Thesis (Ph. D.)--Open University. BLDSC no. DX226217.

published_or_final_version / Mechanical Engineering / Master / Master of Philosophy

Electrochemical promotion (EP) is a new way of controlling catalytic performance. It is implemented by depositing porous thin film metal catalysts on solid electrolyte supports where they act as both a catalyst and a working electrode of an electrochemical cell. The technique entails electrochemical pumping of ions from the solid electrolyte to the surface of the catalytically active metal film with which it is in contact. In short, controlling the potential difference of the electrochemical cell controls the coverage of promoters on the catalyst while a catalytic reaction is taken place. Thus, it provides a unique method for studying promotion in heterogeneous catalysis. My research has focused on elucidating the phenomena that underlie the EP effect. The resulting advances in fundamental understanding have been used to exploit EP as a tool to study alkali promotion in new applications in heterogeneous catalysis and to diversify the catalytic chemistry that can be addressed by EP. Thus, we have used conventional and spatially resolved in situ photoelectron spectroscopic data to demonstrate that EP of thin film metal catalysts deposited on solid electrolyte supports is the result of the spillover phenomena at the three phase boundary between the electrolyte, the catalyst and the gas phase. Ions from the electrolyte are discharged at the catalyst/ electrolyte interface and migrate to cover the catalyst surface whose properties are thereby strongly altered. This is the first time that such advanced spectroscopic techniques have been brought to bear on this fascinating and complex problem. Reactor measurements along with post-reaction photoelectron spectroscopies were used in order to: (i) establish the mechanism of reaction, (ii) determine the mode of promoter action and (iii) identify the chemical state of the promoter phase, in the Na-promoted catalytic control of toxic emissions. Very large increases both in activity and in selectivity of the catalysts were achieved and point the way towards further developments and possible applications. Finally, the use of EP as a mechanistic probe in surface catalysed polymerisation reactions has been demonstrated for the first time, broadening the range of utility of the extraordinary phenomenon of EP.

The gas phase etching of thermal silicon dioxide films was investigated with in situ Fourier Transformed Infrared Spectroscopy (FTIR) and ex situ X-ray Photoelectron Spectroscopy (XPS). The initiation process, the bulk etching of the oxide, and the termination mechanism were characterized as a function of reactant concentration, temperature, and pressure. The experiments were carried out in a custom made vessel with a gas panel and a data acquisition and control system (DA&C) capable of lowering flow and pressure disturbances originated by reactant introduction. The FTIR technique used to monitor the reaction in real time allowed distinguishing reactions that initiated in a gas/solid regime from reactions that started in a gas/liquid/solid regime. This study was focused on the gas/solid initiation process in order to expand the general assumption in published works that a condensed layer is previously required to initiate and sustain the reaction. It was found in this investigation that, depending on the experimental parameters, the water layer is not always a requisite for the initiation of the reaction but a consequence of the etching process. The FTIR data also showed the role in the initiation process of gas phase heterogeneous associated species, specifically (HF)H₂O and (HF)₂H₂O. After the initiation period, the experimental conditions determined the amount of water present on the surface of the sample, which in turn determined the local environment of the reaction and by extension the etching species. Reactions developing in a gas/solid regime were found to be slow, with etching rates of less than 1 °A/sec. Contrarily, reactions taking place in a gas/liquid/solid regime reached etching rates of 100 °A/sec, a maximum value determined by transport limitations. The condensed layer was found to be especially sensitive to temperature since a variation of 15 ° C changed the local environment from gas/liquid/solid to gas/solid. Finally, it was corroborated through the XPS analysis that the removal process in the gas phase leaves the silicon surfaces with high fluorine and oxygen concentrations in the form of SiFₓ and SiOH.

Nesta dissertação avaliou-se o uso de óleos vegetais na descontaminação \"ex-situ\" de solo contaminado por compostos policíclicos aromáticos (PAHs). O processo trata solo com microemulsão (µE) formada por água (A) /tensoativo não-iônico comercial (S) C9/11EO4 /\"óleo\" (O), sendo este ésteres metílicos dos óleos de coco (CME), babaçu (BME), e fração saturada (SME) e insaturada (LME) do azeite de dendê. Estudamos os diagramas de fase dos sistemas acima, em função de ? = O/(A+O) e ? = S/(S+A+O), em peso. Os sistemas pseudo- ternários foram estudados em função da temperatura, T para diferentes ? (? constante) e ? (? constante). Os diagramas de fase foram qualitativamente similares àqueles obtidos para sistemas com água /alcano /tensoativo não- iônico homogêneo. Eles apresentaram o assim chamado diagrama tipo \"peixe\". O \"corpo do peixe\" é trifásico enquanto que sua \"cauda\" é monofásica e isotrópica. As duas áreas se encontram na Temperatura de balanço hidrofílico- lipofílico, THLB (Schubert e Kaler, 1996). As principais diferenças obtidas entre os diagramas baseados em óleos vegetais e os de sistemas água/ alcano/ tensoativo não iônico homogêneo foram: a) Para T em função de ?, o diagrama tipo \"peixe\" é extremamente distorcido para cima, e seu \"corpo\" (área trifásica) é muito reduzido; b) Para T em função de ? (diagrama do \"canal\"), a fase isotrópica ocorre apenas para ? maior ou igual a 0,5. As microestruturas das monofases isotrópicas foram caracterizadas por reologia, difração de raios X e espalhamento quasi-elástico de luz (QELS). A baixa viscosidade e o comportamento Newtoniano destes líquidos mostraram que estes não contém cristais líquidos cúbicos. Esta conclusão foi corroborada por medidas de difração de raios X, que não apresentaram padrões de difração característicos de estruturas organizadas a longa distância. Os coeficientes de difusão das monofases foi medido por QELS. Isto indicou que as soluções monofásicas são compostas por µEs bicontínuas ou água/óleo (A/O), com THLB=37,5ºC para CME e BME e 42,5ºC para SME e LME, respectivamente. Testes indicaram que estrutura da µE, razão µE/solo, e tempo de contato são variáveis importantes na extração. A quantidade de µE deve ser suficiente para molhar toda a superfície do solo, sem causar redeposição dos PAHs. A melhor razão µE/solo foi 6. As µEs bicontínuas foram agentes descontaminantes mais eficientes que µEs A/O, provavelmente por dessorverem PAH do solo pelo decréscimo da tensão interfacial. A descontaminação pelas µEs bicontínuas foi 35% mais eficiente que a extração por tolueno em Soxhlet por 6h (?=0,5 e 0,6, tempo de contato 3h à THLB, razão µE/solo=6). O éster usado influencia principalmente a formação e estabilidade da µE. Depois da descontaminação, o solo foi lavado com água e sua biodisponibilidade foi avaliada pela medição da densidade de carga. Esta aumentou em 63%, 86%, 100% e 162% para as amostras que foram tratadas com µEs com CME, SME, LME e BME, respectivamente (µEs bicontínuas, ?=0,5 e ?=0,3). / In the present project, we were interested in assessing the use of Brazilian vegetable oils in the \"ex-situ\" decontamination of soils from polycyclic aromatic hydrocarbons (PAHs). In this process, contaminated soil is treated with a microemulsion (µE) composed of water (W) /commercial non-ionic surfactant (S) C9/11EO4 /oil (O). The latter term refers to the methyl esters of coconut oil (CME), babaçu oil (BME), and the saturated (SME), and unsaturated (LME) fractions of palm oil. Phase diagram of the above mentioned systems were studied. We used weight fractions, ? = (O / W + O) e ? = (S / S + W + O). The pseudo-ternary systems were then studied as a function of temperature, at different ? (? constant) and ? (? constant). The phase diagrams were qualitatively similar to those previously obtained for systems of water/alkane/homogeneous non-ionic surfactant. These show the so-called \"fish\" type phase diagram. The fish \"body\" is triphasic whereas its \"tails\" is monophasic and isotropic. Both areas meet at the so-called hydrophilic-lipophilic temperature, THLB (Schubert and Kaler, 1996). The following are the main differences between the vegetable oil-based phase diagrams and those of homogeneous component systems: a) The fish diagram is severely skewed upward, and its body area is much reduced; b) In the temperature versus ? channel\" phase diagram; the monophasic region exists only at ? equal or above 0.5. The microstructures of the monophasic regions were studied by rheology, X ray diffraction, and quasi-elastic light scattering, QELS. The low viscosity and Newtonian behavior of these liquids shows that they do not contain cubic liquid crystals. This conclusion was corroborated by X ray diffraction measurements, which did not show diffraction patterns characteristic of systems of long-range structural order. The diffusion coefficients of the species involved were measured with QELS. These indicated that monophasic solutions are composed of bicontinuous and W/O microemulsions, whose THLB, is 37.5 ºC for CME, BME, and 42.5 ºC for SME and LME, respectively. The structure of the µE employed, µE/soil ratio, and contact time are important extraction variables. The amount of the µE should be sufficient to wet the surface of the soil, without causing PAHs redeposition. The optimum ratio was 6. Bicontinuous µEs were more efficient decontaminators than W/O microemulsions probably because they desorb PAH from soil by decreasing the associated interfacial tension. Decontamination by the former µEs was 35% more efficient than by hot toluene (6 hours, Soxhlet). After decontamination, the soil was washed with water, and its bioavailability assessed by measuring its charge density. Relative to the original soil, the charge density of decontaminated soil increased by 63%, 86%, 100% and 162%, for washed samples, which were decontaminated with µEs of CME, SME, LME and BME, respectively (µEs BI; ? = 0.5 e ? = 0.3).

Nesta dissertação avaliou-se o uso de óleos vegetais na descontaminação \"ex-situ\" de solo contaminado por compostos policíclicos aromáticos (PAHs). O processo trata solo com microemulsão (µE) formada por água (A) /tensoativo não-iônico comercial (S) C9/11EO4 /\"óleo\" (O), sendo este ésteres metílicos dos óleos de coco (CME), babaçu (BME), e fração saturada (SME) e insaturada (LME) do azeite de dendê. Estudamos os diagramas de fase dos sistemas acima, em função de ? = O/(A+O) e ? = S/(S+A+O), em peso. Os sistemas pseudo- ternários foram estudados em função da temperatura, T para diferentes ? (? constante) e ? (? constante). Os diagramas de fase foram qualitativamente similares àqueles obtidos para sistemas com água /alcano /tensoativo não- iônico homogêneo. Eles apresentaram o assim chamado diagrama tipo \"peixe\". O \"corpo do peixe\" é trifásico enquanto que sua \"cauda\" é monofásica e isotrópica. As duas áreas se encontram na Temperatura de balanço hidrofílico- lipofílico, THLB (Schubert e Kaler, 1996). As principais diferenças obtidas entre os diagramas baseados em óleos vegetais e os de sistemas água/ alcano/ tensoativo não iônico homogêneo foram: a) Para T em função de ?, o diagrama tipo \"peixe\" é extremamente distorcido para cima, e seu \"corpo\" (área trifásica) é muito reduzido; b) Para T em função de ? (diagrama do \"canal\"), a fase isotrópica ocorre apenas para ? maior ou igual a 0,5. As microestruturas das monofases isotrópicas foram caracterizadas por reologia, difração de raios X e espalhamento quasi-elástico de luz (QELS). A baixa viscosidade e o comportamento Newtoniano destes líquidos mostraram que estes não contém cristais líquidos cúbicos. Esta conclusão foi corroborada por medidas de difração de raios X, que não apresentaram padrões de difração característicos de estruturas organizadas a longa distância. Os coeficientes de difusão das monofases foi medido por QELS. Isto indicou que as soluções monofásicas são compostas por µEs bicontínuas ou água/óleo (A/O), com THLB=37,5ºC para CME e BME e 42,5ºC para SME e LME, respectivamente. Testes indicaram que estrutura da µE, razão µE/solo, e tempo de contato são variáveis importantes na extração. A quantidade de µE deve ser suficiente para molhar toda a superfície do solo, sem causar redeposição dos PAHs. A melhor razão µE/solo foi 6. As µEs bicontínuas foram agentes descontaminantes mais eficientes que µEs A/O, provavelmente por dessorverem PAH do solo pelo decréscimo da tensão interfacial. A descontaminação pelas µEs bicontínuas foi 35% mais eficiente que a extração por tolueno em Soxhlet por 6h (?=0,5 e 0,6, tempo de contato 3h à THLB, razão µE/solo=6). O éster usado influencia principalmente a formação e estabilidade da µE. Depois da descontaminação, o solo foi lavado com água e sua biodisponibilidade foi avaliada pela medição da densidade de carga. Esta aumentou em 63%, 86%, 100% e 162% para as amostras que foram tratadas com µEs com CME, SME, LME e BME, respectivamente (µEs bicontínuas, ?=0,5 e ?=0,3). / In the present project, we were interested in assessing the use of Brazilian vegetable oils in the \"ex-situ\" decontamination of soils from polycyclic aromatic hydrocarbons (PAHs). In this process, contaminated soil is treated with a microemulsion (µE) composed of water (W) /commercial non-ionic surfactant (S) C9/11EO4 /oil (O). The latter term refers to the methyl esters of coconut oil (CME), babaçu oil (BME), and the saturated (SME), and unsaturated (LME) fractions of palm oil. Phase diagram of the above mentioned systems were studied. We used weight fractions, ? = (O / W + O) e ? = (S / S + W + O). The pseudo-ternary systems were then studied as a function of temperature, at different ? (? constant) and ? (? constant). The phase diagrams were qualitatively similar to those previously obtained for systems of water/alkane/homogeneous non-ionic surfactant. These show the so-called \"fish\" type phase diagram. The fish \"body\" is triphasic whereas its \"tails\" is monophasic and isotropic. Both areas meet at the so-called hydrophilic-lipophilic temperature, THLB (Schubert and Kaler, 1996). The following are the main differences between the vegetable oil-based phase diagrams and those of homogeneous component systems: a) The fish diagram is severely skewed upward, and its body area is much reduced; b) In the temperature versus ? channel\" phase diagram; the monophasic region exists only at ? equal or above 0.5. The microstructures of the monophasic regions were studied by rheology, X ray diffraction, and quasi-elastic light scattering, QELS. The low viscosity and Newtonian behavior of these liquids shows that they do not contain cubic liquid crystals. This conclusion was corroborated by X ray diffraction measurements, which did not show diffraction patterns characteristic of systems of long-range structural order. The diffusion coefficients of the species involved were measured with QELS. These indicated that monophasic solutions are composed of bicontinuous and W/O microemulsions, whose THLB, is 37.5 ºC for CME, BME, and 42.5 ºC for SME and LME, respectively. The structure of the µE employed, µE/soil ratio, and contact time are important extraction variables. The amount of the µE should be sufficient to wet the surface of the soil, without causing PAHs redeposition. The optimum ratio was 6. Bicontinuous µEs were more efficient decontaminators than W/O microemulsions probably because they desorb PAH from soil by decreasing the associated interfacial tension. Decontamination by the former µEs was 35% more efficient than by hot toluene (6 hours, Soxhlet). After decontamination, the soil was washed with water, and its bioavailability assessed by measuring its charge density. Relative to the original soil, the charge density of decontaminated soil increased by 63%, 86%, 100% and 162%, for washed samples, which were decontaminated with µEs of CME, SME, LME and BME, respectively (µEs BI; ? = 0.5 e ? = 0.3).

Surface phenomena are an integral part of everyday life -- whether in the appearance of bubbles in the sink after washing one's hands or in the design of water-repellent clothing. Surface phenomena also find application in industrial processes, such as catalysis, fluid purification, or separation. For industrial application, materials with huge surface-to-volume ratios are preferred. Solids with pores in the nanometer range (i.e. nanoporous solids) are such materials, and of these, metal-organic frameworks are the most versatile class. Metal-organic frameworks have already received a high level of attention. The modular structure -- MOFs consist of inorganic nodal building blocks that are connected by organic linking building blocks -- allows almost continuous adjustment of pore size, shape, and environment. However, many aspects of surface phenomena in or on metal-organic frameworks are not yet fully understood. For example, it is known that entropy favors the accumulation of smaller guest molecules in nanoporous solids at high loading. But does entropy also favor the accumulation of water in metal-organic frameworks with internal hydrophobicity? Speaking of which, how is the hydrophobicity of the internal and external surface of metal-organic frameworks related? And how can modern visualization techniques, such as virtual reality, help in studying metal-organic frameworks and the guest molecules within them? This thesis aims to shed light on these questions using classical molecular simulations. Molecular simulations are a helpful tool for studying surface phenomena, because they can complement experiments by providing insights at the microscopic level, and offer the possibility of exploring surface phenomena that can only rarely be investigated in experiments, plus help to improve the efficiency of experiments by predicting metal-organic frameworks with desired properties.

Ion-selective polymeric optical sensors – ion optodes – are a promising alternative to ion-selective electrodes and fluorescent dyes for analytical and biological applications, e.g. extra- and intracellular measurements. They are non-toxic, highly selective robust probes for ionic fluxes monitoring. A large-scale fabrication of ion optodes using a solvent displacement method is introduced. This method is a single-batch process that does not require any additional steps. The influence of numerous parameters, e.g. surfactant concentration, solvent nature and membrane concentration, on the average size of the synthesized optodes was studied. The solvent displacement method allows control of the particle size in 200 nm to 30 μm range. Ion optodes selective for sodium, potassium, and calcium cations were prepared and calibrated for hydrogen (pH), sodium, potassium, and calcium. Fabricated sensors demonstrated excellent selectivity, low drift, high stability and reproducibility. Further studies of ion-optodes of different sizes but the same chemical composition revealed a significant shift in their response function. This bias is clearly seen for all fabricated optodes. A strong correlation between a calculated specific surface area and the apparent ion-exchange constant was observed. Considering this, it may be hypothesized that the surface phenomena are contributing to the overall optode response resulting in the observed effect. As a consequence, the response models, developed for the macroscopic ion optodes, cannot be easily applied to the probes at micron- and nano-scale. A primary concern for continuous sensing application of optical sensors is photobleaching of lipophilic fluorescent dye which prevents quantitative fluorescence measurements. Quantum dots, known for their high photostability, brightness and broad excitation spectra with narrow emission bands, were incorporated into polymeric matrix. They excited a fluorophore indirectly, thus, reducing its photobleaching and increasing sensors life-time. We created a composite, quantum dots doped, polymeric sensor that can be integrated into high-throughput detection platforms, such as flow cytometry, chip-based micro-total analysis system technologies, or bundled optical fiber arrays. Ultimately, a fabricated ion-optode was introduced into a Boolean logic gate serving as a reporting microparticle. It responded to the pH changes generated in situ by the enzyme logic system. The present work aimed scaling down the size of biocomputing functional units which might reach the information processing by single molecules associated with signal-transducing single nanoparticles. / Graduation date: 2012

Hybridstrukturen aus organischen und anorganischen Halbleitern (HIOS) vereinen die besten Eigenschaften beider Materialklassen zu Konjugaten mit großem Anwendungspotential. Ihre engen Struktur-Eigenschafts-Beziehungen, eröffnen viele interessante wissenschaftliche Herausforderungen. Um z.B. ihre optoelektronischen Eigenschaften vorherzusagen, müssen die früher Stadien des Dünnschichtwachstums erforscht werden. Das erste Ziel dieser Arbeit ist es, den Einfluss der Entropie auf die Oberflächendiffusion von kurzen Polyphenyl Molekülen auf amorphem Siliziumdioxid, a-SiO2 zu untersuchen. Das zweite Ziel ist es, den Einfluss partieller Fluorierung auf para-Sexiphenyls (p-6P) zu untersuchen. Des Weiteren untersuchen wir Selbstdiffusion von p-6P auf einer Zinkoxid (ZnO) Oberfläche und Selbstorganisation bzw. Schichtwachstum auf a-SiO2. Hierfür verwenden wir klassische atomistische Molekular- und Langevin-Dynamik-Simulationen, kombiniert mit klassischer Diffusionstheorie. In Bezug auf das erste Ziel quantifizieren wir die entropischen Beiträge zu den Freie-Energie-Barrieren für die Oberflächendiffusion von Polyphenylen unterschiedlicher Länge und zeigen, dass die Entropie zum dominierenden Teil der freien Energie für längere Moleküle wird. Zweitens demonstrieren wir, dass die Erhöhung der Anzahl fluorierter Gruppen im p-6P die Diffusion in der apolaren Richtung der ZnO-Oberfläche verringert, aber die Diffusion in der polaren Richtung erhöht. Drittens untersuchen wir den Einfluss der Fluorierung auf die Nukleation und das Wachstum von p-6P auf a-SiO2 mit einem Simulationsmodell, das experimentelle Gasphasenepitaxie nachahmt. Wir reproduzieren korrekte Einheitszellen bei Raumtemperatur und zeigen, dass die Erhöhung der Anzahl fluorierter Gruppen zu einem Schicht-für-Schicht-Wachstum auf der Oberfläche führt. Diese Arbeit ebnet den Weg für zukünftige Simulationen von Dünnschichtwachstum kleiner organischer Moleküle auf anorganischen Oberflächen. / Hybrid structures of organic molecules and inorganic semiconductors (HIOS) combine favorable properties of each material into conjugates with great application potential. The optoelectronic properties of hybrid materials depend on the structure of individual molecules and their alignment relative to the inorganic surface. It is an interesting scientific challenge to predict the optoelectronic properties of HIOS based on studying the early stages of thin film growth and interface formation. The aim of this thesis is to investigate the effect of entropy in surface diffusion of short polyphenyl molecules on an amorphous silicon dioxide, a-SiO2. Second objective is to study the influence of partial fluorination of the organic para-sexiphenyl molecule (p-6P) on self-diffusion on an inorganic zinc oxide (ZnO) surface and on self-assembly and growth on the a-SiO2. For this we employ all-atom molecular dynamics and Langevin dynamics simulations, combined with classical diffusion theory. In respect to the first aim, we quantify entropic contributions to the free energy barrier of surface diffusion for short oligophenyls of varying length and demonstrate that entropy becomes even the dominant part of the free energy for longer molecules. For the second aim, we demonstrate that the increase in the number of fluorinated groups inside of the p-6P decreases the diffusivity in the apolar direction of the ZnO surface but increases the diffusivity in the polar direction. Thirdly, we study the influence of fluorination on nucleation and growth on a-SiO2 with a simulation model that mimics experimental deposition from the vapor. We reproduce the structures with correct room-temperature unit-cell parameters and demonstrate that the increase in the number of fluorinated groups leads to a layer-by-layer growth on the surface. This work can stimulate ideas for future simulations of nucleation and growth of small organic molecules with high tuning potential, on inorganic surfaces.

As emulsões múltiplas mostram-se como veículos promissores em várias áreas das ciências cosmética e farmacêutica. O estudo do método de obtenção de emulsões múltiplas em etapa única é ferramenta útil para elucidação de seus aspectos físico-químicos e para viabilizar sua aplicação tecnológica. O objetivo da pesquisa foi desenvolver e caracterizar os aspectos físico-químicos do processo de emulsificação em etapa única, das emulsões múltiplas A/O/A obtidas e dos tensoativos empregados. Testes preliminares de estabilidade e avaliação do seu perfil de liberação (cafeína) foram realizados. Nanoemulsões foram inicialmente obtidas pela metodologia proposta, resultado de processo de emulsificação por inversão de fases. Suas características físico-químicas foram determinadas (valores de pH, potencial zeta e granulometria) e a influência de aditivos avaliada. Para o desenvolvimento da emulsão múltipla foram realizadas análises qualitativas e quantitativas das variáveis relevantes à composição (tipo de fase oleosa, de tensoativo hidrofílico, valor de EHL, emprego de diagrama ternário) e ao método de emulsificação (temperatura de aquecimento das fases e de emulsificação, ordem de adição e velocidade de agitação). Os estudos das propriedades físico-químicas dos tensoativos e do filme interfacial formado (cloud point, tensão superficial, CMC, reologia interfacial, reologia de fluxo e isotermas de Langmuir) foram primordiais para compreensão dos fenômenos envolvidos e relevantes ao processo de emulsificação proposto. As emulsões múltiplas foram caracterizadas quanto aos aspectos macro e microscópico, granulometria, valores de pH, potencial zeta, viscosidade relativa, perfil reológico e influência da adição de macromoléculas. A temperatura de manipulação e de emulsificação (78±2grausC) foram parâmetros fundamentais para obtenção destes sistemas em etapa única. Seus aspectos macro e microscópico foram extremamente dependentes da temperatura de emulsificação. Os resultados indicam glóbulos múltiplos consideravelmente menores do que os relatados pela literatura. Foi possível observar, no intervalo de temperatura considerado crítico para o processo, valores de tensão superficial/interfacial mínimos. Os resultados de elasticidade superficial sugerem que o comportamento das moléculas de tensoativos, em associação ou não, foi marcadamente influenciado pela temperatura e que o aumento do número de moléculas do tensoativo hidrofólico na superfície foi desfavorável as interações intramoleculares. A isoterma para os tensoativos em associação e em função da temperatura exibiu marcante inflexão para a faixa de temperatura crítica. Este comportamento indica uma dramática alteração na microestrutura do filme interfacial. O processo de encapsulação foi considerado eficiente. Os resultados obtidos indicam que, no atual estágio de desenvolvimento, não foi possível definir um perfil de liberação para a emulsão múltipla em análise. O método de emulsificação escolhido permitiu a obtenção de sistema múltiplo em etapa única, determinado pelas características físico-químicas dos tensoativos empregados, em especial do tensoativo hidrofílico derivado do óleo de rícino e do processo proposto. A formação de emulsões múltiplas anormais não ocasionais ou momentâneas sugere uma combinação dos processos de inversão de fases transicional, influência do emprego de tensoativos não-iônicos etoxilados, e catastrófica, influência da razão entre o volume da fase dispersa e dispersante. As emulsões múltiplas obtidas apresentaram difícil reprodutibilidade microestrutural; entretanto podem ser consideradas estáveis frente às metodologias de avaliação e análise empregadas. / Multiple emulsions are potential vehicles not only for the cosmetic science, but also for the pharmaceutical science. Study the manufacture process of multiple emulsions by one step is a useful tool for understanding their physical-chemistry aspects and making their technological application practicable as well. The goals of this research were to development and characterize the physical chemistry features of the emulsification process by one step, the W/O/W multiple emulsions produced and the surfactants employed. Preliminary stability tests and evaluation of the release profile (caffeine) were carried out. Initially, nano-emulsions were produced by the proposed methodology, resulting from phase inversion emulsification process. Their physical chemistry aspects (pH and zeta potential values and size distribution) and electrolytes addition influence were evaluated. In order to develop the multiple emulsions, noteworthy qualitative and quantitative variables related to the composition (oil phase and hydrophilic surfactant types, HLB values, phase diagram) and to emulsification process (heating and emulsification temperatures, addition order and agitation speed) were analyzed. Analyses of the physical chemistry aspects of the surfactants in solution and their interfacial film (cloud point, surface tension, CMC, interfacial and flux rheology, and Langmuir isotherms) were essential in order to understand the phenomena related to proposed emulsification process. Multiple emulsion analyses (macroscopic, microscopic, size distribution, pH and zeta potential values, relative viscosity, rheological profile and macromolecule addition influence) were carried out. Production and emulsification temperatures (78±2grausC) were fundamental parameters in order to obtain multiple droplets by one step. Their macro and microscopic aspects were completely conditioned by the emulsification temperature. The sizes of the multiple droplets obtained were significantly smaller than those reported in the literature. For the critical temperature range, the minimum surface tension values were reached. Surface elasticity results suggest that the behavior of the surfactant molecules, in association or not, was fundamentally influenced by the temperature. Increasing surfactant molecule moieties on the surface, the intra molecular interactions were misplaced. The Langmuir isotherm as a function of the temperature demonstrated distinctive behavior for the critical temperature range, where the transition phase into solid state and soon afterwards some collapse could be observed. This phenomenon indicated some dramatic alteration of the surface film microstructure. The encapsulation process was regarded as efficient. The release profile studies demonstrated that the dispersed system in analysis was not ready yet for this research stage. The proposed emulsification process was able to produce multiple droplets by one step; moreover this result presented direct influence of the surfactant physical chemistry features, particularly the hydrophilic one, castor oil derivate, and of the methodology employed. The abnormal, non-occasional and non-transitory, multiple emulsion formation suggest a combination of transitional (ethoxylated non ionic surfactant influence), and catastrophic (dispersed/dispersant ratio influence) phase inversion processes. The obtained multiple emulsions presents microstructure aspects were not easily reproducible; however those were regarded stable for the analysis methodology employed.