Micellar polymerization,characterization, and viscoelasticity of combined thermally insensitive terpolyacrylamides

Polymer chains consisting of water‐soluble polyacrylamides and N‐isopropylacrylamide (NIPAM), hydrophobically modified with low amounts of N,N‐dialkylacrylamides (N,N‐dioctylacrylamide) have been prepared via free radical micellar polymerization, using a hydrophobic initiator derived from 4,4′‐azobis(4‐cyanopentanoic acid) containing a long linear chain of 16 (C16) carbon atoms. This procedure resulted in polyacrylamides containing hydrophobic groups along the chain as well as at the chain ends. These polymers are named “combined associative polymers” and include within their structure a water‐soluble monomer (acrylamide), a thermosensitive monomer (NIPAM) and a hydrophobic monomer. The polymers were characterized by different techniques, also studying the effect of adding a surfactant anion such as sodium dodecylsulfate. The viscoelastic properties as a function of temperature of these associative polymers were investigated using steady‐flow and oscillatory experiments considering the relaxation time (T_R) and the plateau modulus (G₀). The effect of concentration of acrylamide and NIPAM on the viscosity of the associative polymer solutions was investigated. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Combustion synthesis of LaSi3N5:Eu2+ phosphor powders

LaSi₃N₅:Eu²⁺ phosphor powders were prepared by a highly efficient combustion synthesis method. It was found that the compositions of the raw powder mixtures had great influences on the phase compositions and particle morphologies of the synthesized powders. By selecting appropriate starting compositions and combustion parameters, single phase LaSi₃N₅:Eu²⁺ phosphors could be synthesized. When excited by a UV light, the LaSi₃N₅:Eu²⁺ phosphors emitted green light. The wavelength and intensity of the emission spectra were affected by the amount of Eu²⁺ dopant. With increasing amount of Eu²⁺ dopant, concentration quenching could occur and emission spectra shifted to longer wavelengths.     

Flexible and transparent capacitors based on gel-type natural polymers

In this work, we study the capacitive properties of gel-type natural abundant polymers without any dopants, mainly commercial gelatin and agar in deionized water. Here, we propose a facile fabrication of flexible, transparent, and planar electrolytic capacitors using these gel-type and indium tin oxide thin films as electrodes deposited on poly(ethylene terephthalate) substrates. Through cyclic voltammetry and galvanostatic charge–discharge techniques, we found that the devices show a specific capacitance in the order of the millifarads per gram, a specific power of ~10 mW cm⁻², which is sufficient to active low-power devices, and a life cycle with nearly 100% efficiency after 1,000 cycles. We found that we do not need to add dopants that improve the ionic conductivity of the natural polyelectrolytes to obtain capacitances within the millifarads per gram. The flexibility of the capacitors was demonstrated by bending them, after which they exhibited the same electrochemical performance as the unbent devices. The optical transparency of the capacitors was measured by UV–V is spectroscopy showing a high transmittance in the visible region.     

Analysis of the Content of Fatty Acid Methyl Esters in Biodiesel by Fourier-Transform Infrared Spectroscopy: Method and Comparison with Gas Chromatography

The increasing importance of sustainability in energy production has led to a global commitment to the use of fuels derived from renewable biological sources, such as biodiesel produced from plant crops or biomass residues, that do not compete with human food for their production. For a biofuel to be considered biodiesel, it must satisfy the specifications described in the UNE 14214, with the UNE-EN 14103 referring to the determination of fatty acid methyl ester content. This standard applies gas chromatography as an analytical technique. Gas chromatography is a widely used technique in the analysis of methyl ester although it has a number of drawbacks such as: long analysis times, a high consumption of high-quality gases and internal standards, does not allow the analysis of different compounds with the same column, etc. From an industrial production point of view, is necessary to know the fatty acid methyl ester content in biodiesel samples quickly. This paper studies the development of an analytical method using Fourier transform infrared spectroscopy (FTIR) as alternative to gas chromatography (GC), since it is a simple, rapid, and precise analytical technique to quantify fatty acid methyl ester content in biofuel samples.     

Amine-impregnated natural zeolite as filler in mixed matrix membranes for CO2/CH4 separation

Flat mixed matrix membranes (MMMs) comprising polysulfone and clinoptilolite-type natural zeolite were prepared by casting. Zeolite was modified with three alkylamines: ethanolamine (EA), bis(2-hydroxypropyl)amine (BHPA), and polyethylenimine (PEI) by the impregnation method. Impregnated zeolite samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and N₂ adsorption–desorption. The alkylamine loading extent determined by thermogravimetric analysis was 5.2, 4.8, and 8.5% for EA, BHPA, and PEI, respectively. Analyses of MMMs showed that the incorporation of impregnated zeolite affected the glass-transition temperature (T_g) and mixed-gas transport properties. In this regard, a decreasing trend of the T_g values from 185.5 °C for the polymeric membrane up to 176.6 °C for Clino-EA-based MMM was recorded. In addition, the gas separation performance was evaluated at two different feed pressures. At 50 psi, MMMs showed an enhancement up to 30% on the CO₂ permeability (22.79 Barrer) and 55% on the CO₂/CH₄ selectivity (45.78) in comparison with the polymeric membrane (CO₂ permeability 17.34 Barrer; CO₂/CH₄ selectivity 29.38). These values varied depending on the alkylamine, BHPA being the most selective. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48286.     

Melt processing of ethylene–vinyl acetate/banana starch/Cloisite 20A organoclay nanocomposite films: structural,thermal and composting behavior

This work shows the preparation of ethylene vinyl acetate copolymer/banana starch/Cloisite 20A organoclay (EVA/starch/C20A) nanocomposites by melt processing. Wide angle X-ray diffraction (WAXD), field emission scanning electron microscopy (FE-SEM), differential scanning calorimetry and thermogravimetric analysis were used to characterize the obtained nanocomposites. Mechanical properties were also determined. In addition, the performance of the nanocomposite films under composting was preliminarily studied; it was conducted using the soil burial test method. Despite knowing that the starch is difficult to process by extrusion, nanocomposite films with high homogeneity were obtained. In this case, C20A organoclay acts as an effective surfactant to make the starch natural polymer compatible with the EVA synthetic polymer. The good compatibility between EVA, starch and C20A clay was also deduced by the formation of intercalated and intercalated-exfoliated structures determined by WAXD and FE-SEM. Physical evidence of the damage in EVA/starch/C20A nanocomposite films after the composting test was observed. It is worth noting that despite the absence of starch, the EVA/C20A nanocomposite film, used as a control, also showed surface damage. This behavior is related to the organic modifier linked to clay C20A, which contains molecules derived from fatty acids that can be used as a food source for microorganisms.

     

Colloidal processing of Al2O3-doped zirconia ceramics with CaO–P2O5–SiO2 glass as additive

Well-dispersed concentrated aqueous suspensions of Al₂O₃-doped Y-TZP (AY-TZP), AY-TZP with 5.4 vol% of CaO–P₂O₅–SiO₂ (CaPSi) glass (AY-TZP5) and 10.5 vol% CaPSi glass (AY-TZP10), with ammonium polyacrylate (NH₄PA) dispersant were prepared to produce slip cast compacts. The rheological properties of 35 and 40 vol% slips were studied. The densification, microstructure as well as hardness and fracture toughness were investigated as a function of CaPSi glass content at 1300°C-1500°C. The optimum NH₄PA concentration of 35 vol% AY-TZP5 and AY-TZP10 slips at pH ~9 was found to be about 43% and 67% greater than that of AY-TZP slips; this behavior was related to the greater amounts of Ca²⁺ ions leached out from the CaPSi glass surface. The viscosity of stabilized 40 vol% slips with NH₄PA attained a minimum value at 5.4 vol% CaPSi glass addition, and resulted in a more dense packing of cast samples. AY-TZP5 can be sintered at a lower temperature (1300°C) compared to that of AY-TZP. AY-TZP5 exhibited a fine microstructure of tetragonal ZrO₂ (grain sizes below 0.3 µm), and ZrSiO₄–Ca₂P₂O₇ particles homogeneously distributed within the zirconia matrix. It presented similar fracture toughness and a slightly lower hardness compared to those of AY-TZP.     

Poisson’s ratio of porous and cellular materials with randomly distributed isometric pores or cells

The porosity dependence of Poisson's ratio of materials with random microstructure is investigated via analytical and numerical modeling. It is shown that all analytical models predict porosity independence if the solid Poisson ratio is 0.2 and for low porosities a converging trend toward this value with increasing porosity. From all theory-based relations, only power-law and exponential relations allow for auxetic behavior. Numerical calculations on computer-generated digital microstructures (overlapping and isolated spherical pores, pores between overlapping spherical grains, wall-based cellular materials/closed-cell foams, and strut-based cellular materials/open-cell foams) confirm the general qualitative trends of the analytical models, although a closer look reveals significant quantitative differences. Cellular materials and foams exhibit similar features as porous materials in general, but lack their converging trend toward values around 0.2. Comparison of our results with the classical Roberts-Garboczi results shows good agreement, with subtle differences due to the different microstructures generated.     

Random Copolymers with 2,2′-Dioxy-1,1′-biphenyl-phosphazene and Chiral 2,2′-dioxy-1,1′-binaphthylphosphazene Units Functionalized in the 6,6′-Positions with PPh<Subscript>2</Subscript> Groups as Precursors for Ru(arene) Catalysts

The chiral phosphazene copolymers {[NP(O₂C₁₂H₈)]_0.9[NP(O₂C₂₀H₁₂)]_0.1} (1) and {[NP(O₂C₁₂H₈)]_0.9[NP(O₂C₂₀H₁₀Br₂)]_0.1} _n (2) [(O₂C₁₂H₈) = 2,2′-dioxy-1,1′-biphenyl; (O₂C₂₀H₁₂) = R-2,2′-dioxy-1,1′-binaphthyl and (O₂C₂₀H₁₀Br₂) = R-6,6′-dibromo-2,2′-dioxy-1,1′-binaphthyl] were prepared by sequential substitution from [NPCl₂] _n and the corresponding dihydroxy-biphenyl or binaphthyl reagents in the presence of Cs₂CO₃ and K₂CO₃. The reaction of (2) with ^tBuLi in THF, followed by addition of PPh₂Cl and a treatment with SiHCl₃/PPh₃ to eliminate any oxidized OC₆H₄P(O)Ph₂ groups, gave the phosphine containing copolymer {[NP(O₂C₁₂H₈)]_0.9[NP(O₂C₂₀H₁₀[PPh₂]₂)]_0.1} _n (3), that was used as a chiral ligand to support [Ru(p-cymene)Cl] complexes. The resulting catalyst was active for hydrogen transfer from isopropyl alcohol to acetophenone but the placement of the Ru centers in the 6,6′-positions of the binaphthoxyphosphazene units induced no enantioselectivity. Dedicated to Professor Christopher Allen.     

Ocratoxin A in human plasma and coffee from Costa Rica by ELISA

Costa Rica is not an exception in the prevalence of ochratoxin A in human plasma, in this research the presence of the micotoxin was found in 95% of the 149 samples studied. The presence of ocratoxina A also was studied in 110 samples of toasted and grounded coffee from the most important 12 coffee factories of the country and from 7 supermarkets. With the exception of one negative sample the rest of them have concentrations of micotoxin below 4000 ng/kg. An association between the coffee consumption and the presence of ochratoxin A in plasma was attempted to be found as well as in the consumption of beer, but there were any statistically significant difference in the average level of mycotoxin between the coffee consumers and non coffee consumers neither between beer consumers and no beer consumers.