Made available in DSpace on 2014-12-17T15:41:58Z (GMT). No. of bitstreams: 1 VictorAVO_DISSERT.pdf: 1098770 bytes, checksum: b51c2db6f7a42c08650cb24f90bc77c8 (MD5) Previous issue date: 2012-03-30 / Dynamic light scattering was used to monitor relaxation processes in chitosan solutions at concentrations within the semi-dilute and concentrated regimes, Kowhlrausch-Williams-Watts (KWW) equation being successfully fitted to intensity correlation function data. The dependence of KWW equation parameters on chitosan concentration indicated that an increase in concentration from semi-dilute to concentrated regimes resulted in narrowing the distribution of relaxation rates; temperature dependence indicated the relaxation process as described as an energy activated process, whose parameters were function of the interaction between chitosan chains (enthalpy of activation) and rigidity of chitosan conformations (pre-exponential factor) / O espalhamento din?mico de luz foi utilizado para monitorar processos de relaxa??es em solu??es de quitosana em concentra??es dentro dos regimes semidilu?das e concentradas, a equa??o Kowhlrausch-Williams-Watts (KWW) foi ajustada com ?xito para os dados de intensidade de fun??o de correla??o. A depend?ncia dos par?metros da equa??o KWW sobre a concentra??o de quitosana indicam que um aumento na concentra??o de semidilu?da ? concentrada resultou no estreitamento da distribui??o das taxas de relaxa??o; a depend?ncia da temperatura indicada no processo de relaxa??o, foi descrito como energia de ativa??o do processo, cujos par?metros foram fun??es da intera??o entre as cadeias de quitosana (entalpia de ativa??o) e rigidez das conforma??es de quitosana (fator pr?-exponencial)

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-01-12T13:44:03Z No. of bitstreams: 1 ThiagoVasquesDeSouza_DISSERT.pdf: 2115756 bytes, checksum: 3e6dfd05005f83b2fb41d4caa8e343d8 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-01-17T11:45:14Z (GMT) No. of bitstreams: 1 ThiagoVasquesDeSouza_DISSERT.pdf: 2115756 bytes, checksum: 3e6dfd05005f83b2fb41d4caa8e343d8 (MD5) / Made available in DSpace on 2017-01-17T11:45:14Z (GMT). No. of bitstreams: 1 ThiagoVasquesDeSouza_DISSERT.pdf: 2115756 bytes, checksum: 3e6dfd05005f83b2fb41d4caa8e343d8 (MD5) Previous issue date: 2016-07-27 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Os espessantes de l?tex acr?lico ?lcali-sol?veis s?o amplamente utilizados em atividades como fabrica??o de revestimento, cosm?ticos, ind?stria do petr?leo e t?xtil. Eles t?m a fun??o de aumentar a viscosidade aparente do meio, como resultado da neutraliza??o dos grupos carboxila presentes nas part?culas do l?tex. Os espessantes acr?licos hidrofobicamente modificados (HASE) atualmente s?o os mais utilizados como modificadores de reologia e as t?cnicas de reometria s?o o principal m?todo utilizado para monitorar a atividade reol?gica e efici?ncia destas subst?ncias. Nesta disserta??o, propomos o uso de espalhamento din?mico de luz (DLS) como m?todo complementar para obter par?metros quantitativos como taxa de relaxa??o caracter?stica m?dia e largura de distribui??o assim como correlacion?-los com o aumento da viscosidade e a neutraliza??o dos grupamentos carboxila. A partir de an?lise de dados obtidos com a utiliza??o de t?cnicas tradicionais de caracteriza??o como reometria, condutividade e turbidez em compara??o com a t?cnica de espalhamento din?mico de luz (DLS). Identificou-se uma concentra??o cr?tica de ?ons OH- para a neutraliza??o dos grupos carboxila. Foi poss?vel ainda, a partir dos dados de taxa de relaxa??o m?dia ter um melhor entendimento do mecanismo de espessamento deste tipo de pol?mero. / The alkali soluble latex thickeners are extensively used in activities such as coating manufacturing, cosmetics, oil and textile industry. They increase apparent viscosity as a result of neutralization of carboxyl groups in latex particles. The Hydrophobic alkali soluble emulsion (HASE), currently are the thickener most used to increase the material?s rheology and the rheometry techniques is the main method used to monitor the rheological activity of these substances and its efficiency. In this work, we propose the use of dynamic light scattering (DLS) as an additional method to get quantitative parameters like characteristic relaxation rate and distribution width to correlate them to viscosity increase and carboxylic groups neutralization. We got the information obtained from traditional characterization methods as rheometry, conductivity and turbidity to compare with dynamic light scattering parameters. The critical OH- ions concentration was identified using the information about the carboxylic groups neutralization and we could to get more information about this polymer thickening process using de Dynamic Light Scattering for a better understanding about this mechanism.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-03-20T19:31:23Z No. of bitstreams: 1 RogerioPereiraDeQueiroz_DISSERT.pdf: 2044372 bytes, checksum: 84f05f3061b292c5a47b28fb9bdebc12 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-03-22T00:05:51Z (GMT) No. of bitstreams: 1 RogerioPereiraDeQueiroz_DISSERT.pdf: 2044372 bytes, checksum: 84f05f3061b292c5a47b28fb9bdebc12 (MD5) / Made available in DSpace on 2017-03-22T00:05:51Z (GMT). No. of bitstreams: 1 RogerioPereiraDeQueiroz_DISSERT.pdf: 2044372 bytes, checksum: 84f05f3061b292c5a47b28fb9bdebc12 (MD5) Previous issue date: 2016-08-22 / A agarose ? um pol?mero natural extra?do de algas que possui a propriedade de formar g?is f?sicos, quando retirado calor do sistema. Essa propriedade possui grande aplicabilidade nas ind?strias aliment?cia e farmac?utica, principalmente em an?lises de DNA. Para esse trabalho, foram preparadas solu??es aquosas em concentra??es diferentes de agarose. Medidas de espalhamento din?mico de luz foram feitas, enquanto se alterava a temperatura do sistema, a fim de obter estruturas mais ou menos organizadas das macromol?culas. Para as medidas de espalhamento, a equa??o Kohrausch-William-Watts (KWW) foi ajustada aos dados, de modo a obter a taxa de relaxa??o m?dia do processo. Adicionalmente, foram feitos testes de reologia das amostras, tamb?m com a varia??o da temperatura. Para ambas as t?cnicas, foram feitos ajustes matem?ticos, com a inten??o de estudar a transi??o h?lice-novelo das cadeias polim?ricas no decorrer da altera??o da temperatura, relacionando-as atrav?s do c?lculo da energia de ativa??o aparente do processo. Nas duas abordagens foi constatado que a energia tende a diminuir para solu??es dilu?das e para altas temperaturas. / The agarose is a natural polymer extract from red algae (Rhodophyceae). This polysaccharide can form physical gels when is removed heat from the system. This property has great applicability in the food and pharmaceutical industries, particularly in DNA analysis. For this work we prepared aqueous solutions at different concentrations of agarose. Measures of Dynamic Light Scattering (DLS) were made while the system temperature was altered so as to obtain structures more or less organized of macromolecules. For DLS measurements, the Kohrausch-William-Watts equation (KWW) was fitted to the data to obtain the average of relaxation rate of the process. Additionally rheometry tests were made also with the temperature variation. For both techniques, were made mathematical adjustments with the intention of studying the helix-coil transition of the polymer chains during the temperature change, relating them by calculating the apparent activation energy. In both approaches it was found that energy tends to decrease for dilute solutions and higher temperatures.

Made available in DSpace on 2014-12-17T15:41:55Z (GMT). No. of bitstreams: 1 WildsonAM_DISSERTPPGQ.pdf: 2126383 bytes, checksum: 6a1a9e8b2c55caac2fbd3fb938bff756 (MD5) Previous issue date: 2011-07-20 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Gels consist of soft materials with vast use in several activities, such as in pharmaceutical industry, food science, and coatings/textile applications. In order to obtain these materials, the process of gelification, that can be physical (based on physical interactions) and/or chemical (based on covalent crosslinking), has to be carried out. In this work we used dynamic light scattering (DLS) and rheometry to monitor the covalent gelification of chitosan solutions by glutaraldehyde. Intensity correlation function (ICF) data was obtained from DLS and the exponential stretched Kohrausch-William-Watts function (KWW) was fitted to them. The parameters of the KWW equation, β, Γ and C were evaluated. These methods were effective in clarifying the process of sol-gel transition, with the emergence of non-ergodicity, and determining the range of gelation observed in about 10-20 minutes. The dependence between apparent viscosity on reaction time was used to support the discussion proposed. / G?is s?o materiais que possuem aplica??es em v?rias ?reas, tais quais, na ind?stria de tintas, alimentos e farmac?utica. Os m?todos empregados para obten??o dos g?is podem ser f?sicos (intera??es f?sicas) e/ou qu?micos (baseado em intera??es covalentes), tal processo, ? denominado gelifica??o. Neste trabalho, o processo de gelifica??o de quitosana/glutaralde?do foi monitorado utilizando reometria e espalhamento da luz (DLS). As fun??es de correla??o de intensidade (ICF) foram obtidas atrav?s de DLS e a equa??o de Kohrausch-William-Watts (KWW) foi ajustada com os dados experimentais. Os par?metros da equa??o KWW, β, Γ e C foram avaliados. Estes m?todos foram eficazes na clarifica??o do processo que compreende a transi??o sol-gel, com o surgimento da n?o-ergodicidade, e na determina??o da faixa de gelifica??o, observada em torno de 10-20 minutos. A depend?ncia da viscosidade aparente em fun??o do tempo foi utilizada para comprovar o tempo de gelifica??o observado no DLS.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-05-30T22:35:17Z No. of bitstreams: 1 WildsonArcanjoDeMorais_TESE.pdf: 7950168 bytes, checksum: 6a3da8d5da57db90a9fa474b79780a53 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-06-01T21:32:38Z (GMT) No. of bitstreams: 1 WildsonArcanjoDeMorais_TESE.pdf: 7950168 bytes, checksum: 6a3da8d5da57db90a9fa474b79780a53 (MD5) / Made available in DSpace on 2016-06-01T21:32:38Z (GMT). No. of bitstreams: 1 WildsonArcanjoDeMorais_TESE.pdf: 7950168 bytes, checksum: 6a3da8d5da57db90a9fa474b79780a53 (MD5) Previous issue date: 2015-08-18 / A ind?stria de petr?leo necessita de v?rias subst?ncias qu?micas em seus processos de extra??o e investe em novas tecnologias a todo o momento. Os sistemas micelares do tipo-minhoca-WLM e os complexos polieletrol?ticos-PECs est?o sendo estudados para ingressar como novas tecnologias na extra??o de ?leo. Esta tese objetiva obter, caracterizar e identificar esses sistemas coloidais utilizando t?cnicas de espalhamento de luz como principais ferramentas; possibilitando o conhecimento de base para poss?veis aplica??es na ind?stria petrol?fera. Os par?metros obtidos no DLS, b, GC e n sofreram transi??es na concentra??o tensoativo/co-tensoativo 200g/L. A adi??o da fase ?leo, xileno, dificulta a transi??o de micelas esf?ricas para micelas minhoca. No SAXS, a rela??o RG,O/ RG,S atinge um m?ximo que corrobora com a transi??o no DLS. b aumenta bruscamente, n se torna mais homog?neo, GC,2 e a contribui??o para o segundo processo, f2, foram visualizados para raz?es poli?nion/polic?tion WAC pr?ximas de 2. Essa regi?o, no SAXS, aglomerados de PECs se adsorvem nas part?culas prim?rias, que contribuiu para o comportamento dos gr?ficos de Kratky. As fun??es P(r) perdem seu formato ?sino? e se alargam. As contribui??es de ?rea S17 e S29 foram maiores para menores valores de WAC e S37 foi influente em valores maiores. / The oil industry needs various chemicals compounds in their extraction processes and invests in new technologies all the time. Worm-like micelles-WLM and polyelectrolyte complexes-PECs have been studied to join as new technologias in oil extraction processes. This thesis aims to obtain, characterize and identify these colloidal systems using as a tool light scattering experiments; enabling the required knowledge to applied them in oil industry. To the surfactants systems, the parameters from DLS, b, GC and n in a function of surfactant/co-surfactant concentrations suffered transitions around 200 g/L. The addition of oil phase, xylene, hinders the transition from spherical micelles to worm-like micelles. In SAXS, the ratio RG,O/ RG,S reaches a maximum value which corroborates with the transition in DLS. To PECs, b increases sharply, n becomes more homogeneous, GC,2 and second contribution to the process, f2, were visualized for polyanion/polycation ratio with WAC next 2. This region in SAXS, PECs clusters adsorb in primary particles, which contributed to the behavior of Kratky graphics. The pair distribution functin, P(r), lose its bell shape and widen. The S17 and S29 were higher for lower values of WAC ratio. S37 was influential in higher values.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-01-12T13:44:03Z No. of bitstreams: 1 PauloReniereSilvaDeSouza_DISSERT.pdf: 18420723 bytes, checksum: 0dee6d1653465093c4081165eec036ad (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-01-17T11:30:54Z (GMT) No. of bitstreams: 1 PauloReniereSilvaDeSouza_DISSERT.pdf: 18420723 bytes, checksum: 0dee6d1653465093c4081165eec036ad (MD5) / Made available in DSpace on 2017-01-17T11:30:54Z (GMT). No. of bitstreams: 1 PauloReniereSilvaDeSouza_DISSERT.pdf: 18420723 bytes, checksum: 0dee6d1653465093c4081165eec036ad (MD5) Previous issue date: 2016-07-22 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Dispers?es de complexos polieletrol?ticos (PEC) foram preparadas a partir de quitosana e poli(metacrilato de s?dio), atrav?s da mistura de suas solu??es, a diferentes raz?es molares carboxila/amino, rCA. O raio de giro foi determinado por SAXS e revelou que na medida que rCA aumentava as dimens?es das PEC?s decresciam, atingindo um m?nimo a rCA = 0.75, a qual foi considerada a raz?o na qual as dimens?es dos agregados eram m?nimas, sendo seguido de colapso e crescimento de part?culas maiores. Distribui??es de dist?ncia entre pares, P(r), tornaram-se mais estreitas at? rCA = 0.75, aumentando suas larguras a partir deste ponto. Par?metros relacionados ? relaxa??o, retirados de fun??es de correla??o de intensidade (ICF) de DLS identificaram tr?s processos principais de relaxa??o. O processo mais r?pido, relacionado a movimentos aleat?rios de mol?culas de polieletr?lito livres desapareceu, na medida em que rCA aumentou. Os outros dois processos de relaxa??o foram fun??es de rCA e apresentaram mudan?as caracter?sticas a rCA = 0.75. No mesmo valor de rCA, a energia de ativa??o para a taxa de relaxa??o m?dia indicou a ocorr?ncia de uma clara mudan?a na natureza das intera??es nas estruturas de PEC. O di?metro hidrodin?mico, determinado por DLS, foi muito maior que o raio de giro, determinado por SAXS. Part?culas de PEC podem ser descritas, consequentemente, como composta por um caro?o s?lido, rico em material segregado, insol?vel, envelopado por aglomerados sol?veis de PEC, possivelmente na forma de g?is altamente hidratados. / Polyelectrolyte complex (PEC) dispersions were prepared from chitosan and poly(sodium acrylate), NaPMA, by mixing their solutions., at different carboxyl to aminium molar ratio, rCA. Gyration radius was determined by SAXS and showed that, as rCA increased, PEC dimensions decreased and reached a minimum at rCA = 0.75, which was considered the ratio at which PEC cluster dimensions was minimum, following collapse and growth of larger particles. Pair distance distributions, P(r), became narrower up to rCA = 0.75, increasing its width from this point. Relaxation-related parameters from DLS intensity correlation functions (ICF) identified three main relaxation process. The fast process, related to free polyelectrolyte molecules random motion disappeared as rCA was increased. The other two relaxation process were a function of rCA and presented marked changes at rCA = 0.75. At the same value of rCA the energy of activation for the average relaxation rate showed the occurrence of a clear change in the nature of PEC-related interactions. As hydrodynamic diameter, determined by DLS was much larger than the gyration radius determined by SAXS, PEC particles could be described as being composed by a core, rich in segregated, insoluble material, enveloped by PEC soluble clusters, possibly in the form of water-rich gels.

Made available in DSpace on 2014-12-17T15:42:26Z (GMT). No. of bitstreams: 1 ZilvamMS_TESE_reduzido.pdf: 9108618 bytes, checksum: 613dad3fd1a359dce84e2af73b067934 (MD5) Previous issue date: 2013-02-22 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Surfactant-polymer interactions are widely used when required rheological properties for specific applications, such as the production of fluids for oil exploration. Studies of the interactions of chitosan with cationic surfactants has attracted attention by being able to cause changes in rheological parameters of the systems making room for new applications. The commercial chitosan represents an interesting alternative to these systems, since it is obtained from partial deacetylation of chitin: the residues sites acetylated can then be used for the polymer-surfactant interactions. Alkyl ethoxylated surfactants can be used in this system, since these non-ionic surfactants can interact with hydrophobic sites of chitosan, modifying the rheology of solutions or emulsions resultants, which depends on the relaxation phenomenon occurring in these systems. In this work, first, inverse emulsions were prepared from chitosan solution as the dispersed phase and cyclohexane as the continuous phase were, using CTAB as a surfactant. The rheological analysis of these emulsions showed pronounced pseudoplastic behavior. This behavior was attributed to interaction of "loops" of chitosan chains. Creep tests were also performed and gave further support to these discussions. Subsequently, in order to obtain more information about the interaction of chitosan with non-ionic surfactants, solutions of chitosan were mixed with C12E8 and and carried out rheological analysis and dynamic light scattering. The systems showed marked pseudoplastic behavior, which became less evident when the concentration of surfactant was increased. Arrhenius and KWW equations were used to obtain parameters of the apparent activation energy and relaxation rate distribution, respectively, to which were connected to the content of surfactant and temperature used in this work / As intera??es tensoativo-pol?mero s?o amplamente usadas quando s?o necess?rias propriedades reol?gicas para aplica??es espec?ficas, como a produ??o de fluidos para explora??o do petr?leo. Estudos das intera??es de quitosana com tensoativos cati?nicos tem chamado aten??o por serem capazes de causar mudan?as nos par?metros reol?gicos dos sistemas abrindo espa?o para novas aplica??es. A quitosana comercial representa uma alternativa interessante para estes sistemas, uma vez que ela ? obtida a partir da desacetila??o parcial da quitina: os s?tos acetilados residuais podem, ent?o, ser usados para as intera??es pol?mero-tensoativo. Tensoativos alquil etoxilados podem ser utilizados neste sistema, pois estes tensoativos n?o i?nicos podem interagir com s?tios hidrof?bicos da quitosana, modificando a reologia de solu??es ou emuls?es resultantes, os quais dependem do fen?meno de relaxa??o ocorrendo nestes sistemas. Neste trabalho, primeiramente, foram preparadas emuls?es inversas de solu??o de quitosana como fase dispersa e cicloexano como fase cont?nua usando CTAB como tensoativo. A an?lise reol?gica destas emuls?es mostrou pronunciado comportamento pseudopl?stico. Esta pseudoplasticidade foi atribu?da ? intera??o por la?os loops de cadeias de quitosana. Ensaios de flu?ncia tamb?m foram executados e deram maior suporte a estas discuss?es. Em seguida, a fim de se obter maiores informa??es sobre as intera??es da quitosana com tensoativos n?o i?nicos, solu??es de quitosana foram misturadas com C12E8 e levadas ?s an?lises reol?gica e de espalhamento din?mico de luz. Os sistemas tiveram elevado comportamento pseudopl?stico, o qual se tornava menos evidente, quando o teor de tensoativo foi aumentado. Equa??es de Arrhenius e de KWW foram usadas para obter par?metros de energia de ativa??o aparente e de distribui??o da taxa de relaxa??o, respectivamente, aos quais foram relacionados em fun??o do teor de tensoativo e da temperatura, usados neste trabalho