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Abstract Biodegradable starch-glycerol based films were obtained. The influence of lipid compounds (palmitic, stearic and oleic acid), other polymers (hydroxypropylmethylcellulose and sodium caseinate) and bioactive compounds (¿-tocoferol, D-limonene and orange essential oil) on film properties (oxygen and water vapour barrier, optical, mechanical, nano- and microstructural). Furthermore the effect of storage time on films¿ properties was also considered. Fatty acids addition did not improve the water vapour ability of films except for non-stored saturated fatty acids containing films. X-ray diffraction results showed that cristallinity of films increased with storage time, thus increasing the stiffness and decreasing the gloss of films. Furthermore, crystallinity affected the water sorption capacity of films as function of relative humidity and temperature. Glass transition temperature of starch films varied with saturated fatty acids addition. However, oleic acid did not affect this parameter. The presence of fatty acids promoted the formation of V-type structures, thus indicatin the formation of amylose-lipid complexes that inhibited the developmet of other crystalline structures. The effect of the incorporation of other biopolymers to improve the functionality of starch films was also studied. Hydroxypropylmethylcellulose (HPMC) addition inhibited starch retrogradation. However, obtained films were more permeable, specially in case of oxygen. HPMC addition produced phase separation as it was observed by scanning electron microscopy. On the contrary, sodium caseinate incorporation (NaCas) allowed to obtain homogeneous films and less permeable to oxygen. Obtained films showed less mechanical resistance in comparison with pure starch films but a greater flexibility without increasing the water vapour permeability. Rearrangement of polymers chains during storage reduced the mechanical resistance, the extensibility and the gloss of composite films. Regarding the obtained results, the film including a starch:protein ratio of 50:50 was choosen as the film with the most adequate properties. Composite film (starch:Nacas ratio = 50:50) was studied as a matrix for the incorporation o active compounds (¿-tocopherol, D-limonene and orange essential oil). The effect of ¿-tocopherol addition was compared with the incorporation of oleic acid and their mixture. Lipids addition promoted phase separation between starch and NaCas due to the different interactions between each polymer and the lipids. Furthermore, oleic acid addition increased significantly the oxygen permeability whereas ¿-tocopherol greatly improved the antioxidant capacity of films without affecting the oxygen permeability. D-limonene and orange essential oil incorporation was carried out by forming rapeseed and soy nanoliposomes, which acted as carriers of bioactive components. Nanoliposomes incorporation was performed directly in starch-NaCas dispersions without any homogenization, to avoid nanoliposomes damages. Bioactive compounds addition did not confer antimicrobial capacity to the films (except for soy-orange oil nanoliposomes containing film) probably due to the high stability of nanoliposomes and the low antibacterial activity of D-limonene and orange essential oil. / Se han desarrollado y caracterizado films biodegradables a base de almidón de maíz y glicerol como plastificante, evaluando al mismo tiempo el efecto de la adición de componentes lipídicos (ácido palmítico, esteárico y oleico), otros polímeros (hidroxipropilmetilcelulosa y caseinato de sodio) y compuestos bioactivos (¿-tocoferol, aceite esencial de naranja y D-limoneno) sobre las propiedades de los films (propiedades barrera al vapor de agua y al oxígeno, ópticas, mecánicas, micro y nanoestructurales). Asimismo se evaluó la influencia del tiempo de almacenamiento en las propiedades de los films. La adición de ácidos grasos no mejoró notablemente la permeabilidad al vapor de agua excepto en el caso de los films con ácidos grasos saturados y solo en films no almacenados. Los resultados de difracción de rayos X mostraron que la cristalinidad aumentó con el tiempo de almacenamiento, incrementándose la rigidez, y disminuyendo el brillo de los films. Del mismo modo, la cristalinidad afectó a la capacidad de sorción de agua de los films en función de la humedad relativa y la temperatura. La temperatura de transición vítrea de los films de almidón se vio afectada por la adición de ácidos grasos saturados pero no por la adición de ácido oleico. La presencia de dichos componentes promovió la formación de estructuras cristalinas tipo V, indicando la formación de complejos entre los lípidos y las cadenas de amilosa e inhibiendo la formación de otros tipos de formas cristalinas. Se analizó también el efecto de la incorporación de otros biopolímeros en la posible mejora de la funcionalidad de los films de almidón. En las mezclas con hidroxipropilmetilcelulosa (HPMC), se inhibió la retrogradación del almidón en los films composite, pero se observó un efecto negativo en las propiedades barrera de los mismos, que fueron más permeables, principalmente al oxígeno. La adición de HPMC produjo separación de fases en los films (observada por microscopía electrónica de barrido). Por el contrario, la incorporación de caseinato de sodio (NaCas) permitió formar films homogéneos y menos permeables al oxígeno. Los films presentaron una resistencia mecánica algo menor que los films de almidón puro pero una mayor flexibilidad sin incrementar los valores de permeabilidad al vapor de agua. La reorganización de las cadenas de los polímeros con el tiempo de almacenamiento provocó la disminución de la resistencia mecánica, la deformabilidad y el brillo de los films composite. Atendiendo a los efectos observados, se eligió como formulación más adecuada el film composite formado por almidón y NaCas con un ratio de polímeros del 50:50. El film composite de almidón y NaCas (50:50) se estudió como matriz para la incorporación de compuestos bioactivos como son el ¿-tocoferol y el aceite esencial de naranja o su principal componente, el D-limoneno. El efecto de la adición de ¿-tocoferol se comparó con la influencia de la adición de ácido oleico y también con la adición de ambos compuestos. La adición de lípidos provocó una separación de fases entre el almidón y el NaCas debido a la diferente interacción entre cada polímero y los lípidos. Asimismo la adición de ácido oleico incrementó significativamente la permeabilidad al oxígeno, al contrario que el ¿-tocoferol, que además impartió a los films una elevada capacidad antioxidante. La incorporación de aceite esencial de naranja y D-limoneno se realizó utilizando nanoliposomas de lecitina de soja y lecitina de colza que encapsularon los compuestos activos. La incorporación de nanoliposomas en los films se realizó directamente en las dispersiones acuosas sin posterior homogeneización para evitar su ruptura. La adición de los compuestos bioactivos en forma de nanoliposomas no confirió capacidad antimicrobiana a los films, salvo en el caso de los nanoliposomas de lecitina de soja con aceite esencial, debido probablemente a la dificultad de los compuestos encapsulados para difundir en el film por la gran estabilidad de los liposomas y a la baja actividad antilisteria del D-limoneno y el aceite esencial de naranja. / Jiménez Marco, A. (2013). Propiedades de films de almidón de maíz. Influencia de la incorporación de lípidos, biopolímeros y compuestos bioactivos [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/28214 / Premios Extraordinarios de tesis doctorales

Injection molding is one of the most commonly applied processing methods for plastic components. Heat transfer coefficient (HTC), which describes the heat conducting ability of the interface between a polymer and cavity wall, significantly influences the temperature distribution of a polymer and mold during injection molding and thus affects the process and quality of plastic products. This thesis focuses on HTC under diverse processing situations. On the basis of the heat conducting principle, a theoretical model for calculating HTC was presented. Injection mold specially used for measuring and calculating HTC was designed and fabricated. Experimental injection studies under different processing conditions, especially different surface roughness, were performed for acquiring necessary temperature data. The heat quantity across the interface and HTC between a polymer and cavity wall was calculated on the basis of experimental results. The influence of surface roughness on HTC during injection molding was investigated for the first time. The factors influencing the HTC were analyzed on the basis of the factor weight during injection molding. Subsequently FEM (Finite element method) simulations were carried out with observed and preset value of HTC respectively and the relative crystallinity and part density were obtained. In the comparison between results from simulation and experiment, the result calculated with observed HTC shows better agreement with actually measured value, which can verify the reliability and precision of the injection molding simulation with observed HTC. The results of this thesis is beneficial for understanding the heat transfer process comprehensively, predicting temperature distribution, arranging cooling system, reducing cycle time and improving precision of numerical simulation. / Das Spritzgießen ist eines der am häufigsten angewandten Verarbeitungsverfahren zur Herstellung von Kunststoffkomponenten. Der Wärmedurchgangskoeffizient (WDK), welcher den Wärmeübergang zwischen Kunststoff und Werkzeugwand beschreibt, beeinflusst während des Spritzgießens maßgeblich die Temperaturverteilung im Bauteil und dem Werkzeug und folglich den Prozess und die Qualität der Kunststoffprodukte. Der Inhalt dieser Arbeit beschäftigt sich mit dem WDK unter verschiedenen Prozessbedingungen. Auf Grundlage des Wärmeleitungsprinzips wurde ein theoretisches Modell für die Berechnung des WDK vorgestellt. Es wurde dazu ein Spritzgießwerkzeug konstruiert und hergestellt, welches Messungen zur späteren Berechnung des WDK ermöglicht. Praktische Spritzgießversuche unter verschiedenen Prozessbedingungen, insbesondere unterschiedlicher Oberflächenrauheit, wurden für die Erfassung der erforderlichen Temperaturdaten durchgeführt. Auf Grundlage der experimentellen Ergebnisse wurde der Wärmeübergang zwischen dem Polymer und der Werkzeugwand berechnet. Der Einfluss der Oberflächenrauhigkeit auf den WDK wurde hierbei zum ersten Mal untersucht. Auf Grundlage des Bauteilgewichtes wurden anschließend die Faktoren, die den WDK beeinflussen, berechnet. Des Weiteren wurden FEM-Simulationen (Finite Element Methode) mit dem gemessenen und dem voreingestellten WDK durchgeführt und daraus der Kristallinitätsgrad und die Bauteildichte gewonnen. Der Vergleich zwischen den realen Ergebnissen und der Simulation zeigt, dass die Berechnungen mit dem gemessenen WDK eine bessere Übereinstimmung mit den realen Werten aufweist, was die Zuverlässigkeit und Präzision der Spritzgusssimulation bestätigt. Die Ergebnisse dieser Arbeit tragen zum umfassenden Verständnis des Wärmeübergangs im Spritzgießprozess, zur Vorhersage der Temperaturverteilung, zur Auslegung des Kühlsystems, zur Reduzierung der Zykluszeit und zur Verbesserung der Genauigkeit der numerischen Simulation bei.

Polyethylene is used extensively as an insulating material in high voltage power cables, it is therefore important to understand the behaviour of polyethylene under different conditions. This is a study regarding the relation of heat treatment and the effect of morphological changes on the dielectric properties of polyethylene samples. Polyethylene granulates were pressed to 1 mm thick circular plaque samples that were heat treated differently. The heat treatments were conducted in a vacuum oven. Heat treated samples were tested for morphological changes with Differential Scanning Calorimetry (DSC) and dielectric property changes were studied with an IDAX 300 Dielectric Spectroscopy Analyser and a TREK 30/30 high voltage amplifier, allowing measurements in the frequency range 0.1 mHz – 100 Hz for voltages up to 30 kV. The experimental results were analysed to understand the co-relation among these parameters. A literature review has been conducted on polyethylene morphology to understand their behaviour under different annealing conditions. A phenomenon that has been noticed during the experiments is that the samples swell with annealing; the thickness change effects the dielectric measurements as well. For this reason an extensive study has been conducted on the effect different temperature and time of heat treatment had on the samples. Heat treatment has effects on the properties of polyethylene samples, but the effect of heat treatment was not only on the morphology but also on the physical dimension of the samples. The samples change their thickness with heat treatment along with their morphology. The effect of morphological changes on the dielectric property of polyethylene samples has not been found to be eminent. This study was focused on relatively thicker samples (1 mm) compared to the existent scientific literature (0.1-0.2 mm). There are very limited research literatures available on the relation of morphology and electrical properties of polyethylene; this work is an attempt to contribute to the knowledge. Also the effect of samples swelling with annealing and its effect on electric measurements is not found in existing literatures. This work will also contribute understanding the effect of sample swelling on measurements. / Polyeten används i stor utsträckning som ett isolermaterial i högspänningskablar, och därför är det därför viktigt att förstå beteendet hos polyeten under olika förhållanden. Detta är en studie angående relationen mellan värmebehandling och effekten av morfologiska förändringar av de dielektriska egenskaperna hos polyeten. Polyeten granulat pressades till 1 mm tjocka cirkulära skivor som sedan värmebehandlades olika. Värmebehandlingarna utfördes i en vakuumugn. De värmebehandlade proverna testades för morfologiska förändringar med differentiell svepkalorimetri (DSC) och de dielektriskaegenskaperna studerades med en IDAX 300 Dielektrisk spektroskopi Analysator och en TREK 30/30 högspänningsförstärkare, vilken tillåter mätningar i frekvensområdet 0,1 mHz - 100 Hz för spänningar upp till 30 kV. De experimentella resultaten analyserades för att förstå relationen mellan dessa parametrar. En litteratur har utförts på polyeten morfologi för att förstå deras beteende under olika anlöpningsförhållanden. Ett fenomen som har uppmärksammats under experimenten är att proverna sväller med anlöpningenÄven tjockleken påverkar de dielektriska mätningar. Av denna anledning utfördes en omfattande studie av effekten av olika temperatur och tid för värmebehandling hade på proverna. Värmebehandling har effekter på egenskaperna för polyetenprover, men effekten av värmebehandlingen var inte bara på morfologin, utan också på den fysiska dimensionen av proverna. Effekten av morfologiska förändringar på den dielektriska egenskapen hos polyetenprover har inte befunnits vara framstående. Denna studie var inriktad på relativt tjockare prover (1 mm) jämfört med den existerande vetenskapliga litteraturen (0,1-0,2 mm). Det finns mycket lite litteratur kring relationen mellan morfologi och elektriska egenskaper hos polyeten; detta arbete är ett försök att bidra till kunskapen. Även effekten av provernas svällande efter anlöpning och dess effekt på dielektriska mätningar finns befintliga litteraturen.

The synthesis and properties of metal phosphonates prepared using piperazine-based bisphosphonic acids have been investigated. The ligands N,N’-piperazinebis(methylenephosphonic acid) (H₄L), and the 2-methyl (H₄L-Me) and 2,5-dimethyl (H₄L 2,5-diMe) derivatives have been prepared using a modified Mannich reaction. Hydrothermal reaction of gels prepared from metal (II) acetates and the bisphosphonic acids results in the synthesis of four structures: STA-12, Ni VSB-5, Co H₂L.H₂O and Mg H₂L. STA-12, synthesised by reaction of Mn, Fe, Co or Ni acetate with H₄L or H₄L-Me, has been investigated further. STA-12 crystallises in the space group R⁻₃, and Ni STA-12 is the most crystalline version. Its structure was solved from synchrotron data (a = b = 27.8342(1) Å, c = 6.2421(3) Å, α = β = 90°, γ = 120°), and it has large 10 Å hexagonal shaped pores. Helical chains of Ni octahedra are coordinated by the ligands, resulting in phosphonate tetrahedra pointing towards the pore space. Water is present, both coordinated to the Ni²⁺ cations and physically adsorbed in the pores. Mixed metal structures based on Ni STA-12, where some Ni is replaced in the gel by another divalent metal (Mg, Mn, Fe or Co) can also be synthesised. Dehydration of STA-12 results in two types of behaviour, depending on the metal present. Rhombohedral symmetry is retained on dehydration of Mn and Fe STA-12, the a cell parameter decreasing compared to the as-prepared structures by 2.42 Å and 1.64 Å respectively. Structure solution of dehydrated Mn STA-12 indicates changes in the torsion angles of the piperazine ring bring the inorganic chains closer together. Fe and Mn STA-12 do not adsorb N₂, which is thought to be due to the formation of an amorphous surface layer. Dehydration of Ni and Co STA-12 causes crystallographic distortion. Three phases were isolated for Ni STA-12: removal of physically adsorbed water results in retention of rhombohedral symmetry, while dehydration at 323 K removes some coordinated water forming a triclinic structure. A fully dehydrated structure (dehydrated at 423 K) was solved from synchrotron data (a = 6.03475(5) Å, b = 14.9156(2) Å, c = 16.1572(7) Å, α = 112.5721(7)°, β = 95.7025(11)°, γ = 96.4950(11)°). The dehydration mechanism, followed by UV-vis and Infra-red spectroscopy, involves removal of water from the Ni²⁺ cations and full coordination of two out of three of the phosphonate tetrahedra forming three crystallographically distinct Ni and P atoms. No structural distortion takes place on dehydration of Ni and Co STA-12 prepared using the methylated bisphosphonate, and the solids give a higher N₂ uptake as a result. Dehydrated Ni and Co STA-12 were tested for adsorption performance for fuel related gases and probe molecules. Investigations were undertaken at low temperature with H₂, CO and CO₂, and ambient temperature with CO₂, CH₄, CH₃CN, CH₃OH and large hydrocarbons. Due to the presence of lower crystallinity, Co STA-12 has an inferior adsorption performance to Ni STA-12, although it has similar adsorption enthalpies for CO₂ at ambient temperature (-30 to -35 kJ mol⁻¹). Ni STA-12 adsorbs similar amounts of CO₂ and N₂ at low temperature, indicating the adsorption mechanisms are similar. Also, it adsorbs 10 × more CO₂ than CH₄ at low pressure, meaning it could be used for separation applications. Ni STA-12 adsorbs 2 mmol g⁻¹ H₂ with an enthalpy of -7.5 kJ mol⁻¹, the uptake being due to adsorption on only one-third of the Ni²⁺ cations. The uptake for CO is 6 mmol g⁻¹, with adsorption enthalpies ranging from -24 to -14 kJ mol⁻¹. This uptake is due to adsorption on all the Ni²⁺, meaning the adsorption enthalpies are high enough to allow the structure to relax. This is also observed for adsorption of CH₃CN and CH₃OH, where there is a return to rhombohedral symmetry after uptake. The adsorption sites in dehydrated Ni and Co STA-12 were investigated via Infra-red spectroscopic analysis of adsorbed probe molecules (H₂, CO, CO₂, CH₃CN and CH₃OH). The results indicate the adsorption sites at both low and ambient temperature are the metal cations and the P=O groups. The metal cation sites are also characterised as Lewis acids with reasonable strength. STA-12 was shown to have acidic activity for the liquid phase selective oxidations of 1-hexene and cyclohexene, although there is evidence active sites are coordinated by products and/or solvents during the reaction. STA-12 also demonstrates basic activity for the Knoevenagel condensation of ethyl cyanoacetate and benzaldehyde. Modification of STA-12 by adsorption of diamine molecules causes a slight increase in the basicity, and the highest conversions are where water and diamine molecules are both present.

Injection molding is one of the most commonly applied processing methods for plastic components. Heat transfer coefficient (HTC), which describes the heat conducting ability of the interface between a polymer and cavity wall, significantly influences the temperature distribution of a polymer and mold during injection molding and thus affects the process and quality of plastic products. This thesis focuses on HTC under diverse processing situations. On the basis of the heat conducting principle, a theoretical model for calculating HTC was presented. Injection mold specially used for measuring and calculating HTC was designed and fabricated. Experimental injection studies under different processing conditions, especially different surface roughness, were performed for acquiring necessary temperature data. The heat quantity across the interface and HTC between a polymer and cavity wall was calculated on the basis of experimental results. The influence of surface roughness on HTC during injection molding was investigated for the first time. The factors influencing the HTC were analyzed on the basis of the factor weight during injection molding. Subsequently FEM (Finite element method) simulations were carried out with observed and preset value of HTC respectively and the relative crystallinity and part density were obtained. In the comparison between results from simulation and experiment, the result calculated with observed HTC shows better agreement with actually measured value, which can verify the reliability and precision of the injection molding simulation with observed HTC. The results of this thesis is beneficial for understanding the heat transfer process comprehensively, predicting temperature distribution, arranging cooling system, reducing cycle time and improving precision of numerical simulation. / Das Spritzgießen ist eines der am häufigsten angewandten Verarbeitungsverfahren zur Herstellung von Kunststoffkomponenten. Der Wärmedurchgangskoeffizient (WDK), welcher den Wärmeübergang zwischen Kunststoff und Werkzeugwand beschreibt, beeinflusst während des Spritzgießens maßgeblich die Temperaturverteilung im Bauteil und dem Werkzeug und folglich den Prozess und die Qualität der Kunststoffprodukte. Der Inhalt dieser Arbeit beschäftigt sich mit dem WDK unter verschiedenen Prozessbedingungen. Auf Grundlage des Wärmeleitungsprinzips wurde ein theoretisches Modell für die Berechnung des WDK vorgestellt. Es wurde dazu ein Spritzgießwerkzeug konstruiert und hergestellt, welches Messungen zur späteren Berechnung des WDK ermöglicht. Praktische Spritzgießversuche unter verschiedenen Prozessbedingungen, insbesondere unterschiedlicher Oberflächenrauheit, wurden für die Erfassung der erforderlichen Temperaturdaten durchgeführt. Auf Grundlage der experimentellen Ergebnisse wurde der Wärmeübergang zwischen dem Polymer und der Werkzeugwand berechnet. Der Einfluss der Oberflächenrauhigkeit auf den WDK wurde hierbei zum ersten Mal untersucht. Auf Grundlage des Bauteilgewichtes wurden anschließend die Faktoren, die den WDK beeinflussen, berechnet. Des Weiteren wurden FEM-Simulationen (Finite Element Methode) mit dem gemessenen und dem voreingestellten WDK durchgeführt und daraus der Kristallinitätsgrad und die Bauteildichte gewonnen. Der Vergleich zwischen den realen Ergebnissen und der Simulation zeigt, dass die Berechnungen mit dem gemessenen WDK eine bessere Übereinstimmung mit den realen Werten aufweist, was die Zuverlässigkeit und Präzision der Spritzgusssimulation bestätigt. Die Ergebnisse dieser Arbeit tragen zum umfassenden Verständnis des Wärmeübergangs im Spritzgießprozess, zur Vorhersage der Temperaturverteilung, zur Auslegung des Kühlsystems, zur Reduzierung der Zykluszeit und zur Verbesserung der Genauigkeit der numerischen Simulation bei.