O estudo do processo de fusão e solidificação da água contida dentro de materiais confinantes tem sido amplamente discutido em química, biologia, física, geologia, e com diversas aplicações tecnológicas, tais como aplicação na fabricação de etanol de segunda geração, ou etanol celulósico, separação de fases, fabricação de nanomateriais. Pesquisas mostraram que as temperaturas de transição da água nanoconfinada são muito sensíveis ao diâmetro do poro, mas que podem ser pouco afetadas pela natureza, hidrofóbica ou hidrofílica, da superfície do poro. Outra importante constatação em experimentos de fusão e congelamento em nanoporos é que nem toda água presente nos poros pode ser cristalizada até gelo. A existência de uma camada de água pré-fundida em nanoporos tem sido confirmada através de experimentos. Com o objetivo de entender mais profundamente como a temperatura de transição da água confinada depende da natureza da parede confinante e do tamanho do confinamento, propõe-se um modelo de nanoporos de celulose para o confinamento, onde varia-se o diâmetro e comprimento do nanoporo, além da natureza da parede do nanoporo. Nossos estudos, mostram que para sistemas hidrofóbicos, com formação de camada de água líquida na parede, as temperaturas de transição variam desde relativamente baixas, para menores valores de calor latente, até atingindo a temperatura de transição da água bulk, para calor latente mais alto. Enquanto que para sistemas hidrofílicos, para nenhum dos valores de calor latente trabalhados, e para nenhum tamanho do sistema, a temperatura de transição atinge o valor de bulk. / The study of the fusion process and water solidification inside confining materials has been widely discussed in Chemistry, Biology, Physics, and Geology, and has various technological applications as the usage and fabrication of second generation ethanol or cellulosic ethanol, phase separation, and nanomaterials fabrications. Researches have shown that nanoconfined water’s transition temperature are highly sensitive to the pore. Another interesting remark on freezing and fusion experiments on nanopores is that not all water present in pores can be crystallized into ice. The existence of a water layer pre-melted on nanopores has been confirmed through experiments. Aiming at understanding deeply how water’s transition temperature depends on the nature of the confining wall and size, a cellulose nanopore model is proposed to the confinement, where the nanopore diameter and length are varied, besides the nature of the wall of the nanopore. Our studies show that for hydrophobic systems, with the liquid water layer formation on the wall, the transition temperatures vary from relatively low latent heat to smaller values, even reaching the temperature transition on bulk water to higher latent heat. While for hydrophilic systems, for none of the latent heat used and no system size the transition temperature reaches bulk value.

Orientador: Celso Costa Lopes / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-18T08:10:10Z (GMT). No. of bitstreams: 1 LaFuenteArias_CarlaIvonne_M.pdf: 1773876 bytes, checksum: 0229ec1ebad94e8b4ebb343f440c2fd6 (MD5) Previous issue date: 2011 / Resumo: Neste trabalho estudou-se a secagem de banana Nanica empregando um pulso inicial a alta temperatura e curto tempo (150°C e 15 minutos), seguido de uma etapa de resfriamento e uma etapa de secagem convencional a ar quente a 70°C. Na primeira parte do trabalho, avaliou-se especificamente a etapa de resfriamento pós-pulso HTST quanto aos atributos de crocância, encolhimento e cor no produto terminado. Analisaramse também as mudanças estruturais através de microscopia ótica. Na segunda parte do trabalho, estudou-se a temperatura de transição vítrea, através de Calorimetria Diferencial de Varredura, em bananas submetidas a este processo de secagem. Os resultados mostraram que, na etapa de resfriamento, a redução gradual de temperatura associada com tempos longos foi importante para que o produto mantivesse a estrutura porosa e crocante, porém também ocasionou produtos com cor escura, com baixos valores de luminosidade. Em contraposição, a redução acelerada de temperatura na etapa de resfriamento ocasionou a perda da estrutura porosa, além de os produtos finais ficarem duros e encolhidos; no entanto, a degradação de cor foi menor. Uma redução gradual da temperatura, com amplitude de 10°C e período de 7,5 minutos, totalizando 75 minutos, mostrou-se adequada para a manutenção da estrutura porosa e crocante, com a menor degradação de cor. A temperatura de transição vítrea decresceu com o aumento do conteúdo de umidade, para todas as amostras, comprovando o efeito plasticizante da água. O início da crocância nas amostras, expressada em número de picos do gráfico força-deformação, foi identificada entre 11% e 6% de umidade (bu) / Abstract: This work studied the drying of banana Nanica employing an initial pulse at high temperature and short time (150°C and 15 minutes); a cooling stage and a final hot air drying at 70°C. In the first part of this work, it was analyzed the post-pulse stage, as attributes of crispness, shrinkage and color. The structural changes also had been analyzed with optical microscopy. In the second part of this work, glass transition temperature of banana, dried with the same process, was studied by Differential Scanning Calorimetry. The results showed that in the cooling stage, the gradual reduction of temperature with longer times, were important for the product retains the porous structure and crispness, but also caused the formation of dark color products with lowest values of brightness. On the other hand, the sudden reduction of temperature, in the cooling stage, caused the loss of the porous structure, and final products became harder and shrunken but with less color degradation. A gradual decrease of temperature with amplitude of 10°C and period of 7.5 minutes summarizing 75 minutes of the cooling stage, proved to be appropriate for the maintenance of porous and crispness structure, with less color degradation. The glass transition temperature decreased with increasing moisture content for all the samples, confirming the water plasticization effect. Crispness in the samples, expressed in peaks number in stress-strain graphs, was initially observed between 11% and 6% of moisture content (wb) / Mestrado / Engenharia de Alimentos / Mestre em Engenharia de Alimentos

Made available in DSpace on 2014-10-09T12:47:50Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:26Z (GMT). No. of bitstreams: 1 08511.pdf: 4385457 bytes, checksum: a0c4d3d31c582b2a850f8616fec84e9e (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Orientadores: Fernanda Paula Collares, Theo Guenter Kieckbusch / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-08T12:08:34Z (GMT). No. of bitstreams: 1 Takeiti_CristinaYoshie_D.pdf: 20201216 bytes, checksum: c1aa9903ccb493780afa2e5957c1db81 (MD5) Previous issue date: 2007 / Resumo: Maltodextrinas são oligossacarídeos solúveis em água, provenientes da hidrólise de amidos. As condições da hidrólise permitem definir a distribuição de massa molecular das maltodextrinas e, conseqüentemente, suas características funcionais podem ser ajustadas para aplicações distintas e específicas. Estes ingredientes são empregados em formulações de pós alimentícios prontos para o consumo e, portanto, o conhecimento de atributos que afetam sua reconstituição em água é determinante para o desenvolvimento desses produtos. Maltodextrinas comerciais com diferentes graus de dextrose-equivalente (DE) e provenientes de três fábricas nacionais distintas foram avaliadas quanto à: morfologia das partículas, teor de umidade, massa molecular, diâmetro médio, densidade aparente e real, porosidade, tempo de molhamento, tempo de dissolução, grau de cristalinidade, isotermas de sorção de umidade e temperatura de transição vítrea (Tg). Os pós comerciais apresentaram características morfológicas distintas, o que influenciou o seu desempenho quanto às propriedades de reconstituição em água. Os produtos que apresentaram características intermediárias de reconstituição foram submetidos a um processo de aglomeração por jato a vapor em mini-instantaneizador para melhorar suas qualidades tecnológicas. As condições de operação foram otimizadas por metodologia de superfície de resposta. O produto aglomerado de maltodextrina com DE igual a 10 apresentou o melhor rendimento e excelentes propriedades instantâneas, enquanto que, a maltodextrina com maior grau de DE, isto é, com menor Tg apresentou o menor rendimento de processo e um produto com piores características de reconstituição. A tendência geral indica que a morfologia e características instantâneas dos aglomerados obtidos foram influenciadas pela temperatura de transição vítrea. Um estudo complementar realizado em leito fluidizado com paredes de acrílico, utilizando soluções de maltodextrina como ligante entre partículas sólidas inertes, avaliou as condições de solidificação das pontes vítreas. A relação umidade vs temperatura obtida confirmou que o processo de aglomeração é influenciado pela massa molecular das amostras e, conseqüentemente, por suas Tgs. Esses parâmetros devem ser considerados no dimensionamento e/ou condições de operação de aglomeradores / Abstract: Maltodextrins are water soluble oligossacharides produced by starch hydrolysis. Their functional characteristics depend on their molecular mass distributions which can be taylormade for specific applications through the control of the process conditions during hydrolysis. Maltodextrin are widely used as ingredient in instant food powder mixes and the knowledge of their reconstitution attributes would assist the development of new formulations. Commercial maltodextrins produced by three different Brazilian manufacturers with dextrose-equivalent (DE) degrees ranging from 5 to 20 were evaluated with respect to morphology, moisture content, molecular mass distribution, average particle diameter, bulk and true densities, void fraction, wetting and dissolution times, crystallinity degree, equilibrium isotherms and glass transition temperature (Tg). The maltodextrin powder showed distinct morphological features, which influenced their water reconstitution abilities. The products with moderate instant properties were submitted to a steam jet agglomeration process in a pilot plant instantiser in order to improve their technological qualities. The operational conditions were optimized by surface response methodology. The general trend indicated that the agglomerates morphology as well as their instant properties are influenced by the glass transition temperature. The DE10 maltodextrin agglomerates showed the best process yield and superior instant properties. The agglomerates of maltodextrin with the highest DE, which has the lowest Tg , showed the lowest yield and poor reconstitution properties. A complementary study, conducted in an Plexiglassÿ fluidized bed equipment using maltodextrin solutions as ligand, evaluated the formation of vitreous bridges between inert particles. The moisture content/temperature relations obtained supported the assumption that the agglomeration process is influenced by the molecular mass of the samples and, consequently, by their Tgs. These parameters should be considered in the design and /or operational conditions of agglomerators / Doutorado / Tecnologia de Alimentos / Doutor em Tecnologia de Alimentos

Cellular membranes are important targets for many membrane-active peptides and drug compounds. Here we are interested in deciphering how lipid membranes are perturbed by several membrane-active molecules, including the transmembrane domain of the influenza M2 protein (M2TM), aggregates formed by a synthetic polyglutamine peptide, and three polyphenol compounds (i.e., tamoxifen, genistein, and verapamil). We employ phase-separated ternary lipid model membranes in the form of giant unilamellar vesicles (GUVs) to simulate raft-like structures that have been proposed to govern many important processes in plasma membranes (e.g., intracellular singling and trafficking). Specifically, we use fluorescent microscopy to interrogate how those membrane additives modulate the phase behavior of free-standing GUVs, as well as the miscibility transition temperature (Tm). We find that M2TM increases Tm and causes vesicle budding; polyglutamine aggregates disrupt lipid membranes; and the three polyphenol compounds exert disparate effects on GUV Tm.

CHARLES UNIVERSITY Faculty of Pharmacy in Hradec Kralove Department of Pharmaceutical technology Name of the student: Nikola Hluchníková Title of diploma thesis: Solid dispersions with terbinafine Consultant: PharmDr. Eva Šnejdrová, PhD. The diploma thesis deals with the release of terbinafine base and terbinafine hydrochloride from degradable carrier in three different mediums. The carrier was polyester of lactic acid and glycolic acid branched on polyacrylic acid. The theoretical part is focused on the description of properties of drug substance and branched polyester, the bioavailability of poor soluble substances, the types of polymeric carriers and the release of drugs from solid dispersions, the thermal analysis of polymer, drug and the solid dispersion with the incorporated drug. In the experimental part, solid dispersions were prepared by the melting method, dissolution of the drug in water, phosphate buffer pH 5.5 and pH 7.4 were studied. The amount of released drug was determined spectrophotometrically at 223 nm and HPLC. A thermal analysis of polyester carriers and solid dispersions was performed by the DSC. The amount of drug released was affected by the pH of the environment. Prolonged release of terbinafine hydrochloride is carried out in a pH 7.4 phosphate solution. In case of...

Orientador: Alex Antonelli / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-30T22:57:05Z (GMT). No. of bitstreams: 1 AlvarezDonado_ReneAlberto_M.pdf: 4171490 bytes, checksum: e9cef25e59956ed4e6201f408c88c61c (MD5) Previous issue date: 2016 / Resumo: Através de simulações de dinâmica molecular (MD) estudou-se o comportamento da viscosidade como função da temperatura para a liga Cu46Zr47Al7 que apresenta uma transição dinâmica frágil - forte. A interação entre as partículas foi modelada pelo potencial Modified Embeddded Atom Method (MEAM). As simulações de dinâmica molecular foram feitas usando as equações de Nosé-Hover e a viscosidade foi calculada pela fórmula de Green-Kubo. Observou-se que para uma temperatura reduzida (Tg/T ) de 0.8, o comportamento da viscosidade muda de frágil para forte. Usando a equação de Vogel-Fulcher-Tammann (VFT) em nossos resultados da simulação, observou-se que os valores da viscosidade calculados acima de 0.8 não são bem descritos por este ajuste, o que pode ser entendido como uma mudança no comportamento da viscosidade depois de atingir essa temperatura. A regressão feita usando a equação do VFT deu um valor limitante inferior para a temperatura de transição vítrea de 650K, o qual é um valor próximo da temperatura de transição vítrea reportada para estas ligas / Abstract: By means of molecular dynamic simulation (MD) we studied the behavior of the viscosity of a Cu46Zr47Al7 alloy, as a function of temperature, which displays a fragile - strong transition. Interactions between particles are modeled using the Modified Embedded Atom Method (MEAM). For the molecular simulations, we used the Nosé-Hoover equations, while the Green-Kubo formula gave us the viscosity. It was observed that, for a reduced temperature (Tg/T ) of 0.8, the behavior of the viscosity changes from fragile to strong. Using the Vogel-Fulcher-Tammann (VFT) equation in our results from the simulation, we noticed that the viscosity values above of 0.8 reaching this temperature. The regression achieved by VFT equation gave us a lowerbound value of 650K for the glass transition, which is very close to the glass transition temperature reported for this kind of alloys / Mestrado / Física / Mestre em Física / 1370420/2014 / CAPES

Water-borne coatings have increased in popularity due to the recent environmental regulations being placed on coating formulation. The most readily available coatings without volatile organic compounds are thermoplastic polymer dispersions that rely on interdiffusion to form a film. These dispersions are reliant on toxic crosslinking chemistries to achieve adequate coating mechanical properties, but still have significantly inferior properties when compared with current thermosetting industrial coatings that contain volatile organic compounds. As a result, waterborne coatings made with conventional emulsion polymers cannot be considered for high-performance coatings. Polyurethane dispersions have been developed that can meet these demands, but require several lengthy coating applications and are therefore incredibly costly. A water-based acrylic emulsion polymer coating that could self-stratify and apply multiple crosslinkable layers simultaneously, has the potential to revolutionize current coating formulations. Recent advances in anisotropic polymer colloid synthesis offer a potential pathway to make such a high-performance coating. Incorporating unique functionality into each of the lobes of a bilobal particle would enable the formation of a new class of water-based, self-stratifying, high-performance, acrylic coatings. The primary goal of this thesis was to show proof of concept for a bilobal platform that could be used to form water-based self-stratifying coatings. The approach was adapted from recent advances in pigment-associating emulsion polymers used to improve coating pigment dispersion. Butyl acrylate and methyl methacrylate seed particles ~90 nm in size were formed and subsequently used to synthesize preliminary ~130 nm acrylic bilobal particles, within the target size range of water based coating dispersions. Control over the seed particle glass transition temperature, size, and morphology, and synthesis of promising preliminary bilobal particles was demonstrated; this was accomplished using a systematic analysis of various reaction conditions, namely, pre-emulsification, reaction duration, and the concentrations of the monomers. Expanding upon the chemical versatility would enable these particles to be used in a wide variety of applications, but this thesis represents a promising start for the bilobal platform within the coating industry.

No description available.

HSLA-65 steel (6.4 mm thick) was friction stir welded at various welding speeds and spindle speeds. Varying weld parameters provided a range of heat inputs. Impact toughness was evaluated as a function of the different weld parameters and corresponding weld heat inputs. Charpy V-Notch (CVN) tests were conducted in parent material and at both the weld nugget centerline and heat-affected zone (HAZ) locations. The upper shelf CVN impact energy of the weld nugget was above that of the base metal for all weld parameters. The upper shelf impact toughness in the HAZ was largely unaffected by changing weld parameters. The nil-ductility transition (NDT) temperature in the weld nugget increased with increasing heat input. The toughness, with respect to the ductile-to-brittle transition, was negatively affected by the increase in heat input. The NDT temperature in the HAZ did not correlate with heat input. The microstructures and microhardness data were examined. Aspects of variation in the impact energy results were identified as the inhomogeneity of the weld microstructure and the placement of the V-notch. Weld nugget microstructures were more inhomogeneous than base metal. Hardness results showed varying values of hardness from the weld crown to the root, transversely across the weld, and longitudinally along the length. Variation due primarily to the inhomogeneity of the weld microstructure is compounded by the location of the V-notch.