A incorporação de óleos vegetais no desenvolvimento de formulações elastoméricas para bandas de rodagem tem sido umas das alternativas para reduzir o uso de óleos com alto teor de policíclicos aromáticos. Muitas pesquisas propõem a substituição do óleo aromático por óleos vegetais extraídos da palma e da soja, além disso, outros estudos sugerem que óleos vegetais apresentam características reativas capazes de promover a ativação em reações de vulcanização. Neste trabalho, o óleo de soja vegetal foi investigado como lubrificante/plastificante e também como co-ativadores em compostos de borracha natural vulcanizados por enxofre, no estado natural e quimicamente modificados, através da epoxidação do próprio óleo de soja. A caracterização do óleo de soja natural e epoxidado foi realizado através de análise de Espectroscopia no Infravermelho com Transformada de Fourier (FTIR) e Ressonância Magnética Nuclear de Próton (RMN-1H). Uma formulação padrão foi utilizada e partir dela outras 5 misturas foram realizadas com o objetivo de substituir o óleo aromático e o ácido esteárico pelas amostras de óleo vegetal, uma amostra branco, sem o sistema de ativação convencional, também foi preparada. As composições foram processadas em misturador fechado, tipo banbury, e após, a homogeneização foi completada em cilindro. As propriedades de cura foram avaliadas em um reômetro de disco oscilatório, e as características não vulcanizadas por um viscosímetro Mooney e um analisador de processamento de borracha (RPA). As propriedades físico-mecânicas foram avaliadas através dos ensaios de dureza, densidade, resistência à tração e ao rasgamento e abrasão, além da densidade de ligações cruzadas. A análise de FTIR confirmou uma estrutura típica de um éster derivado do óleo de soja e o aparecimento de bandas que indicaram a presença de grupos epóxi para o óleos epoxidado. As propriedades físico-mecânicas apresentaram resultados satisfatórios quando o óleo de soja vegetal foi utilizado como lubrificante/plastificante podendo ser um substituto aos óleos aromáticos, garantindo dessa forma, a redução de policíclicos aromáticos. A avaliação da amostra branco indicou a necessidade de ativadores para a reação de vulcanização, visto que apresentou propriedades inferiores quando comparadas ao padrão, provavelmente causado pela formação ineficiente de ligações cruzadas. O efeito do óleo vegetal como co-ativador pode ser verificada, contudo a reação de epoxidação, mesmo promovendo melhor dispersão, prejudicou a formação de ligações cruzadas quando comparado com o padrão, provocando baixas propriedades mecânicas. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, CAPES. / The incorporation of vegetable oils into the development of tread rubber formulation has been one of the alternatives to reduce the use of oil with high contents of aromatic polycyclics. Many studies suggest the substitution of aromatic oil by vegetable oil extracted from palm and soybean, and other studies propose that vegetable oils have reactive characteristics capable of promoting activation in vulcanization reaction. In this work, vegetable soybean oil was investigated as a lubricant / plasticizer and also as co-activators in natural rubber compounds vulcanized by sulfur, in natural state and chemically modified, through the epoxidation of soybean. The characterization of the natural and epoxidized soybean oil was carried out by Fourier Transform Infrared (FTIR) and Nuclear Magnetic Resonance with Protons (1H-NMR) spectroscopy. A standard formulation was used and from the other 5 mixtures were made with aim of replacing the aromatic oil and the stearic acid with the vegetable oil samples, a white sample, without the System was also prepared. The compositions were processed in a closed Banbury mixer and after the homogenization was performed in a cylinder. The curing properties were evaluated on an oscillatory disk rheometer, and the non-vulcanized characteristics by a Mooney viscometer and a rubber processing analyzer (RPA). The physical-mechanical properties were evaluated through the tests of hardness, density, tensile strength and tear and abrasion, as well as crosslink density. FTIR analysis confirmed a typical structure of an ester derived from soybean oil and the appearance of bands indicating the presence of epoxy groups. The physico-mechanical properties presented satisfactory results when the vegetable soybean oil was used as a lubricant / plasticizer and could be a substitute for the aromatic oils, thus guaranteeing the reduction of aromatic polycyclics. The evaluation of the white sample indicated the need for activators for the vulcanization reaction, since it presented inferior properties when compared to the standard, probably caused by the inefficient formation of cross-links. The effect of vegetable oil as a co-activator can be verified, even promoting better dispersion, detrimental has hampered the formation of cross-links when compared to the standard causing low mechanical properties.

No presente trabalho são relatados os resultados obtidos por meio de ensaios de caracterização para os diferentes tipos de óleos vegetais (algodão, canola, girassol, milho e soja), no estado novo e puro, tais como viscosidade, número de acidez, índice de iodo, índice de saponificação, cromatografia gasosa, curvas de resfriamento e coeficiente de transferência de calor. Esses mesmos ensaios foram realizados também com as amostras de óleo de soja com diferentes concentrações de aditivos antioxidantes. As diferentes formulações feitas com óleo de soja foram submetidas a um processo de envelhecimento acelerado (durante 72 horas), suas propriedades foram comparadas com as de dois óleos minerais utilizados para têmpera. O mesmo foi feito para os óleos vegetais, estes porém foram envelhecidos durante 48 horas. Pode-se então, comparar qual amostra sofreu menor oxidação durante um mesmo tempo de envelhecimento e, desta maneira, avaliar qual aditivo antioxidante obteve melhor desempenho, retardando o processo de oxidação no óleo de soja. Esses estudos também permitiram verificar qual, dentre os óleos vegetais, possui as melhores propriedades para ser utilizado no tratamento térmico de têmpera. Amostras do aço AISI 4140 foram temperadas nos diferentes óleos estudados, obteve-se a curva de dureza e as micrografias óticas para cada amostra temperada. / In this work, the results obtained from the characterization of different vegetable oils (cotton, canola, sunflower, corn and soybean) are reported. The oils were evaluated at \"new condition\" and \"pure\" by viscosity, acid and iodine number, saponification, gas chromatography, cooling curves and heat transfer coefficient. These same analyses were also performed on samples of soybean oil containing various concentrations of antioxidant. The various formulations prepared with soybean oil were accelerated aged for 72 hours and their properties were compared with two mineral oils used for quenching. Likewise, the vegetable oils were aged for 48 hours long. Therefore, it was possible to identify which sample exhibited the lower oxidation process at the same aging time and, thus, evaluate the antioxidant additive that promoted the improved oxidation performance for soybean oil. Also, these studies allowed verifying which of the vegetable oils had the best properties to be used as quenchants. Samples of AISI 4140 steel were quenched in different oils and the hardness curve and optical microscopy for each sample were obtained.

Numerous factors have pushed energy from biomass to the forefront of policy and industry discussions. Large harvests of traditional crops, low farm prices, dependence on foreign energy sources, and environmental problems have increased interest in renewable energy sources. Tools are needed to evaluate and compare different available feedstocks and to identify parameters and modifications for the production of renewable fuels such as biodiesel. The first paper examines the development of a biodiesel process model using commonly available spreadsheet software and process-engineering principles. The basis of the model is a continuous process with two stirred-tank reactors and sodium methoxide catalysis. The process is modeled as 27 units with 51 flows and 18 components. Mass flow rates and compositions of the process input and output streams are quantified using mass and component balances, energy balances, stoichiometric relations, and established process parameters. Oil composition and rate, methanol:triglyceride ratio, and expected transesterification of triglyceride are the user-specified inputs in the model. Based on commonly reported parameters (6: 1 methanol:triglyceride ratio and 98% transesterification) and a basis of 100 kg/h crude soybean oil, the model computes inputs of 13.8, 10.8, and 34.7 (in kg/h) for methanol, 10% sodium methoxide in methanol, and process water, respectively; and outputs of 93.5, 10.3, and 55.6 for soy biodiesel, glycerol, and waste stream, respectively. In the second paper, the mass flow rate data from the developed biodiesel process model are linked to cost data for evaluating the economic feasibility of biodiesel production in North Dakota with canola oil as the feedstock. Estimations of capital investment cost and total annual biodiesel product cost are conducted for two canola biodiesel production plants with 5 and 30 million gallons per year (MGY) capacities. These capacities were selected based on North Dakota and neighboring states' biodiesel demands, respectively. Capital investment cost analysis shows the presence of considerable economies of scale for the biodiesel production process for the two capacities. These cost calculations are based on the purchased equipment cost calculated from the equipment specifications. Total annual biodiesel product cost analysis shows that the major portion (>80%) of the total product cost is the raw material cost, similar to the analysis of previous economic feasibility studies. Cost benefits from the economies of scale are still present for the fixed charges, general expenses, and the manufacturing costs (other than the raw material costs) in the annual product cost calculations for the two production plant capacities. Finally, based on the gross profit evaluation for both plants, this study concludes that it is more worthwhile to invest in the 30 MGY production plant because of the greater cost returns from the economies of scale benefits. The results are more encouraging after the incorporation of the federal biodiesel tax incentive and favor the investment for biodiesel production in North Dakota. / North Dakota. Agricultural Experiment Station / USDA-CSREES (under Agreement No. 2003-34471-13523)

This thesis deals with alternative thermal degradation of electrical insulating liquids. The theoretical part describes the current state of the problem, electrical insulating liquids, their classification and types. There are described properties of electrical insulating liquids, their models of aging and diagnostic methods in accordance with the appropriate standards. In the practical part are chosen by representatives of alternative electrical insulating liquids and there are determined their dielectric characteristics in the initial state. According to the measured values is chosen five candidates for which it is designed and implemented an accelerated degradation test. During the test are measured dielectric parameters of the selected oils. Measured dependencies are mathematically approximated. In conclusion, the results are compared and physically interpreted in view of oxidation stability.

This master thesis deals with clasification of electrical insulating liquids and analysis their reological properties. Theoretical part describes viscosity and possibilities of its measurement, electrical and non-electricl properties of electrical insulating liquids and themselves electrical insulating liquids. Practical part describes measurement of viscosity and density of chosen vegetable oils, their components and transformer oils in wide temperature range. At the conclusion of the thesis, analysis of measurement results is done.

PhD (AGR) (Animal Science) / Department of Animal Science / Horticultural by-products such as seed and nut oil residues have the potential to replace conventional protein and energy sources in diets for ruminants. The objective of the study was to evaluate the nutritive value of Macadamia oil cake and Baobab seed cake as nutrient supplements for feedlot animals. Several experiments were carried-out to evaluate the nutritive value of Macadamia oil cake and Baobab seed cake as feed for ruminants. The nutrient composition of the cakes were determined using both proximate and modern methods of analysis of feeds and a t-test was used to compare the means of Macadamia oil cake and Baobab seed cake. The in sacco technique was used to determine the rumen degradability parameters of dry matter, crude protein and Amino acids of the cakes. This experiment was conducted using a completely randomized design. A three step-in vitro technique was used to conduct a post ruminal digestibility trial and the study was arranged in a completely randomized design. An apparent digestibility trial was conducted using metabolism cages and fecal bags to avoid the mixing of urine and faeces and the experiment was carried out as a completely randomized design arranged in a 2 x 2 factorial. A growth trial was conducted using a completely randomized block design arranged in a 2x2 factorial with two protein supplements and two inclusion levels as factors and blocked by sex of the lambs. The two cakes had similar (P>0.05) dry matter, fat, hemicellulose and gross energy contents. Baobab seed cake had significantly (P<0.05) higher ash, crude protein, acid detergent lignin and nitrogen free extract than macadamia oil cake. Macadamia oil cake had significantly (P<0.05) higher crude fiber, acid detergent fiber, neutral detergent fiber and cellulose concentrations. Baobab seed cake had significantly (P<0.05) higher calcium, magnesium, potassium, phosphorus (macroelements), zinc, and copper than macadamia oil cake. Macadamia oil cake was significantly (P<0.05) higher in manganese and iron contents than Baobab seed cake. Sodium content was not significantly (P>0.05) different between the two cakes. Baobab seed cake had more (Tryptophan, Cysteine, Arginine, Aspartic acid, Glutamic acid, Valine, Phenylalanine, Isoleucine, Leucine) Amino acids which were significantly (P<0.05) higher in quantity than macadamia oil cake with the two cakes having similar (P>0.05) remaining Amino acids contents. Generally Macadamia oil cake had more (P<0.05) saturated and mono-unsaturated fatty acids than Baobab seed cake whereas Baobab seed cake had more (P<0.05) poly-unsaturated fatty acids. v The in sacco rumen degradability characteristics of baobab seed cake and macadamia oil cake were estimated for dry matter and crude protein of the cakes. Macadamia oil cake had significantly (P<0.01) higher a value for dry matter than boabab seed cake. Baoaba seed cake had significantly (P<0.01) higher a value for crude protein than macadamia oil cake. the b, c, and a+b values for dry matter of both Baobab seed cake and Macadamia oil cake were not significantly (P>0.05) different form each other. However, the potential degradability (a+b) value for crude protein of baobab seed cake was significantly (P<0.01) higher than that of macadamia oil cake. The b and c constants of the two cakes for crude protein were not significantly (P>0.05) different from each other. The ED (Effective degradability) values calculated at three outflow rates (0.02, 0.05, 0.08) were estimated for dry matter and crude protein of Baobab seed cake and macadamia oil cake. The ED of the two cakes calculated at 0.02 outflow rate did not significantly (P>0.05) differ from each other. However, baobab seed cake had significantly (P<0.05) higher ED value at outflow rate of 0.05 whereas macadamia oil cake had significantly (P<0.05) higher ED value calculated at outflow rate of 0.08. The ED values of baobab seed cake for crude protein calculated at the three outflow rate were significantly (P<0.01) higher than those of macadamia oil cake. The two cakes did not significantly (P>0.05) differ in dry matter ruminal degradability but baobab seed cake had significantly (P<0.05) higher ruminal crude protein disappearance from 16 to 72 hours of incubation than macadamia oil cake. The in situ Amino acid degradation was determined on 0, 12, 16, 24, and 48 hour of ruminal incubation of the cakes’ samples and generally they were significant (P<0.05) differences for both cakes according to different incubation periods. The 3-step in vitro digestibility trial revealed that baobab seed cake had significantly (P<0.05) higher dry matter, crude protein and Amino acids digestibility values than macadamia oil cake. Apparent digestibility study revealed that nutrient intake, faecal and urine outputs, and digestibility of nutrients were not significantly (P>0.05) different between baobab seed cake and macadamia oil cake. However, lambs on 10% macadamia cake having retained significantly (P<0.05) more nitrogen than the lambs on 15% macadamia oil cake, 10% and 15% baobab seed cakes diets. However, the inclusion of either baobab seed cake or macadamia oil cake at 10% or 15% in the diets of lambs did not significantly (P>0.05) affect the DOMR, microbial protein yield and purine derivates output. For the growth trial the lambs were offered four diets formulated to contain 10% MOC (control), 15% MOC, 10 BSC and 15% BSC. The inclusion of 15% MOC and 10% BSC in the diets of lambs did not significantly (P>0.05) affect their final body weight, total weight gain, average daily feed intake, average daily weight gain, warm and cold carcass masses between these two vi groups. The inclusion of 10% MOC and 15% BSC in the diets of lambs did not significantly affect average daily feed intake and animal performance between these two groups. However, lambs on 10% MOC and 15% BSC had significantly (P<0.05) higher average daily feed intake and animal performance compared to lambs on 15% MOC diet. The feed conversion efficiency and of the lambs in the four diets were not significantly (P>0.05) different. The dressing percentage, carcass length, neck weight, fat thickness, body weight thickness and rib eye area of the carcasses of lambs in this trial did not differ significantly (P>0.05) except for spleen and skin with lambs on 10% BSC diets having the least skin weight and lambs on 10% MOC diet having heaver spleens. Generally BSC had higher (P<0.05) nutrient content than MOC. BSC and MOC were highly degradable in the rumen whereas BSC was higly digestible post-ruminally compared to MOC. The diets of fattening lambs formulated to include 10% or 15% of BSC or MOC as protein supplements did not affect the apparent digestibility of the diets. Macadamia oil cake can be incomporated in the diet of finishing lambs as a protein supplement at 10% inclusion level without compromising the growth and carcass characteristics of the lambs. Baobab seed cake as a protein supplement can be included in the diet of finishing lambs at up to 15% inclusion level without deleteriously compromising on the growth and carcass characteristics of the animals. ______________________________________ / NRF

E PVC est l'un des polymères les plus employés dans les matériaux actuels et l'adjonction de plastifiants permet de modifier ses propriétés (température de transition vitreuse, module…) permettant ainsi l'utilisation de ce polymères dans des applications où de la souplesse est requise (textiles enduits, par exemple). Actuellement, les phtalates sont les plastifiants les plus utilisés même s'ils sont de plus en plus décriés du fait de leur toxicité. Le développement de nouveaux agents plastifiants est un domaine de recherches intenses et les matières premières bio-sourcées s'avèrent être une alternative intéressante aux plastifiants pétro-sourcés. Le travail de cette thèse se propose d'investiguer le développement de plastifiants du PVC bio-sourcés de type lipidique possédant de surcroit des propriétés ignifugeantes évitant ainsi l'ajout d'additifs supplémentaires dans les formulations de PVC devant résister au feu. Dans un premier temps, l'oléate, le linoléate de méthyle et le diacide (D18 : 1) ont été fonctionnalisés par modification chimique de leurs groupements ester et/ou de leurs insaturations pour mener à des dérivés lipidiques phosphorés. Cinq candidats plastifiants bio-sourcés ont ainsi pu être synthétisés et le scale up de la synthèse de l'un des candidats à l'échelle du kilogramme a pu être réalisé dans le cadre de cette thèse. Dans un deuxième temps, des tests de plastification du PVC avec divers candidats ont été réalisés en collaboration avec la société Serge FERRARI. L'étude des propriétés thermiques, mécaniques et thermomécaniques des films de PVC plastifiés obtenus, comparativement au plastifiant phtalate DINP et au plastifiant bio-sourcé commercial RADIA 7295, a permis d'éliminer différents candidats pour n'en finalement retenir que deux. Des profils de dégradation thermique satisfaisants, des basses valeurs de Tg, des allongements à la rupture importants (320 et 365 % respectivement) et proches de ceux obtenus avec le DINP, ont confirmé l'efficacité plastifiante de ces deux composés phosphorés bio-sourcés. Les tests au feu LOI et au cône calorimètre ont également prouvé le caractère ignifugeant de ces deux composés qui conduisent à des résultats du même ordre de grandeur que ceux atteints avec le plastifiant phosphonate commercial de référence S141 / Poly(vinyl chloride) is one of the most manufactured and consumed thermoplastics in the world. The addition of plasticizers allows modifying its properties (glass transition temperature, modulus…) and then to use this polymer for applications where flexibility is needed (coated textiles, for instance). Nowadays, phthalates are the main candidates for PVC even if they have been more and more controversed due to their possible toxicity. To substitute these petro-based plasticizers, researches are focused on alternative plasticizers based on bio-based raw materials. This PhD work proposes to investigate the development of new bio-based plasticizers for PVC, from lipidic derivatives, and having simultaneously flame retardant properties, avoiding the addition of any other additives in PVC during compounding. In the first part, methyl oleate, methyl linoleate and diacid D18 : 1 have been functionalized by modification of their ester groups and/or their doubles bonds to give phosphorylated lipidic derivatives. Thus, five bio-based plasticizers have been synthesized and the synthesis of one candidate on the scale of the kilogram has been successfully performed during this PhD work. Secondly, the plasticizing efficiency of several candidates with PVC has been evaluated in collaboration an industrial company. Thermal, mechanical and thermomechanical properties of the obtained soft PVC films were studied, in comparison with those obtained with the phthalate plasticizer DINP and the commercial bio-based plasticizer RADIA 7295. These analyses allowed the disposal of some of the bio-based plasticizers to finally keep only two candidates. Satisfying thermal degradation profiles, low Tg, and important elongation at break values (320 % and 365 % respectively) close to those obtained with DINP, confirmed the plasticizing efficiency of these two bio-based phosphorylated plasticizers. Fire tests like the LOI test and the cone calorimeter also proved the flame retardant properties of these two candidates, leading to similar results than the ones reached with the phosphonate plasticizer S141

This diploma thesis is focused on issues concerning the stability of selected vegetable oils which are used in cosmetic industry. The stability of eight oils without additives were determined by a differential scanning calorimeter. In the first phase, the temperatures of oil degradation were determined for different rates of heating, i.e. nonisothermal stabilities. They were consequetly used to calculate isothermal stabilities alias induction periods. The calculation of induction periods was completed by using integral isoconversional methods, which applied four different temperature functions. One of the temperature functions corresponded to Arrhenius equation while the others to non-Arrhenius functions. The confrontation of induction periods under standart conditions showed that an optimal temperature function to calculate oil stabilities is one of the non-Arrhenius functions in exponential form. We can state that all oils are degraded by similar, if not the same, mechanism. The specified stabilities, in periods of months, have proved the importance of using stabilizers and other additives in the commercial and technological use of vegetable oils.

[ES] En los últimos años, se ha incrementado la sensibilidad en torno a las cuestiones ambientales derivadas del uso de los materiales poliméricos basados en el petróleo y el impacto de éstos en el medio ambiente. La concienciación social y ambiental adquirida por parte de los consumidores hace que industrias tradicionales, como la del juguete, donde el uso del plástico está ampliamente extendido, desee adaptarse voluntariamente a la demanda del mercado y las empresas quieran desarrollar nuevas líneas de producto empleando materiales más ecológicos y sostenibles. El principal objetivo de esta tesis doctoral es el desarrollo y caracterización de biocomposites (biocompuestos) obtenidos a partir de una matriz polimérica procedente de fuentes renovables y biodegradable, concretamente almidón termoplástico (TPS), y como relleno, cáscara de almendra en polvo (ASP), aptos para ser procesados por inyección cuyas propiedades mecánicas, térmicas y estéticas permitan su uso en el sector del juguete. En un primer bloque, esta investigación estudia la influencia de la variedad de cáscara de almendra en las propiedades finales del biocomposite TPS/ASP desarrollado. Para ello, se seleccionan cinco variedades de almendra: Desmayo Rojo, Largueta, Marcona, Mollar y una mezcla comercial de variedades desconocidas, ya suministrada en formato polvo. También se estudia la influencia del tamaño de partícula de dicha carga (menor a 0.05 mm, 0.05<p<0.08 mm, 0.08<p<0.125 mm y 0.125<p<0.250 mm) considerando una cantidad fija de ASP (30 % en peso). Finalmente, se analiza el efecto del contenido de ASP (5-30 % en peso). Para ello, los diferentes biocomposites son fabricados mediante técnicas convencionales de extrusión e inyección. Se emplea una metodología basada en diferentes técnicas experimentales para la determinación de las propiedades mecánicas (ensayos de tracción, flexión, impacto Charpy y dureza Shore D), propiedades térmicas (análisis calorimétrico (DSC) y termogravimétrico (TGA)), medidas colorimétricas (CIELab) y análisis morfológico (SEM). En general, de este primer bloque se concluye que, la adición de ASP al TPS aumenta la rigidez del material y disminuye su deformación a rotura, la resistencia al impacto y la resistencia térmica con respecto a la matriz polimérica TPS. La incorporación de ASP proporciona un acabado similar a la madera. Una vez seleccionada la variedad, el tamaño de partícula y el contenido de ASP más adecuado, se considera mejorar la interacción carga/matriz con objeto de incrementar las propiedades mecánicas que se han visto afectadas por la adición de la carga. Los métodos de compatibilización que se han llevado a cabo para ello han sido mediante la incorporación de sustancias de origen renovable. En concreto, los compatibilizantes de origen renovable empleados en esta tesis doctoral son tres aceites vegetales epoxidados (EVOs): el aceite de linaza epoxidado (ELO), el aceite de soja epoxidado (ESBO) y el aceite de maíz epoxidado (ECO). Los diferentes EVOs se han incorporado entre 5-20 phr. La caracterización de las propiedades de los bicomposites desarrollados se realiza de forma análoga a los obtenidos en el primer bloque. Los resultados obtenidos muestran una notable mejora de las propiedades mecánicas con el empleo de estos compatibilizantes derivados de aceites vegetales. Además, la adición de estas sustancias tiene un efecto estabilizante en la desintegración del material. Finalmente, se estudia si es posible reprocesar el TPS y el biocomposite TPS/ASP y cómo afecta el reprocesado de estos biomateriales a sus propiedades finales (estéticas, mecánicas y térmicas). A pesar de la progresiva degradación del material, en ambos casos, es técnicamente factible volver a procesar el material al menos tres veces sin necesidad de incorporar material virgen. / [CA] En els últims anys, s'ha incrementat la sensibilitat entorn a les qüestions ambientals derivades de l'ús dels materials polimèrics basats en el petroli i l'impacte d'aquests en el medi ambient. La conscienciació social i ambiental adquirida per part dels consumidors fa que indústries tradicionals, com la del joguet, on l'ús del plàstic està àmpliament estés, desitge adaptar-se voluntàriament a la demanda del mercat i les empreses vullguen desenvolupar noves línies de producte emprant materials més ecològics i sostenibles. El principal objectiu d'aquesta tesi doctoral és el desenvolupament i caracterització de biocomposites obtinguts a partir d'una matriu polimèrica procedent de fonts renovables i biodegradable, concretament almidó termoplàstic (TPS), i com a càrrega, pols de corfa d'ametla (ASP), aptes per a ser processats per injecció, les propietats mecàniques, tèrmiques i estètiques de les quals, permeten el seu ús en el sector del joguet. En un primer bloc, aquesta investigació estudia la influència de la varietat de corfa d'ametla, en les propietats finals del biocomposite de TPS/ASP desenvolupat. Per a això, se seleccionen cinc varietats d'ametla: Desmai Roig, Largueta, Marcona, Mollar i una mescla comercial de varietats desconegudes, ja subministrada en format de pols. També s'estudia la influència del tamany de partícula (menor a 0.05 mm, 0.05<p<0.08 mm, 0.08<p<0.125 mm i 0.125<p<0.250 mm) considerant una quantitat fixa d'ASP (30 % en pes). Finalment, s'analitza l'efecte del contingut d'ASP (5-30 % en pes). Per a això, els diferents biocomposites són fabricats mitjançant tècniques convencionals d'extrusió i injecció. S'empra una metodologia basada en diferents tècniques experimentals per a la determinació de les propietats mecàniques (assajos de tracció, flexió, impacte Charpy, duresa Shore D), propietats tèrmiques (anàlisis calorimètric (DSC) i termogravimètric (TGA), mesures colorimètriques (CIELab) i anàlisi morfològic (SEM). D'aquest primer bloc es conclou que, l'addició d'ASP al TPS augmenta la rigidesa del material, disminuïx la seua deformació a ruptura, la resistència a l'impacte i la resistència tèrmica respecte a la matriu polimèrica TPS. La incorporació d'ASP, proporciona un acabat similar a la fusta. Una vegada seleccionada, la varietat, el tamany de partícula i el contingut d'ASP més adequat, es considera millorar la interacció càrrega/matriu a fi d'incrementar les propietats mecàniques que s'han vist afectades per l'addició de la càrrega. Les tècniques de compatibilització que s'han dut a terme en aquest treball ha sigut mitjançant la incorporació de substàncies d'origen renovable. En concret, els compatibilitzants d'origen renovable utilitzats en aquesta tesi doctoral són tres olis vegetals epoxidats (EVOs): l'oli de llinosa epoxidat (ELO), l'oli de soja epoxidat (ESBO) i l'oli de panís epoxidat (ECO). Els diferents EVOs s'han incorporat entre 5-20 phr. La caracterització de les propietats dels bicomposites desenvolupats es realitza de forma anàloga als obtinguts en el primer bloc. Els resultats obtinguts mostren una notable millora de les propietats mecàniques amb l'ús d'estos compatibilitzants derivats d'olis vegetals. A més, l'addició de EVOs té un efecte estabilitzant en la desintegració del material. Finalment, si és possible reprocessar el TPS i el biocomposite TPS/ASP i com afecta el reprocessat d'estos biomaterials a les seues propietats finals (estètiques, mecàniques i tèrmiques). Malgrat la progressiva degradació del material, en ambdós casos, és tècnicament factible tornar a processar el material almenys tres vegades sense necessitat d'incorporar material verge. / [EN] In recent years, there has been a growing awareness of the environmental issues arising from the use of petroleum-based polymeric materials and their impact on the environment. The social and environmental awareness consumers now have makes traditional industries, such as the toy industry, where the use of plastic is widespread, want to voluntarily adapt to market demand and develop new product lines using more ecological and sustainable materials. The main objective of this doctoral thesis is the development and characterisation of biocomposites developed from a polymeric matrix of renewable and biodegradable sources, specifically thermoplastic starch (TPS), and as a filler, almond shell powder (ASP), suitable for processing by injection moulding whose thermal-mechanical and aesthetic properties allow their use in the toy sector. In the first block, the influence of the variety of almond shells on the final properties of the polymeric matrix is studied. For this purpose, five varieties are selected: Desmayo Rojo, Largueta, Marcona, Mollar, and a commercial mixture of unknown varieties, already supplied in powder form. The influence of particle size (smaller than 0.05 mm, 0.05<p<0.08 mm, 0.08<p<0.125 mm and 0.125<p<0.250 mm) is also studied considering a fixed amount of ASP (30 %). Finally, the effect of ASP content (5-30 %) is analysed. For this purpose, the different biocomposites are manufactured by conventional extrusion and injection techniques. A methodology based on different experimental techniques is used to determine the mechanical properties (tensile, flexural, Charpy impact, Shore D hardness), thermal properties (calorimetric analysis (DSC), and thermogravimetric analysis (TGA), colorimetric measurements (CIELab), and morphological analysis (SEM). In general, it is concluded from this first block that the addition of ASP to the TPS increases the stiffness of the material, but then decreases its deformation at break, impact resistance and thermal resistance in respect to the TPS polymeric matrix. The addition of ASP provides a wood-like finish. Once the most suitable variety, particle size, and ASP content have been selected, consideration is given to improving the particle/matrix interaction. The compatibilisation techniques carried out in this work have been through the incorporation of substances of renewable origin. The compatibilisers of renewable origin used in this doctoral thesis are three epoxidised vegetable oils (EVOs): epoxidised linseed oil (ELO), epoxidised soybean oil (ESBO) and epoxidised corn oil (ECO). The different EVOs have been incorporated between 5-20 phr. The results obtained show a remarkable improvement of the mechanical properties with the use of vegetable oil-derived compatibilisers. Moreover, the addition of EVOs has a stabilising effect on the disintegration of the material. Finally, it is studied how the reprocessing of TPS and TPS/ASP biocomposite affects their final characteristics. Despite the progressive degradation of the material, in both cases, it is technically feasible to reprocess the material at least three times without the need to incorporate virgin material. / Ibáñez García, A. (2021). Desarrollo y caracterización de biocomposites con cáscara de almendra para el sector juguetero [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/172341

<p dir="ltr">Vegetable oils are a fundamental part of human civilization. Beyond their nutritional value and functional implementation in food applications, their triglyceride structure facilitates their implementation as industrial inputs. Furthermore, applications such as metal gear fluids and gear oil represent a valuable market due to their environmental impact and widespread application. Soybean oil is one of the most produced oilseeds in the U.S., and recently, novel oil varieties such as high oleic soybean oil (HOSBO) tackle drawbacks in the use of vegetable oil such as the heterogeneous fatty acid composition by increasing the concentration of oleic acid. This dissertation evaluates the successful implementation of HOSBO and SBO as lubricant and gear oils through epoxy ring opening reactions for synthesizing polyols and estolides. Epoxidation of double bonds in unsaturated fatty acids creates reaction sites for the branching of fatty acids in estolides or hydroxylated moieties in the case of polyols. The difference in fatty acid composition is shown in terms of thermomechanical characteristics. HOSBO polyols and estolides are solid to semi-solid greases with high viscosities and SAE grades as gear oils from 85W up. In contrast, SBO-derived oils have lower viscosities and a larger viscosity index.</p><p dir="ltr">The second part of this research focuses on the kinetics of the hydroxylation defined by distinctive fatty acid compositions. The sites of reaction in the double bonds can be, in part, sterically hindered by the glycerol backbone. Thus, this chapter focuses on the influence of the reaction rates given the fatty acid composition of the oil. Consumption of epoxide groups in HOSBO and SBO was modeled under pseudo-first-order kinetics. The results highlight the benefit of using HOSBO with reaction rates at least 30% faster than SBO. Furthermore, the progress of the reaction was monitored by FTIR, which highlighted the formation of ether groups corresponding to the addition of 1-propanol branches. However, further optimization steps must focus on the controlled removal of water in order to prevent the esterification of the oil and the resulting increase of free fatty <a href="" target="_blank">acids</a><a href="#_msocom_1" target="_blank">[EAS1]</a> .</p><p dir="ltr"><a href="#_msoanchor_1" target="_blank">[EAS1]</a>Seems to end abruptly</p><p><br></p>