The flow properties of polydimethylsiloxane (PDMS) melts at room temperature were studied by measurement of lubrication forces using an Atomic Force Microscopy (AFM) colloidal force probe. A glass probe was driven toward a glass plate at piezo drive rates in the range of 12 – 120 μm/s, which produced shear rates up to ~10⁴ s⁻¹. The forces on the probe and the separation from the plate were measured. Two hypotheses were examined: (1) when a hydrophilic glass is immersed in a flow of polymer melt, does a thin layer of water form at the glass surface to lubricate the flow of polymer and (2) when a polymer melt is subject under a shear stress, do molecules within the melt spatially redistribute to form a lubrication layer of smaller molecules at the solid surface to enhance the flow? To examine the effect of a water lubrication layer, forces were compared in the presence and the absence of a thin water layer. The presence of the water layer was controlled by hydrophobization of the solid. In the second part, the possibility of forming a lubrication layer during shear was examined. Three polymer melts were compared: octamethyltrisiloxane (OMTS, n = 3), PDMS (n _avg = 322), and a mixture of 70 weight% PDMS and 30 weight% OMTS. We examined whether the spatial variation in the composition of the polymer melt would occur to relieve the shear stress. The prediction was that the trimer (OMTS) would become concentrated in the high shear stress region in the thin film, thereby decreasing the viscosity in that region, and mitigating the shear stress. / Master of Science

京都大学 / 新制・課程博士 / 博士(工学) / 甲第25016号 / 工博第5193号 / 新制||工||1991(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)准教授 谷口 貴志, 教授 大嶋 正裕, 教授 古賀 毅 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Ce travail était centré sur les propriétés thermodynamiques et mécaniques des polymères denses et sur leurs liens avec les systèmes de la matière molle et l'étude des propriétés de conformation et les propriétés rhéologiques des polymères hyperbranchés. L'étude de polymères hyperbranchés montre qu'ils sont substantiellement différents de leurs analogues linéaires. En utilisant des méthodes de simulation, nous pouvons obtenir des informations inaccessibles par des méthodes expérimentales et heureusement obtenir de précieuses informations du point de vue industriel et scientifique. Cette étude traite le problème par des simulations et comme expliqué dans le manuscrit, nous avons observé un centre de faible densité pour un grand nombre de générations et une enveloppe extérieure plutôt compacte. Cette tendance se retrouve également pour les propriétés dynamiques. Le manque d’enchevêtrement dans les polymères hyperbranchés fait d'eux des matériaux moins résistant que ceux composés de chaînes linéraires. La viscosité perd sa simple dépendance à la masse dans le cas d'une chaîne linéaire. / This study is focused on thermodynamic and mechanical properties of dense polymers solutions and related soft matter systems and conformational and rheological properties of hyperbranched polymers. Studies of hyperbranched polymers shows that they are substantially different from their linear analogs. By using simulation methods we could reach the information not available by experimental methods and hopefully obtain valuable information from both industrial and scientific points of view.This study is treating this problem by means of computer simulations where as a result we can see a hollow center for high generation numbers and a rather compact outer shell. This tendency expands to dynamical behavior. Lack of chain entanglements in hyperbranched polymers make them not very tough materials in a comparison with linear chains. Another point is a decrease of mobility caused by large amount of branch points. Viscosity loses its simple dependence on the mass as for the case of linear chains.

La connaissance des propriétés physiques, et plus particulièrement le comportement rhéologique, est un paramètre essentiel pour contrôler la mise en forme de polymère fondu dans des procédés tels que la synthèse ou l'extrusion. Cependant, il est parfois difficile de reproduire les conditions de température et de pression rencontrées (ici entre 200°C et 270°C et entre 10bars et 200bars) dans ces procédés par des méthodes de rhéologie standard. C'est pourquoi, ce doctorat propose un important travail expérimental sur le développement d'une cellule de rhéologie sous pression permettant de travailler au-delà du point de fusion du polymère (185°C) mais également sous pression de vapeur d'eau et de dioxyde de carbone supercritique. De plus, de manière à pouvoir améliorer le mélange dans la cellule et se rapprocher des conditions d'extrusion, une géométrie hélicoïdale a été mise à disposition. Premièrement, grâce à cette nouvelle cellule sous pression, l'importance des liaisons hydrogènes, créées par la configuration du polyamide 11, est mise en évidence et explique la viscosité élevée de celui-ci. Deuxièmement, la quantification de la plastification, lorsque le polymère est exposé à de la vapeur d'eau et du dioxyde de carbone supercritique, est mesuré. Ce résultat, combiné à différentes lois, à des approximations thermodynamique et à la compréhension de l'interaction entre les liaisons hydrogènes du polymère et la molécule d'eau ou de dioxyde carbone, conduit à un mécanisme de plastification. Finalement, les différentes géométries permettent de donner différentes informations; un coté procédé qui détermine des cinétiques d'incorporation proches de celles du futur procédé et un aspect diffusionnel avec l'approximation de temps de diffusion grâce à la géométrie Couette. / Mastering extrusion and synthesis processes of melt polymers means to understand their physical properties and, more especially, their rheological behavior. However, these processes operate, sometimes, at particularly high temperature and pressure which are difficult to reach with a classical rheometer (in this thesis the range is between 200°C and 270°C and between 10bars and 200bars). This PhD thesis suggests a new method to understand rheological properties of melt polyamide 11 above its melting point (185°C) and, also, under steam or supercritical carbon dioxide pressure. Moreover, the possibility to replace the classical Couette geometry by a helical ribbon impeller, in order to mimic somehow the mixing process, allows being closer to the extrusion process and opens new perspectives: At first, thanks to this new pressure cell, the high viscosity of the polyamide 11 is explained by the important impact of hydrogen bond, involved by the polyamide 11 structure. Secondly, beyond the plasticization quantification, the plasticization knowledge as a function of temperature, steam and supercritical carbon dioxide pressure is improved. Furthermore, a mechanism, based on hydrogen bond interaction with water and carbon dioxide molecules, is presented and strengthened thanks to the use of different thermodynamical laws and equations of state to describe the steam pressure. To conclude, the geometry change allows obtaining different information. On the one hand, a kinetics incorporation of supercritical carbon dioxide in the polyamide 11, closer to the future process, is determined. On the other hand, their comparison combined to the no-mixing condition encountered in the Couette geometry leads to approach the diffusion time of the CO2 in the polymer.

The growing demand in portable and compact consumer devices and appliances has resulted in the need for the miniaturisation of electronic components. These miniaturised electronic components are sensitive and susceptible to damage by voltages as low as 20V. Electrically conductive styrenic thermoplastics are widely used in electronic packaging applications to protect these sensitive electronic components against electro-static discharge (ESD) during manufacturing, assembly, storage and shipping. Such ESD applications often require the optimal volume resistance range of ≥ 1.0x105 to < 1.0x108 Ω. The best known method to render styrenic thermoplastics conductive is by the incorporation of conductive fillers, such as carbon black but the main limitation is the difficulty in controlling the conductivity level due to the steep percolation curve. Thus the aim of this research is to develop electrically conductive styrenic thermoplastics by blending several styrenic resins with polymeric conductive additives to achieve optimal volume resistance range for ESD applications with the ease in controlling the conductivity level.

The goal of this thesis has been to throw light on a selection of open problems in chemical and biological physics using the general principles of statistical mechanics. These problems are all broadly concerned with the role of fluctuations in the dynamics of macromolecular systems. More specifically, they are concerned with identifying the microscopic roots of a number of interesting and unusual effects, including fractional viscoelasticity, anomalous chain cyclization dynamics in crowded environments, subdifffusion in hair bundles, symmetries in the work distributions of stretched polymers, heterogeneities in the geometries of reptation channels in polymer melts, and non-Gaussianity in the distributions of the end products of gene expression. I have shown here that all these effects are expressions of essentially the same underlying process of stochasticity, which can be described in terms of the dynamics of a point particle or a continuous curve that evolves in simple potentials under the action of white or colored Gaussian noise [8]. I have also shown that this minimal model of time-dependent behavior in condensed phases is amenable to analysis, often exactly, by path integral methods [13-15], which are naturally suited to the treatment of random processes in many-body physics. The results of such analyses are theoretical expressions for various experimentally measured quantities, comparisons with which form the basis for developing physical intuition about the phenomena under study. The general success of this approach to the study of stochasticity in biophysics and molecular biology holds out hopes of its application to other unsolved problems in these fields. These include electrical transport in DNA [143], quantum coherence in photosynthesis [144], power generation in molecular motors [145], cell signaling and chemotaxis [146], space dependent diffusion [147], and self-organization of active matter [148], to name a few. Most of these problems are characterized by non-linearities of one kind or another, so they add a new layer of complexity to the problems considered in this thesis. Although path integral and related field theoretic methods are equipped to handle such complexities, the attendant calculations are expected to be non-trivial, and the challenge to theory will be to devise effective approximation schemes for these methods, or to develop new and more sophisticated methods altogether.

In-line rheological and process measurements are studied, during the primary injection phase, as a potential aid to closed loop process control for injection moulding. The feasibilities of attaining rheological and process measurements of sufficient accuracy and precision for use in process control are investigated. The influence of rheological and process measurements on product quality are investigated for semi-crystalline thermoplastic materials. A computer based process and machine parameter monitoring system is utilised to provide accurate and precise process data for analysis

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.

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.