Nitrophenoxy groups containing polybenzimidazoles as polymer electrolytes for fuel cells: Synthesis and characterization

Polybenzimidazoles containing different contents of pendant nitrophenoxy groups were prepared by condensation of 3,3′‐diamino‐benzidine with a mixture of 3,5‐dicarboxyl‐4′‐nitro diphenyl ether and isophthalic acid (IPA) in different ratios in polyphosphoric acid. The polymers are soluble in polar aprotic solvents, they have inherent viscosities in the range of 0.75–1.10 dL g^?1 and they form tough and transparent films on solution casting. They have good thermal stability with initial decomposition temperature ranging from 380 to 416°C in nitrogen, good tensile strength ranging from 56 to 65 MPa and reasonably good oxidative stability. Phosphoric acid uptake of these polymers is low compared with PBI and membranes doped with phosphoric acid exhibit good proton conductivity in the range of 6.6× 10^?3 to 1.9× 10^?2 S/cm at 25°C and 1.2× 10^?2 to 4.9× 10^?2 S/cm at 175°C, compared with 3.9× 10^?3 S/cm at 25°C and 3.2× 10^?2 S/cm at 175°C for PBI. These membranes are suitable for applications as polymer electrolyte for fuel cell and presumably for gas separation at high temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of new aromatic polyesters containing pendent naphthyl units

Two bisphenols, viz., 4,4′‐[1‐(2‐naphthalenyl)ethylidene]bisphenol and 4,4′‐[1‐(2‐naphthalenyl) ethylidene]bis‐3‐methylphenol were prepared by condensation of commercially available 2‐acetonaphthanone with phenol and o‐cresol, respectively. A series of new aromatic polyesters containing pendent naphthyl units was synthesized by phase‐transfer‐catalyzed interfacial polycondensation of these bisphenols with isophthaloyl chloride, terephthaloyl chloride, and a mixture of isophthaloyl chloride/terephthaloyl chloride (50 : 50 mol %). Inherent viscosities of polyesters were in the range 0.83–1.76 dL g⁻¹, while number average molecular weights (M_n) were in the range 61,000–235,000 g mol⁻¹. Polyesters were readily soluble in organic solvents such as dichloromethane, chloroform, tetrahydrofuran, m‐cresol, pyridine, N,N‐dimethylformamide, N,N‐dimethylacetamide, and 1‐methyl‐2‐pyrrolidinone at room temperature. Tough, transparent, and flexible films were cast from a solution of polyesters in chloroform. X‐Ray diffraction measurements displayed a broad halo at 2θ ≅ 19° indicating the amorphous nature of polyesters. Glass transition temperatures of polyesters were in the range 209–259°C. The temperature at 10% weight loss (T₁₀), determined by TGA in nitrogen atmosphere, of polyesters was in the range 435–500°C indicating their good thermal stability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of biodiesel in supercritical alcohols and supercritical carbon dioxide

Biodiesel was synthesized in supercritical fluids by two routes: non-catalytically in supercritical alcohols and by enzyme catalysis in supercritical carbon dioxide. Two oils, sesame oil and mustard oil, and two alcohols, methanol and ethanol, were used for the synthesis. Complete conversion was observed for synthesis in supercritical alcohols whereas only a maximum of 70% conversion was observed for the enzymatic synthesis in supercritical carbon dioxide. For the synthesis in supercritical alcohols, the activation energies and pseudo-first order rate constants were determined. For the reactions in supercritical carbon dioxide, a mechanism based on ping pong bi-bi was proposed and the kinetic parameters were determined.     

Preparation,characterization, and biodegradation of PS:PLA and PS:PLA:OMMT nanocomposites using Aspergillus niger

Poly(lactic acid) (PLA) was synthesized using l ‐lactic acid by condensation polymerization. Polystyrene (PS) and surface modified montmorillonite (OMMT) was used for the preparation of PS:PLA composites and PS:PLA:OMMT nanocomposites. The composite materials prepared had varying amount of PLA (10–30%) and OMMT (0.5–5 phr). These composites were subjected to degradation in minimal medium using the fungi Aspergillus niger (A. niger) under controlled conditions. Scanning electron microscopy (SEM) showed the growth of microorganism on the polymer surface and fracture within the polymer matrix as a result of degradation. Fourier transform infra red spectroscopy (FTIR) was further used to determine the mechanism leading to biodegradation. It was found that the biodegradation of both PS:PLA and PS:PLA:OMMT took place mainly via break down and utilization of ester group, as can be seen from disappearance of absorption peak of ester group and simultaneous appearance of a typical IR absorption of microbial mass at 1450 cm⁻¹. The thermal stability of PS:PLA:OMMT nanocomposites was found to increase with increasing concentration of OMMT, as observed from thermo gravimetric analysis (TGA), while mechanical property was found to be decreased after degradation at 30% of PLA and 5 wt% of OMMT content. Change in extracellular protein content, biomass production and % degradation with respect to time (up to 28 days) were studied and correlated to evaluate the effectiveness of A. niger in biodegradation of the composites. POLYM. COMPOS., 35:263–272, 2014. © 2013 Society of Plastics Engineers     

Solvothermal synthesis and characterization of acicular α-Fe2O3 nanoparticles

Nanometer-sized α-Fe₂O₃ particles have been prepared by a simple solvothermal method using ferric acetylacetonate as a precursor. The products were characterized by X-ray diffraction (XRD), energy dispersive X-ray microanalysis (EDAX), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transition electron microscopy (TEM), infrared spectroscopy (IR) and thermal analysis (TG-DTA). XRD indicates that the product is single-phase α-Fe₂O₃ with rhombohedral structure. Bundles of acicular shaped nanoparticles are seen in TEM images with an aspect ratio ～ 12; typically 8–12 nm wide and over 150 nm long. The α-Fe₂O₃ nanoparticles posses a high thermal stability, as observed on thermal analysis traces.     

An example of almost universally observable vector fields on P(R)

Using methods of dynamical systems, we construct examples of smooth, almost universally observable vector fields on the projective 1-space. These vector fields are non-linear, non-autonomous and their time dependence is almost periodic.     

Hydrothermal synthesis and characterization of CsNiP and 2(LiZnHP2O7) crystals

CsNiP and 2(LiZnHP₂O₇) crystals were synthesized by hydrothermal technique at moderate P-T conditions. Solubility results of both the compound shown positive thermal coefficient and single crystal X-ray studies revealed, CsNiP crystallized in hexagonal system with cell parameters; a = 7.173(2), c = 5.944(9) Å, V = 264.87(7) ų and space group P63/mmc and 2(LiZnHP₂O₇) crystallized in orthorhombic system with cell parameters; a = 12.3636 Å, b = 27.5330 Å, c = 6.8647 Å and space group, Pca21 exhibiting ring type of cavities with open aperture in the structure. CsNiP is a frequency dependent paramagnetic and 2(LiZnHP₂O₇) is a diamagnetic.     

Nitrogen ion induced nitridation of Si(111) surface: Energy and fluence dependence

We present the surface modification of Si(111) into silicon nitride by exposure to energetic N₂⁺ ions. In-situ UHV experiments have been performed to optimize the energy and fluence of the N₂⁺ ions to form silicon nitride at room temperature (RT) and characterized in-situ by X-ray photoelectron spectroscopy. We have used N₂⁺ ion beams in the energy range of 0.2–5.0 keV of different fluence to induce surface reactions, which lead to the formation of Si_xN_y on the Si(111) surface. The XPS core level spectra of Si(2p) and N(1s) have been deconvoluted into different oxidation states to extract qualitative information, while survey scans have been used for quantifying of the silicon nitride formation, valence band spectra show that as the N₂⁺ ion fluence increases, there is an increase in the band gap. The secondary electron emission spectra region of photoemission is used to evaluate the change in the work function during the nitridation process. The results show that surface nitridation initially increases rapidly with ion fluence and then saturates.     

Computation of entropy generation in dissipative transient natural convective viscoelastic flow

Entropy generation is an important aspect of modern thermal polymer processing optimization. Many polymers exhibit strongly non‐Newtonian effects and dissipation effects in thermal processing. Motivated by these aspects in this study, a numerical analysis of the entropy generation with viscous dissipation effect in an unsteady flow of viscoelastic fluid from a vertical cylinder is presented. The Reiner‐Rivlin physical model of grade 2 (second‐grade fluid) is used, which can envisage normal stress variations in polymeric flow‐fields. Viscosity variation is included. The obtained governing equations are resolved using implicit finite difference method of Crank‐Nicolson type with well imposed initial and boundary conditions. Key control parameters are the second‐grade viscoelastic fluid parameter (), viscosity variation parameter (), and viscous dissipation parameter (). Also, group parameter (), Grashof number (Gr), and Prandtl number (Pr) are examined. Numerical solutions are presented for steady‐state flow variables, temperature, time histories of friction, wall heat transfer rate, entropy, and Bejan curves for distinct values of control parameters. The results specify that entropy generation decreases with augmenting values of , , and Gr. The converse trend is noticed with increasing Pr and . Furthermore, the computations reveal that entropy and Bejan lines only occur close to the hot cylinder wall.