Otimização topológica de estruturas termoelásticas tridimensionais

This work presents an optimization technique based on structural topology optimization methods, TOM, designed to solve problems of thermoelasticity 3D. The presented approach is based on the adjoint method of sensitivity analysis unified design and is intended to loosely coupled thermomechanical problems. The technique makes use of analytical expressions of sensitivities, enabling a reduction in the computational cost through the use of a coupled field adjoint equation, defined in terms the of temperature and displacement fields. The TOM used is based on the material aproach. Thus, to make the domain is composed of a continuous distribution of material, enabling the use of classical models in nonlinear programming optimization problem, the microstructure is considered as a porous medium and its constitutive equation is a function only of the homogenized relative density of the material. In this approach, the actual properties of materials with intermediate densities are penalized based on an artificial microstructure model based on the SIMP (Solid Isotropic Material with Penalty). To circumvent problems chessboard and reduce dependence on layout in relation to the final optimal initial mesh, caused by problems of numerical instability, restrictions on components of the gradient of relative densities were applied. The optimization problem is solved by applying the augmented Lagrangian method, the solution being obtained by applying the finite element method of Galerkin, the process of approximation using the finite element Tetra4. This element has the ability to interpolate both the relative density and the displacement components and temperature. As for the definition of the problem, the heat load is assumed in steady state, i.e., the effects of conduction and convection of heat does not vary with time. The mechanical load is assumed static and distributed

Otimização do fresamento de roscas internas com a técnica de interpolação helicoidal

In machining of internal threads, dedicated tools, known as taps, are needed for each profile type, diameter, and low cutting speed values are used when compared to main machining processes. This restriction in the cutting speed is associated with the difficulty of synchronizing the tool s rotation speed and feed velocity in the process. This fact restricts the flexibility and makes machining lead times longer when manufacturing of components with threads is required. An alternative to the constraints imposed by the tap is the thread milling with helical interpolation technique. The technique is the fusion of two movements: rotation and helical interpolation. The tools may have different configurations: a single edge or multiple edges (axial, radial or both). However, thread milling with helical interpolation technique is relatively new and there are limited studies on the subject, a fact which promotes challenges to its wide application in the manufacturing shop floor. The objective of this research is determine the performance of different types of tools in the thread milling with helical interpolation technique using hardened steel workpieces. In this sense, four tool configurations were used for threading milling in AISI 4340 quenched and tempered steel (40 HRC). The results showed that climb cut promoted a greater number of machined threads, regardless of tool configuration. The upcut milling causes chippings in cutting edge, while the climb cutting promotes abrasive wear. Another important point is that increase in hole diameter by tool diameter ratio increases tool lifetime

Otimização do processo de flotação de emulsão óleo/água através do planejamento fatorial completo

In recent decades, the generation of solid and liquid waste has increased substantially due to increased industrial activity that is directly linked to economic growth. For that is the most efficient process, it is inevitable generation of such wastes. In the oil industry, a major waste generated in oil exploration is produced water, which due to its complex composition and the large amount generated, has become a challenge, given the restrictions imposed by environmental laws regarding their disposal, making if necessary create alternatives for reuse or treatment in order to reduce the content of contaminants and reduce the harmful effects to the environment. This water can be present in free form or emulsified with the oil, when in the form of an emulsion of oil-water type, it is necessary to use chemicals to promote the separation and flotation is the treatment method which has proved to be more efficient, for it can remove much of the emulsified oil when compared to other methods. In this context, the object of this work was to study the individual effects and interactions of some physicochemical parameters of operations, based on previous work to a flotation cell used in the separation of synthetic emulsion oil / water in order to optimize the efficiency of the separation process through of the 24 full factorial design with center point. The response variables to evaluate the separation efficiency was the percentage of color and turbidity removal. The independent variables were: concentration of de-emulsifying, oil content in water, salinity and pH, these being fixed, minimum and maximum limits. The analysis of variance for the equation of the empirical model, was statistically significant and useful for predictive purposes the separation efficiency of the floater with R2 > 90%. The results showed that the oil content in water and the interaction between the oil content in water and salinity, showed the highest values of the estimated effects among all the factors investigated, having great and positive influence on the separation efficiency. By analyzing the response surface was determined maximum removal efficiency above 90% for both measured for turbidity as a measure of color when in a saline medium (30 g/L), the high oil concentrations (306 ppm) using low concentrations of de-emulsifying (1,1 ppm) and at pH close to neutral

Análise de fluxos metabólicos para otimização da síntese do antibiótico cosmomicina por Streptomyces olindensis ICB20

Metabolic flux analysis (MFA) is a powerful tool for analyzing cellular metabolism. In order to control the growth conditions of a specific organism, it is important to have a complete understanding of its MFA. This would allowed us to improve the processes for obtaining products of interest to human and also to understand how to manipulate the genome of a cell, allowing optimization process for genetic engineering. Streptomyces olindensis ICB20 is a promising producer of the antibiotic cosmomycin, a powerful antitumor drug. Several Brazilian researchers groups have been developing studies in order to optimize cosmomycin production in bioreactors. However, to the best of our knowledge, nothing has been done on metabolic fluxes analysis field. Therefore, the aim of this work is to identify several factors that can affect the metabolism of Streptomyces olindensis ICB20, through the metabolic flux analysis. As a result, the production of the secondary metabolite, cosmomycin, can be increased. To achieve this goal, a metabolic model was developed which simulates a distribution of internal cellular fluxes based on the knowledge of metabolic pathways, its interconnections, as well as the constraints of microorganism under study. The validity of the proposed model was verified by comparing the computational data obtained by the model with the experimental data obtained from the literature. Based on the analysis of intracellular fluxes, obtained by the model, an optimal culture medium was proposed. In addition, some key points of the metabolism of Streptomyces olindensis were identified, aiming to direct its metabolism to a greater cosmomycin production. In this sense it was found that by increasing the concentration of yeast extract, the culture medium could be optimized. Furthermore, the inhibition of the biosynthesis of fatty acids was found to be a interesting strategy for genetic manipulation. Based on the metabolic model, one of the optimized medium conditions was experimentally tested in order to demonstrate in vitro what was obtained in silico. It was found that by increasing the concentration of yeast extract in the culture medium would induce to an increase of the cosmomycin production

Análise da adição de resíduo oriundo do tratamento de esgotos em massa cerâmica utilizada para fabricação de telhas

Sludge of Wastewater Treatment Plants (WTPs) disposal is a problem for any municipality, for this reason the amount of sludge production is now a key issue in selecting treatment methods. It is necessary to investigate new applications for this waste type, due to the restrictions imposed by the environmental organs. The raw materials used in the Red Ceramic, are generally very heterogeneous, for this reason, such materials can tolerate the presence of different types of wastes. In Rio Grande do Norte, the roof tiles production corresponds to 60,61% from the total of ceramic units produced. Due to the importance of the ceramic industry of roof tiles for the state, allied to the environmental problem of the sludge disposal, this work had for objective to verify the possibility of the incorporation of sewage sludge in ceramic body used for production of roof tiles. In the research, sludge originating from drying beds of WTP of the Central Campus from UFRN and clays originating from a ceramic industry from Goianinha/RN were used. The raw materials were characterized by techniques of: analysis of particles distribution by diffraction to laser; real density; consistence limits; chemical analysis by X-ray fluorescence; mineralogical analysis by X-ray diffraction; organic matter; and solids content. Five batches of roof tiles were manufactured in the approximate dosages of 2%, 4%, 6%, 8% and 10%. To evaluate the properties of each final product, tests of water absorption, impermeability, bending strength, leachability and solubility were accomplished. The roof tiles manufactured with sludge presented characteristics similar to the roof tiles without sludge in relation to the environmental risk. The results showed that it is possible to use approximately up to 4% of sludge in ceramic bodies for production of roof tiles. However, it is observed that the high amount of organic matter (71%) present in the sludge is shown as factor that limits the sludge incorporation in ceramic bodies, worsening the quality of the roof tiles. It is necessary the use of mixtures of different raw materials under point of view of the granulometry and of the other chemical and mineralogical properties for the obtaining of a satisfactory mass to the production of ceramic roof tiles

Variação, mudança e ensino: o caso dos pronomes possessivos da gente e nosso(a)(s) em uma abordagem sociofuncionalista

In this work, we analyze the variation and change phenomenon involving the possessive pronouns da gente and nosso(a)(s) in the light of the theoretical referentials of the North-american linguistic functionalism and of the variationist sociolinguistics. At first we present the phenomenon itself, highlighting the fact that few studies have considered it as an object, gap which we will try to fill in with our contribution. In the following chapter, we emphasize concepts and principles of the functionalism and the sociolinguistics that are used as our background for the data analysis. In the third chapter, we present what the normative grammars inform about our object of study, besides synthesizing some works on variation and change involving the personal pronouns nós and a gente. In the following chapter, we analyze the data. We used data from the Discurso & Gramática a língua falada e escrita na cidade do Natal (FURTADO DA CUNHA, 1998) corpus. In this chapter we present the results for the groups of social and linguistic factors which we can control. Grounded on these results, we specify the preferential contexts for employing the pronouns da gente and nosso(a)(s) and we observe that the social motivations, the valorization credited to the forms and the identity marks underly the restrictions exercised in their use by social factor groups, besides obtaining signs of ongoing changes in apparent time (from the age factor groups) and possible use specializations of each form, what helped us verify the course of the grammaticalization process of the referred pronouns in the community of Natal. In the sixth chapter, we make some considerations on the teaching of grammar and propose activities which can be carried on in the classroom involving the possessive pronouns da gente and nosso(a)(s) considering the variation and change issue

Gestão de estoques: uma proposta de reposição contínua para material médico hospitalar e medicamentos em um hospital universitário federal do estado do Rio Grande do Norte

The inventory management in hospitals is of paramount importance, since the supply materials and drugs interruption can cause irreparable damage to human lives while excess inventories involves immobilization of capital. Hospitals should use techniques of inventory management to perform replenishment in shorter and shorter intervals, in order to reduce inventories and fixed assets and meet citizens requirements properly. The inventory management can be an even bigger problem for public hospitals, which have restrictions on the use of resources and decisionmaking structure more bureaucratized. Currently the University Hospital Onofre Lopes (HUOL) uses a periodic replacement policy for hospital medical supplies and medicines, which involves one moment surplus stock replenishment, the next out of stock items. This study aims to propose a system for continuous replenishment through order point for inventory of medical supplies and medicines to the hospital HUOL. Therefore, a literature review of Federal University Hospitals Management, Logistics, Inventory Management and Replenishment System in Hospitals was performed, emphasizing the demand forecast, classification or ABC curve and order point system. And also, policies of inventory management and the current proposal were described, dealing with profile of the mentioned institution, the current policy of inventory management and simulation for continuous replenishment order point. For the simulation, the sample consisted of 102 and 44 items of medical and hospital drugs, respectively, selected using the ABC classification of inventory, prioritizing items of Class A, which contains the most relevant items in added value, representing 80 % of the financial value in 2012 fiscal year. Considering that it is a public organization, subject to the laws, we performed two simulations: the first, following the signs for inventory management of Instruction No. 205 (IN 205 ), from Secretary of Public Administration of the Presidency ( SEDAP / PR ), and the second, based on the literature specializing in inventory management hospital. The results of two simulations were compared to the current policy of replenishment system. Among these results are: an indication that the system for continuous replenishment reorder point based on IN 205 provides lower levels of safety stock and maximum stock, enables a 17% reduction in the amount spent for the full replenishment of inventories, in other words, decreasing capital assets, as well as reduction in stock quantity, also the simulation made from the literature has indicated parameters that prevent the application of this technique to all items of the sample. Hence, a change in inventory management of HUOL, with the application of the continuous replenishment according to IN 205, provides a significant reduction in acquisition costs of medical and hospital medicine

A intervenção do poder judiciário no acesso a medicamentos no Rio Grande do Norte: uma análise sob a ótica das políticas nacionais de medicamento e de assistência farmacêutica

The present study aimed to evaluate the inclusion of the principles of the National Medicines Policy - PNM and the Pharmaceutical assistance - PNAF in the prosecution of lawsuits involving medicines. To fulfill this necessity , data collection was performed on the website by the Tribunal Rio Grande do Norte - TJ RN ( Rio Grande do Norte Court) , in 2012 . It was obtained 115 judgments, which were analyzed in order to generate Monitoring Indicators from lawsuits and conduct content analysis proposed by Bardin (2006). The results showed that : a) 100 % of the decisions were favorable to the author , b) 76 % of decisions were requests by the trade name of the drug , c) only one drug (eculizumabe) had not granted by ANVISA , d) 36 % of drugs were present in the list of standard medicines in SUS , 16 % of primary care block and 20 % of specialized component , e) 76 % of the decisions presented the request of at least 01 non-standard medicine. With regard to decentralization of PNM and PNAF we observed a commitment to this principle at judicial decisions, to see that municipalities and states are often forced to buy medicines of responsibility from another federal entity or other tertiary units as CACONs and UNACONS. The content analysis revealed that the argument from the judges used when you utter their decisions was that the right to health is recognized by Brazilian law as a fundamental right and should be guaranteed by the State for all its citizens. So, health is more than budgetary constraints of federal entities, which are severally liable for lawsuits , regardless the medication requested belongs or not to a particular block of a pharmaceutical assistance funding. Given these data, it is observed that there are gaps in the judgment when it comes to the insertion of the words and principles of PNM and PNAF, creating then the need for greater dialogue between the executive and judicial, so that they may consider relevant the effectiveness and application of such principles to minimize the negative consequences of the phenomenon of health judicialisation. Keywords: Judicialisation, Medicines, Public Policy, Pharmaceutical Care

Avaliação da estimulação da medula espinhal como modelo de tratamento da doença de parkinson no primata Callithrix jacchus

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

Comportamento de parâmetros fisiológicos de homens e mulheres em condições de estresse laboral submetidos à técnica Watsu

The physiological variations of parameters in situations of laboral stress can function like indicator in the sprouting of disorder. Those conditions have led researchers to investigate alternatives that can favor the quality of life in persons under stress laboral. The present research had as objectives investigate the physiological behavior of parameters (blood pressure, heart hat and respiratory hat) of men and women in condition of stress laboral submitted to the technique Watsu. It was used a experimental methodology with a group formed by men and women in reproductive age, that work as salesclerk in a supermarket net in Natal/RN. The seven individuals selected were submitted to the three phases of the study (dependent groups), that consisted of the phase 1 of obtaining from the measure basal (control 1), in the phase 2 of immersion in the water (control 2), and phase 3 from the application the technique Watsu (experimental phase). It was verified that during the phase basal (condition 1) the physiological parameters (BPS, BPD, HH and RH) of both sexes evaluated showed the medium values of the women (average±detour-standard: BSP = 104.1±7.92; BPD = 70.83 ±7.92; HH = 77.58 ±3.87; RH = 19.83 ±2.58) similar those presented by the men (BPS = 118.75 ±7.55; BPD = 75.00 ±9.91; HH = 71.75 ±14.95; RH = 16.62 ±3.99). The evaluation of those parameters before and after immersion of the volunteers in the water (condition 2) showed a significant reduction (W = 3.0: p≤0.05) barely for the values of BPS presented by the sex females after immersion. In the men group, all of the physiological parameters analyzed did not vary significantly. Regarding the profile of those variables before and after application of the watsu (condition 3), was verified a significant increase (W= 0,0: p≤0.05) for the BPS one and SABP in the women. The Men did not show significant variation for all of the physiological parameters. Faced with the results presented, we are able to conclude that the systolic and diastolic blood pressures were the physiological parameters that are on influence from the Technique Watsu, only for the kind females

Correlato eletroencefalográfico do estado vibracional

O estado vibracional (EV) é descrito como uma sensação de vibração intensa por todo o corpo, em que o sujeito se mantém num estado de relaxamento psicofisiológico que pode ser gerado de forma espontânea ou autoinduzida. Pessoas que aplicam esta técnica relatam alterações do estado mental e emocional, tais como: relaxamento, disposição, limpidez de pensamento, equilíbrio emocional, melhoria do raciocínio, bemestar, entre outros. Estas são, entretanto observações subjetivas, sendo a mensuração deste fenômeno uma lacuna e um desafio para a ciência. O objetivo desta pesquisa é explorar sistematicamente o estado vibracional no âmbito da neurociência. Desta forma, medidas eletroencefalográficas (EEG) foram utilizadas para observar se a sensação subjetiva de EV é acompanhada por mudanças na atividade elétrica cerebral. Além disso, para avaliar se o EV provoca algum efeito positivo em funções cognitivas como atenção e memória, foi utilizado um teste de reconhecimento de palavras antes e depois da aplicação da técnica de EV. Foram também aplicados questionários de dados gerais socioeconômicos e de saúde, do perfil de estados de humor, de qualidade do sono, além de inventários psicológicos. O foco inicial do trabalho foi a análise estatística dos dados de EEG, ficando as outras análises para uma etapa posterior. Dois grupos de voluntários foram analisados, o primeiro formado por 14 sujeitos que praticam a técnica de EV há pelo menos 10 anos (Grupo Experiente - GEXP), e o segundo formado por 11 sujeitos que nunca haviam realizado a técnica (Grupo Controle - GCONT). O GCONT obteve instruções sobre a técnica de EV antes dos experimentos. Foram realizadas análises estatísticas dos registros eletroencefalográficos, para comparar os grupos, em quatro condições: Basal, Relaxamento, Não-EV (período em que o sujeito está engajado na tarefa, mas ainda não percebe o EV) e EV (período em que o sujeito percebe o EV). Uma vez que os sujeitos do GCONT relataram não ter conseguido atingir a condição de EV propriamente, a comparação entre grupos foi feita apenas nas três condições, Basal, Relaxamento e Não-EV. Para isso, foi usado o teste de Mann-Whitney U com um limiar estatístico de p<0,05. De forma geral, o GEXP apresentou maior potência na banda de frequência alfa 2 (9,5-11,0 Hz) em todas as condições. Durante o período Não-EV, o GEXP também apresentou uma maior potência na banda de frequência alfa 3 (11,5-13,0 Hz) na região temporal esquerda, e gama 1 (30,5-55,0 Hz) e gama 2 (65,0-80,0 Hz) em regiões central, parietal e temporal esquerda, mas menor potência na banda de frequência teta 1 (3,5 - 5,0 Hz), em regiões centro-parietais. Para a análise estatística intragrupo, entre as condições, utilizou-se o teste estatístico Wilcoxon pareado. Observaram-se diferenças significativas (p<0,005), principalmente em regiões centrais, em teta 1 (3,5-5,0 Hz), sendo maior no Relaxamento, quando comparado com as condições Basal e Não-EV, no GCONT, e com o Não-EV e EV, no GEXP. No GEXP, a potência de gama 1 (30,5-55,0 Hz) e gama 2 (65,0-80,0 Hz) foi difusamente maior durante o EV, se comparado às outras três condições. Para o GCONT, apenas a condição Basal apresentou maior potência de gama 1 (30,5-55,0 Hz) e gama 2 (65,0- 80,0 Hz), se comparado com o Relaxamento. O aumento de teta 1 no Relaxamento, principalmente no GCONT, pode estar associado a uma maior sonolência deste grupo durante esta condição. Já o aumento de alfa 2 durante o Não-EV e o EV, pode estar associado com processos de atenção e cognição (DOLPPERMAYR et al., 2002; FELL et al., 2010; KLIMESCH et al., 1999; RAY E COLE, 1985). Por outro lado, o aumento da potência de gama em sujeitos experientes na técnica de EV encontrado aqui e em trabalhos anteriores, em meditadores experientes (FELL et al., 2010; LEHMANN et al., 2001; LUTZ et al., 2004), poderia estar associado a alterações nos processos mentais e cognitivos destes praticantes, tais como atenção, memória operacional, aprendizagem e percepção consciente embora, análises adicionais devam ser realizadas para excluir a possibilidade de interferência de artefatos musculares nos dados de EEG. Estes resultados suscitam a hipótese de que no engajamento da tarefa do EV e durante o EV, os sujeitos do GEXP conseguem manter-se em um estado de alerta, porém com maior nível de relaxamento e concentração. Uma inspeção mais detalhada dos dados, além de outros experimentos com diferentes protocolos, um maior número de sujeitos e pesquisas longitudinais são necessários para que testar esta hipótese

Comportamento de mergulho do boto-cinza, Sotalia guianensis, na enseada do Curral, Praia de Pipa-RN, Brasil :possíveis adaptações cardíacas ao mergulho

The marine tucuxi, Sotalia guianensis, is one of the smallest known cetaceans, has coastal habits, and occurs from Hondures to Santa Catarina, in southern Brazil. The objective of this dissertation was to describe diving behavior of the marine tucuxi in three age classes and to analyze the cardiac capacity to dive through the examination of hearts of stranded specimens. Observations were made from October 2004 to November 2005 from a vantage point, in Curral Bay at Pipa beach-RN. We used Ad Libitum sampling and All occurrences to record the behaviors. The diving was characterized by the total exposition of the tail fluke for a few seconds, in 90° or 45° angles. Were recorded 131 dives in three behavioral contexts: foraging, traveling and socialization. The difference between juveniles and adults in dive time and fluke out at 45° or 90° to search and/or capture prey is probably influenced by the strategy used and ability to capture the prey. The frequency of fluke out at 90° for foraging in adults may be related to increased physiological efficiency of adults in comparison to juveniles. However, in the context of travel and socialization the dive time and fluke out were independent between the age classes. Dive in calves were frequent during socialization (play behavior) and traveling. This, associated with synchronic calve-adult diving suggests that a relationship of these behaviors and the acquisition of experience and foraging skills. As observed in other cetaceans, the heart (n=12) of the estuarine dolphin is broad and presents long ventricles which form a round apex. The right ventricle is long and narrow. The degree of dilatation of the aortic bulb may support the heart during diastole. The characteristic morphology of the heart and short dive duration < 2 min and depth ranged from 10m in the estuarine dolphin, can be likely at physiological adaptation for diving, typical de dolphins with coastal habits. The limitation of diving time in this specie may be influenced by anatomical and physiological restrictions

A Praça André de Albuquerque, Natal/RN, na visão de seus frequentadores

The study offers a global and interpretative view of the person-environment inter-action at André de Albuquerque Plaza, in Natal, RN, according to a descriptive-exploratory approach that aimed at learning about the space converted into place, as it is perceived and experienced by users, who attribute meaning to it. The main objective was to critically analyze the relationship person-plaza, based on data collected about users perception, utilization and ascribed meaning. I have employed an Environmental Psychology multi-method approach, including informal observations, interactive poster session, videotaping and interviews. The results indicated that the plaza, besides being a passage point, is also a spot of urban convergence for several groups, particularly taxi drivers, flanelinhas, skate boarders and students. In regard to the perception of the place, an overall positive evaluation of the plaza was verified, since people perceive selectively what interests them. In terms of usage, different groups of users presented diverse patterns of utilization, also observed in the attributed meanings. The plaza is a work place for taxi drivers and flanelinhas and a sports arena for the skate boarders, with a practical meaning for both groups. For students and other users it is a place for meeting and leisure, revealing a stronger affective quality, responsible for feelings of well being, tranquility and relaxation. The data so obtained could contribute for future government projects of intervention in those spaces, aiming at its preservation as an open spot among the concrete of city buildings, offering better quality of life, not only for today, but also for future generations

Síntese, caracterização e avaliação catalítica do silicoaluminofosfato SAPO-11 sulfatado

Due to environmental restrictions around the world, clean catalytic technology are of fundamental importance in the petrochemical industry and refineries. Creating the face of this a great interest in replacing the liquid acids for solid acids, so as molecular sieves have been extensively studied in reactions involving the acid catalysis to produce chemical substances with a high potential of quality. Being the activity of the catalysts involved in the reaction attributed to the acid character of them involved for the Lewis and Brönsted acid sites. Based on this context, this study aimed to prepare catalysts acids using a molecular sieve silicoalumino-phosphate (SAPO-11) synthesized in hidrotermical conditions and sulphated with sulphuric acid at different concentrations, using to it the method of controlled impregnating. The samples resulting from this process were characterized by x-ray difratometry (DRX), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), thermal analysis (TG-DTG) and determination of total acidity (by n-butilamin adsorption). The results show that the synthesis method used was efficient in the formation of AEL structure of SAPO-11 and when being incorporated the sulfate groups in this structure the acidity of the material was increased, pointing out that to very high concentrations of acid there is a trend of decrease the main peaks that form the structure. Finally they were tested catalytictly by the reaction model of conversion of m-xylene which showed favorable results of conversion for this catalyst, showing to be more selective of cracking products than isomerization, as expected, in order that for the o-xylene selectivity there was no positive change when to sulfate a sample of SAPO-11, while for light gases of C1-C4 this selectivity was remarkably observed

Obtenção de polímeros graftizados de quitosana e estudo das propriedades físico-químicas para aplicação na indústria do petróleo

Chitosan is a biopolymer derived from the shells of crustaceans, biodegradable, inexpensive and renewable with important physical and chemical properties. Moreover, the different modifications possible in its chemical structure generate new properties, making it an attractive polysaccharide owing to its range of potential applications. Polymers have been used in oil production operations. However, growing concern over environmental constraints has prompted oil industry to search for environmentally sustainable materials. As such, this study sought to obtain chitosan derivatives grafted with hydrophilic (poly(ethylene glycol), mPEG) and/or hydrophobic groups (n-dodecyl) via a simple (one-pot) method and evaluate their physicochemical properties as a function of varying pH using rheology, small-angle Xray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. The chitosan derivatives were prepared using reductive alkylation under mild reaction conditions and the chemical structure of the polymers was characterized by nuclear magnetic resonance (1H NMR) and CHN elemental analysis. Considering a constant mPEG/Chitosan molar ratio on modification of chitosan, the solubility of the polymer across a wide pH range (acidic, neutral and basic) could only be improved when some of the amino groups were submitted to reacetylation using the one-pot method. Under these conditions, solubility is maintained even with the simultaneous insertion of n-dodecyl. On the other hand, the solubility of derivatives obtained only through mPEG incorporation using the traditional methodology, or with the ndodecyl group, was similar to that of its precursor. The hydrophilic group promoted decreased viscosity of the polymer solutions at 10 g/L in acid medium. However, at basic pH, both viscosity and thermal stability increased, as well as exhibited a pronounced pseudoplastic behavior, suggesting strong intermolecular associations in the alkaline medium. The SAXS results showed a polyelectrolyte behavior with the decrease in pH for the polymer systems. DLS analyses revealed that although the dilute polymer solutions at 1 g/L and pH 3 exhibited a high density of protonated amino groups along the polymer chain, the high degree of charge contributed significantly to aggregation, promoting increased particle size with the decrease in pH. Furthermore, the hydrophobic group also contributed to increasing the size of aggregates in solution at pH 3, whereas the hydrophilic group helped reduce their size across the entire pH range. Nevertheless, the nature of aggregation was dependent on the pH of the medium. Zeta potential results indicated that its values do not depend solely on the surface charge of the particle, but are also dependent on the net charge of the medium. In this study, water soluble associative polymers exhibit properties that can be of great interest in the petroleum industry