Avaliação do comportamento termoanalítico e oxidativo do biodiesel de mamona

In this work biodiesel was gotten through the transesterification reaction using the oil of castor as source of triglycerides and using the methylic route for obtaining of esters. For the characterization of biodiesel and its mixtures with mineral diesel oil, physical chemical parameters and several analytical techniques had been used, as well as: gas chromatography (GC), nuclear magnetic resonance of proton (1H NMR), infrared spectroscopy (IR) and thermal analysis. The chromatography confirmed the complete reaction of esters in biodiesel presenting a 97,08% conversion. The 1H - NMR presented singlet in 3,6 ppm corresponding to the hydrogen of the group ester RCOO CH3. The infrared presented a strong band in 1741 cm-1 referring to stretching C=O of ester and an average band in 1175 cm-1 referring C O deformation. With the data of thermal analysis it was possible to observe the thermal and oxidative stability of the samples changing the atmospheres of synthetic air and nitrogen, where stages of the thermal decomposition had been verified and had been attributed to the volatilization and/or decomposition of the triacylglycerides. The thermal degradation of the samples was carried through 150 and 210°C during 1, 12, 24 and 48 hours and was observed change in the thermogravimetric profile, therefore an increase in the number of stages of the thermal decomposition also occurred indicating characteristic intermediate composites of polymerization, being this confirmed through the rheological study that presented brusque increase of viscosity. The kinetic study showed that the activation energy has the following order: biodiesel > mineral diesel oil > mixtures biodiesel/diesel

Alquilação redutiva da quitosana a partir do glutaraldeído e 3-amino-1-pr

Chitosan derivatives were prepared by reductive alkylation using glutaraldehyde and 3-amino-1-propanol. The reducing agent used was the sodium borohydride. Tests of solubility, stability and viscosity were performed in order to evaluate these parameters effects in the reaction conditions (molar ratio of the reactants and presence of nitrogen in the reaction system). The molecular structure of commercial chitosan was determined by infrared (IR) and hydrogen nuclear magnetic resonance spectroscopy (1H NMR). The intrinsic viscosity and average molecular weight of the chitosan were determined by viscosimetry in 0.3 M acetic acid aqueous solution 0.2 M sodium acetate at 25 ºC. The derivatives of chitosan soluble in aqueous acidic medium were characterized by 1H NMR. The rheological behavior of the chitosan and of the derivative of chitosan (sample QV), which presented the largest viscosity, were studied as a function of polymer concentration, temperature and ionic strength of the medium. The results of characterization of the commercial chitosan (the degree of deacetylation obtained equal 78.45 %) used in this work confirmed a sample of low molar weight (Mv = 3.57 x 104 g/mol) and low viscosity (intrinsic viscosity = 213.56 mL/g). The chemical modification of the chitosan resulted in derivatives with thickening action. The spectra of 1H NMR of the soluble derivatives in acid aqueous medium suggested the presence of hydrophobic groups grafted into chitosan in function of the chemical modification. The solubility of the derivatives of chitosan in 0.25 M acetic acid aqueous solution decreased with increase of the molar ratio of the glutaraldehyde and 3-amino-1-propanol in relation to the chitosan. The presence of nitrogen and larger amount of reducing agent in reaction system contributed to the increase of the solubility, the stability and the viscosity of the systems. The viscosity of the polymeric suspensions in function of the shear rate increased significantly with polymer concentration, suggesting the formation of strong intermolecular associations. The chitosan presented pseudoplastic behavior with the increase in polymer concentration at a low shear rate. The derivative QV presented pseudoplastic behavior at all concentrations used and in a large range of shear rate. The viscosity of chitosan in solution decreased with an increase of the temperature and with the presence of salt. However, there was an increase of the viscosity of the chitosan solution at higher temperature (65 ºC) and ionic strength of the medium which were promoted by hydrophobic associating of the acetamide groups. The solutions of the chitosan derivatives (sample QV) were significantly more viscous than chitosan solution and showed higher thermal stability in the presence of salt as a function of the hydrophobic groups grafted into chitosan backbone

Preparação de resinas de poliuretana à base de óleo de mamona e dietanolamina

The aim of this work was the preparation of polyols from reactions between castor oil and dietanolamine to increase the hydroxyl content and the network degree in the products to application in electronic devices. The polyols and the mixtures obtained were characterized by nuclear magnetic ressonance. Castor oil (CO) is a natural triglyceride - based polyol possessing hydroxyl groups, which allow several reactions that produce many different products. Among them are the polyurethanes (PU), which have been considered an ideal product for the covering of electricelectronic circuits, due to their excellent electrical, shock-absorbing, solvents resistance and hydrolytic stability properties. About 90% of the fatty acids present in the castor oil are ricinoleic acid (12-hydroxyoleic acid), while the remaining 10% correspond to non-hydroxylated fatty acids, mainly linoleic and oleic acids. The chemical analysis of castor oil indicates a hydroxyl number of 2.7. In this work, a polyol was obtained by the reaction of the CO with diethanolamine (DEA), in order to elevate the hydroxyl value from 160 to 230 or to 280 mgKOH/g, and characterized by nuclear magnetic resonance (NMR) 1H and 13C (Mercury 200). The polyadition of the resulting polyol with isophorone diisocianate (IPDI) was carried out at 60°C, and the reaction kinetics was followed by rheological measurements in a Haake RS150 rheometer. The electrical properties were determined in a HP LCR Meter 4262A, at 1.0 Hz and 10.0 KHz. The chemical analysis showed that the polyols obtained presented hydroxyl number from 230 to 280 mgKOH/g. The polyadition reaction with IPDI produced polyurethane resins with the following properties: hardness in the range from 45 shore A to 65 shore D (ASTM D2240); a dielectric constant of 3.0, at 25°C (ASTM D150). Those results indicate that the obtained resins present compatible properties to the similar products of fossil origin, which are used nowadays for covering electric-electronic circuits. Therefore, the PUs from castor oil can be considered as alternative materials of renewable source, free from the highly harmful petroleum - derived solvents

Avaliação termoanalítica da eficiência de antioxidantes na estabilidade oxidativa do biodiesel de mamona

The biodiesel is defined as the mono-alkyl ester derived from long-chain fatty acids, from renewable sources such as vegetable oils or animal fat, whose use is associated with the replacement of fossil fuels in diesel engine cycle. The biodiesel is susceptible to oxidation when exposed to air and this process of oxidation affects the quality of fuel, mainly due to long periods of storage. Because of this, the oxidation stability has been the focus of numerous researches since it directly affects the producers, distributors and users of fuel. One of the possibilities to increase the resistance of biodiesel is the autoxidation treatment with inhibitors of oxidation. The antioxidants can be used as potential inhibitors of the effects of oxidation on the kinematic viscosity and the index of acidity of biodiesel, thereby increasing oxidative stability. This work aims to examine the efficiency of antioxidants, α-tocopherol and butylated hydroxy-toluene (BHT), added the biodiesel content of remembrance through Pressurized-Differential Scanning Calorimetry (P-DSC), Thermogravimetry (TG) and Petrology. The results showed that the use of antioxidant BHT, at the concentration of 2000ppm, increased resistance to oxidation of the biodiesel and oxidative induction time (OIT), which is a better result as antioxidant than the α-tocopherol. With the thermogravimetric analysis, it was observed that the biodiesel presented an initial decomposition temperature of lower tendency than that of oil, demonstrating to be more volatile, bearing great similarity to the diesel and being characterized as an alternative fuel. The rheological analysis indicated that each sample of biodiesel behaved as a Newtonian fluid

Partículas inteligentes de poli (nisopropilacrilamida), quitosana e poli (ácido acrílico): efeito da temperatura e do pH sobre suas propriedades em suspensões aquosas

The present study describes the stability and rheological behavior of suspensions of poly (N-isopropylacrylamide) (PNIPAM), poly (N-isopropylacrylamide)-chitosan (PNIPAMCS), and poly (N-isopropylacrylamide)-chitosan-poly (acrylic acid) (PNIPAM-CS-PAA) crosslinked particles sensitive to pH and temperature. These dual-sensitive materials were simply obtained by one-pot method, via free-radical precipitation copolymerization with potassium persulfate, using N,N -methylenebisacrylamide (MBA) as a crosslinking agent. Incorporation of the precursor materials into the chemical networks was confirmed by elementary analysis and infrared spectroscopy. The influence of external stimuli such as pH and temperature, or both, on particle behavior was investigated through rheological measurements, visual stability tests and analytical centrifugation. The PNIPAM-CS particles showed higher stability in acid and neutral media, whereas PNIPAM-CS-PAA particles were more stable in neutral and alkaline media, both below and above the LCST of poly (Nisopropylacrylamide) (stability data). This is due to different interparticle interactions, as well as those between the particles and the medium (also evidenced by rheological data), which were also influenced by the pH and temperature of the medium. Based on the results obtained, we found that the introduction of pH-sensitive polymers to crosslinked poly (Nisopropylacrylamide) particles not only produced dual-sensitive materials, but allowed particle stability to be adjusted, making phase separation faster or slower, depending on the desired application. Thus, it is possible to adapt the material to different media

Influência da acrilamida e da poliacrilamida em sistema microemulsionado visando aplicação na recuperação avançada de petróleo

This work aims to study the influence of two additives, the monomer, acrylamide and its polymer, polyacrylamide, solubilized in microemulsion systems and applied on enhanced oil recovery. By the microemulsion system obtained, it was chosen points into the phase diagram, presenting these compositions: 25%, 30%, 35% C/T; 2% Fo (fixed for all points) e 73%, 68% e 63% Fa, respectively. However, the monomer and the polymer were solubilized in these microemulsion points with 0.1%; 0.5%; 1% e 2% of concentration, ordering to check the concentration influence at the physicochemical properties (surface tension and rheology) of the microemulsion. Through the salinity study, was possible to observe that the concentrations of 1% and 2% of polymer made the solution became blurred, accordingly, the study of surface tension and rheology only was made for the concentrations of 0.1% e 0.5% of monomer and polymer, respectively. By the surface tension study it was observed that how the concentration of active matter (C/T) was increasing the surface tension was amending for each system, with or without additives. In the rheology study, as it increases the concentration of active matter increases both the viscosity of the microemulsion system (SME) with no additive, as the SME with polymer (AD2). After the entire study, it was chosen the lower point of active matter (25% C/T; 2% Fo e 73% Fa), plus additives in concentrations of 0.1% and 0.5% to be used on enhanced oil recovery. Assays were made on sandstone from Botucatu Formation, where after the tests, it was concluded that among the studied points, the point who showed the best efficiency of advanced shift was the microemulsion system + 0.5% AD2, with a recovery of 28% of oil in place and a total of 96,49%, while the other solution with 0.5% of polymer presented the worst result, with 14.1% of oil in place and 67,39% of efficiency of total displacement

Novas formulações de fluidos de corte: otimização, propriedades e recuperação do óleo usado

Cutting fluids are lubricants used in metal-mechanical industries. Their complex composition varies according to the type of operation carried out, also depending on the metals under treatment or investigation. Due to the high amount of mineral oil produced in Northeastern Brazil, we have detected the need to better use this class of material. In this work, two novel formulations have been tested, both based on naphthenic mineral oil and additives, such as: an emulsifying agent (A), an anticorrosion agent (B), a biocide (C) and an antifoam agent (D). Each formulation was prepared by mixing the additives in the mineral oil at a 700-rpm stirring velocity for 10 min, at 25°C, employing a 24 factorial planning. The formulations were characterized by means of density, total acid number (TAN), viscosity, flash point and anticorrosion activity. In a subsequent study, oil-in-water emulsions were prepared from these novel formulations. The emulsions were analyzed in terms of stability, corrosion degree, percentage of foam formation, conductivity, accelerated stability and particle size. The samples were appropriately labeled, and, in special, two of them were selected for featuring emulsion properties which were closer to those of the standards chosen as references (commercial cutting oils). Investigations were undertaken on the ability of NaCl and CaCl2 to destabilize the emulsions, at concentrations of 2%, 5% and 10%, at an 800-rpm stirring velocity for 5 min and temperatures of 25º, 40º, 50º and 60ºC. The recovered oils were chemically altered by reincorporating the same additives used in the original formulations, followed by preparation of emulsions with the same concentrations as those of the initial ones. The purpose was to assess the possibility of reusing the recovered oil. The effluents generated during the emulsion destabilization step were characterized via turbidity index, contents of oil and grease, pH, and contents of anions and cations, observing compliance with the parameters established by the current environmental legislation (Brazil s CONAMA 357/05 resolution). It could be concluded that the formulations presented excellent physicochemical properties as compared to commercial cutting fluids, showing that the quality of the newly-prepared fluids is superior to that of the formulations available in the market, enabling technically and environmentally-safe applications

Secagem de misturas de polpa de frutas tropicais em leito de jorro

Drying of fruit pulps in spouted beds of inert particles has been indicated as a viable technique to produce fruit powders. Most of the processes employed to produce dried fruit pulps and juices, such as Foam Mat, encapsulation by co-crystallization and spray drying utilize adjuvant and additives (such as thickeners, coating materials, emulsifiers, acidulants, flavors and dyes), which is not always desirable. The fruit pulp composition exerts an important effect on the fruit powder production using a spouted bed. In the study by Medeiros (2001) it was concluded that lipids, starch and pectin contents play an important role on the process performance, enhancing the powder production; however, the drying of fruit pulps containing high content of reducing sugars (glucose and fructose) is practically unviable. This work has the objective of expanding the studies on drying of fruit pulps in spouted bed with aid of adjuvant (lipids, starch and pectin) aiming to enhance the dryer performance without jeopardizing the sensorial quality of the product. The optimum composition obtained by Medeiros (2001) was the basis for preparing the mixtures of pulps. The mixture formulations included pulps of mango (Mangifera indica), umbu (Spondias tuberosa) and red mombin (Spondia purpurea) with addition of cornstarch, pectin and lipids. Different products were used as lipids source: olive and Brazil nut oils, coconut milk, heavy milk, powder of palm fat and palm olein. First of all, experiments were conducted to define the best formulation of the fruit pulps mixture. This definition was based on the drying performance obtained for each mixture and on the sensorial characteristics of the dry powder. The mixture formulations were submitted to drying at fixed operating conditions of drying and atomizing air flow rate, load of inert particles, temperature and flow rate of the mixture. The best results were obtained with the compositions having powder of palm fat and palm olein in terms of the drying performance and sensorial analysis. Physical and physicochemical characteristics were determined for the dry powders obtained from the mixtures formulations. Solubility and reconstitution time as well as the properties of the product after reconstitution were also evaluated. According to these analyses, the powder from the mixtures formulations presented similar characteristics and compatible quality to those produced in other types of dryers. Considering that the palm olein is produced in Brazil and that it has been used in the food industry substituting the palm fat powder, further studies on drying performance were conducted with the composition that included the palm olein. A complete factorial design of experiments 23, with three repetitions at the central point was conducted to evaluate the effects of the air temperature, feeding flow rate and intermittence time on the responses related to the process performance (powder collection efficiency, material retained in the bed and angle of repose of the inert particles after the process) and to the product quality (mean moisture content, loss of vitamin C and solubility). Powder production was uniform for the majority of the experiments and the higher efficiency with lower retention in the bed (59.2% and 1.8g, respectively) were obtained for the air temperature of 80°C, mixture feed rate of 5ml/min in intervals of 10 min. The statistical analysis of the results showed that the process variables had individual or combined significant influences on the powder collection efficiency, material retention in the bed, powder moisture content and loss of vitamin C. At the experimental ranges of this work, the angle of repose and solubility were not influenced by the operating variables. From the results of the experimental design, statistical models were obtained for the powder moisture content and loss of vitamin C

Obtenção de sistemas microemulsionados e estudo de simulação por dinâmica molecular de sistemas micelares objetivando a veiculação de produtos naturais bioativos

Among the new drugs launched into the market since 1980, up to 30% of them belong to the class of natural products or they have semisynthetic origin. Between 40-70% of the new chemical entities (or lead compounds) possess poor water solubility, which may impair their commercial use. An alternative for administration of poorly water-soluble drugs is their vehiculation into drug delivery systems like micelles, microemulsions, nanoparticles, liposomes, and cyclodextrin systems. In this work, microemulsion-based drug delivery systems were obtained using pharmaceutically acceptable components: a mixture Tween 80 and Span 20 in ratio 3:1 as surfactant, isopropyl mirystate or oleic acid as oil, bidistilled water, and ethanol, in some formulations, as cosurfactants. Self-Microemulsifying Drug Delivery Systems (SMEDDS) were also obtained using propylene glycol or sorbitol as cosurfactant. All formulations were characterized for rheological behavior, droplet size and electrical conductivity. The bioactive natural product trans-dehydrocrotonin, as well some extracts and fractions from Croton cajucara Benth (Euphorbiaceae), Anacardium occidentale L. (Anacardiaceae) e Phyllanthus amarus Schum. & Thonn. (Euphorbiaceae) specimens, were satisfactorily solubilized into microemulsions formulations. Meanwhile, two other natural products from Croton cajucara, trans-crotonin and acetyl aleuritolic acid, showed poor solubility in these formulations. The evaluation of the antioxidant capacity, by DPPH method, of plant extracts loaded into microemulsions evidenced the antioxidant activity of Phyllanthus amarus and Anacardium occidentale extracts. For Phyllanthus amarus extract, the use of microemulsions duplicated its antioxidant efficiency. A hydroalcoholic extract from Croton cajucara incorporated into a SMEDDS formulation showed bacteriostatic activity against colonies of Bacillus cereus and Escherichia coli bacteria. Additionally, Molecular Dynamics simulations were performed using micellar systems, for drug delivery systems, containing sugar-based surfactants, N-dodecylamino-1-deoxylactitol and N-dodecyl-D-lactosylamine. The computational simulations indicated that micellization process for N-dodecylamino-1- deoxylactitol is more favorable than N-dodecyl-D-lactosylamine system.

Influência da densidade de carga e da massa molar da poliacrilamida na reologia de sistemas microemulsionados

The knowledge of the rheological behavior of microemulsionated systems (SME) is of fundamental importance due to the diversity of industrial applications of these systems. This dissertation presents the rheological behavior of the microemulsionated system formed by RNX 95/alcohol isopropyl/p-toulen sodium sulfonate/kerosene/distilled water with the addition of polyacrylamide polymer. It was chosen three polymers of the polyacrylamide type, which differ in molar weight and charge density. It was studied the addition of these polymers in relatively small concentration 0,1% in mass and maximum concentration of 2,0%. It was made analysis of flow to determine the appearing viscosities of the SME and rheological parameters applying Bingham, Ostwald de Waale and Herschell-Buckley models. The behavior into saline environment of this system was studied for a solution of KCl 2,0%, replacing the distilled water. It was determined the behavior of microemulsions in relation with the temperature through curves of flow in temperatures of 25 to 60ºC in variations of 5ºC. After the analysis of the results the microemulsion without the addition of polymer presented a slight increase in its viscosity, but it does not mischaracterize it as a Newtonian fluid. However the additive systems when analyzed with low concentration of polymer adjusted well to the applied models, with a very close behavior of microemulsion. The higher concentration of the polymer gave the systems a behavior of plastic fluid. The results of the temperature variation point to an increase of viscosity in the systems that can be related to structural changes in the micelles formed in the own microemulsion without the addition of polymer

Estudos das interações de quitosana/CTAB/C12E8

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

Interações entre a carboximetilcelulose, carbonato de cálcio e bentonita: repercussões sobre as propriedades dos fluidos de perfuração aquosos

The role of carboxymethylcellulose (CMC) in association to calcium carbonate particles (CaCO3) in most water-based drilling fluids is to reduce the fluid loss to the surrounding formation. Another essential function is to provide rheological properties capable of maintaining in suspension the cuttings during drilling operation. Therefore, it is absolutely essential to correlate the polymer chemical structure (degree of substitution, molecular weight and distribution of substituent) with the physical-chemical properties of CaCO3, in order to obtain the better result at lower cost. Another important aspect refers to the clay hydration inhibitive properties of carboxymethylcellulose (CMC) in drilling fluids systems. The clay swelling promotes an undesirable damage that reduces the formation permeability and causes serious problems during the drilling operation. In this context, this thesis consists of two main parts. The first part refers to understanding of interactions CMC-CaCO3, as well as the corresponding effects on the fluid properties. The second part is related to understanding of mechanisms by which CMC adsorption occurs onto the clay surface, where, certainly, polymer chemical structure, ionic strength, molecular weight and its solvency in the medium are responsible to affect intrinsically the clay layers stabilization. Three samples of carboximetilcellulose with different molecular weight and degree of substitution (CMC A (9 x 104 gmol DS 0.7), CMC B (2.5 x 105 gmol DS 0.7) e CMC C (2.5 x 105 gmol DS 1.2)) and three samples of calcite with different average particle diameter and particle size distribution were used. The increase of CMC degree of substitution contributed to increase of polymer charge density and therefore, reduced its stability in brine, promoting the aggregation with the increase of filtrate volume. On the other hand, the increase of molecular weight promoted an increase of rheological properties with reduction of filtrate volume. Both effects are directly associated to hydrodynamic volume of polymer molecule in the medium. The granulometry of CaCO3 particles influenced not only the rheological properties, due to adsorption of polymers, but also the filtration properties. It was observed that the lower filtrate volume was obtained by using a CaCO3 sample of a low average size particle with wide dispersion in size. With regards to inhibition of clay swelling, the CMC performance was compared to other products often used (sodium chloride (NaCl), potassium chloride (KCl) and quaternary amine-based commercial inhibitor). The low molecular weight CMC (9 x 104 g/mol) showed slightly lower swelling degree compared to the high molecular weight (2.5 x 105 g/mol) along to 180 minutes. In parallel, it can be visualized by Scanning Electron Microscopy (SEM) that the high molecular weight CMC (2.5 x 105 g/mol e DS 0.7) promoted a reduction in pores formation and size of clay compared to low molecular weight CMC (9.0 x 104 g/mol e DS 0.7), after 1000 minutes in aqueous medium. This behavior was attributed to dynamic of interactions between clay and the hydrodynamic volume of CMC along the time, which is result of strong contribution of electrostatic interactions and hydrogen bounds between carboxylate groups and hydroxyls located along the polymer backbone and ionic and polar groups of clay surface. CMC adsorbs on clay surface promoting the skin formation , which is responsible to minimize the migration of water to porous medium. With the increase of degree of substitution, it was observed an increase of pores onto clay, suggesting that the higher charge density on polymer is responsible to decrease its flexibility and adsorption onto clay surface. The joint evaluation of these results indicate that high molecular weight is responsible to better results on control of rheological, filtration and clay swelling properties, however, the contrary effect is observed with the increase of degree of substitution. On its turn, the calcite presents better results of rheological and filtration properties with the decrease of average viii particle diameter and increase of particle size distribution. According to all properties evaluated, it has been obvious the interaction of CMC with the minerals (CaCO3 and clay) in the aqueous medium

Avaliação das propriedades físico-químicas de sistemas a base de carboximetilcelulose e poli (N-isopropilacrilamida) em soluções aquosas para aplicação na indústria do petróleo

Sustainable development is a major challenge in the oil industry and has aroused growing interest in research to obtain materials from renewable sources. Carboxymethylcellulose (CMC) is a polysaccharide derived from cellulose and becomes attractive because it is water-soluble, renewable, biodegradable and inexpensive, as well as may be chemically modified to gain new properties. Among the derivatives of carboxymethylcellulose, systems have been developed to induce stimuli-responsive properties and extend the applicability of multiple-responsive materials. Although these new materials have been the subject of study, understanding of their physicochemical properties, such as viscosity, solubility and particle size as a function of pH and temperature, is still very limited. This study describes systems of physical blends and copolymers based on carboxymethylcellulose and poly (N-isopropylacrylamide) (PNIPAM), with different feed percentage compositions of the reaction (25CMC, 50CMC e 75CMC), in aqueous solution. The chemical structure of the polymers was investigated by infrared and CHN elementary analysis. The physical blends were analyzed by rheology and the copolymers by UV-visible spectroscopy, small-angle X-ray scattering (SAXS), dynamic light scattering (DLS) and zeta potential. CMC and copolymer were assessed as scale inhibitors of calcium carbonate (CaCO3) using dynamic tube blocking tests and chemical compatibility tests, as well as scanning electron microscopy (SEM). Thermothickening behavior was observed for the 50 % CMC_50 % PNIPAM and 25 % CMC_75 % PNIPAM physical blends in aqueous solution at concentrations of 6 and 2 g/L, respectively, depending on polymer concentration and composition. For the copolymers, the increase in temperature and amount of PNIPAM favored polymer-polymer interactions through hydrophobic groups, resulting in increased turbidity of polymer solutions. Particle size decreased with the rise in copolymer PNIPAM content as a function of pH (3-12), at 25 °C. Larger amounts of CMC result in a stronger effect of pH on particle size, indicating pH-responsive behavior. Thus, 25CMC was not affected by the change in pH, exhibiting similar behavior to PNIPAM. In addition, the presence of acidic or basic additives influenced particle size, which was smaller in the presence of the additives than in distilled water. The results of zeta potential also showed greater variation for polymers in distilled water than in the presence of acids and bases. The lower critical solution temperature (LCST) of PNIPAM determined by DLS corroborated the value obtained by UV-visible spectroscopy. SAXS data for PNIPAM and 50CMC indicated phase transition when the temperature increased from 32 to 34 °C. A reduction in or absence of electrostatic properties was observed as a function of increased PNIPAM in copolymer composition. Assessment of samples as scale inhibitors showed that CMC performed better than the copolymers. This was attributed to the higher charge density present in CMC. The SEM micrographs confirmed morphological changes in the CaCO3 crystals, demonstrating the scale inhibiting potential of these polymers

Desenvolvimento de misturas instantâneas de mandioca e caseína: efeito do teor de proteína e parâmetros de extrusão sobre a viscosidade

O interesse da indústria de alimentos por produtos desenvolvidos a partir de farinhas acrescidas de proteína não se deve somente às suas características nutricionais, senão também às suas propriedades funcionais e reológicas, as quais definem as suas aplicações comerciais. Este trabalho teve por objetivo avaliar o efeito de parâmetros operacionais do processo de extrusão sobre as propriedades de pasta de misturas de farinha de mandioca e caseína. O processo de extrusão seguiu o delineamento 'central composto rotacional' para três fatores: teor de proteína (2,5 a 9,5%), umidade (14,5 a 19,5%) e temperatura de extrusão (65 a 135 ºC). As misturas antes e após a extrusão foram analisadas no Rapid Visco Analyser (RVA) quanto a: viscosidade inicial, pico de viscosidade, quebra de viscosidade, viscosidade final e tendência à retrogradação. Os resultados obtidos nas misturas antes da extrusão mostraram aumento dos valores de viscosidade com o aumento da concentração de proteína até o ponto central (6%) e, nos teores mais elevados de proteína, ocorreu redução destes. Após a extrusão, observou-se que o teor de proteína foi a variável de maior efeito sobre as propriedades de pasta, seguida pela umidade das misturas.