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No. of bitstreams: 1 VictorRLO_DISSERT.pdf: 1864412 bytes, checksum: 5110310795a99006bc86a9720eaeb5a4 (MD5) Previous issue date: 2017-05-11 / The development of biodegradable coatings has been potentially discussed due to the exacerbated use of petrochemical polymers, and their non-biodegradable load has been aggravating serious environmental problems. Furthermore the growing worldwide demand for health improvement has reached an interest in technological solutions capable of offering means of conservation and reduction of the metabolic activity of fruits and vegetables to preserve their numerous nutrients effectively for long periods of storage. Biopolymers, which are the polymeric base of the coating, add several positive points: they are attractive for their renewable characteristics, abundance, low cost and easy access in the semi-arid region. The coatings were synthesized by the casting method with three polymer bases: corn starch (3%), cassava starch (2%) and gelatin (5%); beeswax was added as a hydrophobic agent in the polymeric network at different concentrations relative to the dry biopolymer base (0%, 5% and 10%). The effect of the incorporation of the beeswax on the barrier properties was evaluated and the biofilm was determined with the best characteristics for coating in "Paluma" guavas, with a significant difference (p <0.05) in the addition of beeswax in cassava starch films 2%. The surface roughness and the contact angle of the systems containing beeswax indicated the hydrophobic behavior of the films. This was also confirmed by the water vapor transfer rate and solubility and led to a significant improvement in the elasticity of biofilms. "Paluma" guavas were harvested at physiological maturity and selected for the uniformity f shell color and absence of defects, were covered by the casting method with filmogenic solution of cassava starch, cassava starch with the addition of beeswax and uncoated, and then conditioned in regulated chamber at 15 ± 2 ° C and 90% -95% RH for 15 days. The physicochemical and sensorial analyzes showed that the use of the filmogenic solution of cassava starch with the addition of beeswax delayed the loss of chlorophyll and maintained a good maturation index, and consequently increased the shelf life of the guavas. The sensorial attributes: aroma, texture, acceptance and purchase intention, indicated a better acceptability of the fruits with cassava starch coating with addition of beeswax, demonstrating the commercial potential of this cover / O desenvolvimento de coberturas biodegradáveis tem sido potencialmente discutido devido ao uso exacerbado de polímeros petroquímicos, e sua carga não-biodegradável, alavancando graves problemas ambientais. Além disso, a crescente demanda mundial em busca de melhoria da saúde tem alcançado interesse em soluções tecnológicas capazes de oferecer meios de conservação e redução da atividade metabólica dos frutos e hortaliças para preservar seus inúmeros nutrientes de forma eficaz por períodos longos de armazenamento. Os biopolímeros, que são a base polimérica das coberturas propostos nesse trabalho, agregam diversos pontos positivos: são atrativos por suas características renováveis, de abundância, baixo custo e fácil acesso na região do semiárido. Foram sintetizadas coberturas a base de amido de milho (3%), fécula de mandioca (2%) e gelatina (5%); cera de abelha foi adicionada como agente hidrofóbico na rede polimérica em concentrações diferentes em relação à base seca de biopolímero (0%, 5% e 10%). O efeito da incorporação da cera de abelha sobre as propriedades de barreira foi avaliado e elegeu-se o biofilme com as melhores características para cobertura em goiabas “Paluma”. Propriedades mecânicas, de barreira, estruturais, de cor e térmicas foram analisadas. A rugosidade superficial e o ângulo de contato dos sistemas contendo cera de abelha indicaram o comportamento hidrofóbico dos filmes; isto também foi confirmado pela taxa de transferência de vapor de água e solubilidade, e levou a uma importante melhoria na elasticidade dos biofilmes. Goiabas “Paluma”, colhidas na maturidade fisiológica e selecionadas quanto a uniformidade de cor da casca e ausência de defeitos, foram cobertas, pelo método casting, com solução filmogênica de fécula de mandioca, fécula de mandioca com adição de cera de abelha e sem cobertura, e então acondicionadas em câmara regulada para 15ºC±2ºC e 90%-95% UR, durante 15 dias. As análises físico-químicas e sensoriais evidenciaram que o uso da solução filmogênicas de fécula de mandioca com adição de cera de abelha retardou a perda de clorofila e manteve bom índice de maturação, e consequentemente aumentou o tempo de vida útil das goiabas. Os atributos sensoriais: aroma, textura, aceitação e intenção de compra, apontaram melhor aceitabilidade dos frutos revestidos com fécula de mandioca com adição de cera de abelha, demonstrando potencial comercial desta cobertura / 2017-06-27

Yes / Transport and storage vessels in Red Lustrous Wheelmade ware (RLWm ware) were traded across a large area of the eastern Mediterranean for approximately 300 years (c. 1500–1200 BCE) during the Late Bronze Age (c.1600–1000 BCE). The extreme consistency of the ceramic, in form, fabric, chemistry and mineralogy, points to a single production source for the ware, which, although no kiln sites have been identified, is generally accepted to have been on Cyprus. The aim of this study was to determine whether organic residues were present in this very fine, dense ware, and to characterise the contents of RLWm ware vessels from different sites, contexts and periods, and of different forms, to improve our understanding of the trade in this ceramic type. To that end, 101 RLWm ware sherds, together with three visible residues, were examined from sites in Turkey, Cyprus, Egypt and Syria. Residues were identified in more than half of the samples, indicating that organic material is absorbed into and preserved in this very fine fabric. Four commodities were identified: fat (probably plant oil), which in four residues was identified further as castor oil; beeswax; bitumen; and Pinaceae spp. resin. The commodities were found alone or, occasionally, one of the latter three was combined with the fat or oil. Fatty material was the only commodity present at all sites and its wide distribution may indicate that generally the vessels were used for a mixture or mixtures based on plant oils, in some cases containing castor oil. It was impossible to determine whether the beeswax, bitumen and resin formed part of this mixture or represented post-firing treatments of the ceramic to make it less porous. The identification of more than one type of residue indicates that RLWm ware vessels did not always contain the same commodity. No significant correlation could be detected between the vessel forms, and the dating of many of the sherds was not precise enough to reveal any variation through time. The type of residue present did vary depending on the geographical location of its final use. Beeswax was, with two exceptions, only present in samples from Turkey, while bitumen was found exclusively in samples from Cypriot sites. The occurrence of at least one example of every commodity in the samples from Cyprus is consistent with the theory that this ware was manufactured on Cyprus, and indicates that the vessels could also have been filled and exported from there. The variation in content of the vessels found in different geographical areas could highlight a special trading relationship between the Hittite heartland in Turkey and the Cypriot potters who produced the ware, and a possible trade in bitumen as a raw material between the north Syrian coastal area of Ugarit and Cyprus. / This research was funded by an AHRC PhD studentship (number 110786), awarded to V. Steele.

Red Lustrous Wheelmade Ware (RLWm ware) transport and storage vessels have been excavated from Late Bronze Age (LBA) sites across the eastern Mediterranean. These distinctive vessels were traded for the valuable commodity they contained so far unidentified. Seventy-three sherds (61 RLWm ware, 12 in local fabrics) and two visible residues were analysed for organic residues using standard lipid extraction techniques. Seven residues from a previous study were re-examined. Gas chromatography-mass spectrometry identified four materials - beeswax, bitumen, fat/oil and resin. Beeswax, found only in vessels from Hittite sites in Turkey, was probably used as a post-firing treatment. Fat/oil, present in some sherds from every site, represents the contents of the vessels and showed many of the characteristics of degraded plant oil. Two examples contained a plant sterol and three yielded ricinoleic acid, a biomarker for castor oil. Gas-chromatography compound-specific isotope ratio mass spectrometry of selected residues excluded dairy products, ruminant animal fats and fish oils as source materials for the fats/oils, while comparison with a small database of modern oils created during this study does not exclude plant oils. Selected samples analysed by high performance liquid chromatography-tandem mass spectrometry did not reveal wine residues. Data on the elemental composition of the fabric collected during another study was re-analysed and compared with data from a further published study, confirming the remarkable consistency of RLWm ware fabric. Volume calculations were also attempted to give an estimate of the capacity of the main vessel forms.

Red Lustrous Wheelmade Ware (RLWm ware) transport and storage vessels have been excavated from Late Bronze Age (LBA) sites across the eastern Mediterranean. These distinctive vessels were traded for the valuable commodity they contained so far unidentified. Seventy-three sherds (61 RLWm ware, 12 in local fabrics) and two visible residues were analysed for organic residues using standard lipid extraction techniques. Seven residues from a previous study were re-examined. Gas chromatography-mass spectrometry identified four materials ¿ beeswax, bitumen, fat/oil and resin. Beeswax, found only in vessels from Hittite sites in Turkey, was probably used as a post-firing treatment. Fat/oil, present in some sherds from every site, represents the contents of the vessels and showed many of the characteristics of degraded plant oil. Two examples contained a plant sterol and three yielded ricinoleic acid, a biomarker for castor oil. Gas-chromatography compound-specific isotope ratio mass spectrometry of selected residues excluded dairy products, ruminant animal fats and fish oils as source materials for the fats/oils, while comparison with a small database of modern oils created during this study does not exclude plant oils. Selected samples analysed by high performance liquid chromatography-tandem mass spectrometry did not reveal wine residues. Data on the elemental composition of the fabric collected during another study was re-analysed and compared with data from a further published study, confirming the remarkable consistency of RLWm ware fabric. Volume calculations were also attempted to give an estimate of the capacity of the main vessel forms. / Arts and Humanities Research Council / Extensive folders of data and appendices which accompany this thesis are not presently available online.

[ES] El objetivo general de la presente tesis doctoral fue aditivar polímeros biodegradables con colofonia y sus derivados mediante el uso de técnicas de procesamiento convencionales y no convencionales. En esta tesis se presentan siete trabajos dentro de cuatro bloques de estudio que constituyeron los objetivos específicos de la investigación. En el primer bloque de estudio se realizó una caracterización comparativa de cinco colofonias de diferentes fuentes para determinar sus propiedades y establecer las diferencias entre cada colofonia para su posterior uso y aplicación como aditivos sostenibles de polímeros biodegradables. En el segundo bloque de estudio se aditivó colofonia en matrices de polímeros biodegradables para lo cual se realizaron dos trabajos. En el primer trabajo se empleó poli (butilen adipato-co-tereftalato) (PBAT) como matriz polimérica y colofonia (GR) y un pentaeritritol éster de colofonia (UT) como aditivos. El PBAT se mezcló con las resinas en varios contenidos y las formulaciones se procesaron por extrusión y un posterior moldeo por inyección. En el segundo trabajo se empleó poli(¿-caprolactona) (PCL) como matriz polimérica, y como aditivos se emplearon GR y cera de abeja (BW). Las formulaciones se prepararon por mezcla por extrusión y el procesamiento del material se llevó a cabo por una técnica no convencional que es la manufactura aditiva o impresión 3D.En el tercer bloque de estudio se realizó la aditivación de materiales termoplásticos utilizando como base un polímero biodegradable de alto rendimiento ambiental y como aditivo colofonia y sus derivados. Como polímero base se empleó almidón termoplástico (TPS) y como aditivos de usaron los siguientes derivados de colofonia: colofonia sin modificar (GR), colofonia deshidrogenada (RD), colofonia modificada con anhidrido maleico (CM), pentaeritritol éster (LF) y éster de glicerol de colofonia (UG). La colofonia se mezcló con el TPS por extrusión y el procesamiento de las mezclas se llevó a cabo por moldeo por inyección. En el cuarto bloque se estudió la aditivación de colofonia a matrices poliméricas mediante la técnica de electropulverización. Se realizaron tres trabajos en los que se optimizó e implementó el proceso de electrospulverización para la incorporación de microesferas de colofonia en matrices poliméricas. En el primer trabajo se evalúo el uso de un proceso electrohidrodinámico como método de aditivación de colofonia en matrices poliméricas. En el segundo trabajo se optimizó el proceso de electropulverización de colofonia a partir de 24 experimentos. Posteriormente, se depositaron microesferas de GR sobre películas de PCL para obtener sistemas bicapa. Los resultados obtenidos revelaron un gran potencial para procesar fácilmente sistemas bicapa con alto interés en aplicaciones agrícolas, de empaque y/o biomédicas sostenibles. Finalmente, en el tercer trabajo se usó el método optimizado de electrospraying para aditivar microesferas de colofonia sobre la capa exterior de una mascarilla quirúrgica a base de polipropileno (PP), y se determinó que el revestimiento de microesferas ayudó a mantener la hidrofobicidad original de la capa exterior de la mascarilla quirúrgica incluso después de 6 horas de uso, aumentando en el tiempo de vida útil de la mascarilla. Los resultados de la tesis indican que la colofonia y sus derivados son versátiles como aditivos de matrices termoplásticas biodegradables y que el proceso de aditivación puede llevarse a cabo por métodos de procesamiento tanto convencionales como no convencionales. Los hallazgos del estudio son significativos porque la colofonia es un material natural obtenido de fuentes renovables, no es tóxica y es biocompatible, de modo que su uso como aditivo no solo mejora las propiedades de los polímeros biodegradables, sino que promueve el estudio y desarrollo de materiales sostenibles lo que contribuye a la disminución del impacto ambiental de los plásticos. / [CA] L'objectiu general de la present tesi doctoral va ser additivar polímers biodegradables amb colofònia i els seus derivats mitjançant l'ús de tècniques de processament convencionals i no convencionals. En aquesta tesi es presenten set treballs dins de quatre blocs d'estudi que van constituir els objectius específics de la investigació. En el primer bloc d'estudi es va realitzar una caracterització comparativa de cinc colofònies de diferents fonts, per a determinar les seues propietats i establir les diferències entre cada colofònia per al seu posterior ús i aplicació com a additius sostenibles de polímers biodegradables. En el segon bloc d'estudi es additivar colofònia en matrius de polímers biodegradables, per a això es van realitzar dos treballs. En el primer treball es va emprar poli (butilen adipat-co-tereftalat) (PBAT) com a matriu polimèrica i colofònia (GR) i un pentaeritritol èster de colofònia (UT) com a additius. El PBAT es va mesclar amb les resines en diversos continguts i les formulacions es van processar per extrusió i un posterior emotlament per injecció. En el segon treball es va emprar poli(¿-caprolactona) (PCL) com a matriu polimèrica, i com a additius es van emprar GR i cera d'abella (BW). Les formulacions es van preparar per mescla per extrusió i el processament del material es va dur a terme per una tècnica no convencional que és la manufactura additiva o impressió 3D. En el tercer bloc d'estudi es va realitzar l'additivació de materials termoplàstics utilitzant com a base un polímer biodegradable d'alt rendiment ambiental i com a additiu colofònia i els seus derivats. Com a polímer base es va emprar midó termoplàstic (TPS) i com a additius de van usar els següents derivats de colofònia: colofònia sense modificar (GR), colofònia deshidrogenada (RD), colofònia modificada amb anhidrido maleic (CM), pentaeritritol èster (LF) i èster de glicerol de colofònia (UG). La colofònia es va mesclar amb el TPS per extrusió i el processament de les mescles es va dur a terme per emotlament per injecció. En el quart bloc es va estudiar l'additivació de colofònia a matrius polimèriques mitjançant la tècnica d'electrospulverització. Es van realitzar tres treballs en els quals es va optimitzar i va implementar el procés d'electrospulverització per a la incorporació de microesferes de colofònia en matrius polimèriques. En el primer treball s'avalue l'ús d'un procés electrohidrodinàmic com a mètode d'additivació de colofònia en matrius polimèriques i es van obtindre tant microesferes com microfibres de colofònia depenent de la concentració de la solució inicial. En el segon treball es va optimitzar el procés d'electrospulverització de colofònia a partir de 24 experiments. Posteriorment, les microesferes de GR es van depositar sobre pel·lícules de per a obtindre sistemes bicapa. Els resultats obtinguts van revelar un gran potencial per a processar fàcilment sistemes bicapa. Finalment, en el tercer treball es va usar el mètode optimitzat d'electrospulverització per a additivar microesferes de colofònia sobre la capa exterior d'una màscara quirúrgica a base de polipropilè (PP), i es va determinar que el revestiment de microesferes va ajudar a mantindre la hidrofobicitat original de la capa exterior de la màscara quirúrgica. Els resultats de la tesi indiquen que la colofònia i els seus derivats són versàtils com a additius de matrius termoplàstiques biodegradables i que el procés de d'additivació pot dur-se a terme per mètodes de processament tant convencionals com no convencionals. Les troballes de l'estudi són significatius perquè la colofònia és un material natural obtingut de fonts renovables, no és tòxica i és biocompatible, de manera que el seu ús com a additiu no sols millora les propietats dels polímers biodegradables, sinó que promou l'estudi i desenvolupament de materials sostenibles el que contribueix a la disminució de l'impacte ambiental dels plàstics / [EN] The general objective of this doctoral thesis was to add biodegradable polymers with gum rosin and its derivatives, using conventional and unconventional processing techniques. This thesis presents seven works within four study blocks that constitute the specific objectives of the research. The first study block conducts a comparative characterization of five gum rosins from different sources to determine their properties and establish the differences between each rosin for their subsequent use and application as sustainable additives for biodegradable polymers. The second study block examines the compounding of biodegradable polymer matrices with gum rosin, for which two works were developed. The first work uses poly (butylene adipate-co-terephthalate) (PBAT) as the polymeric matrix and rosin (GR) and a rosin pentaerythritol ester (UT) as additives. PBAT was mixed with the resins in various contents, and the formulations were processed by extrusion and subsequent injection molding. The second work uses poly(¿-caprolactone) (PCL) as a polymeric matrix and GR and beeswax (BW) as additives. The three materials mentioned are biocompatible and biodegradable. The formulations were mixed by extrusion, and the material was processed by an unconventional technique: additive manufacturing or 3D printing. The third study block compounded thermoplastic materials using a biodegradable polymer with high environmental performance as a base and gum rosin and its derivatives as additives. This study used thermoplastic starch (TPS) as the base polymer and the following gum rosin derivatives were used as additives: unmodified rosin (GR), dehydrogenated rosin (RD), rosin modified with maleic anhydride (CM), pentaerythritol ester (LF) and ester of rosin glycerol (UG). Gum rosin and TPS were mixed by extrusion and processed by injection molding. The fourth study block studies the addition of rosin to polymeric matrices using the electrospraying technique. Three works were carried out to optimize and implement the electrospraying process for adding rosin microspheres in polymeric matrices. The first work evaluated the use of an electrohydrodynamic process to add gum rosin to polymeric matrices. The process allowed gum rosin microspheres and microfibers depending on the concentration of the initial solution. The second work optimized the gum rosin electrospraying process from 24 experiments. Subsequently, GR microspheres were deposited on compression molded PCL films to obtain bilayer systems. The results revealed a great potential to efficiently process bilayer systems with high interest in sustainable agricultural, packaging, and/or biomedical applications. Finally, the third work used the optimized electrospraying method to add gum rosin microspheres to the outer layer of polypropylene (PP)-based surgical mask. The results showed that the microsphere coating helped maintain the original hydrophobicity of the outer layer of the surgical mask. The thesis results indicate that gum rosin and its derivatives are versatile as additives in biodegradable thermoplastic matrices and that both conventional and unconventional processing methods can carry out the additive process. The study findings are significant because rosin is a natural material obtained from renewable sources; it is non-toxic and biocompatible. Therefore, using gum rosin as an additive not only improves the properties of biodegradable polymers but also promotes the study and development of sustainable materials, which contributes to reducing the environmental impact of plastics. / Gracias a la Conselleria de Innovación, Universidades, Ciencia y Sociedad Digital, por la beca otorgada (GRISOLIAP/2019/113), que me ha permitido dedicarme completamente a la realización de este proyecto. A la Conselleria de Innovación, Universidades, Ciencia y Sociedad Digital por la ayuda para “Subvenciones para estancias de contratados predoctorales en centros de investigación fuera de la Comunitat Valenciana (BEFPI)” (CIBEFP/2021/30) / Pavón Vargas, CP. (2022). Aditivación de materiales biodegradables mediante el uso de derivados de colofonia [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/191385

Abstract This study concerns the Swedish artist Roj Friberg (1934–2016). The essay is based on a study of technique and materiality used by Friberg. He is quite marginalized and slightly forgotten in the Swedish art history and when mentioned merely described as a painter from the 1960´s who used graphite mixed with French turpentine, in order to work on the surface with an eraser attached to an electric drill. However, Friberg used other different and more complex painting techniques in his work, something this essay will notice and highlight. The used method is a biographical, dealing with the references to Friberg. To explain why he was considered an “outsider” in Swedish art, the theory of social capital by Pierre Bourdieu is applied. Also, Wolfgang Kemps concept of reception history, which focus on the arts beholder, rather than the artists itself. From the middle of 1970 Friberg also used an ancient painting technique called encaustic, heated beeswax mixed with pigment. Paintings which have received very little attention; therefore, the focus is on his use of encaustic in combination with his other techniques, such as melted graphite, melted wax crayons or drawn with wax crayons and graphite. The work with lasered layers and the typical method of working from darkness to light in Friberg´s pictures shows resemblance with the ancient encaustic portraits from Fayum, in the 50 AD.