SEM study of the morphology of asymmetric cellulose acetate membranes produced from recycled agro-industrial residues: sugarcane bagasse and mango seeds

Cellulose, obtained both from sugarcane bagasse and mango seeds, was used for synthesizing cellulose acetate in order to produce asymmetric membranes. These were compared to membranes of commercial cellulose acetate (Rhodia). All produced membranes were asymmetric, characterized by the presence of a dense skin and a porous support. Differences regarding the morphology of the surfaces as well as of the porous support can be noticed. Scanning Electron Microscopy (SEM) showed that the morphology of the superficial layer, responsible for transport, depends on the different lignin content of the starting material and also on the viscosity average molecular weight of the cellulose acetates produced from sugarcane bagasse, mango seed, and Rhodia’s commercial cellulose acetate.     

Extensive N‐methylation of chitosan: evaluating the effects of the reaction conditions by using response surface methodology

The effects of reaction time, concentration of aqueous sodium hydroxide and molar ratio iodomethane/chitosan on the yield of the reaction of chitosan with iodomethane in N‐methyl‐2‐pyrrolidone (NMP) at 25.0 ± 0.1 °C, as well as on the characteristics of the resulting N,N,N‐trimethylchitosan (TMCh), were evaluated by using full‐factorial 2³ design analysis and response surface methodology. This study also aimed to determine the reaction conditions allowing the production of water‐soluble TMCh presenting a high average degree of quaternization and intrinsic viscosity at high reaction yield. ¹H NMR spectroscopy was employed for structural characterization, including the determination of average degrees of acetylation () and quaternization (), while capillary viscometry was used to determine intrinsic viscosity [η]. The results show that when the extensive N‐methylation is carried out for 24 h in NMP/15% NaOH (w/v) employing a lower excess of iodomethane (CH₃I/Ch = 9), water‐soluble highly substituted ( = 46.0%) TMCh ([η] = 213.0 mL g^?1) can be produced in high yield (81.8%). The highly significant mathematical models resulting from this study describe the dependence of the experimental responses on the reaction conditions and allow the characteristics and properties of the resulting TMCh to be defined by properly choosing the reaction conditions. © 2015 Society of Chemical Industry     

Experimental campaign,modeling, and sensitivity analysis for the molecular distillation of petroleum residues 673.15 K+

This research activity proposes a sensitivity analysis of the molecular distillation process by focusing the attention on the response of the overall distillate flow rate under several conditions of distillation temperature and feed flow rate. Specific equations to characterize physicochemical properties of petroleum residues have been formulated by means of ASTM-based experimental campaigns combined with specific optimization techniques.     

Esters from castor oil functionalized with aromatic amines as a potential lubricant

Vegetable oils are very promising alternatives to fossil lubricants due to their abundance, low cost, excellent performance, and environmental friendliness. Due to its multifunctional structure, castor oil is an excellent precursor in the synthesis of new biolubricants. However, it showed poor thermal-oxidative stability and a higher pour point. This study used castor oil fatty acids prepared by transesterification (EHRO), epoxidation (TEPO), and oxirane ring opening with the aromatic amines aniline (ANIL) and p-anisidine (ANIS). The chemical structure of these oils was verified by ¹H and ¹³C NMR analysis, and mass spectrometry. Measurements show that the presence of an aromatic amine increases the viscosity resulting in 172 (ANIL) and 199 (ANIS) cSt at 40°C, but reduces viscosity index to 16 and 1, respectively. In addition, the amine groups can scavenge radicals increasing their thermal and oxidative stability. These products do not oxidize copper, and tribological analysis reveals that ANIS has the lowest torque with wear equivalent to commercial mineral lubricant NH-140.     

Beliefs on vitamin and consumption of vitamin supplements among university students in the city of São Paulo

A survey was conducted in a sample of 894 students entering a private university in S?o Paulo to examine the vitamin beliefs and to verify the relation between vitamin beliefs and vitamin supplements consumption. Nineteen statements about the relation between vitamins and health were developed to assess the beliefs; the respondents answered by means of a 5-point agreement scale. Cronbach's alpha coefficient of internal consistency was determined for the total scale. 94.5% of students believe that vitamin C prevents and cures the common cold and 72.5% consider vitamins as an energy source. Many students recognize the possibility of health risks associated to excessive vitamin consumption. Vitamin supplement users had a belief score higher than non-users (p < 0.001). The results indicate that several misconceptions about vitamin benefits are common among the students and suggest a relation between vitamin beliefs and supplements consumption.     

Catalytic conversion ofHevea brasiliensis andVirola sebifera oils to hydrocarbon fuels

Catalytic hydrocracking ofHevea brasiliensis (Seringa) andVirola sebifera (Ucuuba) oils was carried out in the presence of a NiMo/Al₂O₃ catalyst sulfidizedin situ with elemental sulfur at 360°C. The initial pressure of hydrogen was 140 bars. Conversions of nearly 100% of the vegetable oils were achieved. The compositions of the liquid fuels were studied in detail by gas chromatography/mass spectrometry. The main products were found to be alkanes, cycloalkanes, aromatics and carboxylic acids.     

Transport properties of dichloromethane in glassy polymers. I. Atactic polystyrene films

Sorption and diffusion of dichloromethane vapor were measured in atactic polystyrene films, obtained with different cooling conditions and after controlled aging times at different temperatures. The diffusional behavior is characterized by three zones, depending on temperature and penetrant activity. In Zone I, at low activity, the diffusion coefficient is independent of vapor concentration; Zone II is characterized by concentration-dependent diffusion, whereas in Zone III structural transformations are possible. The study of diffusion at three temperatures allowed building of a temperature-penetrant concentration diagram, which is very useful to visualize the different zones of behavior. The aging at room temperature has no effect on the curve of sorption as a function of vapor activity, whereas it determines two effects on the diffusion: a decrease of the zero concentration diffusion coefficient and a more and more anomalous behavior with the aging time. The aging at 70°C produces the same effects on the diffusion behavior as the aging at room temperature; in addition, a decrease sorption is observed at low penetrant activity. The possible presence of ordered domains, impermeable to the vapor, in the samples stored at 70°C, was suggested on the basis of sorption results.     

Freeze drying process: real time model and optimization

Freeze drying is a separation process based on the sublimation phenomenon. This process has the following advantages compared to the conventional drying process: the material structure is maintained, moisture is removed at low temperature (reduced transport rates), product stability during the storage is increased, the fast transition of the moisturized product to be dehydrated minimizes several degradation reactions. Freeze drying process has not been studied well enough. In order to put it to practice, a mathematical model based on fundamental mass and energy balance equations has been developed, based on a deterministic mathematical model proposed by Liapis and Sadikoglu [Drying Technol. 15 (3–4) (1997) 791], and used to calculate the amount of removed water and amount of residual water. The proposed model contains the freeze drying equations, which are solved by the orthogonal collocation and polynomial approximation—Jacobi method. The results show that the dynamic mathematical model represents well the process and is especially well suited for real time optimization. As a case study to illustrate the model utilization in a real time optimization procedure, the freeze drying process was optimized by the method of Successive Quadratic Programming (SQP) used for solution of non-linear equations, for skimmed milk and soluble coffee. The optimization procedure showed to be an important tool to improve the process performance since lower energy consumption and hence lower cost has been achieved to obtain the product with the same quality.     

New Hybrid Nanomaterial Based on Self-Assembly of Cyclodextrins and Cobalt Prussian Blue Analogue Nanocubes

Supramolecular self-assembly has been demonstrated to be a useful approach to developing new functional nanomaterials. In this work, we used a cobalt Prussian blue analogue (PBA, Co₃[Co(CN)₆]₂) compound and a β-cyclodextrin (CD) macrocycle to develop a novel host-guest PBA-CD nanomaterial. The preparation of the functional magnetic material involved the self-assembly of CD molecules onto a PBA surface by a co-precipitation method. According to transmission electronic microscopy results, PBA-CD exhibited a polydisperse structure composed of 3D nanocubes with a mean edge length of 85 nm, which became shorter after CD incorporation. The supramolecular arrangement and structural, crystalline and thermal properties of the hybrid material were studied in detail by vibrational and electronic spectroscopies and X-ray diffraction. The cyclic voltammogram of the hybrid material in a 0.1 mol·L⁻¹ NaCl supporting electrolyte exhibited a quasi-reversible redox process, attributed to Co²⁺/Co³⁺ conversion, with an E_1/2 value of 0.46 V (vs. SCE), with higher reversibility observed for the system in the presence of CD. The standard rate constants for PBA and PBA-CD were determined to be 0.07 and 0.13 s⁻¹, respectively, which suggests that the interaction between the nanocubes and CD at the supramolecular level improves electron transfer. We expect that the properties observed for the hybrid material make it a potential candidate for (bio)sensing designs with a desirable capability for drug delivery.