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[pt] Nas últimas décadas a demanda por elementos terras raras (ETRs) cresceu consideravelmente devido a sua importância estratégica. Os ETRs são amplamente utilizados em diferentes setores, tais como, medicina, engenharia química, eletrônica e fabricação de computadores. Entre os ETRs, está o Neodímio, que é um dos metais mais valiosos utilizados em ligas, componentes eletrônicos e filtros ópticos. A necessidade da alta pureza dessas espécies requer a separação seletiva, e entre os métodos disponíveis, a adsorção ganhou maior atenção devido à sua simplicidade, alta eficiência e baixo custo. Neste trabalho foi avaliado o argilomineral palygorskita como potencial sorvente para remoção de Nd (III) de soluções aquosas através de ensaios em batelada. Para este propósito, a amostra proveniente da região de Guadalupe (Piauí) foi beneficiada e estudada a composição química e mineralógica com o intuito de utilizar no processo adsortivo a amostra com maior grau de pureza. A composição química apresenta teores de óxidos, sendo os principais, SiO2, Al2O3 e MgO corroborando a presença de palygorskita na amostra. Os estudos de potencial zeta apontam que o argilomineral apresenta carga superficial negativa em toda faixa de pH, além disso, a elevada área superficial de 118 metros quadrados por grama justificam a aplicação como adsorvedor de cátions. Diferentes tipos de isotermas de adsorção e modelos cinéticos foram utilizados para descrever o comportamento do Nd (III) na adsorção e os resultados experimentais que melhor se ajustaram são referentes ao modelo de Langmuir, e a capacidade máxima de captação foi de 15,39 mg/L avaliada em pH 5. A cinética de adsorção para o Nd (III) foi modelada pela equação de pseudo segunda ordem. A adsorção foi encontrada e sugere-se que o processo é endotérmico e espontâneo (delta H igual 17,12 KJ/mol; delta G igual -26,3 KJ/mol) em relação aos parâmetros termodinâmicos obtidos. Os resultados gerais sugerem que este adsorvente demonstrou ser um potencial sorvente para separação de Nd(III) a partir de soluções aquosas. / [en] In recent decades, the rare-earth elements (REEs) demand has considerably grown because of its strategic importance. REEs are widely used in different high-tech sectors such as nuclear power, metallurgy, medicine, chemical engineering, electronics and computer manufacturing. Among REEs, is Neodymium, which is one of the most valuable metals used in alloys, electronic components and optical filters. The need for the high purity of these species requires selective separation, between the available methods, adsorption has earned greater attention due to its simplicity, high efficiency and low cost. The removal of metal ions is a complex task due to the high cost of treatment methods. Contributed to the intensification of research for low-cost adsorbent materials, reusable alternatives were added to the adsorption process. In this work was evaluated the clay mineral palygorskite as a sorbent potential for Nd (III) removal from aqueous solutions by batch trials. For this purpose, the sample from Guadalupe (Piauí) was benefited and the composition of the chemical and mineralogical was studied in order to use the sample with the highest purity in the adsorptive process. The samples were found to be essentially composed of palygorskite, kaolinite, quartz and diaspore. The chemical composition presents oxide contents, the main ones being SiO2, Al2O3 and MgO, corroborating the presence of palygorskite in the sample. Zeta Potential studies point out that the clay mineral has a negative surface charge in the whole pH range, in addition, the high surface area of 118.43 square meter per gram justifies the cation adsorber application. Different types of adsorption isotherms and kinetics models were used to describe the behavior of Nd (III) in adsorption and the best experimental results set refer to the Langmuir model and pseudo second order model, respectively, with the maximum uptake capacity was 15.39 mg/L evaluated at pH 5. Adsorption was found as an endothermic and spontaneous process ( delta H equal 17.12 KJ/mol; delta G equal -26.3 KJ/mol) in relation to thermodynamic parameters obtained. Overall results suggest that this adsorbent has been shown to be a potential sorbent for enrichment and separation of Nd (III) from aqueous solutions.

<p>Microfluidic devices using electroosmotic flows (EOFs) in microchannels have been developed and widely applied in chemistry, biology and medicine. Advantages of using these devices include the reduction of reagent consumption and duration for analysis. Moreover the velocity profile of EOFs, in contrast to the parabolic profile found in pressure-driven flows, has a plug-like profile which contributes significantly less to solute dispersion. It also requires no valve to control the flow, which is done with the appropriate application of electrical potentials, thus becomes one of the favourite techniques for sample separation. However, high potentials of several hundred volts are usually required to generate sufficient EOF. These high potentials are not practical for general usage and could cause electrical hazard in some applications. One of the possible solutions is the introduction of zeta potential modulation. The EOF in a microchannel can be controlled by the zeta potential at the liquid/solid interface upon the application of external gate potentials across the channel walls. Combined with AC EOF, it can rectify the oscillating flows and generate pressure that can be used for microfluidic pumping applications. Since the flow induced by the alternating electric field is unsteady and periodic, it is critical to visualize the flow with high spatial and temporal resolutions in order to understand fluid dynamics. A novel method to obtain high temporal resolution for high frequency periodic electrokinetic flows using phase sampling technique in micro particle image velocimetry (PIV) measurements are first developed in order to characterize the AC electroosmotic flow. After that, the principle of zeta potential modulation is demonstrated to transport particles, cells, and other micro organisms using rectified AC EOF in open microchannels. The rectified flow is obtained by synchronous zeta-potential modulation with the driving potential in the microchannel. Subsequently, we found that PDMS might not be the best material for some pumping and biomedical applications as its hydrophobic surface property makes the priming process more difficult in small microchannels and also causes significant protein adsorption from biological samples. A more hydrophilic and biocompatible material, polyurethane (PU), was chosen to replace PDMS. A polyurethane-based soft-lithography microfabrication including its bonding, interconnect integration and in-situ surface modification was developed providing better biocompatibility and pumping performance. Finally, an electroosmotic pumping device driven by zeta potential modulation and fabricated by PU soft lithography was presented. The problem of channel priming is solved by the capillary force induced by the hydrophilic surface. Its flow rate and pressure output were found to be controllable through several parameters such as driving potential, gate potential, applied frequency, and phase lag between the driving and gate potentials.</p> / Doctor of Philosophy (PhD)

Although enormous potential benefits are envisioned with the application of nanotechnology in conjunction with biological systems, interactions of nano particulate materials with biological materials is not well understood. The focus of this dissertation is to determine the mathematical relationships of the forces between nanoparticles and biological agents. The systems under investigation are the alpha-SiC/H2O/LGG polar based systems. The mathematical analysis for the surface forces, based on the attractive van der Waals forces for the alpha-SiC/H2O/alpha-SiC and alpha-SiC/H2O/LGG polar solvent based systems are presented and discussed. The rheological parameters including pH, zeta potential, shear rate, shear stress and viscosity that alter the dispersion mechanisms are also presented and discussed. The concurrence of the experimental analysis with the mathematical modeling is also presented. The rheological analysis in these systems for determining of the optimum amounts of dispersant, binder, plasticizer and solids loading using the Krieger-Dougherty fit and Liu's model are presented and discussed. Alpha-SiC/H2O/alpha-SiC and alpha-SiC/H2O/LGG polar solvent based samples were also fabricated to test for an application area of nano-bio technology: A novel nano and micro porous materials fabrication process. Porous materials are used for a variety of applications including insulation, filtration, catalytic substrates, textiles and consumer goods and accounts for billions of dollars in sales annually. Results from the alpha-SiC/H2O/alpha-SiC and alpha-SiC/H2O/LGG polar solvent based slip and freeze cast samples and their characterization using digital and electron microscopy are presented and discussed. Finally, the green and sintered density, porosity and strength of the alpha-SiC/H2O/alpha-SiC and alpha-SiC/H2O/LGG polar solvent based dispersion samples are determined and discussed. / Ph. D.

Most soil particles loses cohesion and split up the soil mass into individual soil grains when they come in contact with water and get saturated. In dispersive soils the particles detach more spontaneously from each other and go into suspension even in quiet water. Thus the phenomenon of dispersion is common to most soils, the degree varying from soil to soil. Dispersive soils are abundantly found in various parts of the world such as Thailand, United States, Australia, Mexico, Brazil, South Africa and Vietnam. Several geotechnical failures such as piping due to internal erosion, erosion and gullying in relatively flat areas, collapse of sidewalls and topsoil removal have been reported worldwide due to the construction in dispersive soil. Failures as reported could be prevented if such soils are identified before-hand or if the quantification of dispersivity in the soil is done accurately. There are several methods of measuring dispersivity in soils which include several physical tests, chemical tests and some common laboratory tests. It is reported in literature that no method could be completely relied upon to identify dispersive soils with absolute confidence. In addition, when these methods were studied in detail, several flaws surfaced needing a better estimation of dispersivity. In order to develop a new method of estimation of dispersivity, the mechanism of dispersion in soils was studied in depth, which revealed that the existing concepts regarding dispersivity are incomplete in many aspects. An exhaustive philosophy of dispersion which addresses every detail is non-existing. To solve these problems, the concept of dispersivity was investigated in detail. It was found out that the observed dispersivity is a result of repulsion in the soil overcoming the attractive force. Thus a list of factors that could possibly affect the repulsion and attraction (and hence the dispersivity) in soils were found out. Even though literature focuses on exchangeable sodium as the principal reason for dispersivity, from fundamental theoretical considerations several other factors such as Cation exchange capacity (CEC), pH, structure of the soil, electrolyte concentration in the pore fluid, presence of organic matter, clay minerals involved in the soil and dissolved salts in the soil could possibly have an influence on dispersivity. Several studies have reported soils of high dispersivity to possess a high pH, high CEC, high amounts of sodium. The influence of these factors on dispersivity of other soils (or generally in any soil) is not well explored. Research on understanding their mechanism of action led to the conclusion that these parameters could be generalized for any soil. Through the analysis of these parameters, it was found that the fundamental parameter governing the dispersivity of soils is the number of charges on clay particles and that the repulsion in the soils is mainly contributed by the electrostatic repulsion. The attractive force in a soil/clay mass is primarily contributed by the van der Waal’s attraction and dispersion occurs when the electrostatic repulsion (resulting due to permanent and pH dependent charges) dominates over the van der Waal’s attraction. A practical estimation of charge with least effort could be possibly carried out through the measurement of zeta potential of soils. In order to verify whether the effect of all the factors is completely and sufficiently reflected in the zeta potential values, experiments were conducted on various soils. Three soils namely Suddha soil (a locally available dispersive soil), Black cotton soil and Red soil were selected for the study. These soils were chosen as the soil samples as they could display wide ranges of dispersivity values. In order to perform dispersivity tests, soil fraction finer than 75µ (75 micron meter sieve size) was fixed as the sample size as dispersivity pertaining to the finer fractions play a greater role than that of the coarser particles. All the three soil samples were treated with sodium hydroxide and urea solutions to alter the dispersivity so that the influence of all parameters could be studied. The dispersivity of the treated and untreated soils was found out through the various conventional tests and it was found that there exists a good correlation between the dispersivity and the zeta potential of soils. It was also observed that the increase in the dispersivity is higher when treated with salts of monovalent cations. Increase in the organic content also increased zeta potential, but not as significantly. One of the popularized theories on colloidal dispersions is the classical DLVO theory which has formulated the total interaction energy of colloidal particles by estimating the electrostatic repulsion and van der Waal’s attraction energy between two particles. The total interaction energy is then expressed as the difference between them. A similar approach as taken by the DLVO is adopted in this study. The total attractive energy existing in a soil mass is mathematically derived from the expression for van der Waal’s energy between two particles and the total repulsive energy from the zeta potential values. Two different approaches namely an infinitesimal particle approach and a finite particle approach is taken for finding the energy in a soil mass. In the infinitesimal particle approach, a clay particle is assumed to be infinitely small such that any soil particle of a finite radius could be conceived to be formed by a combination of infinite number of these infinitesimal particles. With this setting, the total energy in a soil mass is computed without really bothering about what exact particles constitute the mass. The increase in energy due to the increase in radius is then integrated to obtain the final expression. The dispersivity of the soil is then estimated under defined physical conditions of the soil. In the finite particle approach, each particle is considered to be of finite radius and to estimate the total energy, the total number of particle ombinations is then taken and the total energy is expressed as a sum of all the possible combinations. The dispersivity of a soil in both approaches is expressed as a release of energy when the repulsion rules over the attraction. In order to validate the derived propositions and expressions, experiments were conducted again on soils. The soils were treated with hydroxide salt of monovalent cations such as lithium, sodium and potassium. The dispersivity of the various treated and untreated soils was measured with the conventional methods and with the derived expressions of dispersivity through zeta potential. The similarity in the trend of the dispersivity values confirmed the validity of the derived expression. It was also concluded that the infinitesimal particle approach could be adopted when information about the physical properties are available and when they are not, the finite approach could be used. An accurate determination of zeta potential is critical for representation of dispersivity with zeta potential. Thus the procedure for measurement of zeta potential was standardized. The standardization was primarily focused on establishing the ideal conditions for zeta potential measurement. The role of Brownian motion, in electrophoretic mobility measurements were studied by employing the usage of zeta deviations. Untreated, potassium hydroxide treated, sodium hydroxide treated and lithium hydroxide treated samples of Suddha soil, Black Cotton soil and Red soil (finer than 75µ) were used for the study. Zeta potential measurements on unfiltered soil water suspensions, suspensions passing 2.5µ and suspensions passing 0.45µ were conducted along with recording their zeta deviations. It was observed that soil suspensions finer than 0.45µ show acceptable values of zeta deviations and thus could be used as a standard procedure for estimating zeta potentials. It was also concluded that the presence of Brownian motion makes the assessment of zeta potential through electrophoretic measurements easier and accurate. In an alternate perspective it as deduced that the amount of total monovalent ion concentration in the soil (dissolved and adsorbed) could adequately serves as an ideal parameter that could be used to quantify dispersion in soils. In order to verify the speculation, the variation of repulsive pressure with monovalent cation concentration was studied for the above mentioned treated and untreated soils. Within the monovalent cations, the role of ionic size in repulsion along with physical factors was also studied with the help of Atterberg limits, compaction characteristics, and dispersivity measurements. It could be concluded that even though there are several chemical factors such as CEC, pH, electrolyte concentration, type of clay minerals, dissolved salts etc. and physical factors such as plasticity, water holding capacity, density and structure which influence dispersion in soils, these factors affect either directly forces between the particles or the surface charge of clays which again affect the forces. The two phenomena can be combined through the hydration behaviour of the adsorbed cations on the clay surface in view of dispersivity. It is that force due to hydration which acts as the principal reason to separate the clay particles apart. As the radius of the inner hydration shell is higher for monovalent cations than those of higher valency ions, more force would be offered by the monovalent ions. Higher the charge and higher is the number of monovalent cations, higher will be the repulsion and thus the dispersivity. The repulsive force offered by the monovalent cations in soil was calculated through osmotic pressure differences and the dispersivity was expressed as the release of energy as earlier. In order to validate the proposal, the dispersivity of the samples as measured with the conventional methods was compared and studied with the derived expression. The similarity in the trend of the dispersity values confirmed the validity of the derived expressions. Thus, it can be seen that there are primarily two different methods of quantifying dispersivity of soils. When one method estimates dispersivity by calculating the electrostatic repulsion through zeta potential, the other method gives a dispersivity value based on the repulsive pressure offered by the monovalent cations in the soil. Two methods could be regarded as two different measurements of the electrical double layer. Any method could be used based on the property that could be easily quantified. The applicability of the new approaches – calculation of monovalent cations and zeta potential- for estimating the dispersivity in soils through a complete development of philosophy of dispersion and is presented, in this thesis, in nine chapters as follows: In Chapter 1 the background of the study and review of literature connected with the present study is presented. The mechanism of dispersion and the geotechnical problems associated with dispersion is elaborately presented in this section. As the dispersive soils cannot be identified through conventional tests, a description about the various tests designed to identify dispersive soils is presented. Earlier works relevant to the topic and the shortcomings of those studies are discussed. Finally, the objectives of the current research along with the scope of the work are explained in the concluding part of this chapter. Various factors that could have influence on the dispersivity of soils and their mechanism of action are presented in Chapter 2. The relationship of the factors with zeta potential is discussed. Theories dealing with dispersivity, conventional methods of measurement, role of geotechnical characteristics in assessing dispersivity are being presented. Chapter 3 deals with the various materials and methods used for the study. A locally available dispersive soil called Suddha soil along with Black Cotton soil and Red soil were chosen as the soils for the study of dispersion. The basic material properties and testing programs adopted for the study are presented in this chapter. The codal procedures followed to determine the physical, chemical, index and engineering properties are described in detail. The experimental investigations carried to bring out the role of zeta potential in dispersivity of soils are described in Chapter 4. Detailed analysis of the results showed estimation of zeta potential is possible and can sufficient quantify dispersivity of soils. The formulation of the equation for estimating dispersivity from zeta potential is described in Chapter 5. The estimation dispersivity based on attraction and repulsion energies in a soil mass is presented here. The adoption of the approach and methodologies used based on classical DLVO theory for the current work is explained in detail. The values of dispersivity obtained from the derived equation are compared with those obtained from the conventional tests. The validity of the expression is confirmed with the results of the experiments. Chapter 6 deals with the standardization of the measurement procedure of zeta potential. Role of Brownian motion in the accurate measurement of electrophoretic mobilities are brought out here. Chapter 7 brings out an alternate perspective of quantifying dispersivity through monovalent cations. The role of monovalent cations and the mechanism in which they contribute to the repulsive pressures (hence the dispersivity) are discussed. Experimental research design adopted has brought that the effect of monovalent and ionic size on repulsive pressures leading to dispersivity is described. The results of the experiments added with the inferences drawn are explained at the end. The estimation of repulsive pressures for measuring dispersivity from monovalent cations is discussed in Chapter 8. The dispersivity of a soil mass is derived from monovalent ion concentration and experiments were carried out for verification purposes. The experimental investigation procedure adopted followed by the results are presented in this chapter. It was observed that a good co-relation exists with the dispersivity obtained from the monovalent ion concentration and that obtained from conventional methods. Chapter 9 compares the dispersivity obtained through the various methods proposed in this thesis. The comparison is made in light of the classical electrical double layer theory. The major conclusions of the study are brought out at the end of this chapter.

Made available in DSpace on 2014-12-17T15:41:55Z (GMT). No. of bitstreams: 1 IdyllaST_DISSERT.pdf: 1649846 bytes, checksum: b16782ef605bdc7a1d3225b281a6f2b3 (MD5) Previous issue date: 2011-11-08 / Chitosan nanoparticles have been used in several systems for the controlled release of drugs. The aim of this study was to obtain and characterize chitosan nanoparticles prepared by the method of coacervation / precipitation using sodium sulfate at different concentrations as the crosslinking agent. The characterization was done using zeta potential and small angle Xray scattering, SAXS. The dispersions of chitosan were obtained at pH 1 and pH = 3. The results of zeta potential at pH = 1 ranged from +64.8 to +29.27 mV and for pH = 3 they varied from +72.4 to +23.48 mV, indicating that the chain of chitosan is positively charged in acidic pH and the behavior of nanoparticles in terms of surface charge was independent of pH. However, the results indicated a dependence of particle size in relation to pH. This difference in behavior was explained by the influence of enthalpic and entropic components / Nanopart?culas de quitosana t?m sido utilizadas em v?rios sistemas destinados a libera??o controlada de f?rmacos. O objetivo desse trabalho foi a obten??o e caracteriza??o de nanopart?culas de quitosana atrav?s do m?todo de coacerva??o/precipita??o utilizando o sulfato de s?dio em diferentes concentra??es como agente reticulante. A caracteriza??o foi feita utilizando potencial zeta e espalhamento de pequenos ?ngulos, SAXS. As dispers?es de quitosana foram obtidas a pH=1 e pH=3. Os resultados do potencial zeta variaram no pH = 1 de +64,8 a +29,27 mV e no pH = 3 de +72,4 a +23,48 mV, indicando que a cadeia de quitosana fica carregada positivamente em pH ?cido e que comportamento das nanopart?culas em termos de carga superficial foi independente do pH. Entretanto, os resultados indicaram depend?ncia do tamanho de part?cula em rela??o ao pH. Essa diferen?a em termos de comportamento foi explicada pela influ?ncia dos componentes ent?lpicos e entr?picos

Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2007.

In the past three decades, a new group of concrete admixtures, termed &ldquo / superplasticizers&rdquo / , were introduced to the concrete industry. They have gained wide acceptance because of their many advantages. The addition of superplasticizers to concrete improves the workability and strength of concrete. In this study, the effect of the chemical structure of poly (4-styrenesulfonic acid-co-maleic acid) sodium salt (SSAMA), which contains both sulfonic and carboxylic acid groups, which is a new superplasticizer, was analyzed. Two different molecular weights of PEG (polyethylene glycol monomethyl ether) were grafted to this water-soluble copolymer at different weight compositions. The structures of synthesized copolymers were verified by FTIR and NMR analyses. The molecular weight difference of the grafted copolymers with different side chain lengths was determined by dilute solution viscosimetry. The effects of chemical structure of grafted copolymers on the fluidity of cement paste and the mechanical properties of the mortars were investigated. The zeta potential measurements revealed the interactions between the cement particles and polycarboxylate type superplasticizers. The maximum fluidity was achieved for the PEG grafted copolymer with the weight ratio 3:3. The mechanical properties of this copolymer showed the highest flexural and compressive strength compared to other copolymers. The addition of various Li salts to SSAMA affected the ionic medium, therefore, the dispersion performance of cement paste and the mechanical properties of the mortars improved. The mixture of LiCl: SSAMA in 1:1 mol ratio exhibited the maximum fluidity compared to other Li salts and their compositions. This mixture gave the highest flexural strength but the mixture of Li2CO3 in 1:1 composition gave the highest compressive strength in each salt mixtures.

In recent years the application of single-molecule techniques to probe biomolecules and intermolecular interactions at single-molecule resolution has expanded rapidly. Here, I investigate a series of peptides and proteins in an attempt to gain a better understanding of nanopore sensing as a single-molecule technique. The analysis of retro, inversed, and retro-inversed isomers of glucagon and α-helical Fmoc-D2A10K2 peptide showed that nanopore sensing utilizing a wild-type α-hemolysin pore can distinguish between all four isomers while circular dichroism can only distinguish between chiral isomers, but not between directional isomers. The investigation of a series of proteins of different chemical and physical properties revealed important information about nanopore analysis of proteins. Contrary to some reports in the literature, all proteins analysed here induced large blockade events. The frequency of total events and the proportion of large blockade events were significantly reduced in tris(hydroxymethyl)aminomethane or 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid buffers and were only restored by the addition of ethylenediaminetetraacetic acid or the use of phosphate buffer, both of which can sequester metal ions. Furthermore, the results obtained with the proteins in the presence of ligands demonstrated that transient or partial unfolding of proteins can be detected by nanopore analysis confirming the usefulness of this technique for conformational studies or for protein/ligand interactions. Interestingly, while the blockade current histograms were different for each protein there was no obvious correlation between the properties of the proteins and the blockade current histograms. In an attempt to identify whether the large blockade events were translocation or intercalation, both an indirect and a direct approach were taken. The indirect approach which relies on the effect of voltage on the interaction of the molecule with the pore provided no conclusive answer to the question of protein translocation through the α-hemolysin pore. In contrast, the direct approach in which ribonuclease A is added to the cis side of the pore and then the trans side is tested for enzyme activity showed that ribonuclease A doesn't translocate through the α-hemolysin pore.