Molecular Arrangement, Electronic Structure and Transport Properties in Surfactant Gel- and Related Systems Studied by Soft X-ray and Dielectric Spectroscopy

This thesis concerns studies of aqueous soft matter systems, especially surfactant micelle systems. The aim has been to study the molecular arrangement and electronic structure of the constituents of, as well as transport properties in such a system. The molecular arrangement and electronic structure has been studied by means of X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray spectroscopy (RIXS). The transport properties have been investigated by low-frequency dielectric spectroscopy (LFDS) and small angle X-ray scattering (SAXS) as well as a theoretical modelling. The latter was based on Fick’s laws of the release from binary surfactant system and was validated by experiments. The RIXS and XAS measurements show the electronic structure in bulk water and the influence of the chemical surrounding of the water molecule in bulk water and of the water molecules confined in a micelle lattice. The spectra are highly dependent on the molecular arrangement in such systems. For glycine and sodium polyacrylate RIXS and XAS spectra show features which are unique for carboxyl and carboxylate groups and such measurements can thus be used for fingerprinting. The LFDS and SAXS measurements show a strong correlation between structure in a surfactant/poly-ion system and apparent mobility of surfactants. This conclusion is in line with earlier observations. By the theoretical modelling a predictive model for the surfactant release from a binary surfactant micelle system has been obtained and the importance of different factors for surfactant release has been further clarified

Molecular Arrangement, Electronic Structure and Transport Properties in Surfactant Gel- and Related Systems Studied by Soft X-ray and Dielectric Spectroscopy

This thesis concerns studies of aqueous soft matter systems, especially surfactant micelle systems. The aim has been to study the molecular arrangement and electronic structure of the constituents of, as well as transport properties in such a system. The molecular arrangement and electronic structure has been studied by means of X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray spectroscopy (RIXS). The transport properties have been investigated by low-frequency dielectric spectroscopy (LFDS) and small angle X-ray scattering (SAXS) as well as a theoretical modelling. The latter was based on Fick’s laws of the release from binary surfactant system and was validated by experiments. The RIXS and XAS measurements show the electronic structure in bulk water and the influence of the chemical surrounding of the water molecule in bulk water and of the water molecules confined in a micelle lattice. The spectra are highly dependent on the molecular arrangement in such systems. For glycine and sodium polyacrylate RIXS and XAS spectra show features which are unique for carboxyl and carboxylate groups and such measurements can thus be used for fingerprinting. The LFDS and SAXS measurements show a strong correlation between structure in a surfactant/poly-ion system and apparent mobility of surfactants. This conclusion is in line with earlier observations. By the theoretical modelling a predictive model for the surfactant release from a binary surfactant micelle system has been obtained and the importance of different factors for surfactant release has been further clarified

Molecular Arrangement, Electronic Structure and Transport Properties in Surfactant Gel- and Related Systems Studied by Soft X-ray and Dielectric Spectroscopy

This thesis concerns studies of aqueous soft matter systems, especially surfactant micelle systems. The aim has been to study the molecular arrangement and electronic structure of the constituents of, as well as transport properties in such a system. The molecular arrangement and electronic structure has been studied by means of X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray spectroscopy (RIXS). The transport properties have been investigated by low-frequency dielectric spectroscopy (LFDS) and small angle X-ray scattering (SAXS) as well as a theoretical modelling. The latter was based on Fick’s laws of the release from binary surfactant system and was validated by experiments. The RIXS and XAS measurements show the electronic structure in bulk water and the influence of the chemical surrounding of the water molecule in bulk water and of the water molecules confined in a micelle lattice. The spectra are highly dependent on the molecular arrangement in such systems. For glycine and sodium polyacrylate RIXS and XAS spectra show features which are unique for carboxyl and carboxylate groups and such measurements can thus be used for fingerprinting. The LFDS and SAXS measurements show a strong correlation between structure in a surfactant/poly-ion system and apparent mobility of surfactants. This conclusion is in line with earlier observations. By the theoretical modelling a predictive model for the surfactant release from a binary surfactant micelle system has been obtained and the importance of different factors for surfactant release has been further clarified

The Release of Catanionic Mixtures Embedded in Gels : An Approximate Analytical Analysis

We present an approximate analytical analysis of the release of catanionic mixtures from gels. The starting points are the monomer-mixed micelle equilibrium, described by using regular solution theory, and the one-dimensional diffusion equation. Focusing on a half-infinite planar system, we first point out an exact reduction of the problem to a system of ordinary differential equations. By using the pseudo-steady-state approximation and the integral-balance method, we then derive a single nonlinear equation for the mole fraction of drug in micelles at the extraction front. This equation may be readily solved numerically (or graphically), and once the solution is found, all quantities of interest may be determined in closed form. Comparisons with numerical solutions of the fully nonlinear problem indicate that the errors resulting from the approximations typically do not exceed 10%

Mechanical behaviour of ideal elastic-plastic particles subjected to different triaxial loading conditions

The contact force development for two types of polymeric elastoplastic particles subjected to different triaxial loading conditions was studied experimentally utilising a unique triaxial testing apparatus. In order to evaluate the experimental results, a finite element analysis was performed. The experimental findings highlighted the importance of contact dependence, which manifested itself in two principally different ways. Firstly, a reduced stiffness was observed when plastic deformation ceased to be fully contained, which, depending on the loading conditions, occurred at an engineering strain of about 5-10%. Secondly, a markedly increased stiffness was observed when particle confinement inhibited further plastic deformation, making elastic volume reduction the predominant deformation mode. The experimental results could be well reproduced by the numerical simulations, provided that isotropic hardening was included in the elastoplastic model. In an attempt to invariantly describe the data, a nominal contact pressure was determined as a function of the volumetric constraint of the particle. This resulted in an adequate collapse of results obtained for different loading conditions onto a single master curve at large volumetric constraint. In summary, this paper should be considered as a step along the pathway towards our long term goal of introducing novel and improved contact models

The Release of Catanionic Mixtures Embedded in Gels : An Approximate Analytical Analysis

We present an approximate analytical analysis of the release of catanionic mixtures from gels. The starting points are the monomer-mixed micelle equilibrium, described by using regular solution theory, and the one-dimensional diffusion equation. Focusing on a half-infinite planar system, we first point out an exact reduction of the problem to a system of ordinary differential equations. By using the pseudo-steady-state approximation and the integral-balance method, we then derive a single nonlinear equation for the mole fraction of drug in micelles at the extraction front. This equation may be readily solved numerically (or graphically), and once the solution is found, all quantities of interest may be determined in closed form. Comparisons with numerical solutions of the fully nonlinear problem indicate that the errors resulting from the approximations typically do not exceed 10%

Comminution-amorphisation relationships during ball milling of lactose at different milling conditions

The purpose of the study was to investigate the relationship between comminution and amorphisation of alpha-lactose monohydrate particles during ball milling under different milling conditions, including ball-to-powder mass ratio, milling time and ball diameter. The results revealed that at a constant ball filling ratio, ball-to-powder mass ratio of 25:1 resulted in the lowest minimum particle diameter of similar to 5 mu m and the highest degree of apparent amorphous content of 82%. The rate of comminution was high during early stage of milling whereas the degree of apparent amorphous content increased gradually at a slow rate. An increased ball-to-powder mass ratio during milling increased both the rate of comminution and the rate of amorphisation. Using a given ball-to-powder mass ratio, the ball diameter affected the degree of apparent amorphous content of the particles while the particle diameter remained unchanged. The relationship between comminution and amorphisation could be described as consisting of two stages, i.e. comminution dominated and amorphisation dominated stage. It was proposed that the rate constant of comminution and amorphisation are controlled by stress energy distribution in the milling jar and the stress energy distribution is regulated by the ball motion pattern that can be affected by the process parameter used.Title in dissertation list of articles: "Comminution-amorphisation relationships during ball milling of lactose at different stress energies"</p

Considerations on the quantitative analysis of apparent amorphicity of milled lactose by Raman spectroscopy

The main purpose of the study was to evaluate various pre-processing and quantification approaches of Raman spectrum to quantify low level of amorphous content in milled lactose powder. To improve the quantification analysis, several spectral pre-processing methods were used to adjust background effects. The effects of spectral noise on the variation of determined amorphous content were also investigated theoretically by propagation of error analysis and were compared to the experimentally obtained values. Additionally, the applicability of calibration method with crystalline or amorphous domains in the estimation of amorphous content in milled lactose powder was discussed. Two straight baseline pre-processing methods gave the best and almost equal performance. By the succeeding quantification methods, PCA performed best, although the classical least square analysis (CLS) gave comparable results, while peak parameter analysis displayed to be inferior. The standard deviations of experimental determined percentage amorphous content were 0.94% and 0.25% for pure crystalline and pure amorphous samples respectively, which was very close to the standard deviation values from propagated spectral noise. The reasonable conformity between the milled samples spectra and synthesized spectra indicated representativeness of physical mixtures with crystalline or amorphous domains in the estimation of apparent amorphous content in milled lactose

Effect of fluid velocity and particle size on the hydrodynamic diffusion layer thickness

The aim of this study was to determine the thickness of the hydrodynamic diffusion layer (h(HDL)) of three poor water-soluble compounds under laminar fluid flow using a single particle dissolution technique. The single particle dissolution experiments were performed in a flowing aqueous medium using four different fluid velocities (v), ranging from 46 to 103 mm/s. The particles used had an initial radius (r) of 18.8 to 52.3 mu m. The determined h(HDL) values were calculated from both dissolution experiments and computational fluid dynamics (CFD) simulation. In this study, single particle dissolution experiments gave, with one exception, h(HDL) values in the range of 2.09 to 8.85 mu m and corresponding simulations gave h(HDL) values in the range of 2.53 to 4.38 mu m. Hence, we found a semi-quantitative concordance between experimental and simulated determined h(HDL) values. Also, a theoretical relation between the dependence of hHDL on particle radius and flow velocity of the medium was established by a series of CFD simulations in a fluid velocity range of 10-100 mm/s and particle size (radius) range of 5-40 mu m. The outcome suggests a power law relation of the form h(HDL)alpha r(3/5)v(-2/5). In addition, the h(HDL) seems to be independent of the solubility, while it has a diffusion coefficient dependence. In conclusion, the hHDL values were determined under well-defined conditions; hence, this approach can be used to estimate the h(HDL) under different conditions to increase the understanding of the mass transfer mechanisms during the dissolution process

Optimal (s, S) policies with delivery time guarantees for manufacturing systems with early set-up

We consider optimal (s, S) policies with delivery time guarantees for production planning in one-machine manufacturing systems with early set-up. The machine produces one type of product and delivery time guarantee is offered to the customers for each unit of ordered product. The inter-arrival time of the demand and the processing time for one unit of product are assumed to be exponentially distributed. In a (s, S) policy, the machine will shut down when an inventory level of S is attained and once the inventory level drops to s, the machine will re-start. A set-up time is required for the machine. We model the set-up by the exponential distribution. We obtained an analytical form of the steady state probability distribution for the inventory levels derived. The average profit of the system can be written in terms of this probability distribution. Hence the optimal (s, S) policy can be obtained by varying different possible values of s and S. © 2001 Elsevier Science Ltd.link_to_subscribed_fulltex