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.

The presence of Ca(OH)2 (or free lime) in lime mud can cause many problems in the recovery process of kraft pulp mills. Conventional free lime analyses require extensive laboratory work and give inconsistent results. A systematic study was performed to determine if zeta potential, a quickly measurable dispersion characteristic, can be used to indicate the presence of free lime in the recovery process. Measurements were made on synthetic wet lime mud to simulate samples collected after the white liquor clarifier in pulp mills. The results show that zeta potential increases from negative to positive when the free lime content in the lime mud exceeds a critical threshold. This change from negative to positive zeta potential of the lime mud slurry can be used as a basis for developing an on-line monitoring system that effectively detects free lime in the lime mud in order to avoid problems associated with overliming in the recovery process.

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.

Pheroid is a patented system comprising of a unique submicron emulsion type formulation. Pheroid vesicles consist mainly of plant and essential fatty acids and can entrap, transport and deliver pharmacologically active compounds and other useful molecules. The aim of this study was to show that a modulation of components and parameters is necessary to obtain the optimum formula to be used in pharmaceutical preparations. Non-optimal or non-predictable stability properties of emulsions can be limiting for the applications of emulsions (Bjerregaard et al., 2001:23). Careful consideration was given to the apparatus used during the processing along with the ratios of the various components added to the formulation and the storage conditions of the Pheroid vesicles. A preliminary study was performed to optimize the most accurate processing parameters during emulsification. The effect of emulsification rate and time, the temperature of the aqueous phase, the number of days the water phase were gassed, the concentration of the surfactant, cremophor® RH 40, used and the concentration of Vitamin F Ethyl Ester CLR added to the oil phase of the o/w emulsion has been studied. Quantification of the mean particle size, zeta potential, turbidity, pH and current values were used to characterize the emulsions. The samples were characterised after 1, 2, 3, 7, 14, 21 and 28 days of storage. The emulsions were also characterised with confocal laser scanning microscopy (CLSM) to measure the number and size and size distribution of the vesicles. After determination of the processing variables influencing the emulsion stability an accelerated stability test was conducted on a final formula. In the present study, accelerated stability testing employing elevated temperatures and relative humidity were used with good accuracy to predict long-term stability of an o/w emulsion kept at both 5 and 25 OC with 60 % relative humidity and 40 OC with 75 % relative humidity. The results of the stability tests were presented in histograms of the physical properties 24 hours, 1 month, 2 months and 3 months after preparation of the emulsion. It was concluded that Pheroid vesicles demonstrate much potential as a drug delivery system. The high stability of this formula allows its use in a wide variety of applications in the pharmaceutical industry. / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2007.

Pheroid is a patented system comprising of a unique submicron emulsion type formulation. Pheroid vesicles consist mainly of plant and essential fatty acids and can entrap, transport and deliver pharmacologically active compounds and other useful molecules. The aim of this study was to show that a modulation of components and parameters is necessary to obtain the optimum formula to be used in pharmaceutical preparations. Non-optimal or non-predictable stability properties of emulsions can be limiting for the applications of emulsions (Bjerregaard et al., 2001:23). Careful consideration was given to the apparatus used during the processing along with the ratios of the various components added to the formulation and the storage conditions of the Pheroid vesicles. A preliminary study was performed to optimize the most accurate processing parameters during emulsification. The effect of emulsification rate and time, the temperature of the aqueous phase, the number of days the water phase were gassed, the concentration of the surfactant, cremophor® RH 40, used and the concentration of Vitamin F Ethyl Ester CLR added to the oil phase of the o/w emulsion has been studied. Quantification of the mean particle size, zeta potential, turbidity, pH and current values were used to characterize the emulsions. The samples were characterised after 1, 2, 3, 7, 14, 21 and 28 days of storage. The emulsions were also characterised with confocal laser scanning microscopy (CLSM) to measure the number and size and size distribution of the vesicles. After determination of the processing variables influencing the emulsion stability an accelerated stability test was conducted on a final formula. In the present study, accelerated stability testing employing elevated temperatures and relative humidity were used with good accuracy to predict long-term stability of an o/w emulsion kept at both 5 and 25 OC with 60 % relative humidity and 40 OC with 75 % relative humidity. The results of the stability tests were presented in histograms of the physical properties 24 hours, 1 month, 2 months and 3 months after preparation of the emulsion. It was concluded that Pheroid vesicles demonstrate much potential as a drug delivery system. The high stability of this formula allows its use in a wide variety of applications in the pharmaceutical industry. / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2007.

Made available in DSpace on 2015-05-14T12:56:03Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2756793 bytes, checksum: 52c334e99949464b4e3237ddf1e202c6 (MD5) Previous issue date: 2014-02-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The transport of materials through the tooth enamel is conventionally derived from the diffusion process, which leads to a number of limitations, because the pores of the enamel are extremely small, requiring a certain extension, as occurs in adhesive techniques by the etching process. An alternative method to this technique is the electrokinetic flow (EKF), which promotes the unidirectional flow of substances through the pores of the enamel by applying an external electric field. Based on this premise it was promoted the infiltration of a composite resin with low viscosity (Icon DMG, Hamburg, Germany) on the surface of 20 extracted human teeth by EKF, using an electric field (1.5V) in two stages: (1) infiltration of potassium chloride 0.1M (KCl) during 3h and (2) infiltration of the resin during 2h. Longitudinal histological sections of &#8776; 100&#956;m were analyzed by fluorescence microscopy and polarized light microscopy associated with the "polscopesingle"system, after 24h of dehydration and along 50, 100, 150, 200, 250, 300, 350, 400, 450 and 500&#956;m deep. Electric voltage (&#956;A) presented to be positive during infiltration. Images from Fluorescence Microscopy revealed fluorescence of the infiltrated enamel areas for all samples, from the surface to the dentin-enamel junction (DEJ), indicating the formation of a hybrid layer with average depth of 1627.66 &#956;m and a standard deviation of 284.20 &#956;m. The records of the phase delay during dehydration of the infiltrated and non-infiltrated areas did not present changes in the infiltrated area. It was observed that the water was replaced by the resin (p<0.000001), with high effect size (>0.8). Based on these results, it was concluded that the EKF resulted in infiltration of the resin into the enamel nanochannels. / O transporte de materiais através do esmalte dentário é limitado já que convencionalmente depende do processo de difusão, em virtude do volume nanométrico dos poros do esmalte. Um método alternativo pode ser o uso do Fluxo Eletrocinético (FEC), que promove o fluxo unidirecional de substâncias através dos poros do esmalte pela aplicação de um campo elétrico externo. Por conseguinte, este estudo promoveu a infiltração de resina fluida na superfície de 20 dentes humanos extraídos através do FEC, utilizando um campo elétrico de 1,5 volt em duas etapas: (1) infiltração de Cloreto de Potássio (KCl) 0,1M por 3h (2) infiltração da resina Icon (DMG, Alemanha) por 2h. Cortes histológicos por desgaste com &#8776; 100&#956;m foram analisados por Microscopia de Fluorescência (MF) e por Microscopia de Luz Polarizada (MLP) associada ao sistema single polscope , durante a desidratação das amostras por um período de 24h e analisando pontos histológicos a 50, 100, 150, 200, 250, 300, 350, 400, 450 e 500&#956;m a partir da superfície de áreas infiltradas e não infiltradas. A variação da corrente elétrica (mA) mostrou-se positiva durante a infiltração. As imagens da MF demonstraram fluorescência do esmalte na região infiltrada desde a superfície até a junção amelo-dentinária (JAD), indicando a formação de uma camada híbrida com profundidade média de 1627,66 &#956;m e desvio padrão de 284,20 &#956;m. Comportamentos distintos foram identificados para as áreas infiltrada e não infiltrada durante a desidratação. A área não infiltrada perdeu água, conforme verificado através da redução do retardo de fase. A área infiltrada não perdeu água, uma vez que o retardo manteve-se constante, sugerindo que a água fracamente aderida foi substituída pela resina durante a infiltração. As diferenças estatísticas entre os pontos histológicos das duas áreas foram calculadas através do teste de Mann-Whitney, com nível de significância de 5%, confirmando que a água foi substituída pela resina (p< 0,000001), com alta magnitude do efeito (>0,8). Portanto, pode-se concluir que a utilização do FEC resultou na infiltração da resina nos nanocanais do esmalte, formando camada híbrida de grande profundidade.

Thesis is indirectly connected to many years of research in field of sulphate binders. Work is focused on modifying of properties of alfa and beta gypsum, mainly on reduction of water ratio. We monitored effect of addition of chloride salts, carbonates and sulphates on zeta potential and its measurement. Part of thesis is also focused on laboratory production of beta plaster from secondary materials and optimization of grinding process to achieve required criteria.