Desenvolvimento de sistemas líquido-cristalinos empregando silicone fluido de co-polímero glicol e poliéter funcional siloxano

For the construction of the phase diagrams, the method of the aqueous titration was used. There were prepared 5 ternary diagrams, varying the surfactant and the oil phase. The liquid-crystalline phases were identified by polarized light microscopy. The formulations prepared with silicon glycol copolymer, polyether functional siloxane (PFS) and water (S1) and with diisopropyl adipate, PFS and water (S4) presented liquid-crystalline phases with lamellar arrangement. Moreover, after 15 days in hot oven (37 ºC), the formulations presented hexagonal arrangement, evidencing the influence of the temperature in the organization of the system.

Caracterização da fusão peritética do cloreto de sódio di-hidratado por curvas de aquecimento

Binary mixture phase diagrams are normally obtained from thermal analysis involving freezing point curves. However, that approach is not always reliable and easy to follow to all kinds of mixtures in any proportion. In fact, even for a simple system, such as NaCl-H2O, this freezing methodology gives mixed results when one starts from a solid-solution system, due mostly to the formation of the NaCl.2H2O, which has an incongruent melting point, and the dependence of its solubility with the temperature. In this work we report a trustworthy, simple and cheap method involving heating curves to drawn the NaCl-H2O phase diagram.

Caracterización de cristales líquidos por microscopía óptica en sistemas surfactante polietoxilado-alcano-agua

The phase behavior of an alcohol polyethoxylated surfactant with decane and dodecane oil phase varying the water proportion from 5 to 90% to determine compositions in which the formation of liquid crystals and microemulsions ocurred was investigated. Pseudoternary phase diagrams were built to represent the regions of liquid crystals, biphases and microemulsions. Polarized light optical microscopy was used for the analysis and characterization of the separate phases. The micrographs obtained showed characteristics of hexagonal and lamellar phases of liquid crystal, isotropic phases, microemulsions and vesicles. This study is important to propose hypothesis regarding the factors determining the formation and stability of phases composed by surfactant/oil/water systems.

On non-ideal and non-linear portal frame dynamics analysis using bogoliubov averaging method

We apply the Bogoliubov Averaging Method to the study of the vibrations of an elastic foundation, forced by a Non-ideal energy source. The considered model consists of a portal plane frame with quadratic nonlinearities, with internal resonance 1:2, supporting a direct current motor with limited power. The non-ideal excitation is in primary resonance in the order of one-half with the second mode frequency. The results of the averaging method, plotted in time evolution curve and phase diagrams are compared to those obtained by numerically integrating of the original differential equations. The presence of the saturation phenomenon is verified by analytical procedures.

Characterisation of waste for combustion : with special reference to the role of zinc

Waste combustion has gone from being a volume reducing discarding-method to an energy recovery process for unwanted material that cannot be reused or recycled. Different fractions of waste are used as fuel today, such as; municipal solid waste, refuse derived fuel, and solid recovered fuel. Furthermore, industrial waste, normally a mixture between commercial waste and building and demolition waste, is common, either as separate fuels or mixed with, for example, municipal solid waste. Compared to fossil or biomass fuels, waste mixtures are extremely heterogeneous, making it a complicated fuel. Differences in calorific values, ash content, moisture content, and changing levels of elements, such as Cl and alkali metals, are common in waste fuel. Moreover, waste contains much higher levels of troublesome trace elements, such as Zn, which is thought to accelerate a corrosion process. Varying fuel quality can be strenuous on the boiler system and may cause fouling and corrosion of heat exchanger surfaces. This thesis examines waste fuels and waste combustion from different angles, with the objective of giving a better understanding of waste as an important fuel in today’s fuel economy. Several chemical characterisation campaigns of waste fuels over longer time periods (10-12 months) was used to determine the fossil content of Swedish waste fuels, to investigate possible seasonal variations, and to study the presence of Zn in waste. Data from the characterisation campaigns were used for thermodynamic equilibrium calculations to follow trends and determine the effect of changing concentrations of various elements. The thesis also includes a study of the thermal behaviour of Zn and a full—scale study of how the bed temperature affects the volatilisation of alkali metals and Zn from the fuel. As mixed waste fuel contains considerable amounts of fresh biomass, such as wood, food waste, paper etc. it would be wrong to classify it as a fossil fuel. When Sweden introduced waste combustion as a part of the European Union emission trading system in the beginning of 2013 there was a need for combustion plants to find a usable and reliable method to determine the fossil content. Four different methods were studied in full-scale of seven combustion plants; 14Canalysis of solid waste, 14C-analysis of flue gas, sorting analysis followed by calculations, and a patented balance method that is using a software program to calculate the fossil content based on parameters from the plant. The study showed that approximately one third of the coal in Swedish waste mixtures has fossil origins and presented the plants with information about the four different methods and their advantages and disadvantages. Characterisation campaigns also showed that industrial waste contain higher levels of trace elements, such as Zn. The content of Zn in Swedish waste fuels was determined to be approximately 800 mg kg-1 on average, based on 42 samples of solid waste from seven different plants with varying mixtures between municipal solid waste and industrial waste. A review study of the occurrence of Zn in fuels confirmed that the highest amounts of Zn are present in waste fuels rather than in fossil or biomass fuels. In tires, Zn is used as a vulcanizing agent and can reach concentration values of 9600-16800 mg kg-1. Waste Electrical and Electronic Equipment is the second Zn-richest fuel and even though on average Zn content is around 4000 mg kg-1, the values of over 19000 mg kg-1 were also reported. The increased amounts of Zn, 3000-4000 mg kg-1, are also found in municipal solid waste, sludge with over 2000 mg kg-1 on average (some exceptions up to 49000 mg kg-1), and other waste derived fuels (over 1000 mg kg-1). Zn is also found in fossil fuels. In coal, the average level of Zn is 100 mg kg-1, the higher amount of Zn was only reported for oil shale with values between 20-2680 mg kg-1. The content of Zn in biomass is basically determined by its natural occurrence and it is typically 10-100 mg kg-1. The thermal behaviour of Zn is of importance to understand the possible reactions taking place in the boiler. By using thermal analysis three common Zn-compounds were studied (ZnCl2, ZnSO4, and ZnO) and compared to phase diagrams produced with thermodynamic equilibrium calculations. The results of the study suggest that ZnCl2(s/l) cannot exist readily in the boiler due to its volatility at high temperatures and its conversion to ZnO in oxidising conditions. Also, ZnSO4 decomposes around 680°C, while ZnO is relatively stable in the temperature range prevailing in the boiler. Furthermore, by exposing ZnO to HCl in a hot environment (240-330°C) it was shown that chlorination of ZnO with HCl gas is possible. Waste fuel containing high levels of elements known to be corrosive, for example, Na and K in combination with Cl, and also significant amounts of trace elements, such as Zn, are demanding on the whole boiler system. A full-scale study of how the volatilisation of Na, K, and Zn is affected by the bed temperature in a fluidised bed boiler was performed parallel with a lab-scale study with the same conditions. The study showed that the fouling rate on deposit probes were decreased by 20 % when the bed temperature was decreased from 870°C to below 720°C. In addition, the lab-scale experiments clearly indicated that the amount of alkali metals and Zn volatilised depends on the reactor temperature.

Dynamics of two coupled chaotic multimode Nd:YAG lasers with intracavity frequency doubling crystal

The effect of coupling two chaotic Nd:YAG lasers with intracavity KTP crystal for frequency doubling is numerically studied for the case of the laser operating in three longitudinal modes. It is seen that the system goes from chaotic to periodic and then to steady state as the coupling constant is increased. The intensity time series and phase diagrams are drawn and the Lyapunov characteristic exponent is calculated to characterize the chaotic and periodic regions.

Suppression of chaos through reverse period doubling in coupled directly modulated semiconductor lasers

The effect of coupling on two high frequency modulated semiconductor lasers is numerically studied. The phase diagrams and bifurcatio.n diagrams are drawn. As the coupling constant is increased the system goes from chaotic to periodic behavior through a reverse period doubling sequence. The Lyapunov exponent is calculated to characterize chaotic and periodic regions.

Numerical studies on bi-directionally coupled directly modulated semiconductor lasers

Results of a numerical study of synchronisation of two directly modulated semiconductor lasers, using bi-directional coupling, are presented. The effect of stepwise increase in the coupling strength (C) on the synchronisation of the chaotic outputs of two such lasers is studied, with the help of parameter space plots, synchronisation error plots, phase diagrams and time series outputs. Numerical results indicate that as C increases, the system achieves synchronisation as well as stability together with an increase in the output power. The stability of the synchronised states is checked by applying a perturbation to the system after it becomes synchronised and then noting the time it takes to regain synchronisation. For lower values of C the system does not regain synchronisation. But, with higher values synchronisation is regained within a very short time.

Continuum Double Exchange Model

We present a continuum model for doped manganites which consist of two species of quantum spin-1 / 2 fermions interacting with classical spin fields. The phase structure at zero temperature turns out to be considerably rich: antiferromagnetic insulator, antiferromagnetic two band conducting, canted two band conducting, canted one band conducting, and ferromagnetic one band conducting phases are identified, all of them being stable against phase separation. There are also regions in the phase diagram where phase separation occurs

Integer filling facfor phases and isospin in vertical diatomic artificial molecules

Integer filling factor phases of many-electron vertically coupled diatomic artificial quantum dot molecules are investigated for different values of the interdot coupling. The experimental results are analyzed within local-spin density functional theory for which we have determined a simple lateral confining potential law that can be scaled for the different coupling regimes, and Hartree-Fock theory. Maximum density droplets composed of electrons in both bonding and antibonding or just bonding states are revealed, and interesting isospin-flip physics appears for weak interdot coupling when the systematic depopulation of antibonding states leads to changes in isospin.

First-principles electronic theory of non-collinear magnetic order in transition-metal nanowires

The structural, electronic and magnetic properties of one-dimensional 3d transition-metal (TM) monoatomic chains having linear, zigzag and ladder geometries are investigated in the frame-work of first-principles density-functional theory. The stability of long-range magnetic order along the nanowires is determined by computing the corresponding frozen-magnon dispersion relations as a function of the 'spin-wave' vector q. First, we show that the ground-state magnetic orders of V, Mn and Fe linear chains at the equilibrium interatomic distances are non-collinear (NC) spin-density waves (SDWs) with characteristic equilibrium wave vectors q that depend on the composition and interatomic distance. The electronic and magnetic properties of these novel spin-spiral structures are discussed from a local perspective by analyzing the spin-polarized electronic densities of states, the local magnetic moments and the spin-density distributions for representative values q. Second, we investigate the stability of NC spin arrangements in Fe zigzag chains and ladders. We find that the non-collinear SDWs are remarkably stable in the biatomic chains (square ladder), whereas ferromagnetic order (q =0) dominates in zigzag chains (triangular ladders). The different magnetic structures are interpreted in terms of the corresponding effective exchange interactions J(ij) between the local magnetic moments μ(i) and μ(j) at atoms i and j. The effective couplings are derived by fitting a classical Heisenberg model to the ab initio magnon dispersion relations. In addition they are analyzed in the framework of general magnetic phase diagrams having arbitrary first, second, and third nearest-neighbor (NN) interactions J(ij). The effect of external electric fields (EFs) on the stability of NC magnetic order has been quantified for representative monoatomic free-standing and deposited chains. We find that an external EF, which is applied perpendicular to the chains, favors non-collinear order in V chains, whereas it stabilizes the ferromagnetic (FM) order in Fe chains. Moreover, our calculations reveal a change in the magnetic order of V chains deposited on the Cu(110) surface in the presence of external EFs. In this case the NC spiral order, which was unstable in the absence of EF, becomes the most favorable one when perpendicular fields of the order of 0.1 V/Å are applied. As a final application of the theory we study the magnetic interactions within monoatomic TM chains deposited on graphene sheets. One observes that even weak chain substrate hybridizations can modify the magnetic order. Mn and Fe chains show incommensurable NC spin configurations. Remarkably, V chains show a transition from a spiral magnetic order in the freestanding geometry to FM order when they are deposited on a graphene sheet. Some TM-terminated zigzag graphene-nanoribbons, for example V and Fe terminated nanoribbons, also show NC spin configurations. Finally, the magnetic anisotropy energies (MAEs) of TM chains on graphene are investigated. It is shown that Co and Fe chains exhibit significant MAEs and orbital magnetic moments with in-plane easy magnetization axis. The remarkable changes in the magnetic properties of chains on graphene are correlated to charge transfers from the TMs to NN carbon atoms. Goals and limitations of this study and the resulting perspectives of future investigations are discussed.

Electric field alignment in thin films of cylinder-forming diblock copolymer

We investigate thin films of cylinder-forming diblock copolymer confined between electrically charged parallel plates, using self-consistent-field theory ( SCFT) combined with an exact treatment for linear dielectric materials. Our study focuses on the competition between the surface interactions, which tend to orient cylinder domains parallel to the plates, and the electric field, which favors a perpendicular orientation. The effect of the electric field on the relative stability of the competing morphologies is demonstrated with equilibrium phase diagrams, calculated with the aid of a weak-field approximation. As hoped, modest electric fields are shown to have a significant stabilizing effect on perpendicular cylinders, particularly for thicker films. Our improved SCFT-based treatment removes most of the approximations implemented by previous approaches, thereby managing to resolve outstanding qualitative inconsistencies among different approximation schemes.

Step edges in thin films of lamellar-forming diblock copolymer

Self-consistent field theory (SCFT) is used to study the step edges that occur in thin films of lamellar-forming diblock copolymer, when the surfaces each have an affinity for one of the polymer components. We examine film morphologies consisting of a stack of ν continuous monolayers and one semi-infinite bilayer, the edge of which creates the step. The line tension of each step morphology is evaluated and phase diagrams are constructed showing the conditions under which the various morphologies are stable. The predicted behavior is then compared to experiment. Interestingly, our atomic force microscopy (AFM) images of terraced films reveal a distinct change in the character of the steps with increasing ν, which is qualitatively consistent with our SCFT phase diagrams. Direct quantitative comparisons are not possible because the SCFT is not yet able to probe the large polymer/air surface tensions characteristic of experiment.

Equilibrium behavior of symmetric ABA triblock copolymer melts

Melts of ABA triblock copolymer molecules with identical end blocks are examined using self-consistent field theory (SCFT). Phase diagrams are calculated and compared with those of homologous AB diblock copolymers formed by snipping the triblocks in half. This creates additional end segments which decreases the degree of segregation. Consequently, triblock melts remain ordered to higher temperatures than their diblock counterparts. We also find that middle-block domains are easier to stretch than end-block domains. As a result, domain spacings are slightly larger, the complex phase regions are shifted towards smaller A-segment compositions, and the perforated-lamellar phase becomes more metastable in triblock melts as compared to diblock melts. Although triblock and diblock melts exhibit very similar phase behavior, their mechanical properties can differ substantially due to triblock copolymers that bridge between otherwise disconnected A domains. We evaluate the bridging fraction for lamellar, cylindrical, and spherical morphologies to be about 40%–45%, 60%–65%, and 75%–80%, respectively. These fractions only depend weakly on the degree of segregation and the copolymer composition.