The rheological behavior analysis of Engineered Cementitious Composites (ECC) is key to understand how the different preparation techniques affect the composite mechanical performance. However, the rheological assessment of reinforced materials becomes more complex since fibers usually cause flow disturbances not found in nonreinforced cementitious materials. Besides that, simple workability measurement techniques are not able to fully understand the composite behavior in the fresh state creating the need for more precise techniques to be employed. The main objectives of this study were to evaluate the ECC rheological behavior using different rheometer devices (Vane system and Ball measuring system) and investigate the influence of mixing processes on the fiber homogenization and rheological behavior. Additionally to this, a link between rheological behavior and mechanical performance was investigated. In the end, the ball measuring system revealed to be more efficient than the vane system when evaluating the composite rheological behavior. In addition, the mixing process influenced the rheological behavior of PVA-ECC especially regarding the moment which fibers are added. Fiber addition after mortar mixture improved fibers homogenization and reduced mixing energy by around 8%. Moreover, a correlation between rheological and mechanical properties showed that a 2-times variation in either yield stress or viscosity can lead to a variation of more than 50% in flexural strength without significantly affecting the composite compressive strength. It was also found that the lower the composite yield stress and viscosity the higher was its ultimate strain. To conclude, all those parameters contributed to understand the composite rheological behavior and globally optimize its performance. / Sem resumo

Memoria para optar al título de Ingeniero Civil / El siguiente trabajo presenta un estudio del comportamiento de hormigones tradicionales al ser reforzados con microfibras de polivinilo de alcohol. Específicamente, este analiza cambios en propiedades mecánicas de este material como lo son su resistencia y su ductilidad. Esto último, sin dejar de lado la posibilidad de estudiar otros fenómenos que se pudieran observar a lo largo de la investigación. Esta investigación consiste tanto en experimentación en laboratorio como en análisis mediante el uso de software computacional. La primera parte mencionada contempla la elaboración de tandas de probetas cilíndricas de hormigón con y sin fibra. Diferentes cantidades de fibra son utilizadas en distintas mezclas buscando contrastar resultados con mezclas sin fibra. De igual manera, las proporciones agua/cemento y áridos/cemento y el tamaño máximo de árido en cada set de probetas son diferentes con el fin de obtener un espectro mayor de resultados y de esta forma poder realizar un análisis más completo. Existe un primer grupo de probetas que se elabora para llevar a cabo ensayos preliminares a modo de prueba y obtener algún tipo de tendencia general. Un segundo grupo para ajustar dosificaciones y un último grupo, mucho más amplio en cantidad que el primero, el cual es necesario para efectuar un estudio más complejo y global del comportamiento del hormigón tradicional reforzado con microfibras de PVA. De las probetas finales, cuyas variables más características son: la cantidad de fibra y el tamaño máximo de árido (0%, 1% y 2% de fibra y tamaños de árido de 0.3 mm, 4.75 mm y 9.5 mm), se obtiene que a compresión la resistencia siempre es mayor (entre 5% y casi 400% veces) sin microfibra que con microfibra, mientras que la deformación última, en casos con PVA puede llegar a ser hasta 8 veces mayor. De esta etapa, sin embargo, no es posible obtener resultados claros a tracción. Por otro lado, con lo que respecta a la parte computacional, diferentes softwares se utilizan como herramienta para procesar la información obtenida en el campo experimental. Además, se realizan parametrizaciones que representen las curvas obtenidas y así obtener fórmulas generales. Dichas modelaciones, provenientes de combinar modelos ya ampliamente conocidos con regresión de datos experimentales, son utilizadas en un análisis de tipo Pushover en el programa SAP2000 con el fin de tener una idea general del comportamiento estructural del hormigón fibroreforzado. Para efectos prácticos, el análisis es llevado a cabo en una torre de 10 pisos de muros con confinamiento de borde. De esto último y empleando las mismas cantidades de fibra e iguales tamaños máximos de árido que en las probetas finales, se puede constatar que para todos los casos, previo a los 0.6 metros de desplazamiento de techo, la carga requerida es siempre mayor en hormigones sin PVA alcanzando a ser esta, en casos extremos como aquellos con árido de 9.5 milímetros, hasta 1.2 veces mayor.

Memoria para optar al título de Ingeniera Civil Mecánica / El presente trabajo es un estudio de carácter exploratorio sobre el tema de materiales compuestos de alcohol polivinílico y diferentes nanopartículas. El objetivo es estudiar la influencia del tipo, tamaño y morfología de nanopartículas sobre las propiedades mecánicas de PVA reforzada con ellas. El alcohol polivinílico es un polímero no tóxico para el ser humano, esta característica hace que sea interesante de estudiar en aplicaciones como transporte de fármacos y revestimiento de heridas. En estos casos los materiales compuestos nanopartículas pueden actuar como agentes transportadores de los fármacos y la matriz de PVA actúa aglomerando estas nanopartículas. Además tienen amplias aplicaciones como membranas. El estudio mecánico de este tipo de materiales es relevante a la hora de la fabricación en masa. En este caso se observa que los materiales tienen propiedades similares al PVA con respecto al módulo de Young y al esfuerzo de fluencia y no así con respecto a la deformación. La síntesis de las nanopartículas puede ser controlada mediante el pH y la temperatura. En este caso se utilizan cantidades similares de NaOH y temperatura de 80°C para todas las nanopartículas. El análisis mediante TEM muestra que estas condiciones de síntesis no son las ideales para la mayoría de las nanopartículas. En la síntesis de las nanopartículas y nanocompuestos con ferritas es necesario disminuir la temperatura de 80°C a 30-40°C y controlar cuidadosamente el pH de la solución en 9.5 u 11 para obtener partículas de menor tamaño con desviaciones estándar más acotadas. El impacto de la morfología y tamaño en las propiedades mecánicas no es del todo claro. Sí se observa una tendencia general a mejorar el módulo de Young y el esfuerzo de fluencia con la adición de nanopartículas, sin embargo, existen excepciones como la muestra de CuO/CoFe2O4 en la que disminuye E y el esfuerzo de fluencia. El incremento de E ocurre porque las nanopartículas tienden a generar enlaces secundarios entre las cadenas de polímeros, generando un efecto de reticulación, dándole mayor rigidez al sistema. El cambio en el esfuerzo de fluencia depende más de la interacción entre nanopartículas y matriz que de los enlaces. Depende de si la matriz tiene un contacto uniforme con las nanopartículas, de si las nanopartículas se aglomeran y de la morfología de las mismas nanopartículas. Estas características no pueden ser estudiadas con los resultados obtenidos en este estudio. El estudio puede ser continuado de distintas maneras. En primera instancia se puede orientar a caracterizar un tipo de material separando las nanopartículas según tamaño. Se puede estudiar el área superificial para buscar una correlación entre este valor y las propiedades mecánicas. Además, como el PVA es un material viscoelástico se sugiere hacer otras pruebas de estabilidad térmica y de dinámica de las piezas.

>Magister Scientiae - MSc / Rapid industrialization growth without appropriate emission standards for discharging environmental pollutants had exposed the ecosystem to detrimental effect. Due to their bioaccumulation propensity in organisms, toxicity and non-biodegradable aspect, heavy metal spoliation is currently a significant ecological obligation. Owing to their natural abundance and extensive use, cadmium (Cd) and lead (Pb), among different heavy metals, are the predominant toxic metals. The intrusion of Cd and Pb metal ions into the ecosystem is accomplished by widely accepted methods such as anticorrosive coating of steel, electronic circuit and batteries. / 2023

Emulsion polymerizations of vinyl acetate (VAc) were performed by fully or partially replacing poly(vinyl alcohol) (PVA) with renewable materials as protective colloids or by adding renewable materials, as additives or fillers, to the emulsions during or after polymerization. The purpose of the study was to increase the amount of renewable materials in the emulsion. A total of 19 emulsions were synthesized. Different recipes were used for the synthesis. The following renewable materials were studied; hydroxyethyl cellulose (HEC) with different molecular weights, starch and proteins. HEC and starch were used as protective colloids. Proteins were used as additives or fillers. Cross-linking agent A and Cross-linking agent B were used as cross-linking agents. A total of 26 formulations were pressed, either cold or hot. The synthesized emulsions were evaluated with respect to pH, solids content, viscosity, minimum film formation temperature (MFFT), glass transition temperature (Tg), particle size and molecular weight (Mw). The tensile shear strengths of the emulsions were evaluated according to EN 204 and WATT 91. It was possible to fully, or partially, replace PVA as protective colloid with renewable materials. It was also possible to use renewable materials as additives or fillers in the emulsions. The emulsions obtained properties that differed from the reference. Generally, emulsions with HEC as protective colloid showed lower viscosity and slightly higher MFFT, Tg and molecular weight than emulsions with PVA as protective colloid. Larger particle sizes than the reference were obtained for emulsions containing PVA combined with renewable materials. The emulsion with starch as protective colloid exhibited the largest particle size. 10 formulations passed the criteria for D2. The emulsions where PVA was fully or partially replaced with HEC or starch showed a water resistance similar to the reference (around D2). The addition of protein did not decrease the water and heat resistance compared to the reference. Addition of protein after polymerization increased the water resistance (D2) compared to addition during polymerization. Addition of cross-linking agents did not increase the water resistance further. Two formulations passed the criteria for D3. The emulsion in the first formulation had PVA as protective colloid and protein B was added during polymerization. The emulsion in the second formulation had HEC as protective colloid. To both of these emulsions, protein A was added after polymerization, as a filler, combined with Cross-linking agent B as cross-linking agent before hot pressing. The first formulation also showed a good heat resistance (passed the criteria for WATT 91).

The aim of the project was to investigate a green and sustainable replacement for boric acid in polyvinyl alcohol (PVA) adhesives for solid paperboard production. Boric acid acts as a cross-linker and tackifier in the adhesive but is classified as a harmful substance. Microfibrillated cellulose (MFC) was therefore investigated as a possible replacement for boric acid since it is produced from renewable and sustainable resources. In addition, it has hydroxyl groups available for interaction with the PVA, can be used to modulate the viscosity and can function under a variety of pH-values.  For the industrial process, there are three basic characteristics which must be met by the newly developed adhesive, which have to be the same as for the boric acid-containing reference. These three are the viscosity, the pH-value, and the dry content. Furthermore, it is important that the initial wet tack and the final adhesive strength are at least as high as the reference’s.  In this context, eight types of samples were investigated in total. Two were references, one prepared on industrial and the second on a laboratory scale according to a current industrial recipe. In the other six samples, the boric acid from the recipe was replaced by three different weight percentages of MFC of two different industrial grades. Both the dry content and the pH-value were not noticeably influenced by the addition of MFC. The viscosity however increased drastically with the increasing amount of MFC. The addition of MFC was enough to reach the three basic characteristics. In addition it was observed positive effects on a couple of other parameters that is beneficial for the glue.   A test method for evaluating the initial wet tack of the adhesive was developed. It was shown, that the tack of the adhesive containing MFC is 40 % lower than the one of the reference material. Therefore, five additives were tested in the formulation, in combination with MFC. The most promising result led to a comparable initial tack and final strength as the reference.

The harmonic generation due to the nonlinear behavior of Ultrasound Contrast Agents (UCAs) must be exploited for improved efficiency when imaging vascular targets in the neighborhood of highly echogenic tissue. One may even further improve the efficiency by focusing on the subharmonic generation of the UCAs, which is an even more exclusive property than the generation of higher harmonics, for improved Contrast-to-Tissue ratio (CTR). The aim of this work was first, the design of a set-up for nonlinear imaging of Poly-Vinyl Alcohol (PVA) based UCAs on The Verasonics Research System with special focus on nondestructive Subharmonic Imaging. The second part of the work addressed the evaluation of the subharmonic response provided by the agents in the developed setup. Six different imaging techniques were developed. These were Fundamental B-mode imaging (FB), Pulse Inversion imaging (PI), and a Contrast Pulse Sequence based on three pulses (CPS3), with and without a focus on the subharmonic component by the implementation of a Linear Bandpass Filter (LBF). Experiments were performed on a tissue mimicking flow phantom and the performance of the agents for each technique was determined in terms of CTR and CNR. The PVA agents provided a backscattering enhancement of the order of 23 dB through FB imaging. However, the performance of the FB technique was unsatisfactory in terms of CTR. The CPS3 sequence performed best of the six techniques with an improvement of 14 dB and 13 dB in CTR and CNR, respectively, compared with the FB technique. Combining the LBF around the subharmonic component with the multi-pulse techniques of PI and CPS3 resulted in a degraded CTR performance due to significant amount of signals from tissue around the subharmonic component and insufficient subharmonic detection from the PVA agents.

The induced rupturing of Poly Vinyl Alcohol (PVA) microbubbles with high mechanical index (MI)ultrasound beam is used in multiple medical application such as drug delivery, image contrastenhancement and perfusion imaging.In this work, Triggered imaging technique with subtraction algorithm is used to enhance themicrobubble’s (MB) contrast over tissue (CTR). The technique is performed by rupturing MBwith one destruction wave sequence followed by 100 B-mode imaging pulse sequences. Theimages obtained are then subtracted by a base image that is selected after the destruction pulse[1].The result of this technique depends mainly on the effectiveness of destruction pulse inrupturing highest number of MB. This has been tested through tissue mimicking phantomwithout replenishing the MB. The evaluation of the methods is done through the CTR and CNRcalculation for each of the 100 frames.The contrast enhancement technique used has also been tested with similar setup but withcontinuous replenishment of MB. The evaluation is done by comparing CNR and CTR results forthe 100 frames obtained by B-mode imaging with the ones resulted from the subtractionalgorithm.The contrast values obtained from both experiments are used in driving the characterization ofPVA response to high MI.The result for the destruction pulse effectiveness shows that the pulse indeed managed toreduce number of MB, but not to the lowest. This is because of leaked gas from cracked shell,the shell acoustic enhancement effect, and large bubbles which managed to survive.The Triggered imaging has shown large improvement in CTR value with use of the subtractionalgorithm when compared to B-mode results. In addition, it has provided an experimental wayfor perfusion imaging and quantification by monitoring CTR value after the destructive pulse[2]. This sets the bases for experimental research relevant to tissue perfusion at ultrasound labof KTH.

In radiation therapy, gel dosimetry is used to measure radiation doses for treatment verification. Gel dosimeters have the ability to record dose information in three dimensions. The objective of this thesis was to fabricate a transparent cryogel radiochromic dosimeter with poly(vinyl alcohol) (PVA) as the gelling agent. A transparent dosimeter may be analyzed using an optical read out technique, which is desirable. PVA cryogels can be made transparent by adding dimethyl sulfoxide (DMSO). Measurements of dose response were performed and various parameters were adjusted, including: numbers of freeze-thaw cycles (FTCs); concentrations of PVA; DMSO concentration. The measured absorption coefficient increased linearly with dose up to approximately 10 Gy. The sensitivity was increased for higher PVA concentrations, larger numbers of FTCs, and less DMSO. The resulting dosimeter was stable and showed no significant dose rate or photon energy dependence. The cryogels were later formed into 5 mm thick films and used as a tool for performing in vivo dosimetry. The dose response of the radiochromic bolus was characterized by irradiating it on a flat surface at different gantry angles. The dose measured in the bolus was approximately 0.80 of the dose measured by Gafchromic film at the skin surface, taking the obliquity into account. IMRT treatments were delivered to a RANDO phantom. The radiochromic bolus was used to measure skin surface dose in two dimensions at various locations. The 0.80 factor was used to calibrate the bolus, which was then compared to an accompanying film measurement. Good agreement was observed between the measurements (>95% gamma pass rate), suggesting the radiochromic bolus may be suitable for in vivo applications. The radiochromic bolus was then used to evaluate errors associated with the breath hold technique often used with left chest wall tangential irradiation. Treatment plan incorporating the radiochromic bolus was delivered at the planned position and shifted anterior-posteriorly (A/P) up to 5 mm. Large discrepancies from the planned two dimensional skin surface distribution were observed for shifts as small as 3 mm in the A/P direction. The study demonstrated that the cryogel was sensitive to small positioning uncertainties for chest wall irradiations, potentially allowing for the detection of clinically relevant errors. Other potential formulations of PVA-based radiochromic cryogels are discussed briefly as avenues to future research projects. / Thesis / Doctor of Philosophy (PhD)

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