Surface tension of a polymer melt in a supercritical fluid is a principal factor in determining cell nucleation and growth in polymer microcellular foaming. Previous work has presented the surface tension of the amorphous polymer, polystyrene (PS), in supercritical CO2 determined by Axisymmetric Drop Shape Analysis-Profile (ADSA-P), together with theoretical calculations for a corresponding system. The dependences of the surface tension on temperature, pressure and polymer molecular weight were discussed and the physical mechanisms for three main experimental trends were explained using Self Consistent Field Theory (SCFT). This thesis introduces recent work on the surface tension measurement of the crystalline polymer, high density polyethylene (HDPE), in supercritical N2 under various temperatures and pressures. The surface tension was determined by ADSA-P and the results were compared with those of the amorphous polymer PS. The dependence of the surface tension on temperature and pressure, at temperatures above the HDPE melting point, ~125°C, was found to be similar to that of PS; that is, the surface tension decreased with increasing temperature and pressure. Below 125°C and above 100°C, HDPE underwent a process of crystallization, where the surface tension dependence on temperature was different from that above the melting point, i.e., decreased with decreasing temperature. Differential Scanning Calorimetry (DSC) characterization of the polymer was carried out to reveal the process of HDPE crystallization and relate this to the surface tension behavior. It was found that the amount of the decrease in surface tension was related to the rate of temperature change and hence the extent of polymer crystallization. In the second part of the thesis, surface tension dependences on temperature, pressure and clay concentrations were studied for HDPE nano-clay composites (HNC) and compared with pure HDPE. It was found the trends with temperature and pressure were the same with PS in CO2 and HDPE in N2; that is, the surface tension decreased with increasing temperature and pressure. In all nanocomposite samples, the surface tension decreased compared with pure HDPE. This could be a good explanation for the better polymer foaming quality with the addition of clay in the polymer. A minimum surface tension was found with the sample at ~3% concentration of clay. The degree of crystallinity of HNC was analyzed by Differential Scanning Calorimetry (DSC) at different clay concentrations. A minimumz crystallinity was also found at the clay concentration of 3%. The possible relationship between surface tension and polymer crystallinity was discussed.

The effect of molecular weight on polypropylene (PP) extrusion foaming was investigated and the process to make soft touch, largely expanded, high cell density non-crosslinked PP foam using environmental friendly CO2 is presented. In previous research, when the cell density was high, cell opening was dominant and large expansion could not be achieved even in HMS PP materials. The effects of processing and material parameters on the foam morphologies of PP materials with three different melt flow rate (MFR) were studied using single-screw tandem foam extrusion system. By selecting proper material and die, and by tailoring the processing conditions, large expansion (25 fold) and high cell density (>109 cells/cm3) was successfully achieved in the high MFR PP without any additives. The mechanism of locally induced crystallization was found to be significantly affecting the foaming behavior of PP and was successfully verified using SEM, DSC, HPDSC, shear viscosity and solubility measurements.

The effect of molecular weight on polypropylene (PP) extrusion foaming was investigated and the process to make soft touch, largely expanded, high cell density non-crosslinked PP foam using environmental friendly CO2 is presented. In previous research, when the cell density was high, cell opening was dominant and large expansion could not be achieved even in HMS PP materials. The effects of processing and material parameters on the foam morphologies of PP materials with three different melt flow rate (MFR) were studied using single-screw tandem foam extrusion system. By selecting proper material and die, and by tailoring the processing conditions, large expansion (25 fold) and high cell density (>109 cells/cm3) was successfully achieved in the high MFR PP without any additives. The mechanism of locally induced crystallization was found to be significantly affecting the foaming behavior of PP and was successfully verified using SEM, DSC, HPDSC, shear viscosity and solubility measurements.

No description available.

This work investigates the interactions of carbonaceous materials (metallurgical coke, natural graphite and HDPE/coke blends) with three EAF slags [FeO: 24% to 32%]. Experiments were conducted using the sessile drop technique (1500??C-1600??C) with off-gases (CO, CO2) measured using an IR analyzer; the wetting behaviour was determined from contact angle measurements. Estimation of slag foaming behaviour was determined from the droplet volume changes calculated using specialized software. At 1550??C, all slags were non-wetting with coke due to increased surface tension due to sulphur. At 1550??C, slag 1 was initially non-wetting on natural graphite due to gas entrapment in the slag droplet; the wetting improved after that. Other slags showed comparatively better wetting. At 1600??C, all slags were non-wetting with coke. Slags showed a shift from non-wetting to wetting behaviour with natural graphite. Slag/coke reactions produced high off-gases levels causing extensive FeO reduction; gas entrapment in the slag was poor (small volume droplets). Slag/natural graphite interactions revealed both slow gas generation rates and FeO reduction, and excellent gas entrapment (higher droplet volumes) with minor changes in slag properties due to low ash levels. The iron oxide reduction rates were determined to be 1.54x10-5 and 4.2x10-6 mol.cm-2/sec (Slag 1, 1550??C) for metallurgical coke and natural graphite respectively. Slag interactions with coke/HDPE blends showed increasing off-gas levels with increasing HDPE levels. Blend#3 produced the highest off-gas levels, extensive FeO reduction and displayed significantly higher slag foaming and better wetting compared to coke. Our line on trends compared well for slag/carbon interactions and resulted in deceased specific energy consumption and carbon usage and increased productivity. These findings have enhanced the possibility of utilizing polymeric wastes in blends with coke in EAF steelmaking for slag/carbon interactions.

This thesis highlights a comprehensive research for the cell nucleation, growth and coarsening mechanisms during plastic foaming processes. Enforced environmental regulations have forced the plastic foam industry to adopt alternative blowing agents (e.g., carbon dioxide, nitrogen, argon and helium). Nevertheless, the low solubilities and high diffusivities of these viable alternatives have made the production of foamed plastics to be non-trivial. Since the controls of the cell nucleation, growth and coarsening phenomena, and ultimately the cellular morphology, involve delicate thermodynamic, kinetic, and rheological mechanisms, the production of plastics foams with customized cell morphology have been challenging. In light of this, the aforementioned phenomena were investigated through a series of theoretical studies, computer simulations, and experimental investigations. Firstly, the effects of processing conditions on the cell nucleation phenomena were studied through the in-situ visualization of various batch foaming experiments. Most importantly, these investigations have led to the identification of a new heterogeneous nucleation mechanism to explain the inorganic fillers-enhanced nucleation dynamics. Secondly, a simulation scheme to precisely simulate the bubble growth behaviors, a modified heterogeneous nucleation theory to estimate the cell nucleation rate, and an integrated model to simultaneously simulate cell nucleation and growth processes were developed. Consequently, through the simulations of the cell nucleation, growth, and coarsening dynamics, this research has advanced the understanding of the underlying sciences that govern these different physical phenomena during plastic foaming. Furthermore, the impacts of various commonly adopted approximations or assumptions were studied. The end results have provided useful guidelines to conduct computer simulation on plastic foaming processes. Finally, an experimental research on foaming with blowing agent blends served as a case example to demonstrate how the elucidation of the mechanisms of various foaming phenomena would aid in the development of novel processing strategies to enhance the control of cellular structures in plastic foams.

This thesis highlights a comprehensive research for the cell nucleation, growth and coarsening mechanisms during plastic foaming processes. Enforced environmental regulations have forced the plastic foam industry to adopt alternative blowing agents (e.g., carbon dioxide, nitrogen, argon and helium). Nevertheless, the low solubilities and high diffusivities of these viable alternatives have made the production of foamed plastics to be non-trivial. Since the controls of the cell nucleation, growth and coarsening phenomena, and ultimately the cellular morphology, involve delicate thermodynamic, kinetic, and rheological mechanisms, the production of plastics foams with customized cell morphology have been challenging. In light of this, the aforementioned phenomena were investigated through a series of theoretical studies, computer simulations, and experimental investigations. Firstly, the effects of processing conditions on the cell nucleation phenomena were studied through the in-situ visualization of various batch foaming experiments. Most importantly, these investigations have led to the identification of a new heterogeneous nucleation mechanism to explain the inorganic fillers-enhanced nucleation dynamics. Secondly, a simulation scheme to precisely simulate the bubble growth behaviors, a modified heterogeneous nucleation theory to estimate the cell nucleation rate, and an integrated model to simultaneously simulate cell nucleation and growth processes were developed. Consequently, through the simulations of the cell nucleation, growth, and coarsening dynamics, this research has advanced the understanding of the underlying sciences that govern these different physical phenomena during plastic foaming. Furthermore, the impacts of various commonly adopted approximations or assumptions were studied. The end results have provided useful guidelines to conduct computer simulation on plastic foaming processes. Finally, an experimental research on foaming with blowing agent blends served as a case example to demonstrate how the elucidation of the mechanisms of various foaming phenomena would aid in the development of novel processing strategies to enhance the control of cellular structures in plastic foams.

This work investigates the interactions of carbonaceous materials (metallurgical coke, natural graphite and HDPE/coke blends) with three EAF slags [FeO: 24% to 32%]. Experiments were conducted using the sessile drop technique (1500??C-1600??C) with off-gases (CO, CO2) measured using an IR analyzer; the wetting behaviour was determined from contact angle measurements. Estimation of slag foaming behaviour was determined from the droplet volume changes calculated using specialized software. At 1550??C, all slags were non-wetting with coke due to increased surface tension due to sulphur. At 1550??C, slag 1 was initially non-wetting on natural graphite due to gas entrapment in the slag droplet; the wetting improved after that. Other slags showed comparatively better wetting. At 1600??C, all slags were non-wetting with coke. Slags showed a shift from non-wetting to wetting behaviour with natural graphite. Slag/coke reactions produced high off-gases levels causing extensive FeO reduction; gas entrapment in the slag was poor (small volume droplets). Slag/natural graphite interactions revealed both slow gas generation rates and FeO reduction, and excellent gas entrapment (higher droplet volumes) with minor changes in slag properties due to low ash levels. The iron oxide reduction rates were determined to be 1.54x10-5 and 4.2x10-6 mol.cm-2/sec (Slag 1, 1550??C) for metallurgical coke and natural graphite respectively. Slag interactions with coke/HDPE blends showed increasing off-gas levels with increasing HDPE levels. Blend#3 produced the highest off-gas levels, extensive FeO reduction and displayed significantly higher slag foaming and better wetting compared to coke. Our line on trends compared well for slag/carbon interactions and resulted in deceased specific energy consumption and carbon usage and increased productivity. These findings have enhanced the possibility of utilizing polymeric wastes in blends with coke in EAF steelmaking for slag/carbon interactions.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24642号 / 工博第5148号 / 新制||工||1983(附属図書館) / 京都大学大学院工学研究科化学工学専攻 / (主査)教授 大嶋 正裕, 教授 竹中 幹人, 教授 佐野 紀彰 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Les extraits polysaccharidiques totaux (EPS) produits par LOCA-1 et LOCA-2, deux souches de levures isolées de la peau de raisin en Champagne viticole, ont été isolés en vue de leur caractérisation tant biochimique que fonctionnelle. La caractérisation structurale par GC démontre que ces EPS sont des hétéropolymères complexes de haut poids moléculaires (~2.106 g/mol) et sont composés de monomères de mannose, glucose, xylose et d’acide glucuronique, et deux types de substituants mis en évidence par analyse MALDI (sulfate et phosphate). L’élucidation de l’enchaînement structural des résidus osidiques au sein de ces EPS, sur la base des analyses GC/MS et RMN, a mis en évidence la présence d’une ossature principale linéaire constituée d’unités α-(1→3)-D-mannopyranosyles. Toutefois, des différences sont notables entre ces deux souches du même genre. Pour la souche LOCA-1, de courtes chaines latérales de β-(1,2)-xyloses (2-5 résidus) se ramifient à la chaine principale sur ses positions C-2 et/ou C-6. A l’opposé, la chaine mannosidique principale, plus longue chez la souche LOCA-2 (˃40 unités), est substituée en ses positions 2 et/ou 4 par des antennes de xylomannanes. Les caractéristiques structurales de ces EPS n’avaient jamais été observées auparavant chez d’autres microorganismes. La seconde partie de ce travail de thèse est dédiée aux propriétés fonctionnelles (pouvoirs moussant, gélifiant, viscosifiant) de ces EPS. Des propriétés viscosifiantes et moussantes tout à fait exceptionnelles ont été observées à l’issue d’une analyse comparative avec des biopolymères industriels commercialisés.Les propriétés intrinsèques des polymères naturels produits par ces souches indigènes de baies de raisin, en font des candidats potentiels pour une exploitation dans divers domaines d’applications biotechnologiques, et notamment oenologique. / The total polysaccharide extracts (EPS) produced by LOCA-1 and LOCA-2, two yeast strains collected from grape skin in Champagne, were isolated for both their biochemical and functional characterization. Their structural characterization by GC analysis show that EPS were complex heteropolymers with high molecular weight (~2.106 g/mol), and were composed of mannose, glucose, xylose and glucuronic acid as monosaccharide constituents, and 2 types of substituents (sulphate and phosphate) evidenced by MALDI analysis. Elucidation of the structural enchainment of these EPS carbohydrates based on GC-MS and NMR analyses revealed in both studied cases, a linear main backbone built up of α-(1→3)-D-mannopyranosyl residues. However differences have been noted between these two strains. For LOCA-1 EPS, some short side chains of β-(1→2)-xyloses (2-5 residues) are branched to the main linear backbone on its C-2 and/or C-6 positions. In contrast, the LOCA-2 main backbone that is more extended (˃40 units) than the former, is substituted on its C-2 and/or C-4 positions by xylomannan antennas. This is the first report of these yeasts’ polysaccharides with such structural characteristics. The second part of this thesis is devoted to the functional properties (foaming, gelling, and viscosifying abilities) of the EPS. Very exceptional viscosifying and foaming properties were observed after a comparative analysis with some marketed industrial biopolymers.The intrinsic properties of these natural polymers produced by these grape berries indigenous yeast strains, make them potential candidates for operating in various fields of biotechnology applications, especially enology.