The value of the surface charge density of polypropylene reported in literature has a three order of magnitude discrepancy. Nauruzbayeva et al report a 0.7nCcm−2 as the surface charge density of polypropylene as measured using the charge of electrified droplets[1]. Meagher and Craig reported result 111nCcm−2 as estimated by electric double layer theory from colloidal probe Atomic force microscopy (AFM) force spectroscopy [2]. We show that oxidation of hydrophobic surfaces as a potential mechanism in origin of these surface charges. Using colloidal probe AFM We measured the surface charge densities of Teflon AF, perfluorodecanethiol, Perfluorodecyltrichlorosilane(FDTS), Octadecyltrichlorosilane, polystyrene, and polypropylene. Also, The pH dependence of the surface charge density for FDTS was studied and it shows the behavior expected of a weak acid in response to pH. We suspect that the origin of the surface charges is mostly likely impurities or surface oxidation. We conclude that the electrometer and dispensed droplets approach cannot detect these charges because of the process of de-wetting all the surface be neutralized to maintain charge neutrality. This explanation supports Nauruzbayeva et al claims about surface bound charges[1].

A funcionalização de materiais poliméricos para a produção de superfícies superhidrofóbicas é importante para uma série de aplicações, principalmente as associadas com superfícies autolimpantes e anti-aderentes. Uma abordagem para obter superhidrofobicidade é combinar polímeros hidrofóbicos com outros materiais passíveis de ser microestruturados. Neste estudo, copolímeros hidrofóbicos foram sintetizados através de polimerização radicalar convencional usando os monômeros 2,2,3,3,4,4,5,5 octafluorpentil metacrilato (OFPMA) ou 2,2,2 trifluoretil metacrilato (TFEMA) copolimerizado com o azo monômero 4-[N-etil-N-(2-metacriloxi-etil)]amino-4-nitro-azobenzeno (DR13-MA) em proporções distintas. A polimerização foi bem sucedida, apresentando massas molares acima de 10.000 g / mol, com uma polidispersividade relativamente baixa. Os copolímeros e homopolímeros, derivados de OFPMA e TFEMA - usados para comparação tiveram sua estrutura confirmada através de espectroscopia no infravermelho (FTIR) e ressonância magnética nuclear (RMN). A proporção de azo monômero incorporada foi estimada por RMN e espectroscopia no UV-vis e foram condizentes com a relação utilizada, ou seja, 10, 20 e 30% em massa. Foram formados filmes de Langmuir estáveis dos copolímeros na interface ar / água, cuja isoterma de pressão superficial apresentou transição de fase provavelmente atribuída a um rearranjo molecular. O potencial de superfície dos filmes dos copolímeros foi negativo, o que indica que os átomos de flúor estavam direcionados para o ar. Esta organização molecular foi mantida após a transferência de filmes sobre substratos sólidos na forma de filmes Langmuir-Blodgett (LB), formando superfícies hidrofóbicas com ângulos de contato próximos de 90 º para todos os copolímeros, independentemente do número de camadas depositadas. A natureza organizada dos filmes LB não contribuiu para a hidrofobicidade, pois o ângulo de contacto é semelhante ao obtido com filmes cast. Grades de relevo foram inscritas nos filmes cast, mas o ângulo de contato não foi afetado significativamente. Portanto, uma otimização na inscrição de nanoestruturas será necessária para se alcançar a superhidrofobicidade. / The functionalization of polymer materials to produce superhydrophobic surfaces is an important goal for a number of applications, especially those associated with self-cleaning and anti-adherent surfaces. A possible approach to achieve superhydrophobicity is to combine hydrophobic polymers with other materials amenable to be microstructured. In this study, hydrophobic copolymers were synthesized through conventional radicalar polymerization using the monomers 2,2,3,3,4,4,5,5 octafluorpenthyl methacrylate (OFPMA) or 2,2,2 trifluorethyl methacrylate (TFEMA) copolymerized with the azomonomer 4-[N-ethyl-N-(2methacryloxy-ethyl)]amine-4-nitrobenzene methacrylate (DR-13MA) in distinct proportions. Polymerization was successful leading to molar masses above 10,000 g/mol, with a relatively low polydispersity. The copolymers and the homopolymers from OFPMA and TFEMA used for comparison had their structure confirmed with Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) measurements. The proportion of azomonomer incorporated estimated via NMR was consistent with that determined with UV-vis. spectroscopy for the relative concentrations used, namely 10, 20 and 30% in mass. The copolymers formed stable Langmuir films at the air/water interface, whose surface pressure isotherms featured a phase transition probably associated with molecular rearrangement. The surface potential of the condensed copolymer Langmuir films was negative, which indicates that the fluorine atoms were directed toward the air. This molecular organization was maintained upon film transfer onto solid substrates in the form of Langmuir-Blodgett (LB) films, leading to hydrophobic surfaces with contact angles close to 90º for both copolymers, which did not depend on the number of layers deposited. The organized nature of the LB films did not contribute to the hydrophobicity, however, as similar contact angles were measured for the cast films made with the copolymers. Surface-relief gratings could be inscribed on the cast films, but the contact angle was not affected significantly. Therefore, an optimization in the inscription of such nanostructures will be required for achieving superhydrophobicity.

A funcionalização de materiais poliméricos para a produção de superfícies superhidrofóbicas é importante para uma série de aplicações, principalmente as associadas com superfícies autolimpantes e anti-aderentes. Uma abordagem para obter superhidrofobicidade é combinar polímeros hidrofóbicos com outros materiais passíveis de ser microestruturados. Neste estudo, copolímeros hidrofóbicos foram sintetizados através de polimerização radicalar convencional usando os monômeros 2,2,3,3,4,4,5,5 octafluorpentil metacrilato (OFPMA) ou 2,2,2 trifluoretil metacrilato (TFEMA) copolimerizado com o azo monômero 4-[N-etil-N-(2-metacriloxi-etil)]amino-4-nitro-azobenzeno (DR13-MA) em proporções distintas. A polimerização foi bem sucedida, apresentando massas molares acima de 10.000 g / mol, com uma polidispersividade relativamente baixa. Os copolímeros e homopolímeros, derivados de OFPMA e TFEMA - usados para comparação tiveram sua estrutura confirmada através de espectroscopia no infravermelho (FTIR) e ressonância magnética nuclear (RMN). A proporção de azo monômero incorporada foi estimada por RMN e espectroscopia no UV-vis e foram condizentes com a relação utilizada, ou seja, 10, 20 e 30% em massa. Foram formados filmes de Langmuir estáveis dos copolímeros na interface ar / água, cuja isoterma de pressão superficial apresentou transição de fase provavelmente atribuída a um rearranjo molecular. O potencial de superfície dos filmes dos copolímeros foi negativo, o que indica que os átomos de flúor estavam direcionados para o ar. Esta organização molecular foi mantida após a transferência de filmes sobre substratos sólidos na forma de filmes Langmuir-Blodgett (LB), formando superfícies hidrofóbicas com ângulos de contato próximos de 90 º para todos os copolímeros, independentemente do número de camadas depositadas. A natureza organizada dos filmes LB não contribuiu para a hidrofobicidade, pois o ângulo de contacto é semelhante ao obtido com filmes cast. Grades de relevo foram inscritas nos filmes cast, mas o ângulo de contato não foi afetado significativamente. Portanto, uma otimização na inscrição de nanoestruturas será necessária para se alcançar a superhidrofobicidade. / The functionalization of polymer materials to produce superhydrophobic surfaces is an important goal for a number of applications, especially those associated with self-cleaning and anti-adherent surfaces. A possible approach to achieve superhydrophobicity is to combine hydrophobic polymers with other materials amenable to be microstructured. In this study, hydrophobic copolymers were synthesized through conventional radicalar polymerization using the monomers 2,2,3,3,4,4,5,5 octafluorpenthyl methacrylate (OFPMA) or 2,2,2 trifluorethyl methacrylate (TFEMA) copolymerized with the azomonomer 4-[N-ethyl-N-(2methacryloxy-ethyl)]amine-4-nitrobenzene methacrylate (DR-13MA) in distinct proportions. Polymerization was successful leading to molar masses above 10,000 g/mol, with a relatively low polydispersity. The copolymers and the homopolymers from OFPMA and TFEMA used for comparison had their structure confirmed with Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) measurements. The proportion of azomonomer incorporated estimated via NMR was consistent with that determined with UV-vis. spectroscopy for the relative concentrations used, namely 10, 20 and 30% in mass. The copolymers formed stable Langmuir films at the air/water interface, whose surface pressure isotherms featured a phase transition probably associated with molecular rearrangement. The surface potential of the condensed copolymer Langmuir films was negative, which indicates that the fluorine atoms were directed toward the air. This molecular organization was maintained upon film transfer onto solid substrates in the form of Langmuir-Blodgett (LB) films, leading to hydrophobic surfaces with contact angles close to 90º for both copolymers, which did not depend on the number of layers deposited. The organized nature of the LB films did not contribute to the hydrophobicity, however, as similar contact angles were measured for the cast films made with the copolymers. Surface-relief gratings could be inscribed on the cast films, but the contact angle was not affected significantly. Therefore, an optimization in the inscription of such nanostructures will be required for achieving superhydrophobicity.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23503号 / 工博第4915号 / 新制||工||1768(附属図書館) / 京都大学大学院工学研究科機械理工学専攻 / (主査)教授 黒瀬 良一, 教授 花崎 秀史, 教授 岩井 裕 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

No description available.

L’utilisation de nanoparticules (NPs) dans un milieu biologique est de plus en plus importante, alors que leur assimilation et leur toxicité reste peu maitrisée. Dans ce contexte l’objectif de ce travail est d’étudier l’interaction entre nanoparticules de dioxyde de titane (TiO2) avec des protéines ainsi que leur possible impact sur leurs propriétés structurales. Trois protéines d’intérêt ont été choisies: une protéine de la matrice extra cellulaire, le collagène, et deux protéines du plasma sanguin, l’albumine et le fibrinogène. Le choix a été basé sur l’importance biologique de ces protéines lors des interactions avec des NPs et sur la différence de leurs structures tridimensionnelles. L’étude de l’interaction protéine-NPs a été réalisée en solution et en phase adsorbée dans différentes conditions de température et de temps d’incubation. Dans un premier temps des nanoparticules de dioxyde de titane ont été synthétisées par voie solvothermale, afin d’obtenir des nanoparticules de tailles et de formes contrôlées. Deux types de nanoparticules ont été sélectionnés en vues d’étudier l’effet de forme et de taille sur l’interaction protéines-nanoparticules: des nano-sphères de diamètre de 8 à 10 nm et des nano-bâtonnets d’environ 8 nm de largeur et 23 nm longueur. Leur comportement en solution physiologique ainsi que leur réactivité ont été caractérisé par DSL et absorption UV montrant une inhibition des propriétés catalytiques ainsi qu’une forte agrégation en solution tampon phosphate saline (PBS). Dans un deuxième temps les propriétés d’adsorption du collagène en présence de nanoparticules furent étudiées sur deux types de surfaces l’une hydrophobe et l’autre hydrophile par XPS et imagerie AFM ainsi que par des mesures de forces AFM. Le comportement du collagène en solution en présence de nanoparticules a été caractérisé par ATR liquide. Les observations suggèrent que la formation des fibrilles à l’interface surface-solution de collagène est affectée par le caractère hydrophobe ou hydrophile de la surface ainsi que par la présence de nanoparticules. Enfin les propriétés d’adsorption de la HSA et du fibrinogène en présence de nanoparticules furent étudiées sur une surface hydrophile par imagerie AFM et analyses XPS. Leur comportement en solution en présence de nanoparticules fut étudié par ATR liquide. Les résultats suggèrent deux comportements différents des protéines en présence de nanoparticules pouvant être attribués propriétés physicochimiques différentes des protéines. La HSA subit d’importants changements structuraux en présence de nanoparticules contrairement au fibrinogène.L’étude en phase liquide de l’interaction protéine-nanoparticules couplé à l’étude en phase adsorbées des protéines permet de déterminer les phénomènes impliqués lors de cette interaction ainsi que leurs conséquences sur les protéines, de plus l’utilisation de nanoparticules de taille et forme différentes permet d’étudier la sensibilité des protéines à ces facteurs. / The extensive use of NPs in a biological environment raises the problem of their assimilation or their toxicity, the main objective of this work is to study the interaction of TiO2 NPs with proteins as well as their possible impact on the structural properties of proteins. Three proteins were chosen, a protein of the extracellular matrix, the collagen, and two proteins of the plasma blood, the albumin and the fibrinogen for their biological importance as well as for their various tridimensional structures. The study of the protein-nanoparticle interaction was realized in solution and in the adsorbed phase under various condition of temperature and incubation time. First, titanium dioxide NPs were synthesized by a solvothermal method, NPs with controlled size and form were obtained. Two types of NPs were selected in order to study the effect of shape and size on the protein-NPs interaction: nano-spheres with a diameter of 8 to 10 nm and nano-rods with a width about 8 nm and a length of 23 nm. The behavior in physiological solution as well as the reactivity were characterized by DSL and UV absorption showing an inhibition of catalytic properties as well as a strong aggregation in phosphate buffer saline solution (PBS). Second, the adsorption properties of the collagen in the presence of NPs were studied on two kinds of surfaces, one hydrophobic and the other hydrophilic by XPS and AFM imaging as well as by AFM force measurements. The behavior of the collagen in solution in the presence of NPs was characterized by liquid ATR. The observations suggest that the formation of fibrils at the surface- collagen solution interface is affected by the hydrophobic or the hydrophilic character of the surface as well as by the presence of NPs. In the last part the adsorption properties of HSA and fibrinogen in the presence of NPs were studied on a hydrophilic surface by AFM imaging and XPS analyses. Their behaviors in solution in the presence of NPs were studied by liquid ATR. The results suggest two different behaviors of proteins in the presence of NPs, which can be attributed to the different physico-chemical properties of the proteins. HSA undergoes important structural changes in the presence of NPs but not fibrinogen. The study in the liquid phase of the protein-nanoparticle interaction, coupled to study of proteins in the adsorbed phase allows determining the involved phenomenon during the protein-nanoparticle interaction as well as the consequences on protein adsorption. Moreover, the use of NPs with different sizes and shapes revealed the sensitivity of proteins to these factors.

No description available.

This thesis presents investigations on air-cooled air gap membrane distillation for desalination and the application of radial waveguides based on total internal reflection for solar thermal desalination. Using an air-cooled design for an air gap membrane distillation (AGMD) process may result in significantly lower energy requirements for desalination. Experiments were conducted on AGMD module to study the effect of air gap, support mesh conductivity and hydrophobicity, condensing surface hydrophobicity. A novel modular design was used in which modules could be used in a series configuration to increase the flux value for the distillate. The output from the series configuration was found to have about three times the production from a single pass water-cooled system with the same temperature difference between the saline and clear water streams. The results also indicated that the mesh conductivity had a favorable effect on the flux value whereas the hydrophobicity of the mesh had no significant effect. The hydrophobicity of the condensing surface was favorable on two accounts: first, it led to an increase in the flux of the distillate at temperatures below 60 °C and second, the temperature difference of the saline feed when it enters and leaves the module is lower which can lead to energy savings and higher yields when used in a series configuration. The second part of the thesis considers use of low-cost radial waveguides to collect and concentrate solar energy for use in thermal desalination processes. The optical-waveguide-based solar energy concentrators are based on total internal reflection and minimize/eliminate moving parts, tracking structures and cost. The use of optical waveguides for thermal desalination is explored using an analytical closed-form solution for the coupled optical and thermal transport of solar irradiation through a radial planar waveguide concentrator integrated with a central receiver. The analytical model is verified against and supported by computational optical ray tracing simulations. The effects of various design and operating parameters are systematically investigated on the system performance, which is quantified in terms of net thermal power delivered, aperture area required and collection efficiency. Design constraints like thermal stress, maximum continuous operation temperature and structural constraints have been considered to identify realistic waveguide configurations which are suitable for real world applications. The study provides realistic estimates for the performance achievable with radial planar waveguide concentrator-receiver configuration. In addition to this, a cost analysis has been conducted to determine the preferred design configurations that minimize the cost per unit area of the planar waveguide concentrator coupled to the receiver. Considering applications to thermal desalination which is a low temperature application, optimal design configuration of waveguide concentrator-receiver system is identified that result in the minimum levelized cost of power (LCOP). / Master of Science

A corrosão é um fenômeno de interface que deteriora um metal através de reações químicas ou eletroquímicas, sendo caracterizada como um processo espontâneo, onde os materiais são transformados do estado metálico para uma forma combinada, decorrente da interação dos compostos metálicos com as substâncias do meio que estão inseridos. Como os prejuízos oriundos de processos corrosivos são elevados (estimativas mostram que os valores variam em torno de 3% a 4% do PIB de uma nação), estudos que minimizem estes processos são de vital importância econômica. Nos últimos anos, diversas pesquisas foram realizadas com o intuito de estudar superfícies hidrofóbicas e super-hidrofóbicas devido à sua função de autolimpeza, baixa aderência de contaminantes e proteção contra os efeitos corrosivos. Estudos recentes propõem a utilização de ácidos carboxílicos como percussores à formação destas camadas protetoras, sendo que melhores resultados foram obtidos utilizando ácidos carboxílicos de cadeias longas (acima de 11 carbonos). O ácido n-tetradecanóico (CH3(CH2)12COOH) pode ser utilizado sobre cobre e, após 10 dias de imersão em solução alcoólica de 0,06 mol/L, uma película super-hidrofóbica é formada sob o substrato, porém as características superficiais do metal são afetadas e uma camada esverdeada de carboxilato de cobre é formada. O presente trabalho, além de comprovar o efeito protetor desta camada superhidrofóbica formada, propôs a utilização do ácido n-tetradecanóico em um tratamento superficial, de forma a atuar como uma película protetora contra processos corrosivos, considerando curtos períodos de imersão em solução de ácido mirístico de forma a preservar as características superficiais do metal utilizado e torná-lo comercialmente e esteticamente mais atrativo. Os metais avaliados foram: cobre, latão e aço carbono. As técnicas eletroquímicas empregadas para a avaliação da película formada foram: curva de polarização, resistência de polarização linear (Rp) e espectroscopia de impedância eletroquímica (EIE). Medidas de ângulo de contato foram realizadas a fim de comprovar a viii hidrofobicidade do filme formado e espectroscopia de infravermelho e Raman, além da difratometria de raios X, a fim de caracterizar sua composição química. Melhores resultados foram obtidos para cobre, onde os ensaios comprovaram um aumento da hidrofobicidade da superfície metálica à medida que se aumentava o tempo de imersão dos corpos-de-prova em solução alcoólica 0,06 mol/L de ácido ntetradecanóico, atingindo valores de 116,1o e 149,8o após, respectivamente, 12 horas e 5 dias de imersão. Além disso, através de medidas de espectroscopia de impedância eletroquímica, também foi avaliado o grau de proteção da película hidrofóbica formada com relação ao substrato puro, sendo observado um aumento na proteção da superfície após 12 horas de imersão. / Corrosion is an interface phenomenon that deteriorates a metal by chemical or electrochemical reactions. It is characterized as a spontaneous process, where materials are transformed from the metallic state to a combined form. As corrosive processes damages are high (estimates show that the values vary around 3% to 4% of a nation GDP), studies that minimize corrosion reactions are of vital economic importance. Recently, several studies were performed in order to study hydrophobic and superhydrophobic layers due to its self-cleaning function, low adherence of contaminants and protection against corrosive effects. Recent studies propose the use of carboxylic acids as precursors to the formation of such protective layers, with best results being obtained using long chain carboxylic acids (up to 11 carbons). Over copper, the usage of n-tetradecanoic acid (CH3(CH2)12COOH) has showed good results after 10 days immersion in 0.06 mol/L ethanolic solution. Experimental results proved that the super hydrophobic surface could improve significantly the corrosion resistance of copper, although the surfaces have been strongly modified and a green oxidation layer (which is a copper carboxylate) has been formed over the etched copper surface. Besides proving the protective effect of the super-hydrophobic layer formed, this work also studied the use of n-tetradecanoic acid as a temporary protective layer, considering short immersion periods. In this way, the metal surface characteristics were preserved. The metals studied were: copper, brass and carbon steel. The electrochemical techniques employed for evaluation of the formed film were: polarization curves, linear polarization resistance (Rp) and electrochemical impedance spectroscopy (EIS). Contact angle measurements were performed to prove the hydrophobicity of the film and X-ray diffraction, Raman and Infrared spectroscopy were also utilized to characterize its composition. x Test samples of these metals were immersed, at ambient temperature, in 0.06 mol/L of n-tetradecanoic ethanolic solution, for different immersion periods, in order to monitor the formation of the protective layer and its hydrophobicity. Furthermore, in order to study the formation and persistence of the formed film, electrochemical tests were also performed in 3.5 wt. % NaCl solution. The results obtained for copper demonstrate an increase of the metal surface hydrophobicity for longer immersion time in 0.06 mol/L n-tetradecanoic acid solution, reaching values of 116.1o and 149.8o after, respectively, 12 hours and 5 days of immersion. Furthermore, the degree of protection of hydrophobic film was also evaluated by electrochemical impedance spectroscopy measurements and the best results were obtained for 12hs of immersion.

The use of hydrophobic surfaces is important for many processes both in nature and industry. Interactions between hydrophobic species play a key role in industrial applications such as water-cleaning procedures and pitch control during papermaking but they also give information on how to design surfaces like hydrophobic mineral pigments. In this thesis, the influence of surface properties on wetting and interaction forces has been studied. Surfaces with close-packed particles, pore arrays, randomly deposited nanoparticles as well as reference surfaces were prepared. The atomic force microscope (AFM) was utilized for force and friction measurements while contact angles and confocal Raman microscopy experiments were mainly used for wetting studies. The deposition of silica particles in the size range of nano- to micrometers using the Langmuir-Blodgett (LB) technique resulted in particle coated surfaces exhibiting hexagonal close-packing and close to Wenzel state wetting after hydrophobization. Force measurements displayed long-range interaction forces assigned to be a consequence of air cavitation. Smaller roughness features provided larger forces and interaction distances interpreted as being due to fewer restrictions of capillary growth. Friction measurements proved both the surface structure and chemistry to be important for the observed forces. On hydrophobic pore array surfaces, the three-phase contact line of water droplets avoided the pores which created a jagged interface. The influence of the pores was evident in the force curves, both in terms of the shape, in which the three-phase contact line movements around the pores could be detected, as well as the depth of the pores providing different access and amount of air. When water/ethanol mixtures were used, the interactions were concluded to be due to ethanol condensation. Confocal Raman microscopy experiments with water and water/ethanol mixtures on superhydrophobic surfaces gave evidence for water depletion and ethanol/air accumulation close to the surface. Force measurements using superhydrophobic surfaces showed extremely long-range interaction distances. This work has provided evidence for air cavitation between hydrophobic surfaces in aqueous solution. It was also shown that the range and magnitude of interaction forces could, to some extent, be predicted by looking at certain surface features like structure,roughness and the overall length scales. / <p>QC 20121011</p>