Polypropylene (PP) is a common thermoplastic and frequently adapted permanently with increasing requirements by adding fillers as well as reinforcing materials. Because of incompatibility of non-polar PP and polar inorganic filler, resulting composites are brittle which has a detrimental effect on the desired properties. Improvements in mechanical properties can be reached by compatibilization, creating of chemical couplings between phases and by increasing of inhomogeneity. Thus, maleic anhydride grafted PP is used as well as reactive processing of PP in presence of peroxide radical initiators. The temperature dependence of peroxide decay as well as the dependence of radical generation rate on time are two disadvantages of peroxide induced reactive processing. Modification of polymers with high energy electron treatment is also well known and used to form parts (after) molding as well as raw materials (pellets, powders, fibers) in solid state and at room temperature. The spatially and temporally precise input of energy is used to produce desired material properties on radical-induced chemical reactions. Coupling of high energy electron modification of polymers and melt mixing offers a new possibility of reactive processing. In this case, radical generation is independent of temperature, can be easily controlled by beam current and kept constant over time. Absence of any crystallinity, high reaction rates as well as intensive macromolecular mobility and intensive mixing are reasons to expect novel structures and properties. Electron beam induced reactive processing is a novel technique where chemical reactions are induced by spatial and temporal precise energy input via high energy electrons under dynamic conditions of melt mixing. This method gives the possibility to increase surface energy of polypropylene (PP) effectively as well as to generate chemical couplings between filler and PP. The process was applied to a proved system consisting of PP (38 wt%), magnesium hydroxide (MH) (60 wt%), triallyl cyanurate (TAC) (2 wt%). This composite system was successful tested in peroxide induced conventional reactive processing. Absorbed dose imparted per rotation of rotors is a new parameter controlling mechanical properties of polymer composites. Improved properties were found in tensile strength (150 %), elongation at break (175 %), and impact strength (175 %). It can be shown that chemical couplings are generated during electron induced reactive processing in comparison to only compatibilized material.

For the commercial success of polymer - multiwalled carbon nanotube (MWNT) composites the production of these materials on industrial scale by melt processing is of significant importance. The complete dispersion of primary MWNT agglomerates in a polymer melt is difficult to achieve, making it an important and challenging technological problem. Hence, it is necessary to understand the process of MWNT agglomerate dispersion in a polymer melt. Based on an intensive literature research on mechanisms and influencing factors on dispersion of other agglomerated nanostructured fillers (e.g. carbon black), the main dispersion steps were evaluated and investigated concerning the agglomerated MWNT.Consequently, systematic investigations were performed to study the effect of the melt infiltration on MWNT agglomerate dispersion and to analyse the corresponding main dispersion mechanisms, namely rupture and erosion. The states of MWNT agglomerate dispersion were assessed by quantifying the agglomerate area ratio and particle size distribution using image analysis of optical transmission micrographs. Additionally, the composite’s electrical resistivity was determined. In the prevailing study, polycarbonates (PC) varying in molecular weight were used to produce composites containing 1 wt% MWNT (Baytubes C150HP) as model systems and a discontinuous microcompounder was applied as melt mixing device. The agglomerate structure of the used MWNT material made them especially suitable for the reported investigations. The step of melt infiltration into the primary nanotube agglomerates plays a crucial role for their dispersion in the PC melt. During melt mixing when low shear rates were applied, better state of MWNT dispersion was obtained in high viscosity matrices because applied shear stresses were high. On the contrary, if high shear rates were applied, similar states of MWNT dispersion were obtained in low and high viscosity matrices although significantly lower shear stresses were applied in the low viscosity matrix as compared to the high viscosity matrix. The results indicate that if the applied shear stress values are compared, with increasing matrix viscosity the agglomerate dispersion gets worsen. This is attributed to the fact that low viscosity matrices can infiltrate relatively faster than high viscosity matrices into the agglomerate making them weaker and reducing the agglomerate strength. Thus, at sufficient shear rates MWNT agglomerates disperse relatively faster in low viscosity matrix. This illustrates a balance between the counteracting effects of viscosity on agglomerate infiltration and agglomerate dispersion. Additionally, the effect of matrix molecular weight on the size of un-dispersed MWNT agglomerates was investigated. Under similar conditions of applied shear stress, the composites based on low molecular weight matrix showed smaller sized un-dispersed primary agglomerates as compared to composites with higher molecular weight matrices. This again highlights the role of matrix infiltration as the first step of dispersion. Following the step of melt infiltration, agglomerate size gets reduced due to the dispersion mechanisms. To analyse the corresponding contributions of different dispersion mechanisms (rupture and erosion), the kinetics of MWNT agglomerate dispersion was investigated. If high mixing speeds are employed dispersion is quite fast and needs less time as compared to low mixing speed. A model is proposed to estimate the fractions of rupture and erosion mechanisms during agglomerate dispersion based on the kinetic study in the discontinuous mixer. Under the employed experimental conditions, at high mixing speeds, the dispersion was found to be governed by rupture dominant mechanism, whereas at low mixing speeds the dispersion was controlled by both mechanisms. As far as electrical resistivity is concerned, for a given content of MWNT as the state of dispersion improves, the resistivity values decrease significantly but only up to a plateau value. The composites produced using low viscosity matrices have lower resistivity values as compared to high viscosity matrices. Additionally, composites were prepared using additives, whereas the additives were found to be useful for improving filler dispersion and electrical conductivity.

Esta dissertação tem como objetivo, a apresentação de uma proposta para os resíduos agroextrativistas a fim de encontrar um composto orgânico ideal para ser utilizado na agricultura do Município de Laranjal do Jari, no Estado do Amapá. A técnica em questão será a compostagem, gerando uma alternativa de utilização para os resíduos de natureza local, onde atualmente não vêm sendo aproveitados. Para se chegar ao composto ideal serão utilizados basicamente: caroços de açaí e cascas de castanha. Esses resíduos vêm sendo relegados através dos Serviços de Limpeza Pública, constituindo não só um problema estético ou ambiental, mas de desperdício de energia e materiais que poderiam ser utilizados na recuperação de áreas degradadas ou como composto orgânico, na fixação de nutrientes e água no solo a fim de melhorar as práticas agrícolas, reduzir custos e a importação de fertilizantes químicos. A metodologia envolve estudo bibliográfico sobre a técnica de compostagem, consistindo em desenvolver todas as etapas que se darão mais claras, no desenvolver dos trabalhos de campo, para uma futura implantação de uma Unidade de Compostagem, a ser aplicável para a agricultura do referido município. / This work has the objective, to present a proposal for the agriculture-extractive residues to find an organic compound ideal for use in agriculture of the Laranjal do Jari, in the state of Amapá. The technique in question will be composting, generating an alternative to use for the residues of local nature, where currently they do not come being used to advantage. To arrive itself at the ideal composition they be used basically: açaí seeds and chestnut rinds. These residues came being relegated through the Services Public Cleaning, constituting not only an aesthetic or environmental problem, but of wastefulness of energy and materials that could be used in the recovery of degraded areas or as organic compound, in the setting of nutrients and water in the ground in order to improve the practical agriculturists, to reduce costs and the "importation" of chemical fertilizers. The methodology involves bibliographical study on the composting technique, consisting of developing all the stages that will be given clearer in the developing of the field works, for a future deployment of a unit of Composting, to apply for agriculture of the related city.

This thesis addresses the problem of the lack of a systematic approach to the modernisation of the indigenous languages of South Africa, with particular reference to Venda. Thus, a systematic approach is proposed in this study for the development of modem terminology in Venda. This approach is based on the canonical model for language planning. In this model, terminology development should follow the following four steps: (1) analysis of the terminological needs of the situation, (2) preparation of a plan and strategies for research, (3) implementation of terminology in practice by means of suitable policies, and lastly, (4) evaluation and constant updating of terminology. Within the canonical model for language planning, different models or frameworks are proposed. First is the theoretical model, which follows the pragmatic approach rather than a purist approach and takes into consideration other extralinguistic factors such as the nature of the special subject field, the needs of the target users and the socio-cultural context. The pragmatic approach is divided into two phases, namely the borrowing phase and the indigenisation phase. In the borrowing phase the borrowed terms are incorporated into the language with immediate effect and these terms may be replaced by indigenous terms in the indigenisation phase where less specialised communication is used. In the indigenisation phase, different language internal term formation strategies were identified, namely semantic shift, derivation, compounding, paraphrasing, initialisms, acronyms, clipping and new word manufacture. It was established that the use of these term formation strategies in Venda requires linguistic expertise, technical expertise and cultural expertise. Accordingly, a sociolinguistic approach is recommended rather than a purely linguistic approach. Lastly, a model of practical terminology work and a model for cooperation and coordination are proposed for terminology work in this language. With regard to the former, various steps that should be followed in terminology work are outlined. In the latter model various language agencies, such as government departments, parastatals and non-governmental organisations that may be involved in the modernisation of this language are identified. A framework in which these agencies could cooperate and coordinate their terminology work is proposed. / Linguistics and Modern Languages / D.Litt. et Phil. (Linguistics)

This study is in the area of terminology activities in Zimbabwe and it analyses the term creation used in the following selected specialised terms dictionaries: Duramazwi Reurapi Neutano (Dictionary of Biomedical Terms), Duramazwi Remimhanzi (Dictionary of Shona Musical Terms), and Duramazwi Redudziramutauro NeUvaranomwe (Dictionary of Shona Linguistic and Literature Terms). The study specifically analyses and explores how terminographers together with health, music, language and literature specialists made use of their term creation skills and strategies in the creation of new specialised terms for the field of music, health and linguistics. In addition, this research takes into account the impact of factors such as culture, socio- economic, etymological purity, attitudes of the target users, language policy, as well as availability of resourceson term creation. Hence, term creation is an exercise that involves many aspects and interlinked factors. This research advances the argument that while some term creation strategies (compounding, coining and derivation) can be adequate and appropriate, however, at times; they are some which result in created terms that are rather cumbersome, vague, artificial, and difficult to master and remember. In addition, this study found out that some term creation strategies (semantic expansion and loan translations) are unproductive; that means they do not add any value on the Shona language vocabulary. Moreover, the borrowing term creation strategy was analysed on the basis of whether it is promoting and elevating the Shona language or is it undermining its value and vitality. This study emphasises the need for a collaborative approach to term creation, with terminologists, linguists, subject area specialists and target language users during the different phases of word formation processes for the collective ownership of the created term and their acceptability to the target users. This study highlights that, through good term creation strategies the Shona Language can significantly contribute to the promotion and development of Shona language in Zimbabwe. Overally, the research yields a substantial amount of information in the terminological formation processes as well as the identification of factors that can be used to improve term creation strategies in order to develop indigenous languages for use in all spheres of life.The major contribution of this study is the identification and highlighting of the major strength and weaknesses of term creation strategies as a way of developing indigenous languages. The useful findings in this study will benefit the indigenous language development and language policy planners and terminologists in Zimbabwe and other African languages in similar situations. The significant amount of information about term creation that was used in the analysis of term creation in the three dictionaries was solicited from questionnaires and interviews that were carried out with linguists, the specialised dictionary compilers, music students, medical students and high school students doing Shona language and literature subject in Zimbabwe. More information on the term creation was done through content analysis of the three specialised dictionaries and the present researcher’s own experiences as a former Shona high school teacher, linguist and above all as a Shona language speaker. / African Languages / D. Litt. et Phil. (African Languages)

Esta dissertação tem como objetivo, a apresentação de uma proposta para os resíduos agroextrativistas a fim de encontrar um composto orgânico ideal para ser utilizado na agricultura do Município de Laranjal do Jari, no Estado do Amapá. A técnica em questão será a compostagem, gerando uma alternativa de utilização para os resíduos de natureza local, onde atualmente não vêm sendo aproveitados. Para se chegar ao composto ideal serão utilizados basicamente: caroços de açaí e cascas de castanha. Esses resíduos vêm sendo relegados através dos Serviços de Limpeza Pública, constituindo não só um problema estético ou ambiental, mas de desperdício de energia e materiais que poderiam ser utilizados na recuperação de áreas degradadas ou como composto orgânico, na fixação de nutrientes e água no solo a fim de melhorar as práticas agrícolas, reduzir custos e a importação de fertilizantes químicos. A metodologia envolve estudo bibliográfico sobre a técnica de compostagem, consistindo em desenvolver todas as etapas que se darão mais claras, no desenvolver dos trabalhos de campo, para uma futura implantação de uma Unidade de Compostagem, a ser aplicável para a agricultura do referido município. / This work has the objective, to present a proposal for the agriculture-extractive residues to find an organic compound ideal for use in agriculture of the Laranjal do Jari, in the state of Amapá. The technique in question will be composting, generating an alternative to use for the residues of local nature, where currently they do not come being used to advantage. To arrive itself at the ideal composition they be used basically: açaí seeds and chestnut rinds. These residues came being relegated through the Services Public Cleaning, constituting not only an aesthetic or environmental problem, but of wastefulness of energy and materials that could be used in the recovery of degraded areas or as organic compound, in the setting of nutrients and water in the ground in order to improve the practical agriculturists, to reduce costs and the "importation" of chemical fertilizers. The methodology involves bibliographical study on the composting technique, consisting of developing all the stages that will be given clearer in the developing of the field works, for a future deployment of a unit of Composting, to apply for agriculture of the related city.

Si la traduction est simplement définie comme un processus de communication bilingue dont le but général est de reproduire en langue cible un texte qui soit fonctionnellement équivalent au texte de départ (Reiss 2004 : 168-169), l’approche empruntée dans la présente thèse est celle d’une opération interculturelle et systématique qui vise à capturer le message issu d’une langue étrangère, à le décrypter en tenant en compte des nuances culturelles ou inhérentes à la discipline, et à le rendre le plus clairement possible en se servant d'éléments linguistiques et extralinguistiques compréhensibles dans la langue du locuteur cible. L'objectif est de déterminer la contribution de la traduction à l’expansion lexicale du sesotho, domaine qui demeure peu exploré par les spécialistes de cette langue. La problématique de ce travail repose sur la constatation que les néologismes en sesotho ne sont pas documentés de manière satisfaisante, si bien qu’il est difficile d'évaluer la contribution de la traduction à l’expansion lexicale. Les études antérieures sur la morphologie, la dérivation, la composition, l’emprunt et la dénomination s’appuient sur la mesure de la productivité, soulevant la question de savoir si la traduction en soi contribue à l’enrichissement terminologique du sesotho. Le point de départ de la thèse est l'hypothèse selon laquelle l’interaction avec le monde européen a nécessité de traduire de nombreux concepts qui n’existaient pas dans les systèmes traditionnels du Lesotho, ce qui a entraîné un nouveau dynamisme qui a permis de combler des lacunes terminologiques évidentes et de s’ouvrir et de s’adapter aux nouvelles réalités. Pour mettre cette hypothèse à l’épreuve et arriver à des conclusions éclairées et fiables, je cherche à répondre à trois questions : 1) Quelle est la structure des mots sesothos par rapport à celle de l’anglais en tant que langue source de traduction en sesotho, et du français en tant que langue de rédaction de la thèse ? 2) Etant donné que le sesotho est utilisé concomitamment avec l’anglais sans pour autant être la langue d'une culture inventrice en matière technologique, quel est le rôle que joue l’emprunt dans son expansion lexicale ? 3) D’un point de vue lexicologique, comment le sesotho répond-il aux besoins terminologiques dans les domaines de spécialité techno-scientifiques ? Pour y répondre, je m'appuie sur Doke (1954) et Matšela et al. (1981) pour situer le sesotho parmi les langues bantoues, préciser les fonctions du préfixe classificateur et établir la différence entre les composés sesothos d'une part et les composés anglais et français d'autre part. J’utilise ensuite la théorie avancée par Lederer (1990) pour démontrer l’influence syntaxique, sémantique et morphologique que l’anglais a sur le sesotho et pour présenter les différents procédés d’emprunt du sesotho. Diki-Kidiri (2008), Dispaldro et al. (2010) et Baboya (2008) démontrent la nécessité de faire appel aux informateurs-spécialistes pour confirmer l’hypothèse de départ. Les résultats obtenus mettent en évidence qu’en effet, la traduction a contribué à l’expansion du sesotho moderne, bien que cela n’ait pas été documenté, d’où la recommandation d'un travail collaboratif entre lexicologues au Lesotho, au Botswana, en Namibie et en Afrique du Sud, pour ouvrir de nouvelles perspectives d’études linguistiques sur le sesotho et pouvoir suivre et mesurer l’évolution de la langue. / Whilst translation is simply defined as a communication process whose main objective is to reproduce in the target language a text that is functionally equivalent to the source text (Reiss 2004: 168-169), the approach taken in this study views translation as an intercultural and systematic operation whose objective is to capture the message from the foreign language, to decrypt it taking into account cultural nuances or those inherent in the field at hand and to render it in the clearest possible manner using linguistic and extra linguistic elements which are comprehensible to the speaker of the target language. This study is aimed at determining the contribution of translation to the lexical expansion of Sesotho, an area which has been little explored by specialists of the language. The core issue is centred on the observation that Sesotho neologisms are not well documented, so that it is hard to measure the contribution of translation towards the lexical expansion of Sesotho. Analyses of morphology, derivation, compounding, borrowing and denomination are mainly focused on productivity in order to determine whether translation as a discipline contributes towards the creation of new words in the language.The study begins by positing the hypothesis that the interaction with the Western world necessitated the translation of numerous concepts which were absent from the then existing Sesotho systems. This process of interaction contributed a new dynamism that helped the language to bridge the terminological gap, to open up and adapt to new realities. In order to put this hypothesis to the test and arrive at well-researched and reliable conclusions, I attempt to probe three issues of concern: firstly, what is the structure of the Sesotho language compared to that of the English language as the source language of most translations into Sesotho and compared to that of the French language as the language in which this study is presented? Secondly, considering that Sesotho is used simultaneously with English even though it is not a techno-scientifically inventing language, what is the role played by the processes of borrowing in the lexical expansion of Sesotho? Thirdly, from the word-formation point of view, how does Sesotho respond to the terminological deficiencies in various fields of specialisation?To address these issues, Doke (1954) and Matšela et al. (1981) serve as references to situate Sesotho among the Bantu languages, to highlight the functions of the class prefix and to establish the difference between Sesotho and English and French compounding. Secondly, the theory advanced by Lederer (1990) serves as a springboard to analyse the syntactic, semantic and morphological influences that English has on Sesotho and to present the different borrowing processes. The third issue is addressed based on the theories presented by Diki-Kidiri (2008) while the theories proposed by Dispaldro et al. (2010) and Baboya (2008) led to the decision to call upon specialist informants to confirm the original hypothesis. The results obtained provide evidence that translation has, in fact, contributed to the lexical expansion of modern Sesotho, even though this has not been well documented. The study recommends collaborative work between Lesotho, Botswana, Namibian and South African linguists in order to open new avenues of linguistic studies on Sesotho with the aim to measure and monitor the evolution of the language.

Polypropylene (PP) is a common thermoplastic and frequently adapted permanently with increasing requirements by adding fillers as well as reinforcing materials. Because of incompatibility of non-polar PP and polar inorganic filler, resulting composites are brittle which has a detrimental effect on the desired properties. Improvements in mechanical properties can be reached by compatibilization, creating of chemical couplings between phases and by increasing of inhomogeneity. Thus, maleic anhydride grafted PP is used as well as reactive processing of PP in presence of peroxide radical initiators. The temperature dependence of peroxide decay as well as the dependence of radical generation rate on time are two disadvantages of peroxide induced reactive processing. Modification of polymers with high energy electron treatment is also well known and used to form parts (after) molding as well as raw materials (pellets, powders, fibers) in solid state and at room temperature. The spatially and temporally precise input of energy is used to produce desired material properties on radical-induced chemical reactions. Coupling of high energy electron modification of polymers and melt mixing offers a new possibility of reactive processing. In this case, radical generation is independent of temperature, can be easily controlled by beam current and kept constant over time. Absence of any crystallinity, high reaction rates as well as intensive macromolecular mobility and intensive mixing are reasons to expect novel structures and properties. Electron beam induced reactive processing is a novel technique where chemical reactions are induced by spatial and temporal precise energy input via high energy electrons under dynamic conditions of melt mixing. This method gives the possibility to increase surface energy of polypropylene (PP) effectively as well as to generate chemical couplings between filler and PP. The process was applied to a proved system consisting of PP (38 wt%), magnesium hydroxide (MH) (60 wt%), triallyl cyanurate (TAC) (2 wt%). This composite system was successful tested in peroxide induced conventional reactive processing. Absorbed dose imparted per rotation of rotors is a new parameter controlling mechanical properties of polymer composites. Improved properties were found in tensile strength (150 %), elongation at break (175 %), and impact strength (175 %). It can be shown that chemical couplings are generated during electron induced reactive processing in comparison to only compatibilized material.:1 Einleitung 6 2 Stand der Technik 8 2.1 Werkstoffeigenschaften von Polypropylen-Kompositen 8 2.1.1 Polypropylen 8 2.1.2 Füll- und Verstärkungsstoffe 10 2.1.3 Phasengrenze und Phasenmorphologie 12 2.1.3.1 Füllstoffmodifizierung 15 2.1.3.2 PP-Modifizierung 16 2.1.3.3 Mehrkomponentensysteme 17 2.1.3.4 Ansätze aus anderen Werkstoffsystemen 18 2.2 Reaktive Aufbereitung 19 2.3 Polymermodifizierung mit energiereichen Elektronen 22 2.3.1 Einordnung und Wechselwirkungsmechanismen 22 2.3.2 Einfluss von Polymerstruktur und G-Wert 25 2.3.3 Steuerparameter 26 2.3.3.1 Parameter der chemischen Umgebung 26 2.3.3.2 Parameter der Elektronenmodifizierung 28 2.3.4 Bestrahlung von Polypropylen 32 2.3.5 Bestrahlung von partikelgefüllten Thermoplastkompositen 33 2.3.6 Bestrahlung von Füll- und Verstärkungsstoffen 33 2.4 Zusammenfassung Stand Technik 34 3 Zielstellung 37 4 Aufgabenstellung 39 5 Experimentelles 40 5.1 Anlagentechnik 40 5.1.1 Stationäre Behandlung 40 5.1.2 Elektronen induzierte reaktive Aufbereitung 41 5.1.2.1 Aufbau u. Funktionsweise 41 5.1.2.2 Parameter der Elektronen induzierten reaktiven Aufbereitung 42 5.1.2.3 Dosimetrie 44 5.2 Probenherstellung 45 5.2.1 Materialien 45 5.2.2 Aufbereitung 45 5.2.3 Prüfkörperherstellung 46 5.3 Modifizierungsparameter 47 5.4 Vorgehensweise 49 5.5 Analytische Methoden 51 5.5.1 Zugversuch 51 5.5.2 Schlagbiegeversuch (nach Charpy) 52 5.5.3 Größenausschlusschromatographie (SEC) 54 5.5.4 Dynamische Differenzkalorimetrie (DSC) 55 5.5.5 Laserbeugungsspektrometrie 57 5.5.6 Rasterelektronenmikroskopie (REM) 58 5.5.7 Fourier-Transmissions-Infrarot-Spektroskopie (FTIR) 58 5.5.8 Dynamische Kontaktwinkelmessung 59 5.5.9 Schmelzerheologische Untersuchungen von Polymerschmelzen 60 5.5.9.1 Ungefüllte Polymerschmelzen 62 5.5.9.2 Partikelgefüllte Polymerschmelzen 63 6 Ergebnisse 68 6.1 Mechanische Kompositeigenschaften 68 6.2 Matrixpolymersysteme PP und PPTAC 69 6.3 Partikelgröße und -verteilung 75 6.4 Kompatibilität 77 6.5 Phasenkopplung 82 6.6 Inhomogenität 86 6.7 Einfluss verschiedener Prozessparameter auf die mechanischen Eigenschaften 87 6.7.1 Dosis 88 6.7.2 Elektronenenergie 90 6.7.3 Bestrahlungsdauer 91 6.7.4 Aufbereitungszeit 93 6.7.5 Dosisleistung im Modifizierungsvolumen 96 7 Zusammenfassung 98 8 Ausblick 100 9 Anhang 104 10 Literaturverzeichnis 112 11 Abkürzungsverzeichnis 115

For the commercial success of polymer - multiwalled carbon nanotube (MWNT) composites the production of these materials on industrial scale by melt processing is of significant importance. The complete dispersion of primary MWNT agglomerates in a polymer melt is difficult to achieve, making it an important and challenging technological problem. Hence, it is necessary to understand the process of MWNT agglomerate dispersion in a polymer melt. Based on an intensive literature research on mechanisms and influencing factors on dispersion of other agglomerated nanostructured fillers (e.g. carbon black), the main dispersion steps were evaluated and investigated concerning the agglomerated MWNT.Consequently, systematic investigations were performed to study the effect of the melt infiltration on MWNT agglomerate dispersion and to analyse the corresponding main dispersion mechanisms, namely rupture and erosion. The states of MWNT agglomerate dispersion were assessed by quantifying the agglomerate area ratio and particle size distribution using image analysis of optical transmission micrographs. Additionally, the composite’s electrical resistivity was determined. In the prevailing study, polycarbonates (PC) varying in molecular weight were used to produce composites containing 1 wt% MWNT (Baytubes C150HP) as model systems and a discontinuous microcompounder was applied as melt mixing device. The agglomerate structure of the used MWNT material made them especially suitable for the reported investigations. The step of melt infiltration into the primary nanotube agglomerates plays a crucial role for their dispersion in the PC melt. During melt mixing when low shear rates were applied, better state of MWNT dispersion was obtained in high viscosity matrices because applied shear stresses were high. On the contrary, if high shear rates were applied, similar states of MWNT dispersion were obtained in low and high viscosity matrices although significantly lower shear stresses were applied in the low viscosity matrix as compared to the high viscosity matrix. The results indicate that if the applied shear stress values are compared, with increasing matrix viscosity the agglomerate dispersion gets worsen. This is attributed to the fact that low viscosity matrices can infiltrate relatively faster than high viscosity matrices into the agglomerate making them weaker and reducing the agglomerate strength. Thus, at sufficient shear rates MWNT agglomerates disperse relatively faster in low viscosity matrix. This illustrates a balance between the counteracting effects of viscosity on agglomerate infiltration and agglomerate dispersion. Additionally, the effect of matrix molecular weight on the size of un-dispersed MWNT agglomerates was investigated. Under similar conditions of applied shear stress, the composites based on low molecular weight matrix showed smaller sized un-dispersed primary agglomerates as compared to composites with higher molecular weight matrices. This again highlights the role of matrix infiltration as the first step of dispersion. Following the step of melt infiltration, agglomerate size gets reduced due to the dispersion mechanisms. To analyse the corresponding contributions of different dispersion mechanisms (rupture and erosion), the kinetics of MWNT agglomerate dispersion was investigated. If high mixing speeds are employed dispersion is quite fast and needs less time as compared to low mixing speed. A model is proposed to estimate the fractions of rupture and erosion mechanisms during agglomerate dispersion based on the kinetic study in the discontinuous mixer. Under the employed experimental conditions, at high mixing speeds, the dispersion was found to be governed by rupture dominant mechanism, whereas at low mixing speeds the dispersion was controlled by both mechanisms. As far as electrical resistivity is concerned, for a given content of MWNT as the state of dispersion improves, the resistivity values decrease significantly but only up to a plateau value. The composites produced using low viscosity matrices have lower resistivity values as compared to high viscosity matrices. Additionally, composites were prepared using additives, whereas the additives were found to be useful for improving filler dispersion and electrical conductivity.

El presente trabajo tiene por objetivo estudiar las aplicaciones de los nanocristales o ¿nanowhiskers¿ extraídos mediante hidrólisis ácida de celulosa bacteriana (BCNW) para el desarrollo de materiales poliméricos y biopoliméricos con propiedades mejoradas para su uso en aplicaciones de envasado de alimentos. En primer lugar se estudió y optimizó el proceso de extracción de BCNW. Se desarrolló un procedimiento de extracción con ácido sulfúrico, que permitió obtener nanocristales con elevada relación de aspecto y cristalinidad y al mismo tiempo, un elevado rendimiento de extracción. Este procedimiento comprende una posterior etapa de neutralización que resultó ser necesaria para garantizar la estabilidad térmica de los nanocristales. El siguiente paso consistió en la formulación de materiales nanocompuestos con propiedades mejoradas incorporando BCNW en diferentes matrices plásticas, en concreto copolímeros de etileno-alcohol vinílico (EVOH), ácido poliláctico (PLA) y polihidroxialcanoatos (PHAs). Mediante las técnicas de electroestirado y estirado por soplado se generaron fibras híbridas de EVOH y PLA con BCNW. La incorporación de BCNW en las disoluciones empleadas para producir fibras modificó significativamente sus propiedades (viscosidad, tensión superficial y conductividad) y por tanto, la morfología de las fibras se vio afectada. Además, se generaron fibras con propiedades antimicrobianas mediante la incorporación de aditivos, maximizando el efecto antimicrobiano con la adición de sustancias de carácter hidrofílico. Seguidamente, se produjeron nanocompuestos por mezclado en fundido y se desarrollaron técnicas de pre-incorporación de BCNW para evitar la aglomeración de los mismos no sólo en matrices hidrofílicas como el EVOH, sino también en matrices hidrofóbicas como el PLA. La dispersión óptima de BCNW resultó en una mejora de las propiedades mecánicas y de barrera de los nanocompuestos. También se estudió la modificación de la superficie de los nanocristales mediante copolimerización con poli(glicidil metacrilato) para mejorar la compatibilidad de BCNW con una matriz hidrofóbica como el PLA. Se incluyen además los primeros resultados obtenidos en cuanto a la producción de nanobiocompuestos sintetizados por microorganismos, que consisten en PHAs con diferentes contenidos de hidroxivalerato reforzados con BCNW. Por último, se desarrollaron películas con propiedades de alta barrera basadas en películas de BCNW recubiertas con capas hidrofóbicas. El recubrimiento mediante la deposición de fibras por electrospinning seguido de homogeneización por calentamiento garantizó una buena adhesión entre las diferentes capas, protegiendo así las películas de BCNW del efecto negativo de la humedad. / Martínez Sanz, M. (2013). Bacterial cellulose nanowhiskers to enhance the properties of plastics and bioplastics of interest in food packaging [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/30312 / TESIS / Premios Extraordinarios de tesis doctorales