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The area of particle characterization is expansive; it contains many technologies and methods of analysis. Light spectroscopy techniques yield information on the joint property distribution of particles, comprising the chemical composition, size, shape, and orientation of the particles. The objective of this dissertation is to develop a hybrid scattering-absorption model incorporating Mie and Rayleigh-Debye-Gans theory to characterize submicron particles in suspension with multiwavelength spectroscopy.Rayleigh-Debye-Gans theory (RDG) was chosen as a model to relate the particles joint property distribution to the light scattering and absorption phenomena for submicron particles. A correction model to instrument parameters of relevance was implemented to Rayleigh-Debye-Gans theory for spheres. Behavior of nonspherical particles using RDG theory was compared with Mie theory (as a reference). A multiwavelength assessment of Rayleigh-Debye-Gans theory for spheres was conducted where strict adherence to the limits could not be followed. Reported corrections to the refractive indices were implemented to RDG to try and achieve Mies spectral prediction for spheres.The results of studies conducted for RDG concluded the following. The angle of acceptance plays an important role in being able to assess and interpret spectral differences. Multiwavelength transmission spectra contains qualitative information on shape and orientation of non-spherical particles, and it should be possible to extract this information from carefully measured spectra. There is disagreement between Rayleigh-Debye-Gans and Mie theory for transmission simulations with spherical scatterers of different sizes and refractive indices.

This study aims to deduce an appropriate shape and density for an electronic free-cell that could be placed into a silo so that position and other desired physical parameters could be recorded. To determine how density and shape affects the trajectory and displacement of free cells, the trajectory and displacement of cylindrical, cuboid and triangular prism free-cells of equivalent volume was investigated in a discharging quasi 3D silo slice. The free-cells were placed at twelve different starting positions spread evenly over one half of the 3D slice. Tests were conducted using a monosized batch of spherical particles with a diameter of approximately 5 mm. Tests were also conducted in a binary mixture consisting of particles of different sizes (5 mm/4 mm) and the same density (1.28 g/cm3) and a binary mixture consisting of particles of different size (6 mm/5 mm) and different densities (1.16 g/cm3/1.28 g/cm3).The rotation of the free cells was also briefly discussed.Computer simulations were conducted using the Discrete Element Method (DEM). The simulation employed the spring-slider-dashpot contact model to represent the normal and tangential force components and the modified Euler integration scheme was applied to calculate the particle velocities and positions at each time step. One trial of each of the metal and plastic, cylindrical, cuboid and triangular prism free cells was compared with the average of three experimental trials. The trajectory and displacement of a representative particle positioned at the same starting position as the free cell was also obtained from DEM simulation and compared with the path and displacement of each of the free cells to determine which free cell followed the particle most closely and hence to determine a suitable free cell that would move with the rest of the grains. Spherical particles are idealised particles. Therefore tests were also conducted with a small number of polyhedral particles, to deduce their flow rate and the critical orifice width at which blockages were likely to form. Simulations were also conducted to test the feasibility of the DEM in modelling the behaviour of these polyhedral particles.Results indicate that for a free cell to move along the same trajectory and have the same displacement and velocity as an equivalent particle in the batch it should have a similar density to the majority of the other particles. A cylindrical free cell of similar density to the particles was found to follow the path of the representative particle more closely than the cuboid or triangular prism. Polyhedral particles were found to have a greater flow rate than spherical particles of equivalent volume.

Over the past couple of decades interest in particle-stabilised emulsions or Pickering emulsions has greatly increased. When using particles as stabilisers, as opposed to surfactants, the interface becomes more rigid and this can lead to interesting physical properties. In addition, the resulting emulsions are found to be longer-lived garnering commercial interest. This thesis aims to explore the mechanical properties of some specific systems containing particle-stabilised interfaces. The main system investigated was the bicontinuous interfacially jammed emulsion gel or bijel. The bijel has two continuous interpenetrating liquid phases separated by a particle-stabilised interface. Therefore, the structure has a very large interface in a fairly small volume and the pore size is under the experimentalist's control giving it promise in a variety of applications, particularly those based on catalysis. The response of bijels stabilised by either spherical particles or anisotropic rod-shaped particles to centrifugal compression has been investigated in this thesis. It was found that, in both cases, the structure was distorted to create anisotropic particle-stabilised sheets orientated perpendicular to the force. The original method for fabricating bijels involves the arrested spinodal decomposition of partially miscible liquids. This method requires partially miscible liquid pairs and particles that are equally wetted by each phase. Due to these requirements, a new method for making bijels using mixing was developed by others and the bijel made by mixing has been tested with oscillatory rheology combined with imaging and squeeze flow experiments. It was found that at low strain the bijel displayed solid-like behaviour and the structure remained intact until well past the yielding point. In addition, two further systems were investigated. The first system was rod-shaped particle-stabilised emulsion droplets that stick together by particle bridging. Bridging is where one particle can stabilise two droplet interfaces, preventing coalescence and leading to droplet clusters. Particle bridging was found to occur regardless of shear rate, particle volume fraction and to some extent aspect ratio with these anisotropic rod-shaped particles. This behaviour is hypothesised to be a consequence of the charged nature of the silica surface above pH 2. The second system was large particle-stabilised water droplets that can sprout tubes by the partitioning of solute from a bath into the droplet. By using different solutes and mixtures of different alcohols, the key requirements for sprouting behaviour have been ascertained. The most important requirement was found to be achieving the correct balance between the interfacial tension and the amount of solute partitioning into the droplet.

Made available in DSpace on 2014-06-11T19:22:54Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-07-29Bitstream added on 2014-06-13T20:10:04Z : No. of bitstreams: 1 basso_gg_me_sjrp_parcial.pdf: 127718 bytes, checksum: 3bfde1c4f9ff597bf78cc0fd338d9fe8 (MD5) Bitstreams deleted on 2015-08-28T16:08:53Z: basso_gg_me_sjrp_parcial.pdf,. Added 1 bitstream(s) on 2015-08-28T16:09:58Z : No. of bitstreams: 1 000670722.pdf: 6039395 bytes, checksum: a8326c9658e562fa0ebe828de242a31a (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Financiadora de Estudos e Projetos (FINEP) / Partículas poliméricas com tamanho e morfologia controlados e propriedades físico-químicas adequadas são amplamente utilizadas em aplicações médicas, como na embolização, uma técnica cirúrgica utilizada para tratar malformações arteriovenosas (MAVs), conter hemorragias, tratar localmente tumores hipervascularizados (THVs) e outras doenças vasculares. Este procedimento é realizado com materiais de diferentes formas e composições, sendo as partículas de poli(álcool vinílico) (PVA) freqüentemente utilizadas por apresentarem um alto grau de desempenho. Elas estão disponíveis no mercado nas morfologias esférica e não-esférica, sendo que as esféricas apresentam uma maior eficácia no tratamento. O presente trabalho objetivou desenvolver e aprimorar partículas esféricas de PVA e poli(acetato vinílico) (PVAc) para serem utilizadas em embolização. Suas sínteses foram realizadas em duas etapas: a polimerização em suspensão do monômero acetato vinílico (VAc) em PVAc e a saponificação do polímero PVAc em PVA, com variações na velocidade de agitação e na concentração da solução de hidróxido de sódio (NaOH), na etapa da saponificação. As partículas foram caracterizadas por microscopia eletrônica de varredura (MEV), difração de raios-X (DRX), calorimetria diferencial de varredura (DSC) e ressonância magnética nuclear de 13 C - cross polarization / magic angle spinning (13 C RMN CP/MAS). Foram analisadas a distribuição de tamanhos, a dimensão fractal, a determinação da biocarga, que determinou os parâmetros de esterilização por radiação gama, e a citotoxicidade, pelo teste de “Reatividade Biológica in vitro”. Os resultados indicaram que a morfologia esférica foi obtida durante a primeira etapa da síntese e que essa morfologia não foi afetada pelo segundo processo. A velocidade de agitação e a concentração de NaOH influenciaram... / Polymeric particles with controlled size and morphology and appropriated physicochemical properties are widely used in medical applications, such as embolization, a surgical technique used to treat arteriovenous malformations (AVMs), stop bleedings, treat locally hypervascular tumors (HVTs) and other vascular diseases. This procedure is performed with materials of different shapes and compositions, and the poly(vinyl alcohol) (PVA) particles are often used for presenting a high degree of performance. They are commercially available in spherical and non-spherical morphologies, and the spherical particles have a greater efficacy in the treatment. This study aimed to develop and improve spherical PVA and poly(vinyl acetate) (PVAc) particles for use in embolization. Their syntheses were performed in two stages: the suspension polymerization of vinyl acetate (VAc) monomer in PVAc and the saponification of PVAc polymer in PVA, with variations in the stirring speed and the concentration of sodium hydroxide (NaOH) solution, at the saponification step. The particles were characterized by scanning electronic microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and 13 C nuclear magnetic resonance - cross polarization / magic angle spinning (13 C NMR CP/MAS). We analyzed the size distribution, the fractal dimension, the determining of the bioburden, which determined the parameters of sterilization by gamma irradiation, and the cytotoxicity, by the “Biological Reactivity in vitro”. The results indicated that the spherical morphology was obtained during the first stage of the synthesis and that this morphology was not affected by the second process. The stirring speed and the NaOH concentration influenced the size of the particles. The commercial particles have a fractal dimension greater than the synthesized particles... (Complete abstract click electronic access below)

Resumo: Partículas poliméricas com tamanho e morfologia controlados e propriedades físico-químicas adequadas são amplamente utilizadas em aplicações médicas, como na embolização, uma técnica cirúrgica utilizada para tratar malformações arteriovenosas (MAVs), conter hemorragias, tratar localmente tumores hipervascularizados (THVs) e outras doenças vasculares. Este procedimento é realizado com materiais de diferentes formas e composições, sendo as partículas de poli(álcool vinílico) (PVA) freqüentemente utilizadas por apresentarem um alto grau de desempenho. Elas estão disponíveis no mercado nas morfologias esférica e não-esférica, sendo que as esféricas apresentam uma maior eficácia no tratamento. O presente trabalho objetivou desenvolver e aprimorar partículas esféricas de PVA e poli(acetato vinílico) (PVAc) para serem utilizadas em embolização. Suas sínteses foram realizadas em duas etapas: a polimerização em suspensão do monômero acetato vinílico (VAc) em PVAc e a saponificação do polímero PVAc em PVA, com variações na velocidade de agitação e na concentração da solução de hidróxido de sódio (NaOH), na etapa da saponificação. As partículas foram caracterizadas por microscopia eletrônica de varredura (MEV), difração de raios-X (DRX), calorimetria diferencial de varredura (DSC) e ressonância magnética nuclear de 13 C - cross polarization / magic angle spinning (13 C RMN CP/MAS). Foram analisadas a distribuição de tamanhos, a dimensão fractal, a determinação da biocarga, que determinou os parâmetros de esterilização por radiação gama, e a citotoxicidade, pelo teste de "Reatividade Biológica in vitro". Os resultados indicaram que a morfologia esférica foi obtida durante a primeira etapa da síntese e que essa morfologia não foi afetada pelo segundo processo. A velocidade de agitação e a concentração de NaOH influenciaram... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Polymeric particles with controlled size and morphology and appropriated physicochemical properties are widely used in medical applications, such as embolization, a surgical technique used to treat arteriovenous malformations (AVMs), stop bleedings, treat locally hypervascular tumors (HVTs) and other vascular diseases. This procedure is performed with materials of different shapes and compositions, and the poly(vinyl alcohol) (PVA) particles are often used for presenting a high degree of performance. They are commercially available in spherical and non-spherical morphologies, and the spherical particles have a greater efficacy in the treatment. This study aimed to develop and improve spherical PVA and poly(vinyl acetate) (PVAc) particles for use in embolization. Their syntheses were performed in two stages: the suspension polymerization of vinyl acetate (VAc) monomer in PVAc and the saponification of PVAc polymer in PVA, with variations in the stirring speed and the concentration of sodium hydroxide (NaOH) solution, at the saponification step. The particles were characterized by scanning electronic microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and 13 C nuclear magnetic resonance - cross polarization / magic angle spinning (13 C NMR CP/MAS). We analyzed the size distribution, the fractal dimension, the determining of the bioburden, which determined the parameters of sterilization by gamma irradiation, and the cytotoxicity, by the "Biological Reactivity in vitro". The results indicated that the spherical morphology was obtained during the first stage of the synthesis and that this morphology was not affected by the second process. The stirring speed and the NaOH concentration influenced the size of the particles. The commercial particles have a fractal dimension greater than the synthesized particles... (Complete abstract click electronic access below) / Orientador: José Geraldo Nery / Coorientador: Ana Paula Marques de Lima Oliveira / Banca: Rosa Sayoko Kawasaki Oyama / Banca: Moacir Fernandes de Godoy / Mestre

In this study the breakage mechanics of brittle glass marbles was investigated. The pro-cess was to firstly investigate them in laboratory environment. The marbles or specimens was loaded until a crushing breakage occurred in a single point load test called Single Sphere Point load test in this document. From the test we could derive the crushing load, the deformation and strain, the tensile strength and other parameters needed for the second part of this work. Namely the numerical modelling, here we investigated the specimen with the Discrete Element method or DEM for shorts. The software used was an open sourced software created in MATLAB called DICE2D. Since the software was developed to only include the mathematical part of the numerical model several re-coding processes were needed, with other words the creation of add-ons to the software. The add-ons were automatic code created in Python where the user now are able to create a geometrical model for the specimen that the software can interpret. There were two add-ons created in order to generate a geometry, called the circumference method and the random generation method, i.e. different methods of creating a geometry. The first method, the circumference method creates circumferences filled with smaller particles with the same radii, then moves a step inward to the specimens center and fills another circumference until the center is reached. The second method, the random method generates particles positioned randomly inside the specimen with a random radii, created such that the radius of the particles is chosen with an interval, were the user can choose the smallest and the largest particle radius. It was found that both these add-ons were of great use with different purposes in mind. The circumference method was able to create a brittle material where the deformations were low. The random method also created a brittle material but since the particles were randomly positioned there also was empty space created such that the deformations were larger than the one found in the laboratory environment, since the empty space between the particles was closed before the plastic deformation could occur. Hence the second method of generation is more relevant for concrete and rock mechanics since in these cases this is the actual process, where the micro-cracks first closes then the elastic and plastic deformation occurs [Martin, 1993]. The first method, the circumference method is of great use when investigating the elastic deformations since here the particles are in contact. Thus creating the scenario for granular particles, In this thesis however the circumference method was used in order to create a solid specimen. For future use this add-on should be used in order such that each particle simulates an actual grain. The results found with both of these methods follows the results found in the laboratory test for the crushing load. But the incremental increase of force when the load is applied on the specimen was not able to be simulated. It is believed that the software is having difficulties to simulate brittle material due to the small deformations and the large loads.

The interest of how small non-spherical particles transport behaviour when transported in pipe-flow is of large interest in a variety applications. This kind of theory have been used when studying composite manufacturing and how particles behaves in the human lungs. The main focus is to study the statistical deposition rate in a flow-field with and without capillary action and gravity. Two kind of particle shapes are of main interest which are prolate and oblate spheroids. In this study the method of vector projection is used to track particle orientation instead of the more common methods of Euler-angles or quaternions. The method of tracking the particle motion used is Lagrangian tracking method which solves the equations of motion for the particles individually. When studying particles of nano-scale the importance of the phenomenon called Brownian motion arises. The inclusion if the Brownian motion gives rise to the solving of stochastic differential equations for the particle transport. To solve the resulting equations of transport a MATLAB program was developed to using the numerical Euler-Maruyama scheme. Simulations is done with a large amount of particles with a varying particle size and aspect ratio. The deposition results are compared between the different particles shape and sizes. It is seen that the effect of the Brownian motion on particle deposition rate increases with a smaller particle size. It is also concluded that the Brownian motion is the dominating reason for particle deposition. From comparing particle shape and size it is seen to have a major effect of the particles deposition. Including capillary action or gravity the inclusion doesn't affect particles deposition as much.

Dispersed particle flows occur in many industrial, biological and geophysical applications. The knowledge of how these flow behave can for example lead to improved material processes, better predictions of vascular diseases or more accurate climate models. These particle flows have certain properties that depend on single particle motion in fluid flows and especially how they are distributed both in terms of spatial position and, if they are non-spherical, in terms of orientation. Much is already known about the motion of perfectly spherical particles. For non-spherical particles, apart from their translation, it is important to know the the rotational motion due to local velocity gradients. Such studies have usually been restricted by the assumption that particles are extremely small compared to fluid length scales. In this limit, both inertia of the particle and inertia of the fluid can be neglected for the particle motion. This thesis gives a complete picture of how a spheroidal particle (a particle described by a rotation of an ellipse around one of its principal axes) behave in a linear shear flow when including both fluid and particle inertia, using numerical simulations. It is observed that this very simple problem possess very interesting dynamical behavior with different stable rotational states appearing as a competition between the two types of inertia. The effect of particle inertia leads to a rotation where the mass of the particle is concentrated as far away from the rotational axis as possible, i.e.\ a rotation around the minor axis. Typically, the effect of fluid inertia is instead that it tries to force the particle in a rotation where the streamlines of the flow remain as straight as possible. The first effect of fluid inertia is thus the opposite of particle inertia and instead leads to a particle rotation around the major axis. Depending on rotational state, the particles also affect the apparent viscosity of the particle dispersion. The different transitions and bifurcations between rotational states are characterized in terms of non-linear dynamics, which reveal that the particle motion probably can be described by some reduced model. The results in this theses provides fundamental knowledge and is necessary to understand flows containing non-spherical particles. / Flöden med dispergerade partiklar påträffas i många industriella, biologiska och geofysiska tillämpningar. Kunskap om hur dessa flöden beter sig kan bl.a. leda till förbättrade materialprocesser, bättre förutsägelser om hjärt- och kärlsjukdomar eller mer noggranna väderprognoser. Dessa flödens egenskaper beror på hur enskilda partiklar rör sig i en fluid och speciellt hur de är fördelade både i termer av position och, om de är icke-sfäriska, i termer av orientering. Mycket är redan känt om rörelsen av perfekt sfäriska partiklar. För icke-sfäriska partiklar är det inte bara translationen som är av intresse utan det är även viktigt att veta hur partiklarna roterar till följd av lokala hastighetsgradienter. Sådana studier har tidigare varit begränsade av antagandet att partiklarna är extremt små jämfört med fluidens typiska längdskalor. I denna gräns kan både partikelns och fluidens tröghet antas försumbar. Den här avhandlingen ger en komplett bild av hur en sfäroidisk partikel (en partikel som beskrivs av en rotation av en ellips runt en av dess huvudaxlar) beter sig i ett linjärt skjuvflöde när tröghetseffekter inkluderas. Resultaten har erhållits genom numeriska simuleringar. Det visar sig att detta enkla problem är väldigt rikt på olika dynamiska beteenden med flera stabila rotationstillstånd som uppstår tilll följd av både partikel- och fluidtröghet. Inverkan av partikeltröghet leder till en rotation där massan av partikeln är koncentrerad så långt ifrån rotationsaxeln som möjligt, d.v.s. en rotation runt lillaxeln. Den typiska inverkan av fluidtröghet är istället att fluiden försöker påtvinga partikeln en rotation där strömlinjer förblir så raka som möjligt. Primärt leder detta till att partikeln istället roterar runt storaxeln. Beroende på rotationstillstånd, så har partikeln även olika inverkan på den märkbara viskositeten av partikeldispersionen. De olika övergångarna och bifurkationerna mellan rotationstillstånd är karaktäriserade i termer av icke-linjär dynamik, vilket visar på att partikelrörelserna förmodligen kan beskrivas med en reducerad modell. Resultaten i denna avhandling är därför fundamental kunskap och ett nödvändigt steg mot att förstå beteendet av flöden med dispergerade, icke-sfäriska partiklar. / <p>QC 20140328</p>

Numerous practical applications exist where dispersed solid particles are transported within a turbulent accelerating or decelerating gaseous flow. The large density variation between phases creates the potential for significant differences in velocity known as velocity slip. Flow over a backward facing step provides a well characterized, turbulent, decelerating flow useful for measuring the relative velocities of the solid and gaseous phases in order to determine velocity slip and particle drag. Numerous investigations have been conducted to determine the gas phase velocity in a backward facing step for both laminar and turbulent flows and therefore the gas phase flow is well know and documented. Furthermore, some studies have also been conducted to determine the velocity of various sizes of spherical particles in a backward facing step and compared with their corresponding gas phase velocities. Few if any velocity measurements have been made for non-spherical particles in a backward facing step. In this work, a Phase Doppler Particle Analyzer (PDA) was used to measure gas and particle phase velocities in a backward facing step. The step produced a 2:1 increase in cross sectional area with a Reynolds number of 22,000 (based on step height) upstream of the step. Spherical particles of 1 – 10 μm with an average diameter of 4μm were used to measure the gas phase velocity. At least three sizes in the range of (38 – 212 μm) for four different particles shapes were studied. The shapes included: spheres, flakes, gravel, and cylinders. Since the PDPA is not able to measure the size of the non-spherical particles, the particles were first separated into size bins and a technique was developed using the PMT (photo multiplier tubes) gain to isolate the particle size of interest for each size measured. The same technique was also used to measure terminal velocities of the particles in quiescent air. The measured gas phase velocity and spherical solid phase particles were in good agreement with previous measurements in the literature. The results showed relative velocities between the particles and gas phase to be in the range of 0 – 3 m/s which is in transition between stokes flow and fully developed turbulent flow. Drag coefficients were an order magnitude higher for non-spherical particles in turbulent flows in comparison to stokes flow which agreed reasonably well with quiescent terminal velocity drag. This information is valuable for modeling turbulent two-phase flows since most assumptions of the drag are currently based on correlations from empirical data with particles moving through a still fluid.