In this work, Doehlert experimental design was used to optimize the Transesterification Double Step Process (TDSP) method of methyl soybean oil biodiesel production which starts with a basic catalysis followed by an acidic catalysis. The conversion values were calculated from NMR spectra. Response surface was used to show the results of the interactions between the variables. This experimental design evaluated variables like catalyst and alcohol amount for the basic catalysis and time and temperature for the acidic catalysis. According to results obtained after Doehlert design application the alcohol amount was the main factor that influenced on the basic catalysis but for the acidic catalysis both time and temperature are important and their effects are opposite. It resulted on excellent conversions for both steps obtaining for the basic catalysis about 100% when was used like optimal conditions catalyst amount equal to 0.40 g and volume of methanol equal to 60 mL and for the acidic catalysis about 99% when was used like optimal conditions temperature of 65 °C and 90 minutes for reaction time.

In this study, hierarchical cluster analysis (HCA) and principal component analysis (PCA) were used to classify blends produced from diesel S500 and different kinds of biodiesel produced by the TDSP methodology. The different kinds of biodiesel studied in this work were produced from three raw materials: soybean oil, waste cooking oil and hydrogenated vegetable oil. Methylic and ethylic routes were employed for the production of biodiesel. HCA and PCA were performed on the data from attenuated total reflectance Fourier transform infrared spectroscopy, showing the separation of the blends into groups according to biodiesel content present in the blends and to the kind of biodiesel used to form the mixtures.

Methanolic transesterification of oils and fats was carried out in a two steps procedure, under basic and acidic catalysis. Palm, soybean, canola, corn, rice, grapeseed, sunflower, peanut, pequi and olive oils, besides tallow and lard were used as feedstock. Specific gravity, relative viscosity, thin layer chromatography and gas chromatography were used to characterize the biodiesel. Biodiesel was obtained in high yield and purity. Results were used to discuss the following key-concepts: 1 - triglycerides, composition and properties; 2 - nucleophilic acyl substitution under basic and acid conditions, 3 - thin layer chromatography, 4 - gas chromatography and its quantitative methods.

On undergraduate courses, practical classes represent periods in which students can verify the concepts presented in theoretical classes. Conversely, the teaching internship in graduate programs allows these students to incorporate pedagogical practices into their experience, predominantly involving observation and reproduction of methods adopted by supervisors. We propose internship teaching as a period for reflection on our pedagogical practice and present a methodology for an experimental physical chemistry classroom. The students can interact with the experiment and instructor, furthering the study of ternary systems while developing their skills for investigative work.

A dynamic mechanical analysis (DMTA) study was conducted on epoxy-amine networks crosslinked in the presence of low contents of hydroxypropyl cellulose (HPC). The epoxy resin chosen was diglycidylether of bisphenol-A (DGEBA) and the crosslinker was 4,4'-diaminodiphenylmethane (DDM). In the glassy region, primary (α) and secondary (β, γ) relaxations originating from the epoxy and HPC components were well detected. Two primary relaxations of neat epoxy and epoxy/HPC systems, referred to as αepoxy and α'epoxy, could be detected, showing a particular glassy behavior for the systems studied in comparison with systems cured in bulk. The main relaxation temperature Tα (at the peak of αepoxy relaxation) of the epoxy systems increased slightly with the addition of HPC. The activation energy for this transition (Tα) of the epoxy-amine networks was determined both from tan δ and the peak temperatures for the loss modulus measured at various frequencies. The activation energy of the αepoxy relaxation determined from the loss modulus was more reliable than that based on tan δ. The addition of HPC lowered the activation energy of this αepoxy relaxation.

Estudou-se a agregação de surfactantes aniônicos em soluções aquosas diluídas de (hidroxipropil)celulose (HPC) sob moderada força iônica (NaCl 0,1 mol L-1). Empregaram-se os surfactantes colato de sódio (CS), deoxicolato de sódio (DC) e dodecil sulfato de sódio (SDS). Observou-se decréscimo da concentração de agregação crítica (C1) para SDS e DC em comparação à concentração micelar crítica (CMC), enquanto ocorreu aumento para CS, a 298 K. A viscosidade relativa apresentou um máximo para o sistema SDS/HPC, mas permaneceu constante para CS/HPC ou DC/HPC. Houve aumento da temperatura de turbidez para todos os sistemas. Utilizando-se espalhamento de luz dinâmico, verificou-se que, a baixas concentrações de surfactante, o modo rápido da HPC relaciona-se a agregados surfactantes/HPC e cadeias poliméricas curtas; a altas concentrações, a micelas livres. O modo lento relaciona-se a complexos surfactante/HPC ou a "clusters" de HPC. Nos sistemas sais biliares/HPC, o mecanismo de agregação pode ocorrer em duas etapas.

The aggregation of different anionic surfactants in dilute aqueous solutions of (hydroxypropyl)cellulose (HPC) under moderate ionic strength (NaCl 0.1 mol L-1) was studied. The surfactants were sodium cholate (CS), sodium deoxycholate (DC) and sodium dodecylsulphate (SDS). By fluorescence probing, the critical aggregate concentration (C1) decreased for SDS and DC in comparison to the critical micelle concentration (CMC) whereas it increased for CS at 298 K. The relative viscosity reached a maximum for SDS/HPC but remained constant for CS/HPC and DC/HPC. By light scattering, cloud points were verified to increase. By dynamic light scattering, it was concluded that, at low surfactant contents, the fast mode of HPC is related to surfactant/HPC aggregates and shorter HPC chains; at high contents, to free micelles. The slow mode is linked to interchain polymer-surfactant complexes and HPC clusters. For the bile salts/ HPC systems, the mechanism of aggregation may occur in two steps.

The introduction of epoxy groups into the main chain of elastomers has emerged as a promising alternative, considering the monitoring of polymer-filler interaction leading to changes in the properties of vulcanizates. The epoxidation reaction (in situ) was chosen to modify elastomers, such as polybutadiene (BR) and copolymer of styrene-butadiene-rubber (SBR), because it is a simple, easily controlled reaction, even considering the small epoxidation degree. The modification degree of the polymeric chain was studied with FT-IR and ¹H-NMR. The shift of the Tg to high temperatures with the increase of the epoxy group in the polymer chain was monitored through differential scanning calorimetry (DSC). An analysis of the dynamic modulus of the material in relation to its dependence on the amplitude and temperature was carried out. The interaction between epoxidized elastomeric matrix and silica as filler was extremely improved, even in the presence of very low content of epoxy groups into the polymer chain.

A new construction of a capillary electrophoresis instrument with a universal conductivity detector (oscillometric detector) is described. The performance of the electrophoresis equipment was evaluated through the separation and detection of inorganic anions and cations in aqueous solutions. The results reproduced those found in the literature for the investigated probe ions, showing an efficient separation and good repeatability.

New types of polyurethanes were prepared by reacting diisocyanates and formiated soy polyols with different OH functionalities. Thermal properties and degradation kinetics were investigated by TGA. All prepared PU's showed at least two-weight loss steps, the first one, around 210 °C. Thermal stability of these PUs depends strongly on urethane groups per unit volume and an increase in the weight loss was observed as a result of the increased amount of urethane groups. Degradation kinetics behavior of the soy-based polyurethanes was investigated according to the Flynn method. Different average activation energy values were obtained from isothermal and isoconversional curves, 140.6 KJ/mol and 62.8 KJ/mol, respectively, indicating the complexity of the PUs degradation process.

A utilização de modificações químicas de polidienos comerciais tem sido estudada como um meio alternativo à síntese de novos polímeros, para otimização das propriedades finais destes materiais através da introdução de diferentes grupamentos reativos na cadeia polimérica. A modificação química pode ser feita através de diferentes métodos, os quais podem ser realizados tanto em solução como em massa, onde podem ser destacadas as reações de epoxidação, sulfonação, maleinização, carboxilação, etc. Neste trabalho foi estudado o método de epoxidação de borrachas do tipo SBR e BR. Foi possível observar que mesmo pequenos graus de modificação química causam mudanças marcantes nas propriedades finais dos polímeros, como determinado para a temperatura de transição vítrea.

Chemical modification of polydiene has been studied as an alternative route to obtain modified polymers with improved final properties. This improvement is due to the introduction of different kinds of reactive groups into a polymer chain, and it can be done in solution as well as in bulk. The chemical modification can be carried out by different methods such as epoxidation, maleination, carboxylation, sulfonation etc. In this work we show that in the epoxidation of SBR and BR even a small degree of modification can change the final properties of the polymer, as it occurred for the glass transition temperature.

Este artigo apresenta um procedimento para determinar a condutividade térmica de gases através de injeção por pulso, utilizando um detector de condutividade térmica (TCD). As medidas foram efetuadas à 323K e pressão atmosférica, com um sensor de filamento de tungstênio de 160 ômega. Através de aproximações bem definidas, foi possível transformar uma equação de segunda ordem não-linear, que descreve a saída do sensor como uma função de condutividade térmica e calor específico a volume constante (Cv), em uma equação linear de primeira ordem. De acordo com esta equação, o sinal elétrico do sensor, elevado ao quadrado e integrado em função do tempo, multiplicado pelo Cv, é proporcional a razão do Cv pela condutividade térmica. Os resultados experimentais obtidos com os gases Ar, N2, O2, CH4, CO2, C2H4, C3H6 e i-C4H8 estão de acordo com o modelo teórico proposto e a correlação de linearidade confirma a validade do método proposto.

This paper presents a procedure to determine the thermal conductivity of gases by pulse injection, using a thermal conductivity detector (TCD). The measurements are taken at 323K and atmospheric pressure with a 160 omega tungsten filament sensor. Under well defined approximations the original nonlinear second order equation, which describes the sensors output, as a function of thermal conductivity and constant volume specific heat was transformed into a linear first order equation. According to this equation the time integrated, second order sensors electrical output signal, multiplied by the constant volume heat capacity is proportional to the constant volume heat capacity, divided by the thermal conductivity. The experimental results obtained with Ar, N2, O2, CH4, CO2, C2H4, C3H6 and i-C4H8 gases are in good agreement with the proposed theoretical model and the linearity correlation confirms the validity of the proposed method.

Fluorescence probing, viscosity and light scattering measurements have been combined to study the aggregation of different anionic surfactants mainly in dilute solutions (0.5% w/v) of (hydroxypropyl)cellulose (HPC MW 173,000), in moderate ionic strength (NaCl 0.1 mol.L-1). The set of surfactants includes natural cholesterol derivatives, sodium cholate (CS) and sodium deoxycholate (DC), and the alkylsulphate, sodium dodecylsulphate (SDS). At 298 K the critical surfactant concentration related to aggregate/HPC formation (C1) decreases for SDS and DC whereas it increases slightly for CS. At 312 K the C1 values for CS and DC are slightly shifted toward higher values whereas it is not changed for SDS. All surfactant/HPC systems increase C1 values as the HPC concentration increases to 1.2%. Above C1 the viscosity increases for all surfactant/HPC systems but it is sharper in the increasing order CS, DC and SDS. The hydrodynamic behavior indicates that CS induces higher diffusion to HPC than SDS and DC. The aggregation in the surfactant/HPC systems is analyzed through the feature of surfactant/aggregate structure (size, charge density, etc).

The development of simple methods for removal of heavy metals from aqueous samples is a relevant field of research. In this connection, the electrodeposition of the Cd+2 ion, one of the most toxic species for animals and human beings, was investigated in aerated pH 4.8 sulfuric-sulfate solutions. In potentiostatic conditions, the maximum rate of cadmium deposition at a neutral polypyrrole (PPy0) coated reticulated vitreous carbon (RVC) working electrode occurs at -3.0 V vs. the saturated calomel reference electrode (SCE). Moreover, the conversion rate depends both on the applied potential and on the mass transport regime, and, for solutions containing 10 mg L-1 of Cd2+, the highest removal efficiency achieved is 84% after 90 min of electrolysis. The concentration decay of the Cd+2 ion in the solution was monitored by anodic stripping voltammetry (ASV) at a hanging mercury drop electrode. Besides, metallic cadmium deposited onto the polypyrrole modified RVC electrode was evidenced by Scanning Electron Microscopy (SEM) analysis using the backscattered electron image (BEI) technique and by Energy Dispersive Spectrometry (EDS).

We evaluate the orientation of microstructural elements of isotatic polypropylene (i-PP) before and after deformation using computerized "Quantikov" software analysis of Scanning Electron Microscopy (SEM) images. We observed that before deformation through uniaxial compression, the polymeric material doesn’t exhibit any significant orientation. After deformation at 1349 MPa the material clearly showed preferential orientation that was attested by the orientation axis seen between two petals of the rose of the number of intercepts. This effect was more pronounced after deformation at 2699 MPa.

Neste trabalho, estudou-se o efeito do envelhecimento físico nas propriedades térmicas e mecânicas em sistemas diglicidil éter do bisfenol-A (DGEBA)/diaminodifenilmetano (DDM), em função do grau de conversão, induzido pela cura e do tempo de envelhecimento. A cura isotérmica foi realizada em uma etapa a 115°C por diversos tempos e o envelhecimento foi conduzido a 100°C por períodos de 240 a 4320 min. Considerando que o envelhecimento físico acarreta variações estruturais as quais afetam tanto o desempenho mecânico quanto as propriedades termodinâmicas do material, as técnicas de DSC e DMA são complementares. Através de Calorimetria Exploratória Diferencial (DSC), observou-se que o envelhecimento físico está associado ao pico endotérmico que ocorre na região da transição vítrea e que a entalpia de relaxação, calculada a partir da área deste pico, aumenta gradualmente com o tempo de envelhecimento. Os resultados obtidos por Análise Dinâmico-Mecânica (DMA) mostraram um aumento do módulo elástico E' com o tempo de envelhecimento. As velocidades de envelhecimento foram obtidas a partir da temperatura do pico endotérmico, a partir do módulo elástico E' e a partir da temperatura de transição vítrea e resultaram tanto menores quanto maior o grau de conversão da matriz. Os resultados salientam a importância da seleção adequada das condições de cura para que se possam obter as melhores propriedades destes materiais. A importância dos fenômenos observados é considerada, tendo-se em vista a grande utilização e aplicabilidade das resinas epóxi.

Physical aging effect on thermal and mechanical properties of a series of diglycidyl ether of bisphenol-A (DGEBA)/diaminodiphenylmethane (DDM) systems has been investigated as a function of conversion, induced by cure, and aging time. The isothermal curing was carried out in one step at 115°C for various times. Samples were aged at 100°C for periods of time from 240 to 4320 min. Since physical aging causes structural changes which affect the mechanical performance as well as the thermodynamic properties of the material, DSC and DMTA techniques are complementary in monitoring physical aging processes. Through Differencial Scanning Calorimetry (DSC) it was found that the extent of physical aging can be associated with the area of the endothermic peak which appears within the glass transition region. The enthalpy relaxation (area of the peak) increases gradually with aging time. The Dynamic Mechanical Thermal Analysis (DMTA) results showed that the elastic modulus (E') increases with aging time. Aging rates were obtained through the endothermic peak temperature, through the storage modulus E'and through the glass transition temperature and displayed a decrease with increasing conversion degree. The DMTA technique is very sensitive to structural changes in the investigated epoxy systems due to curing and physical aging . The DMTA results obtained from mixtures cured according to different thermal histories underline the importance of adequate selection of curing conditions in order to obtain the optimum properties from these materials. The importance of the observed phenomena is considered in view of the widespread use of epoxy resins.