Self-Assembly of Supramolecules Consisting of Octyl Gallate Hydrogen Bonded to Polyisoprene-block-poly(vinylpyridine) Diblock Copolymers

Synchrotron radiation was used to investigate the self-assembly in two comb-shaped supramolecules systems consisting of octyl gallate (OG), i.e., 1-octyl-3,4,5-trihydroxybenzoate, hydrogen bonded to the pyridine groups of polyisoprene-block-poly(vinylpyridine) diblock copolymers. In the case of the 1,2-polyisoprene-block-poly(4-vinylpyridine)(OG)x system, self-assembly was only observed for x ≥0.5, where x denotes the number of OG molecules per pyridine group. For x = 0.5, 0.75, 1.0, and 1.2 the system self-assembled in the form of hexagonally ordered cylinders of P4VP(OG) throughout the entire temperature range of 25-200 °C investigated. For the 1,4-polyisoprene-block-poly(2-vinylpyridine)(OG)x system, on the other hand, a considerably more complex phase behavior was found, including the formation of cubic, hexagonally ordered cylinders and lamellar morphologies. In this case several order-order transitions were observed as a function of temperature, including a lamellar to lamellar transition involving a collapse of the layer thickness. The absence of hydrogen bonding between the octyl gallate molecules and the pyridine groups at elevated temperatures is argued to be a key factor for many of the phenomena observed.

Magnetic nanocomposites at microwave frequencies

Most conventional magnetic materials used in the electronic devices are ferrites, which are composed of micrometer-size grains. But ferrites have small saturation magnetization, therefore the performance at GHz frequencies is rather poor. That is why functionalized nanocomposites comprising magnetic nanoparticles (e.g. Fe, Co) with dimensions ranging from a few nm to 100 nm, and embedded in dielectric matrices (e.g. silicon oxide, aluminium oxide) have a significant potential for the electronics industry. When the size of the nanoparticles is smaller than the critical size for multidomain formation, these nanocomposites can be regarded as an ensemble of particles in single-domain states and the losses (due for example to eddy currents) are expected to be relatively small. Here we review the theory of magnetism in such materials, and we present a novel measurement method used for the characterization of the electromagnetic properties of composites with nanomagnetic insertions. We also present a few experimental results obtained on composites consisting of iron nanoparticles in a dielectric matrix.Comment: 20 pages, 10 figures, 5 table

Extended conformations of isolated molecular bottle-brushes:Influence of side-chain topology

A Monte Carlo study is presented to discuss the influence of the side-chain topology on the enhancement of the persistence length of a molecular bottle-brush in a dilute athermal solution due to the excluded volume interactions between the side chains. The structures investigated consisted of freely jointed backbones of 100 hard spheres (beads) of diameter 1 to which 50 equally flexible side chains were grafted. The diameter of the side-chain beads was varied from 1 to 3 in the same units. For every given size of the side-chain bead, the length of the side chains was varied from 4 to 20 beads. The ratio between the persistence length and the bottle-brush diameter, which is the determining factor for lyotropic behavior of conventional semi-flexible chains, was found to be almost independent of the side-chain length. At the same time, it was found to increase considerably with increasing size of the side-chain beads, suggesting that by a proper choice of the chemistry lyotropic behavior of molecular bottle-brushes due to excluded-volume interactions between the side chains might be achieved. Moreover, relatively short side chains can be used since the side-chain length has only a minor influence on the ratio between the persistence length and the diameter. These findings are in a good agreement with recent experimental observations

Magnetically tunable electrokinetic instability and structuring of non-equilibrium nanoparticle gradients

Inspired by emergent behaviors of living matter, there is increasing interest in developing approaches to create dynamic patterns and structures in synthetic materials with controllable complexity to enable functionalities that are not possible in thermodynamic equilibrium. Here we show that electrophoretically driven and maintained non-equilibrium gradients of magnetic nanoparticles in non-polar solvent can undergo electrokinetic instabilities (EKI), leading to various electrically controllable spatiotemporally patterned states. These electrokinetic instabilities and patterns can be tuned with a magnetic field via magnetostatic energy reduction mechanism to both increase and decrease the pattern complexity. We reflect the experimental observations on the theoretical electrokinetic and magnetostatic arguments. We further show that small amounts of polar water in the otherwise non-polar system are critical enablers for the electrophoretic mobility of the nanoparticles. Since functionalities of magnetic nanoparticles are widely tunable, we foresee that the combination of dissipative electrokinetic driving and magnetic energy reduction can lead to novel functional dissipative materials

Ferromagnetic resonance in ϵ\epsilon-Co magnetic composites

We investigate the electromagnetic properties of assemblies of nanoscale $\epsilon$-cobalt crystals with size range between 5 nm to 35 nm, embedded in a polystyrene (PS) matrix, at microwave (1-12 GHz) frequencies. We investigate the samples by transmission electron microscopy (TEM) imaging, demonstrating that the particles aggregate and form chains and clusters. By using a broadband coaxial-line method, we extract the magnetic permeability in the frequency range from 1 to 12 GHz, and we study the shift of the ferromagnetic resonance with respect to an externally applied magnetic field. We find that the zero-magnetic field ferromagnetic resonant peak shifts towards higher frequencies at finite magnetic fields, and the magnitude of complex permeability is reduced. At fields larger than 2.5 kOe the resonant frequency changes linearly with the applied magnetic field, demonstrating the transition to a state in which the nanoparticles become dynamically decoupled. In this regime, the particles inside clusters can be treated as non-interacting, and the peak position can be predicted from Kittel's ferromagnetic resonance theory for non-interacting uniaxial spherical particles combined with the Landau-Lifshitz-Gilbert (LLG) equation. In contrast, at low magnetic fields this magnetic order breaks down and the resonant frequency in zero magnetic field reaches a saturation value reflecting the interparticle interactions as resulting from aggregation. Our results show that the electromagnetic properties of these composite materials can be tuned by external magnetic fields and by changes in the aggregation structure.Comment: 14 pages, 13 figure

In-situ SAXS study on the alignment of ordered systems of comb-shaped supramolecules:A shear-induced cylinder-to-cylinder transition

A tooth rheometer, designed to investigate in-situ the influence of large-amplitude oscillatory shear on the macroscopic orientation of complex fluids, is used to study the alignment of two supramolecular systems composed of a polyisoprene-block-poly(2-vinylpyi-idine) block copolymer with octyl gallate (OG) hydrogen bonded to the vinylpyridine block. The molecular ratio x between OG and pyridine groups in these two PI-b-P2VP(OG)(x) systems is 0.50 and 0.75, respectively. In both cases, a hexagonally ordered cylindrical self-assembly was revealed by small-angle X-ray scattering in a broad temperature range. The spacing of the hexagonal structure decreases significantly on heating and reversibly increases on cooling. In in-situ SAXS experiments, performed with the tooth rheometer, a gradual macroscopic alignment of the nanoscale structure is observed on heating for both supramolecular systems. The most striking feature is a shear-induced transition from one hexagonal structure to another, more aligned, hexagonal structure observed for PI-b-P2VP(OG)0.75 in the temperature range 120-140degreesC. The transition is accompanied by an abrupt reduction of the domain spacing and additionally by a decrease of the phase angle measured by the rheometer. In the PI-b-P2V-P(OG)(0.5) system a comparable reduction in the spacing is observed at 90-95degreesC. In this case, it coincides with the most intensive macroscopic alignment of the sample, proceeding in a continuous rather than discontinuous fashion. This behavior is discussed in terms of the breaking of the hydrogen bonds between OG and P2VP being facilitated by shear

Разработка технологии художественного изделия из металла по технологии ковки

Выпускная квалификационная работа 80с., 24 рис., 16 табл., 10 источников, 2 прил. Ключевые слова: художественная ковка, сварка, технология, светильник, металл, бионический стиль, стилизация. Объектом исследования является технология художественной ковки, как в целом, так и применительно к конкретному изделию. Цель работы – создание декоративного напольного светильника по технологии художественной ковки. В процессе исследования проводились классификационные и комплексные анализы функций светильника, элементов конструкции, этапов формообразования и стилизации, а также свойств материалов, применяемых для создания изделия. В результате исследования были получены и классифицированы данные о различных функциях и параметрах разрабатываемого объекта, что позволило в дальнейшем создать рабочFinal qualifying work of 80c., 24 fig., 16 tab., 10 sources, 2 adj. Keywords: art forging, welding, technology, lamp, metal, bionic style, stylization. The object of research is the technology of artistic forging, both in general and in relation to a particular product. The purpose of the work - the creation of a decorative floor lamp by art forging technology. The study carried out classification and complex analyzes luminaire features design elements, the stages of shaping and styling, as well as the properties of the materials used to create the product. The study was prepared and classified data about the various features and options developed by the object, which will continue to create the workpiece in real using the claimed technology. The basic constructive, technological a

Self-Assembly of Supramolecular Triblock Copolymer Complexes

Four different poly(tert-butoxystyrene)-b-polystyrene-b-poly(4-vinylpyridine) (PtBOS-b-PS-b-P4VP) linear triblock copolymers, with the P4VP weight fraction varying from 0.08 to 0.39, were synthesized via sequential anionic polymerization. The values of the unknown interaction parameters between styrene and tert-butoxystyrene and between tert-butoxystyrene and 4-vinylpyridine were determined from random copolymer blend miscibility studies and found to satisfy 0.031<χS,tBOS<0.034 and 0.39<χ4VP,tBOS<0.43, the latter being slightly larger than the known 0.30<χS,4VP≤0.35 value range. All triblock copolymers synthesized adopted a P4VP/PS core/shell cylindrical self-assembled morphology. From these four triblock copolymers supramolecular complexes were prepared by hydrogen bonding a stoichiometric amount of pentadecylphenol (PDP) to the P4VP blocks. Three of these complexes formed a triple lamellar ordered state with additional short length scale ordering inside the P4VP(PDP) layers. The self-assembled state of the supramolecular complex based on the triblock copolymer with the largest fraction of P4VP consisted of alternating layers of PtBOS and P4VP(PDP) layers with PS cylinders inside the latter layers. The difference in morphology between the triblock copolymers and the supramolecular complexes is due to two effects: (i) a change in effective composition and, (ii) a reduction in interfacial tension between the PS and P4VP containing domains. The small angle X-ray scattering patterns of the supramolecules systems are very temperature sensitive. A striking feature is the disappearance of the first order scattering peak of the triple lamellar state in certain temperature intervals, while the higher order peaks (including the third order) remain. This is argued to be due to the thermal sensitivity of the hydrogen bonding and thus directly related to the very nature of these systems.

NMR Experiments on Rotating Superfluid 3He-A : Evidence for Vorticity

Experiments on rotating superfluid 3He-A in an open cylindrical geometry show a change in the NMR line shape as a result of rotation: The amplitude of the peak decreases in proportion to f(T)g(Ω), where Ω is the angular velocity of rotation; at the same time the line broadens. Near Tc, f(T) is a linear function of 1−T/Tc. At small velocities g(Ω)∝Ω. These observations are consistent with the existence of vortices in rotating 3He-A.Peer reviewe