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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
31

Use of Supercritical Propylene to Produce Polypropylene/Clay Nanocomposites via in situ Polymerization

Lisboa da Silva Neto, Manoel January 2014 (has links)
Nanocomposites have been receiving a lot the attention in the last decade from both industry and academia, since a small amount of nanofiller can significantly improve the materials properties. In the field of thermoplastics, polypropylene (PP) is one of the most used materials , due its easy processability, good balance of mechanical properties, and low cost. However, PP has certain shortcomings such as poor gas barrier and low thermal stability which limit its application. In order to be classified as nanocomposite the material needs to have at least one phase with one dimension less than 100nm. The properties achieved by nanocomposites will depend on the type of polymer, type of dispersed phase (filler), surface interaction between filler and polymer, and the production method. Nanofillers present many shapes and sizes, but they can be grouped in nanoparticles, nanotubes and nanoplates. Montmorillonite (MMT) is a clay that has been extensively studied to produce PP nanocomposites, due to its availability, high aspect ratio, high modulus and high cation exchange capacity, characteristics that result in composite with improved properties. Three different morphologies can be observed in PP/MMT nanocomposites: agglomerates (similar to the conventional composites); intercalated; or exfoliated. Among these morphologies, exfoliation is the most desirable and the hardest to be achieved in PP/MMT nanocomposites. Several methods have been used to produce PP nanocomposites. They can be grouped in three main groups: solution blending; melt processing; and in situ polymerization. In order to produce an exfoliated nanocomposite, some methods have assisted the exfoliation using supercritical fluids. Supercritical carbon dioxide is by far the most explored one. Polypropylene is a semi-crystalline polymer and its properties rely on amount of its crystallinity, which is related to its stereochemical configurations. Isotactic PP and syndiotactic PP result in a semi-crystalline polymer while atactic results in an amorphous polymer. Two catalyst systems can be used to produce isotactic PP: Metallocene and Ziegler-Natta (ZN). This research study was carried out in order to develop an appropriated process to produce PP/MMT nanocomposites with a high level of exfoliation using in situ polymerization assisted by supercritical propylene. The main idea is to use supercritical propylene to treat the montmorillonite before polymerization. In this process, the small molecules of propylene diffuse inside the clay galleries under supercritical conditions (high pressure and temperature) until reaching complete saturation. Once this saturation is reached the mixture of polypropylene and clay is catastrophically decompressed and fed into an autoclave reactor. The propylene polymerization reaction is them catalyzed by ZN catalyst. The pressure of the mixture of propylene-montmorillonite from the supercritical condition to the reactor autoclave decreased significantly, allowing propylene to expand and exfoliate the clay as it was fed in the reactor. Propylene in supercritical conditions was used in this works because it is the monomer for the subsequently polymerization and because its good properties at supercritical conditions. In order to evaluate the results the following methods were used: transmission electron microscopy (TEM) to investigate the nanoscale sample morphology and evaluate the clay exfoliation, X-ray diffraction (XRD) to determine interlamellar distance, d001, of the clay, differential scanning calorimetry (DSC) to determine the amount of crystallization of polymer and composite, thermogravimetric analysis (TGA) to determine composite clay content, scanning electron microscopy (SEM) to evaluate the morphology, and clay swelling test to evaluate the compatibility among various pairs clays-solvent. The first part of this work evaluated the interaction and swelling effects of different pairs of clay-solvent with or without sonication. This was necessary in order to choose the best clay to carry out the study. Four solvents with different polarity (chlorobenzene, toluene, cyclohexane and hexane) and eight clays (seven organically modified and one unmodified) were evaluated with or without sonication. Closite 15A and 93A presented the best results with different solvents and they were selected for further experiments. The experiments also showed that sonication improves the swelling of the clay. Initial screening of the polymerization reaction was carried out using two conditions: feeding supercritical propylene without clay and adding clay without the addition of supercritical fluid. The addition of supercritical propylene did not modify the morphology and properties of PP in comparison to the normal polymerization. The addition of Cloisite 15A or Cloisite 93A (pre-treated with toluene, not with supercritical propylene) produced nanocomposites. Although Cloisite 15A showed better results on the swelling tests, Cloisite 93A presented much better polymerization yield, therefore it was selected for further investigation using treatment with supercritical propylene. Cloisite93A was submitted to a treatment under four different supercritical propylene conditions (temperature and pressure) for thirty minutes. Each mixture was subsequently fed to the reactor through a catastrophic expansion inside an autoclave reactor running a propylene polymerization reaction. The results from XRD and TEM show a significant improvement on the exfoliation when treating the clay under supercritical propylene conditions followed by in situ polymerization, as compared to the in situ polymerization without treating the clay with supercritical propylene. In conclusion, the utilization of supercritical propylene has improved the dispersion of the clay at the nanoscale during the preparation of these nanocomposites by in situ polymerization.
32

STUDI DI TERMINOLOGIA CINESE: APPROCCI DIACRONICI E SVILUPPI APPLICATIVI CONTEMPORANEI / STUDIES OF CHINESE TERMINOLOGY: DIACHRONIC APPROACHES AND CONTEMPORARY APPLICATION DEVELOPMENT

LU, HUIZHONG 28 April 2014 (has links)
La ricerca intende illustrare le modalità applicative attraverso le quali si possono esprimere in lingua cinese le terminologie specialistiche dei campi tecnici e scientifici del XXI secolo. Un percorso che attraversa la storia delle scienze in Cina dal terzo secolo a.C. fino ai nostri giorni, ricostruisce le regole che passo dopo passo, non senza deviazioni e ripensamenti, gli studiosi cinesi hanno stabilito per creare e gestire le loro “parole” composte con innumerevoli caratteri, gli hanzi, simbolo della cultura e della civiltà cinese, icone che ancora oggi “parlano” ai lettori, espressioni grafiche di oggetti e di concetti. La presentazione dell'opera di Feng Zhiwei, uno tra i maggiori esponenti della terminologia cinese contemporanea, ci accompagna nell'approfondimento degli orientamenti degli studi terminologici cinesi e nel confronto con quelli euro americani, a partire dagli studi svolti da Eugen Wüster all'inizio del XX secolo. L'analisi della terminologia cinese nella tecnologia del fotovoltaico e nel mondo economico-finanziario, costituisce il terreno di verifica delle pratiche terminologiche in essere nella lingua cinese e delle tendenze nella costruzione neologica e neonimica. / This research aims to illustrate the methodes used for creation of the specialized terminologies in the technical and scientific fields in the XXI century’s Chinese language. A pathway crossing the history of sciences in China from the III century B.C. until our days, reconstructs the rules that step after step the Chinese scholars have established in order to create and manage their “words” with the lot of characters, the hanzi, symbol of the Chinese culture and civilization, icons that still today “speak” to the readers, graphical expressions of objects and concepts. The presentation of the work of Feng Zhiwei, one among the greatest exponents of the contemporary Chinese terminology, is our guideline in a close examination of the Chinese terminological studies’ orientations, in comparison with the euro-americans ones, starting from the studies developed by Eugen Wüster at the beginning of the XX century. The analysis of the Chinese terminology in the photovoltaic technology and in the economic-financial world, constitutes the ground of verification of the actual terminological practices in the Chinese language and the tendencies in the neological and neonymical construction.
33

Preparation and characterization of polyethylene based nanocomposites for potential applications in packaging

Gill, Yasir Q. January 2015 (has links)
The objective of my work was to develop HDPE clay nanocomposites for packaging with superior barrier (gas and water) properties by economical processing technique. This work also represents a comparative study of thermoplastic nanocomposites for packaging based on linear low density polyethylene (LLDPE), high density polyethylene (HDPE) and Nylon12. In this study properties and processing of a series of linear low density polyethylene (LLDPE), high density polyethylene (HDPE) and Nylon 12 nanocomposites based on Na-MMT clay and two different aspect ratio grades of kaolinite clay are discussed.

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