Síntese, caracterização e estudo da associação em meio aquoso de copolímeros responsivos de carboximetilcelulose-g-Jeffamine®

This thesis presents the synthesis, characterization and study of the associative behaviour in aqueous media of new responsive graft copolymers, based on carboxymethylcellulose as the water-soluble backbone and Jeffamine® M-2070 e Jeffamine® M-600 (commercial polyetheramines) as the thermoresponsive grafts with high cloud point temperatures in water. The synthesis was performed on aqueous medium, by using 1-ethyl-3- (3-(dimethylamino)-propyl)carbodiimide hydrochloride and N-hydroxysuccinimide as activators of the reaction between carboxylategroupsfrom carboxymethylcellulose and amino groups from polyetheramines. The grafting reaction was confirmed by infrared spectroscopy and the grafting percentage by 1H NMR. The molar mass of the polyetheramines was determined by 1H NMR, whereas the molar mass of CMC and graft copolymers was determined by static light scattering. The salt effect on the association behaviour of the copolymers was evaluated in different aqueous media (Milli-Q water, 0.5M NaCl, 0.5M K2CO3 and synthetic sea water), at different temperatures, through UV-vis, rheology and dynamic light scattering. None of the copolymers solutions, at 5 g/L, turned turbid in Milli-Q water when heated from 25 to 95 °C, probably because of the increase in hydrophibicity promoted by CMC backbone. However, they became turbid in the presence of salts, due to the salting out effect, where the lowest cloud point was observed in 0.5M K2CO3, which was attributed to the highest ionic strength in water, combined to the ability of CO3 2- to decrease polymer-solvents interactions. The hydrodynamic radius and apparent viscosity of the copolymers in aqueous medium changed as a function of salts dissolved in the medium, temperature and copolymer composition. Thermothickening behaviour was observed in 0.5M K2CO3 when the temperature was raised from 25 to 60°C. This performance can be attributed to intermolecular associations as a physical network, since the temperature is above the cloud point of the copolymers in this solvent.

Avaliação tribológica dos polímeros NBR, PTFE e PTFE gravitado em contato com aço AISI 52100

Low cost seals are made of NBR, Nitrile Butadiene Rubber, a family of unsaturated copolymers that is higher resistant to oils the more content of nitrile have in its composition, although lower its flexibility. In Petroleum Engineering, NBR seal wear can cause fluid leakage and environmental damages, promoting an increasing demand for academic knowledge about polymeric materials candidate to seals submitted to sliding contacts to metal surfaces. This investigation aimed to evaluate tribological responses of a commercial NBR, hardness 73 ± 5 Sh A, polytetrafluoroethylene (PTFE), hardness 60 ± 4 HRE and PTFE with graphite, 68 ± 6 HRE. The testings were performed on a sliding tribometer conceived to explore the tribological performance of stationary polymer plane coupons submitted to rotational cylinder contact surface of steel AISI 52100, 20 ± 1 HRC Hardness, under dry and lubricated (oil SAE 15W40) conditions. After screening testings, the normal load, relative velocity and sliding distance were 3.15 N, 0.8 m/s and 3.2 km, respectively. The temperatures were collected over distances of 3.0±0.5 mm and 750±50 mm far from the contact to evaluate the heating in this referential zone due to contact sliding friction by two thermocouples K type. The polymers were characterized through Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA). The wear mechanisms of the polymer surfaces were analyzed by Scanning Electron Microscopy (SEM) and EDS (Energy-Dispersive X-ray Spectroscopy). NBR referred to the higher values of heating, suggesting higher sliding friction. PTFE and PTFE with graphite showed lower heating, attributed to the delamination mechanism

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

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

Contribuição ao estudo avançado das argamassas de alto desempenho para reparos estruturais

Inúmeras estruturas de concreto no Brasil e no mundo estão atingindo o limite de sua vida útil projetada, completando um ciclo de cinco ou mais décadas de uso e operação. Além das estruturas mais antigas, existem ainda estruturas com reduzido tempo de serviço, e qualidade discutível, que já apresentam patologias em estado tão avançado que chegam a comprometer o seu desempenho. Vindo ao encontro dessas necessidades e no sentido de contribuir para o avanço científico e tecnológico do setor, este trabalho apresenta um método para dosagem, preparo e aplicação de argamassas de alto desempenho para recuperação de estruturas deterioradas, além de sugerir procedimentos para a realização desses reparos, fomentando a cultura das manutenções preventivas e desmistificando a complexidade atribuída a tais operações. Para tanto, foram realizados ensaios mecânicos, microestruturais e relacionados à durabilidade em corpos-de-prova moldados com sílica ativa e látex de estireno-butadieno. Os resultados indicaram que a adoção desses ingredientes, na composição da argamassa de reparo, provocou uma redução significativa da permeabilidade total e descontinuidade de poros, assim como promoveu uma melhor integridade dos constituintes da argamassa, traduzindo-se em uma ampliação, expressiva, das suas capacidades mecânicas. Quando comparada aos produtos industrializados da construção civil, com padrões similares, proporcionou uma economia da ordem de 85%, que permitiria recuperar, com os mesmos custos, quase cinco vezes mais estruturas comprometidas. Este estudo, de viés altamente tecnológico, vem oferecer à construção civil uma argamassa polimérica de alto desempenho, com função reparadora e custo mais acessível, que pode ser adotada em canteiros de obras, implementando ações de natureza sustentável e ainda atendendo às atuais exigências elencadas pela literatura, relacionadas à desempenho, vida útil e durabilidade das estruturas reparadas.

Revestimento decorativo monocamada pigmentado, com resíduo de vidro temperado, para aplicação em fachadas

Although efficient from a technical point of view, mortar layers that make up the traditional masonry coating (slurry mortar, plaster and plaster) have to be in contradiction with the new construction technologies and more efficient methods of consumption and work rationalization. From an environmental point of view, the recovery of waste into new composites for the building has been a growing strand of studies in the scientific community, may prove to be a cost-effective solution in some cases. Thus, this research proposes the development of a mortar Decorative Coating Monolayer (RDM), for use in facades, produced on site, incorporating tempered glass waste (RVT) in the cement matrix, as a partial substitute for aggregate. Therefore, we adopted the binder respect / aggregate of 1: 6 (by volume), consistency index 250mm ± 20, sand substitution levels of glass waste 20%, 50% and 80% and relative water / cement varied in many traits. Two additives were used, a polymer, styrene-butadiene-based, and other chemical, besides mineral and silica fume inorganic pigment in colors red, yellow and blue. Mechanical tests were carried out on fresh pasta and hardened, as well as for the applied coating on masonry, so as to demonstrate the feasibility of the material. In addition, it verified the adequacy of the RDM built environment by means of thermal tests. The results demonstrated the feasibility of the proposed RDM with significantly higher values when compared to norms, especially the dash-added replacement content of 20% and addition of pigment in red. Therefore, the study shows the scientific community as an incentive to the use of technological innovations in construction, increasing the range of alternatives available for housing production, with the proposition of a material that achieves the desired functionality and obtain environmental gain, and may be adopted on construction sites as an alternative industrialized mortars.