M.Tech. / Due to electric (E) and magnetic (H) fields that vary with space (r) and time (t) in the microwave cavity, and due to the inhomogeneous nature of the minerals, heating a mineral in a microwave oven gives an inherently non-uniform temperature distribution. The objective of the project is to introduce a mathematical model that will demonstrate the thermal interaction between ilmenite mineral (FeTiO3) and microwaves. The simulation presents the temperature distribution in the sample based on the conditions imposed on its boundaries. The field distribution in the cavity is simulated, and then the thermal analysis is performed using the lumped thermal capacity model. The temperature distribution in the sample is also simulated using the general heat conduction equation. Finite difference method is used two solve the two-dimensional unsteady heat conduction equation. The simulation of the field distribution in the cavity reveals that there are position of intense electric and magnetic field in the oven. This is demonstrated by experiment 6, where samples are heated at different positions in the oven for the same duration and different temperatures in the samples were measured. Electromagnetic wave propagation was also studied. It became apparent that the electric and magnetic field can not be treated independently from each other, because the changing electric field produces a changing magnetic field and the newly produced changing magnetic field produces a changing electric field, which is an electromagnetic wave. It is also proved that, considering the relationship given by Maxwell's equations, the electric and magnetic fields are not only space out of phase but they are also time out of phase, meaning that the one quantity is leading while the other is lagging. Based on the available mathematical evidence it was suggested to fit the conventional representation of the electromagnetic field, which show the electric field and the magnetic field at right angle to each other and in time phase, to the new representation which would highlight the fact that the electric and magnetic fields are time out of phase. The study of electromagnetic wave propagation has proved that the one-dimensional conventional representation of electromagnetic waves is inadequate. It does not support the fact that there are a number of resonant modes that exists in the cavity which has long been proved and accepted by authors in the field of electromagnetism. This is very much clear when dealing with electromagnetic waves in three dimensional space.

L'objet de cette thèse est la conception, le développement et la caractérisation d'un réacteur micro-ondes en continu pour mener tout type de réactions chimiques à températures élevées de manière fiable et dans des conditions optimisées. Le développement de ce réacteur a tout d'abord nécessité la caractérisation diélectrique et magnétique des matériaux et milieux utilisés. La simulation numérique a ensuite été utilisée afin de prédire les distributions de champ et température au sein des matériaux. L'interaction entre les ondes et les différents milieux a été finement étudiée. Elle démontre non seulement l'influence de la nature diélectrique du milieu réactionnel et du ratio volumique du fluide dans le réacteur sur le chauffage micro-ondes, mais aussi celle des dimensions de l'applicateur et de la disposition du réacteur dans ce dernier. L'hydrodynamique a également été introduite dans la simulation permettant de prédire les profils de température dans le réacteur en fonctionnement continu. L'ensemble des résultats numériques a fait l'objet de validations expérimentales qui ont aussi permis d'affiner le modèle thermique de l'ensemble conçu. Au final, une réaction de diestérification a été mise en œuvre et démontre l'efficacité thermique et chimique du réacteur. Au-delà de ce prototype, cette thèse établit un schéma général de conception d'un procédé chimique continu sous micro-ondes en ordonnant les étapes, respectant les règles clés de l'électromagnétisme, optimisant la propagation des ondes et les performances thermiques du système. / The aim of this thesis is the development and characterisation of an intensified continuous microwave reactor for green chemistry. The development of this reactor required, at first, the characterisation of the dielectric and magnetic properties of the used materials. A numerical simulation was then used to predict the field and temperature profiles within the materials. The influence of different parameters on the microwave heating was also studied, such as the influence of the dielectric nature of the reaction medium, the ratio of the fluid in the reactor, the arrangement of the reactor in the applicator and the size and shape of the latter. Hydrodynamics were also taken into account in the simulation to predict the temperature profiles in the reactor. All the numerical results were validated experimentally. Experimental results also made it possible to refine the thermal model of the reactor. In the end, an esterification reaction was carried out and it proved the thermal and chemical efficiency of the designed reactor. Beyond this prototype, this thesis establishes a general scheme for the design of a continuous chemical process under microwaves whilst following the key rules of electromagnetism and optimising the wave propagation and the thermal performance of the reactor.

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Freeze-drying (lyophilization) is a drying process which is used to remove water from heat sensitive products, usually for the purpose of preservation. By removing water, the product becomes more stable at room temperature. This is a common process in the pharmaceutical industry because freeze-drying offers the advantage of drying at low temperatures and producing very low residual moisture contents. Often the materials dried in this manner are heat sensitive and require the highest possible quality. However, freeze-drying is a very slow process, often requiring 24 to 48 hours. During the process, vacuum pumps and refrigeration systems run continuously, making freeze-drying a very expensive process. The goal of this project was to show that volumetric heating can be used in pharmaceutical freeze-drying and that this mode of heating offers some advantages. There were two approaches taken to the work, one experimental and one analytical. The experimental approach was broken into two phases, one focused on comparing microwave and conventional freeze-drying and the other focused on demonstrating the advantages of volumetric heating. In the analytical approach, a mathematical model was used to confirm the trends observed in phase II of the experimental work. Experiments were conducted in a conventional laboratory freeze-dryer and the drying rate results were compared to the results obtained with an experimental microwave freeze-drying apparatus. Experiments were also conducted with the vaccine strain <i>A. pleuropneumoniae</i>. A viability study was conducted, comparing the viability loss caused by each process. The viability study showed a slightly higher viability loss for the microwave process. A comparison of drying curves showed that the microwave process resulted in a slight improvement in primary drying time: 2.5 hours for the microwave process compared to 3 hours for the conventional process. There was a significant difference in overall drying times: 4 hours for the microwave process compared to 11 hours for the conventional process. This result was caused by a lower residual moisture content at the start of secondary drying and a higher secondary drying temperature for the microwave process. Experiments were also conducted to show that using lower chamber pressure results in higher drying rates. This is not the case in a conventional freeze-dryer since heating is dependent on the chamber pressure in the low pressure environment of freeze-drying. Thus, an advantage of volumetric heating was demonstrated. The results show that a modest increase in pressure, from 0.05 to 0.3 Torr, caused a one third reduction in primary drying time. The mathematical model developed in the analytical work relied on the D'Arcy equation to describe the flow of vapor in the porous dried layer. The results of the model confirm trends seen in the measured temperature and weight profiles. Analyzing the effect of varying the chamber pressures shows that lowering the pressure in the range of 1 to 0.01 Torr results in a significant increase in drying rate giving as much as a two thirds reduction in drying time for the case studied. A model incorporating mass transport equations derived from the dusty gas model was also presented. This model offers the benefit of a more accurate prediction of mass transport through the porous dried layer. NOTE: (09/2008) An updated copy of this ETD was added after there were patron reports of problems with the file. / Ph. D.

Microwave heating of different polymer systems (epoxy-amine. polypropylene-iron, carbon-black-filled perfiuoroelastomer) was evaluated using dielectric testing and monitored processing in a multimode microwave cavity. Dielectric measurements were made using a field perturbation technique and a transmission/reflection technique. The electric loss factor of the epoxy system continuously decreased during cure. Results for the microwave heating of the polypropylene-iron composites show that heating is enhanced with increased iron concentration and smaller iron particle size, although the penetration depth of the microwaves Is decreased, especially after the onset of percolation. A novel solidstate processing technique for thermoset systems was also evaluated. By milling the reactants to a fine powder, and mixing them completely, the extent to which diffusion limited the process was significantly reduced: increased milling resulted in higher activation energies. In addition to the inherent advantages of solid-state processing. it Is possible that processing times for solid-state processing could approach processing times for traditional melt processing. / Master of Science

The purpose of this work was to study the heating and curing rate of polymers with continuous and pulsed microwave radiation and compare with conventional thermal energy. The heating rate of poly(ethylene glycol) and poly(propylene glycol) has been studied as a function of molecular weight with pulsed as well as continuous microwave radiation, at constant average power. The curing rate of poly(amic acids) have also been studied with thermal energy, continuous and pulsed microwave radiation to better understand the interaction between pulsing the microwave and the polymeric material. Results from the heating rate studies indicate that the enhancement in heating rate with pulsed microwave radiation depends on the low frequency absorption spectrum (i.e., less than 10,000 Hz) of the polymer. The heating rate of poly(propylene glycol), which has a low frequency absorption, was enhanced by pulsing the microwave energy whereas the heating rate of poly(ethylene glycol), which does not have a low frequency absorption, remained the same when compared to continuous wave. Also results from the curing rate studies with poly(amic acids) indicate that the enhancement in curing rate observed in samples cured by microwave radiation as opposed to those thermally cured may be partially due to microwave power distribution in the cavity. This has been tested by agitating the sample to reduce any temperature gradient arising from the power distribution in the cavity. According to the experimental results, as the agitation rate was increased, the rate of imidization of poly(amic acids) with microwave radiation approached the rate of thermal imidization, at constant temperature. However, more research is required to clarify this complex phenomenon. / Master of Science

Tesis por compendio / [ES] «Aplicación de nuevas tecnologías a la alcalinización de cacao» es una tesis doctoral centrada, por un lado, en el estudio de los cambios fisicoquímicos y funcionales causados por dos técnicas de alcalinización alternativas a la convencional y, por otro, en la comparación de dichas propiedades con las de muestras comerciales. En el capítulo I, se describe un sistema de alcalinización basado en extrusión. Esta tecnología se ha aplicado a la alcalinización de cacao dada su capacidad de tratar la materia prima de forma rápida y continúa, y su bajo consumo energético. En primer lugar, se estudiaron los efectos de diversas variables de proceso sobre las propiedades fisicoquímicas y funcionales de cacaos en polvo. En general, de todas las variables, el tipo y la concentración de álcali fueron las principales responsables del incremento de pH, del oscurecimiento de las muestras y de la reducción en el contenido de compuestos funcionales. En cuanto a la humedad, fueron la temperatura y el contenido en agua las que mostraron causar los mayores efectos, llegando a producir reducciones de casi un 50%. Además de evaluarse el efecto de las diferentes variables, en este capítulo también se compararon los cacaos producidos mediante extrusión con los alcalinizados por el método convencional. Los resultados mostraron que la extrusión, en menos de cinco minutos, fue capaz de oscurecer y de producir cacaos en polvo con un perfil sensorial, una capacidad antioxidante y un contenido en polifenoles totales relativamente similar al de los productos comerciales. En cuanto al capítulo II, en este se ha estudiado la técnica de calentamiento por microondas como una alternativa al tratamiento de alcalinización tradicional. La tecnología microondas ha demostrado ser rápida, versátil y capaz de preservar las características funcionales y sensoriales, lo que ha hecho interesante su aplicación a la alcalinización de cacao. En los trabajos que forman este segundo capítulo, se estudiaron los efectos de diversas variables de proceso sobre el producto. En general, el tipo y la concentración de álcali fueron las variables principalmente responsables del oscurecimiento del cacao, del incremento del pH y de la reducción de las concentraciones de catequina y epicatequina. Sin embargo, el álcali empleado no redujo la actividad antioxidante ni al contenido en fenoles totales, propiedades que se vieron incrementadas por la presión, la potencia y la duración del tratamiento. Estos incrementos se relacionaron con la capacidad de estas variables para liberar a los polifenoles no extractables y para promover determinadas reacciones químicas. Además, también se estudió el efecto de las diferentes variables sobre la humedad. La potencia y la duración del tratamiento fueron las que se mostraron esenciales para lograr el secado del producto, llegando a producir reducciones de hasta el 70%. Por otro lado, además de estudiarse el impacto de las diferentes variables, también se compararon cacaos producidos por microondas con muestras producidas por el método convencional para evaluar su similitud con los cacaos comerciales. Los resultados mostraron que el microondas, en solo cuatro minutos, fue capaz de oscurecer el cacao y de mantener un perfil sensorial similar al producido por el método tradicional, a la par que conducía a una mejora en sus propiedades funcionales. En resumen, los métodos para la alcalinización de cacao desarrollados en el marco de la presente tesis doctoral han demostrado ser unas alternativas muy prometedoras a la tecnología convencional. Ambas técnicas no solo han sido capaces de oscurecer el cacao tanto como el método comercial en un tiempo mucho menor, sino que también han conseguido el secado parcial de la muestra y unas características sensoriales y funcionales comparables o incluso mejores que las del método convencional. / [CA] «Aplicació de noves tecnologies a l'alcalinització de cacau» és una tesi doctoral centrada, d'una banda, en l'estudi dels canvis fisicoquímics i funcionals causats per dos tècniques d'alcalinització alternatives a la convencional i, d'altra banda, en la comparació d'aquestes propietats amb les de mostres comercials. En el capítol I, es descriu un sistema d'alcalinització similar al convencional però basat en extrusió. Aquesta tecnologia s'ha aplicat a l'alcalinització de cacau per la seua capacitat de tractar la matèria primera de forma ràpida i continua, i pel seu baix consum energètic. En primer lloc, es van estudiar els efectes de diverses variables de procés sobre les propietats fisicoquímiques i funcionals de cacaus en pols. En general, de totes les variables, el tipus i la concentració d'àlcali van ser les principals responsables de l'increment de pH, de l'enfosquiment de les mostres i de la reducció en el contingut de compostos funcionals. Pel que fa a la humitat, van ser la temperatura i el contingut en aigua les que van causar els majors efectes, arribant a produir reduccions d'un 50%. A més d'avaluar l'efecte de les diferents variables, en aquest capítol també es van comparar els cacaus produïts mitjançant extrusió amb els alcalinizats pel mètode convencional. Els resultats van mostrar que l'extrusió, en menys de cinc minuts, va a ser capaç d'enfosquir i de produir cacaus en pols amb un perfil sensorial, una capacitat antioxidant i un contingut en polifenols totals relativament similar al dels productes comercials. Pel que fa al capítol II, en aquest s'ha estudiat la tècnica de calfament per microones com una alternativa a l'alcalinització tradicional. La tecnologia microones ha demostrat ser ràpida, versàtil i capaç de preservar les característiques funcionals i sensorials, el que ha fet interessant la seua aplicació a l'alcalinització de cacau. En els treballs que formen aquest segon capítol, es van estudiar els efectes de diverses variables de procés sobre el producte. En general, el tipus i la concentració d'àlcali van ser les variables principalment responsables de l'enfosquiment del cacau, de l'increment del pH i de la reducció de les concentracions de catequina i epicatequina. No obstant això, l'àlcali empleat no va reduir l'activitat antioxidant ni al contingut en fenols totals, propietats que es van incrementar per la pressió, la potència i la duració del tractament. Aquests increments es van relacionar amb la capacitat d'aquestes variables per alliberar els polifenols no extractables i per promoure determinades reaccions químiques. A més, també es va estudiar l'efecte de les diferents variables sobre la humitat. La potència i la duració del tractament van ser les que es van mostrar essencials per aconseguir la deshidratació del producte, arribant a produir reduccions de fins al 70%. D'altra banda, a més d'estudiar-se l'impacte de les diferents variables, també es van comparar els cacaus produïts per microones amb mostres produïdes pel mètode convencional per tal d'avaluar la seua similitud amb els cacaus comercials. Els resultats van mostrar que el microones, en només quatre minuts, va ser capaç d'enfosquir el cacau i de mantenir un perfil sensorial similar al produït pel mètode tradicional, al mateix temps que conduïa a una millora en les seues propietats funcionals. En resum, els mètodes per a l'alcalinització de cacau desenvolupats en el marc de la present tesi doctoral han demostrat ser unes alternatives molt prometedores per a substituir la tecnologia convencional. Les dos tècniques no només han estat capaces d'enfosquir el cacau tant com el mètode comercial en un temps molt menor, sinó que també han aconseguit la deshidratació parcial de la mostra i unes característiques sensorials i funcionals comparables a les del mètode convencional. / [EN] "Application of new technologies to cocoa alkalization" is a PhD thesis that aims to study the effects of two alternative techniques on the physicochemical and functional features of alkalized cocoa, and to evaluate their suitability to replace the traditional treatment. In chapter I, the conventional system for alkalization in closed and pressurized vessels has been replaced by extrusion. This technique has been proved to be a fast, continuous and less energy-consuming method, characteristics that the traditional system lacks and that have promoted its application to cocoa alkalization. On the one hand, the effects produced by temperature, water content and alkali type and concentration were evaluated on the physicochemical and functional features of cocoa. In general, alkali type and concentration were the main variables increasing the pH, darkening the sample, but also reducing the functional content, while water content and temperature exerted minor effects. On the other hand, the temperature and the water content were the variables exhibiting the greatest effect on the moisture content, leading to reductions of almost 50%. Moreover, the extrusion alkalization products were compared to traditionally produced cocoa powders based on physicochemical, functional and sensory criteria. The results revealed that extrusion was faster and able to dark cocoa in a greater extent than the conventional treatment and to produce sensory acceptable powders. These results confirm that extrusion is a feasible and promising alternative method able to alkalize cocoa in a fast, continuous and less energy-consuming manner. In chapter II, microwave heating has been studied as a substitute of the traditional alkalization treatment. This heating method has proven to be fast, versatile and able to preserve functional and sensory features of the treated products, which has made interesting its application to cocoa alkalization. The effects of the microwave heating technique on water content, power, duration, pressure application and alkali type and concentration were analyzed. In general, alkali type and concentration were the main variables inducing the darkening of cocoa, increasing its pH and reducing the concentrations of catechin and epicatechin. However, these variables did not affect the antioxidant activity and the total phenol content of the treated cocoas in comparison to the untreated one. Treatment pressure, power and duration exerted positive effects on the antioxidant activity, the total phenol content or both. These changes were related to the capacity of these variables, in combination with the alkali agent, to release non-extractable polyphenols from the matrix and to the induction of different chemical reactions. Additionally, the effects of the different variables were studied on the moisture content. Power and duration of the microwave heating treatment were decisive in the reduction of the water content, which was significantly reduced up to 70%. In terms of the evaluation of the suitability of the developed microwave heating alkalization method, the produced cocoas were compared to the traditionally alkalized ones in their physicochemical, functional and sensory characteristics. The developed fast microwave heating treatment showed to be able to dark cocoa as much as the traditional method, to produce sensory equivalent powders and to lead to the obtaining of cocoas with higher antioxidant activity and phenol content. In conclusion, this PhD thesis has applied extrusion and microwave heating as promising alternatives to cocoa alkalization. These technologies have demonstrated to dark cocoa in a significantly faster fashion than the traditional alkalization treatment, while keeping similar sensory profile and functional features, and substantially drying the product. / The authors would like to acknowledge the financial support of the Spanish Government and European Regional Development Fund (Project RTC-2016-5241- 2) / Valverde García, D. (2020). Application of new technologies to cocoa alkalization [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/140311 / Compendio

A fundamental problem of microwave (MW) thermal processing of materials is the intrinsic non-uniformity of the resulting internal heating pattern. This project proposes a general technique to solve this problem by using comprehensive numerical modeling to determine the optimal process guaranteeing uniformity. The distinctive features of the approach are the use of an original concept of uniformity for MW-induced temperature fields and pulsed MW energy as a mechanism for achieving uniformity of heating. The mathematical model used to represent MW heating describes two component physical processes: electromagnetic wave propagation and heat diffusion. A numerical solution for the corresponding boundary value problem is obtained using an appropriate iterative framework in which each sub-problem is solved independently by applying the 3D FDTD method. Given a specific MW heating system and load configuration, the optimization problem is to find the experiment which minimizes the time required to raise the minimum temperature of the load to a prescribed goal temperature while maintaining the maximum temperature below a prescribed threshold. The characteristics of the system which most dramatically influence the internal heating pattern, when changed, are identified through extensive modeling, and are subsequently chosen as the design variables in the related optimization. Pulsing MW power is also incorporated into the optimization to allow heat diffusion to affect cold spots not addressed by the heating controlled by the design variables. The developed optimization algorithm proceeds at each time-step by choosing the values of design variables which produce the most uniform heating pattern. Uniformity is measured as the average squared temperature deviation corresponding to all distinct neighboring pairs of FDTD cells representing the load. The algorithm is implemented as a collection of MATLAB scripts producing a description of the optimal MW heating process along with the final 3D temperature field. We demonstrate that CAD of a practical applicator providing uniform heating is reduced to the determination of suitable design variables and their incorporation into the optimization process. Although uniformity cannot be attained using“static" MW heating, it is achievable by applying an appropriate pulsing regime. The functionality of the proposed optimization is illustrated by computational experiments which show that time-to-uniformity can be reduced, compared to the pulsing regime, by up to an order of magnitude.