. Liquid crystals in PSCOFs exhibit electro-optical properties not observed in devices prepared by conventional methods, polymer dispersion, or polymer stabilization methods. Devices incorporating FLCs possess grey scale and switch 100 times faster at low fields than conventional surface stabilized devices. This method makes it possible to prepare very flexible devices and devices with liquid crystal film thickness comparable to optical wavelengths with great ease.     

Correlation between microstructure and optical properties of nano-crystalline TiO2 thin films prepared by sol-gel dip coating

Titanium dioxide thin films have been prepared from tetrabutyl-orthotitanate solution and methanol as a solvent by sol-gel dip coating technique. TiO₂ thin films prepared using a sol-gel process have been analyzed for different annealing temperatures. Structural properties in terms of crystal structure were investigated by Raman spectroscopy. The surface morphology and composition of the films were investigated by atomic force microscopy (AFM). The optical transmittance and reflectance spectra of TiO₂ thin films deposited on silicon substrate were also determined. Spectroscopic ellipsometry study was used to determine the annealing temperature effect on the optical properties and the optical gap of the TiO₂ thin films. The results show that the TiO₂ thin films crystallize in anatase phase between 400 and 800 °C, and into the anatase-rutile phase at 1000 °C, and further into the rutile phase at 1200 °C. We have found that the films consist of titanium dioxide nano-crystals. The AFM surface morphology results indicate that the particle size increases from 5 to 41 nm by increasing the annealing temperature. The TiO₂ thin films have high transparency in the visible range. For annealing temperatures between 1000 and 1400 °C, the transmittance of the films was reduced significantly in the wavelength range of 300-800 nm due to the change of crystallite phase and composition in the films. We have demonstrated as well the decrease of the optical band gap with the increase of the annealing temperature.     

Trimers of bivalent copper impurity ions in CaF<Subscript>2</Subscript> crystals: The structure and mechanism of formation

Crystals of CaF₂: Cu (with a copper impurity content higher than 0.1 at. %) grown by the Czochralski method from a melt in a mixed helium-fluorine atmosphere are investigated using electron paramagnetic resonance (EPR) spectroscopy. It is found that the crystals contain paramagnetic centers whose magnetic properties at low temperatures are identical to those of [CuF₄F₄]^6? (S=1/2) single centers. The magnetic properties of the centers exhibit a qualitative change in the temperature range 77–300 K. These changes are described within a model according to which the center is treated as a cluster composed of three [CuF₄F₄]^6? impurity complexes involved in exchange interactions and interactions occurring in the field of Jahn-Teller lattice distortions.     

Synthesis,growth and characterization of 4-dimethylaminobenzaldehyde-4-nitrophenylhydrazone single crystals

4-Dimethylaminobenzaldehyde-4-nitrophenylhydrazone (DANPH) single crystals exhibit polymorphism such as DANPH-G form (greenish red) and DANPH-R form (red). The different polymorphic phases of the grown crystals have been identified by X-ray diffraction studies. The functional groups of the crystals have been identified by FT-IR study. Crystallographically independent environment of polymorphs has been confirmed by NMR study. The thermal properties such as melting and decomposition temperatures of the compound have been analyzed. Optical constants of DANPH polymorph crystals have been calculated.     

p-type conductivity and green photoluminescence of CuGaS2 grown by iodine transport

Crystals of CuGaS₂ grown from the vapor phase by iodine transport can be made usefully p-type (resistivity of 1 Ω cm at room temperature) by post annealing in saturated sulfur vapor. At 2°K these crystals exhibit efficient green photoluminescence.     

碳气凝胶薄片的制备及表面密度致密层去除工艺

研究了不同密度和厚度的碳气凝胶薄片的制备及其表面致密层去除工艺。在以间苯二酚、甲醛为原料制备有机及碳气凝胶块体材料的基础上,结合自制活动式微模具成型工艺,制备了厚度在80~350 μm,密度在50~600 mg·cm-3范围内变化的碳气凝胶薄片。采用场发射扫描电镜、X射线相衬成像和表面轮廓仪-台阶仪等手段对其表面和内部微观结构进行了表征。测试结果表明,碳气凝胶薄片与块体的内部结构相同,但薄片表面存在一层和内部结构截然不同的致密层。采用不同粗糙程度的材料对薄片进行了表面微处理,成功去除该致密“皮”层。