No / The in-line development of crystalline morphology and orientation during melt extrusion of low density polyethylene (LDPE) tape at nil and low haul-off speeds has been investigated using Small-Angle X-Ray Scattering (SAXS). The processing parameters, namely haul-off speed and distance down the tape-line have been varied and the resulting crystalline morphology is described from detailed analysis of the SAXS data. Increasing haul-off speed increased orientation in the polymer tape and the resulting morphology could be described in terms of regular lamellar stacking perpendicular to the elongation direction. In contrast, under nil haul-off conditions the tape still showed some orientation down the tape-line, but a shish-kebab structure prevails. The final lamellae thickness (similar to 50 angstrom) and bulk crystallinity (similar to 20%), were low at, for all processing conditions investigated, which is attributed to the significant short-chain branching in the polymer acting as point defects limiting lamellae crystal growth. (C) 2013 Elsevier Ltd. All rights reserved.

Thesis (PhD)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: An instrument, named solution crystallization analysis by laser light scattering (SCALLS), that measures the solution melting and crystallization of polymers in solution was developed further in this study. The instrument was tested in a theoretical study to evaluate the Flory-Huggins relationship of melting point depression in solution of copolymers. It was found that the solvent interaction parameter for propylene/higher 1-alkene copolymers, with low comonomer content is dependent on the comonomer type. It was also showed that the melting point depression is dependent on both the type and amount of comonomer included in the copolymer. The instrument was further developed to include a total of three lasers with different wavelengths. Initial problems with laser interference was rectified by the introduction of dichroic mirrors to direct the laser light to the relevant detectors and broad pass filters in front of the the detectors to ensure that only the relevant laser light passes through. For homogenous polypropylene samples it was found that even though a slower cooling rate increases the relative peak temperatures as well as the relative temperature differences between the peaks, detail in the peak profiles is the same for the faster cooling rate. The subsequent heating analysis does show that there is a definite dependence on the cooling rate. The ZNPP-4 sample shows that the appearance of a shoulder in the heating analysis becomes more defined as a peak if the preceding cooling analysis is slower. Complex impact-polypropylene samples, differing only in the amount of ethylene were analysed and even small differences between samples were detected. The possible application of the SCALLS instrument was investigated. It was proven that the instrument can be used as a screening method for prep-TREF to determine the fractionation temperatures. / AFRIKAANSE OPSOMMING: 'n Instrument, genoem oplossing kristallisasie-analise deur laser lig verstrooiing (SCALLS), wat die smeltpunt asook die kristallisasie temperatuur in oplossing kan meet is verder ontwikkel in hierdie studie. Die Flory-Huggins verhouding oor die smeltpunt depressie in oplossing van ko-polimere is ondersoek in ‘n teoretiese studie. Daar is bevind dat die oplossing interaksie parameter vir propileen/hoër 1-alkeen kopolimere, met lae ko-monomeer inhoud is afhanklik op die ko-monomeer tipe. Dit is ook getoon dat die smeltpunt depressie afhanklik is van beide die tipe en hoeveelheid ko-monomeer in die ko-polimeer. Die instrument is verder ontwikkel om 'n totaal van drie lasers met verskillende golflengtes in te sluit. Aanvanklike probleme met laser inmenging is reggestel deur die bekendstelling van dichromatiese spieëls wat die laser lig na die regte ooreenstemmende detektor rig en filters voor die detektors verseker dat net die relevante laser lig die detektor bereik. Vir homogene polipropileen monsters is dit bevind dat selfs al is die analises gedoen teen ‘n stadiger afkoelings tempo wat lei tot ‘n verhoging in die piek kristallisasie temperatuur asook die relatiewe temperatuur verskille tussen die lasers, bly die detail in die piek profiele dieselfde as wat gesien word met ‘n vinniger afkoelings tempo. Die daaropvolgende verhitting analise toon dat die analise definitief afhanklik is op die voorafgaande afkoelings analise. Die ZNPP-4 monster toon dat die voorkoms van 'n skouer in die verwarming-analise word meer gedefinieerd en ‘n piek word gevorm soos die voorafgaande afkoelings tempo verlaag. Komplekse impak-polipropileen monsters, wat net verskil in die hoeveelheid etileen inhoud is geanaliseer en verskille is bepaal. Moontlike toepassings van die SCALLS instrument is ondersoek. Dit is bewys dat die instrument gebruik kan word om die fraksionering temperature vooraf te bepaal vir prep-TREF.

Pharmaceutical solids tend to exist in different physical forms termed as polymorphs. Issues about pharmaceutical systems are mainly concerned with the active ingredient's physico-chemical stability and bioavailability. The main aim of this study is to investigate the non-bonded interactions in pharmaceutical solids that govern the physical pharmaceutics performance of such materials and through the use of structural techniques and correlation of these results with crystal structural database to establish the presence of physical motifs in selected systems. Structural motifs were identified by the use of single crystal and crystal packing analysis on diverse range of pharma-relevant materials including chalcones, cryptolepines, biguanides and xanthines. These selected systems were validated using functional group and molecular analysis and correlating them to the Cambridge Structural Database. Crystallization studies are done on these selected systems as well as exploiting those using synthetic analogues. A total of 51 crystal structures were investigated including 16 new structure determinations. Addition synthesis of new xanthines to investigate novel intermolecular patterns was also undertaken. The understanding and exploitation of intermolecular interactions involving hydrogen bonds and coordination complexation during packing can be used in the design and synthesis of solid state molecular structures with desired physical and chemical properties.

<p>Crystal structure, morphology and crystallization kinetics of melt-crystallized polypropylene and poly(propylene-stat-ethylene) fractions with 2.7 to 11.0 mol% of ethylene were studied by differential scanning calorimeter, wide- and small-angle X-ray scattering, polarized light microscopy, transmission electron microscopy and infrared spectroscopy. With increasing ethylene content the poly(propylene-stat-ethylene) fractions showed unchanged crystallinity, increased unit cell volume and constant crystal thickness in combination with a shortened helix length. This indicated that a fraction of ethylene defects were incorporated into the crystal structure. During the isothermal crystallization both α- and γ-crystals could be formed. The γ-crystal fraction increased with increasing ethylene content and increasing crystallization temperature. For samples with α- and γ-crystal contents, multimodal melting was observed and a noticeable γ- to α-crystal conversion was observed on slow heating. The spherulitic structure of the copolymers was coarser than that for the homopolymer.</p><p>The crystalline lamellae in copolymers exhibited profound curvature in contrast to the straighter cross-hatched α-crystals typical to the homopolymer. Area dependence of electrical breakdown strength was studied for thin polypropylene homopolymer films. The measurements were performed with an automatic measurement system equipped with a scanning electrode arm. Five different electrodes having areas between 0.045 cm2 and 9.3 cm2 were used and typically 40-80 breakdowns per sample and electrode area were collected. All measurements were performed on dry samples in air at room temperature. The data was analyzed statistically and the Weibull function parameters α and β, the first one related to 63% probability for the sample to break down and the second one to the width of the distribution were fitted to the obtained data. Different features concerning the measurement system and conditions, e.g. criteria for the automatic detection of the breakdowns, effect of electrode edge design, partial discharges, DC ramp speed and humidity were critically analyzed. It was concluded that the obtained α-parameter values were stable and repeatable over several years of time. The β-parameter values, however, varied ± 10-30%, more for the large than the small electrodes, and were also sensitive to the changes both in the sample itself and in the measurement conditions.</p><p>Breakdown strengths of over 50 capacitor grade polypropylene films were analyzed. The obtained α-parameter values were between 450 and 850 V/μm, depending on the film grade and electrode area. In addition to the high breakdown strengths, reflected by the obtained α-values, another, sparse distribution consisting of low breakdown strengths was revealed when the amount of measurement points was high enough. This means that more than one Weibull distribution could be needed to describe the breakdown strength behavior of a polypropylene film. Breakdown values showed decreasing area dependence with decreasing electrode area. Breakdown strengths for larger sample areas were predicted from the small area data by area- and Weibull extrapolation. The area extrapolation led to predicted α-values 50% higher than measured at 4 m² whereas the Weibull extrapolation showed an accuracy of ±15 % when predicted and measured values were compared.</p><p>Breakdown strengths were also extrapolated for film areas similar to those in impregnated power capacitors. It turned out that the power capacitors, tested at the factory, performed much better than predicted by the extrapolation. However, a few weak spots with very low breakdown values were also found. For the poly(ethyelene terephtalate) dielectric, which is not swelled by the impregnation liquid, the large area breakdown strength was predictable. This indicates that for polypropylene film processing and impregnation led, in addition to the improved large area breakdown performance, also to sparse weak spots with low breakdown probabilities. Different Weibull distributions were responsible for the breakdown strengths for the processed and impregnated polypropylene than for the dry film samples.</p>

A waste acid stream is being produced by a local petrochemical company (SASOL) at a rate of 10 000 -12 000 tons per annum and contains approximately 44-mole % butyric acid, 20 % isobutyric acid and 10 % valeric acid. Whilst this stream is currently being incinerated, SASOL has requested an investigation into the possibility of separating and purifying butyric acid and isobutyric acid from this waste acid stream. The goal of this project was to determine a separation and purification route for butyric acid and isobutyric acid from SASOL'S waste acid stream. In order to achieve this, vacuum distillation and freeze crystallization were chosen for the recovery and purification of the acids respectively. Vapour-liquid equilibrium data for key component pairs present in the waste acid stream (propionic acid + butyric acid, isobutyric acid + butyric acid, butyric acid + isovaleric acid and butyric acid + hexanoic acid) were experimentally determined in a dynamic VLE still. The measured VLE data was successfully correlated us ing the gamma-phi approach. with the NRTL activity coefficient model representing the liquid phase and the virial equation of state describing the vapour phase. Using these equations. the VLE data obtained from the experimental work was then regressed to provide interaction coefficients for the NRTL model. which were then used in the Hysys process simulator to explore a range of design alternatives for distillation. Hysys simulations showed that greater than 80 % butyric acid and isobutyric acid can be recovered from the waste acid stream in a single distillation column containing 18 theoretical stages and an optimum reflux ratio of 3.8. The simulation was performed at a pressure of 58kPa and a maximum operating tempe rature of 150°C. Batch distillation experiments performed in a batch rectification column at 250kPa recovered more than 90% of both the butyric acid and isobutyric acid from a 450ml sample of the waste acid stream. A subsequent batch experiment concentrated the recovered acids into a distillate containing more than 95 % butyric acid and isobutyric acid combined. To investigate freeze crystallization as a suitable operation for purifying butyric acid and isobutyric acid a solid-liquid phase equilibrium curve for the system was generated us ing the Van Hoft equation. The generated curve showed that butyric acid and isobutyric acid could be theoretically purified (>98%) by operating two crystallizers at -20°C and -55°C respectively. A simple freeze crystallization experiment produced butyric acid with greater than 94% purity. An economic feasibility study conducted on the process showed that separation and purification of the acids by this process (distillation and crystallization) could create a business opportunity with revenue of approximately R47 million per annum. Preliminary estimates for capital investment amounted to approximately R5.4 million. for which the payback period was estimated at less than one year. / Thesis (M.Sc.Eng.)-University of Natal, Durban, 2001.

An exploration of the interpersonal experiences of loneliness by older people in a residential care facility It is estimated that there were about 3, 8 million older people in South Africa in 2010 (Statistics South Africa, 2010). Many older people have to be cared for in residential care facilities due to their weakening health, the migration of children and grandchildren, or due to limited financial resources. This has led to the attempt in this research study to explore the interpersonal experiences of loneliness by older people living in a residential care facility. Loneliness is an unpleasant experience associated with inadequate interpersonal contact. It is widely accepted that loneliness is closely associated with ageing as a consequence of multiple losses – loss of abilities, loss of and changes in personal relationships, loss of relationships with familiar environments and changed contact with friends and relatives resulting in reduced relationships. Changes in the relationship with the environment are regarded as a particular loss by older people, especially if they have to rely on institutionalized care and loose contact with familiar social networks and the free association with other people. Lonely people are isolated people. For the purpose of this study, loneliness is regarded as a relational phenomenon, and the theory of complex responsive processes of relating will be used as the theoretical framework for this study. In an attempt to understand the interpersonal experiences associated with loneliness, a qualitative and exploratory research method was used. The research was conducted in a residential care facility in Johannesburg, South Africa. The group of older people, who was purposively selected for the study, consisted of 10 older persons: 7 female and 3 male and with ages ranging between 62 and 82 years of age. The data was collected by means of various qualitative techniques, including the Mmogo-methodTM and visual drawings. The collected data was analysed by using thematic analysis, visual analysis and key-words-in-context, and crystallization was used to increase the trustworthiness of the findings. Ethical approval for the research project was obtained from the North-West University. Two themes emerged from the findings, being: 1) Relationships are experienced in terms of the interactions in relationships as well as in terms of preferred interpersonal styles; and 2) The relationships experienced in the context of the residential care facility are described as being unsafe and lacking in care, while the environment is described as non-stimulating. Some of the findings are confirmed by existing literature. However, the unique contribution of the study is the finding that the environment in which the relationships are embedded is perceived to be dangerous, and that it is perceived to be a risk to become visible to each other in order to establish meaningful interpersonal relationships. Several suggestions regarding future interventions are made and some limitations of the study are mentioned. The contribution of the study is that loneliness are expressed and described in terms of interpersonal relationships embedded in the broader environment. Thus, the potential of older people to form meaningful interpersonal relationships are limited in the broader environment if the environment is experienced as unsafe and lacking in care. / Thesis (MSc (Research Psychology))--North-West University, Potchefstroom Campus, 2012

Cette étude s’intéresse aux mélanges Polyamide 6 / Polyéthylène Haute Densité compatibilisés par voie réactive, plus particulièrement aux relations entre (1) la formulation, les paramètres de mise en œuvre en extrusion bivis corotative et (2) la morphologie et la microstructure des mélanges. Des morphologies multi-échelles ont été observées en Microscopie Électronique à Balayage et en Transmission. À l’échelle micrométrique, les morphologies suivantes ont été développées : dispersion nodulaire, nodules étirés et co-continuité. Les paramètres procédés n’influençant pas le type morphologie, les régions correspondant aux types de morphologies ont pu être rassemblées sur des diagrammes ternaires. Dans le cas des mélanges compatibilisés, deux mécanismes de formation de ces morphologies sont proposés : (1) la réaction de compatibilisation très rapide et efficace entraîne la formation de nano-dispersions par instabilités d’interface et (2) le mécanisme classique de rupture/coalescence de domaines moins riches en copolymère permet de former des morphologies jusqu’à l’échelle micrométrique. L’évolution de la taille maximale des domaines en fonction de la composition ainsi que la distribution de tailles ont été modélisés par des mécanismes de percolation. La stabilité des morphologies en statique, sous cisaillement contrôlé et au cours d’une deuxième étape de mise en forme a ensuite été étudiée. Le copolymère formé à l’interface permet de stabiliser la taille des morphologies. Enfin, une cristallisation à plus basse température a été mise en évidence en Calorimétrie Différentielle à Balayage lorsque les polymères sont confinés dans des domaines submicroniques. / This study deals with reactively compatibilized Polyamide 6 / High Density Polyethylene blends. More precisely, it focuses on the relationship between (1) the formulation, the processing parameters in corotating twin screw extrusion and (2) the morphologies and the microstructures of blends. Multi-scale morphologies were observed by Scanning and Transmission Electron Microscopy. At the micron scale, the following morphologies were developed: nodular dispersions, stretched nodules and co-continuous morphology. As the processing conditions did not influence the types of morphology, the different morphological regions were reported in ternary diagrams. In the case of compatibilized blends, two mechanisms for morphology development have been proposed: (1) the compatibilization reaction, being very fast, leads to the formation of nano-dispersions by interfacial instabilities and (2) the standard break-up/coalescence mechanism of domains poor in copolymer could lead to the formation of morphologies up to the micron scale. Both the evolution of the largest size as a function of the composition and the distribution of sizes were modeled using percolation concepts. The stability of the morphologies was then studied either during static annealing or controlled shear or in a second step processing. The copolymer formed at the interface allows stabilizing the size of the morphologies. Finally, crystallization at lower temperature was observed by Differential Scanning Calorimetry when the polymers are confined in submicron domains.

L’objectif de ce travail est d’étudier l’influence de jets d’impact libres utilisés comme mode de mise en contact des phases dans les procédés de recristallisation utilisant un fluide supercritique comme anti-solvant. L’influence des variations de plusieurs paramètres opératoires sur l’hydrodynamique des jets et sur les caractéristiques des poudres de Sulfathiazole a été étudiée. Les paramètres sont la vitesse des jets (de 0,25 m.s-1 à 25,92 m,s-1), le rapport molaire solvant/CO2 (de 2,5 % à 20 %), la température (de 313 K à 343 K), la pression (10 MPa à 20 MPa) et la concentration du soluté dans la solution (de 0,5 % à 1,8 %). Les conditions de mélange ont été caractérisées par l’estimation des puissances dissipées par les jets d’impact, variant de 0,1 à 158 W.kg-1 dans les conditions étudiées. Les résultats ont montré que la vitesse des jets et la sursaturation sont deux paramètres-clés contrôlant la cristallisation avec un effet prépondérant de la sursaturation. Les cristaux obtenus ont des tailles, distributions de taille, faciès et nature polymorphique différents selon les conditions. La forme polymorphique la plus stable a été obtenue pure ou en mélange. Une comparaison avec le procédé SAS classique a montré que les particules sont significativement plus petites lorsqu’elles sont cristallisées avec les jets d’impact, ce qui confirme que ce dispositif créant un mélange plus intense, permet d’accélérer la cinétique de nucléation.Ce travail devrait contribuer à une meilleure maîtrise des procédés de cristallisation en milieu supercritique. / The aim of this work is to study the influence of free impinging jets used for the fluids’introduction in supercritical anti-solvent (SAS) processes. The influence of the variations of several operating parameters upon jets’ hydrodynamics and upon the powder characteristics is studied. Parameters are jets velocity (0.25 m.s-1 to 25.92 m.s-1), molar ratio solvent / CO2 (2.5 % to 20 %), temperature (313 K to 343 K), pressure (10 MPa to 20 MPa) and solute concentration in the organic solution (0.5 % to 1.8 %). Mixing conditions have been characterized estimating the dissipated powers of the impinging jets, varying from 0,1 à 158 W.kg-1 in the studied conditions. The results showed that jets velocity and supersaturation are two key-parameters controlling the crystallization with a preponderant effect of supersaturation. The obtained crystals have different size, particle size distribution, habit and polymorphic nature depending on the conditions. The most stable polymorphic form has been obtained pure or in mixture.A comparison with the classical SAS process showed that mean particle sizes are significantly smaller with impinging jets device proving that this device, creating a more efficient mixing, enhances the nucleation kinetics.This work may contribute to a better control of processes of crystallization in supercritical media.

Sous l'effet d'une forte impulsion mécanique, d'une chaleur très forte ou d'une décharge électrostatique, un explosif comme le TNT ou le RDX peut accidentellement être initié. L'énergie apportée à l'explosif est convertie en chaleur, appelée point-chaud, dans des endroits spécifiques, contenant des impuretés, bulles de gaz, pores ouverts ou autres hétérogénéités. La taille d'un point-chaud de quelques micromètres peut être déjà suffisante pour initier une déflagration ou même une détonation. En réduisant la taille des particules de l'explosif, la formation des points-chauds est empêchée conduisant à un matériau moins sensible. Au sein de ce travail, un procédé continu est développé, fondé sur le principe de la cristallisation-flash, et permettant la préparation de particules énergétiques submicroniques en quantité de plusieurs grammes. Le procédé repose sur une opération de séchage par atomisation, au cours de laquelle une solution surchauffée est atomisée d'une manière continue. Afin de diminuer la taille moyenne des particules et d'obtenir une distribution de taille des particules très étroite, une étude paramétrique est réalisée. Au moyen de la cristallisation-flash, la préparation de composites énergétiques de haute qualité en grandes quantités est un succès. La qualité et quantité de ce composite énergétique sont uniques. Grâce au potentiel de ce procédé, la cristallisation-flash peut permettre la préparation de nombreuses substances et compositions énergétiques ou inertes / High explosives, such as TNT or RDX, may be accidentally initiated under the influence of a strong mechanical impulse, great heat or an electrostatic discharge. Smallest impurities, open pores, entrapped gases or other inhomogeneities within the explosive matrix may convert the delivered energy into heat, causing the formation of a so called hot-spot. A hot-spot size of a few micrometers can already be sufficient to initiate a deflagration or even a detonation of the explosive. By decreasing the particle size of the explosive, the formation of hot-spots is inhibited, resulting in a less sensitive material. In this work, a continuous operating flash-crystallization process was developed, being able to produce energetic submicron particles in a multigram scale. The process bases on a spray drying process where superheated solutions are continuously atomized. A parametric study was performed on this process in order to decrease the particle size and obtaining a narrower particle size distribution. By means of this flash-crystallization process, highly homogeneous energetic composites were prepared in a large scale. The quality and amount of the energetic composite are unique. The versatility of the flash-crystallization process allows the preparation of a large number of energetic and inert substances and compositions

Ce travail de thèse porte sur l'étude du comportement rhéologique de deux mélanges élastomères chargés en noir de carbone dans une gamme de températures rencontrée en extrusion (90°C à 40°C) et sur la modélisation du procédé d'extrusion. La caractérisation rhéologique des deux matériaux de l'étude a mis en évidence leur comportement rhéologique différent. En effet, le SBR et ses mélanges chargés avec différentes teneurs en noir de carbone montrent une courbe d'écoulement en deux branches stables (branche I et branche II) séparées par un plateau. La présence d'un glissement, faible en branche I et important en branche II, a été mis en évidence. Le second matériau, le NR (pur et chargé), montre, quant à lui, un comportement en deux parties distinctes : une partie sans rhéodurcissement et une autre avec rhéodurcissement dû à la mise en place d'une cristallisation sous contrainte de cisaillement. L'existence d'un temps caractéristique de cristallisation, diminué par la vitesse de cisaillement, a pu être mise en évidence. Les lois de comportement pour chacun des matériaux ont été déterminées. La réalisation d'une superposition temps/taux de charge a permis de définir une loi de comportement générale ; dans la gamme de température de 40°C à 90°C pour les mélanges SBR/noir de carbone et dans la gamme de température de 50°C à 90°C pour le NR. La loi rhéologique déterminée pour le mélange SBR chargé à 33% en masse en noir de carbone a été implémentée dans un modèle 1D et 3D. Les résultats numériques ont alors été comparés aux résultats expérimentaux, obtenus suite à des essais sur une extrudeuse instrumentée. Le modèle 1D s'est avéré insuffisant pour rendre compte des phénomènes se déroulant lors du procédé d'extrusion. L'implémentation d'un modèle 3D a été effectuée afin de prendre en compte des phénomènes tels que les effets de bords et les gradients de températures. L'importance de prendre en compte le phénomène de glissement dans le modèle 3D a été démontrée. / The present work deals with the characterization of the rheological behaviour of two rubbers filled with carbon black in a range of temperature encountered in extrusion (90°C to 40°C) and the modelling of the single screw extrusion process. The rheological characterization of the two rubbers shows behaviour totally different. The synthetic SBR rubber and SBR compounds filled with carbon black (with different amounts, from 16 to 33 wt%) showed a flow curve that can be divided in two stable parts (branch I and branch II) separated by a plateau. The occurrence of wall slip, low in branch I and important in branch II has been highlighted. The second rubber of the study, natural rubber, showed a different behaviour with a strain hardening due to the occurrence of a strain induced crystallization. The flow curve can be thus divided in two different parts: the first part without strain hardening and the second part with this phenomenon. The existence of a characteristic crystallization time, reduced by the shear rate, has been evidenced. By analysing data respectively on branch I for SBR and without strain hardening for NR, viscosity curves for all tested materials have been defined. General viscosity law have been proposed: for the SBR compound filled with carbon black valid in the range of temperature from 40°C to 90°C and for NR in the range of temperature from 50°C to 90°C. The rheological law defined for the SBR compound filled 33%wt with carbon black has been implemented in two different models: 1 D and 3D. Numerical results have been compared to experimental results obtained after experimentations on instrumented single screw extruder. The 1D approach was not sufficient to take into account all phenomena occurring during extrusion process. Then a 3D approach has been developed in order to take into account some effects as side effects and temperature gradients. The presence of the slip phenomenon in the modeling has been proved.