Polyethylene Glycol–Enhanced Chemoselective Synthesis of Organic Carbamates from Amines,CO2, and Alkyl Halides

An efficient and environmentally benign method for the synthesis of organic carbamates was developed. Amines, CO₂, and alkyl halides underwent a three-component reaction with the aid of K₂CO₃ and polyethylene glycol (PEG, MW = 400), affording the organic carbamates under ambient conditions. PEG could presumably act as a solvent and phase-transfer catalyst (PTC). Notably, the presence of PEG could also depress the alkylation of both the amine and the carbamate, thus resulting in enhanced selectivity toward the target carbamate.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.      

Microstructural evolution during oxidative ablation in air for polyacrylonitrile based carbon fibers with different graphite degrees

Polyacrylonitrile‐based carbon fibers with different graphite degrees were oxidative ablated at 500 and 600 °C in air. By Thermal gravimetric (TG), Raman spectroscopy, X‐ray diffraction, and SEM, the mass loss, microstructure, and surface morphology of carbon fibers were investigated. The mass loss of carbon fiber increases linearly with increasing oxidative ablated time under 500 and 600 °C. The carbon fiber with higher graphite degree shows higher oxidative resistance, and the surface roughness increases gradually because of chemical ablation during the whole oxidation. A gloss morphology appears on the surface primarily because of physical denudation for carbon fibers with lower graphite degree and then burn off according to carbon and oxygen reaction. The crystallite size (La) decreases significantly, while interlayer spacing(d₀₀₂) remains nearly unchanged. SEM observation suggests the two kinds of ablation mechanisms for carbon fibers with different graphite degrees indicating that CC band in sp³ hybridization prefers to be attacked by oxygen molecule more than that in sp² hybridization during oxidation ablation in air. Copyright © 2012 John Wiley & Sons, Ltd.     

Ultra‐low friction of fluorine‐doped hydrogenated carbon film with curved graphitic structure

Fluorine‐doped hydrogenated carbon film was grown by chemical vapor deposition technique using CH₄ and CF₄ as feedstock, with a pulse DC‐bias power supply. The structure of as‐deposited film was characterized by transmission electron microscopy and Raman spectra. The results suggested that the film could be considered as composite thin film with curved graphitic structures embedded in amorphous carbon matrix. The mechanical properties and friction coefficient were tested by TI 950 TriboIndenter and UMT‐2 at humidity of 30%, respectively. The results showed that the film exhibited high hardness (~11.04 GPa), good elasticity recovery(~83%) and ultra‐low coefficient of friction (~0.01). Copyright © 2013 John Wiley & Sons, Ltd.     

Influence of oxygen flow rate on the surface chemistry and morphology of radio frequency (RF) magnetron sputtered zinc oxide thin films

Zinc oxide thin films were deposited, by radio frequency magnetron sputtering, on heated and unheated substrates. The oxygen flow rate was varied during deposition, and its effects on the structural and chemical properties of the films were investigated. The films had oriented c‐axis growth with nano‐crystallite size. Their surfaces manifested columnar microstructure, with a surface roughness that was suppressed by the introduction of oxygen. Chemical analysis showed that deposition under an oxygen atmosphere resulted in substantial reduction of oxygen vacancies, with a corresponding incorporation of chemisorbed species. Copyright © 2013 John Wiley & Sons, Ltd.     

Various ways to strengthen the fiber‐matrix interface for enhanced composite performance

Surface treatment (ST) of carbon fibers (CF) leads to an enhancement in fiber‐matrix adhesion. However, it deteriorates the strength of a fiber which makes its reinforcing action less effective in a composite. These effects in opposite directions control the net strength of a composite, and hence, the treatment has to be judiciously applied, which would enhance the first factor and minimize the second one. Authors have recently reported on four effective techniques (using various doses) such as treatments with nanoparticles of Ytterbium fluoride (YbF₃)_, cold remote nitrogen–oxygen plasma (CRNOP), γ‐ray irradiation and nitric acid oxidation. Amongst these methods, nitric acid oxidation is studied in depth in the literature, and γ‐ray irradiation is sparingly studied. However, nano‐YbF₃ and CRNOP were first time reported in the literature by the authors. However, comparative aspects of all these methods were not addressed. In this paper, these aspects in details are discussed to lay down the right criteria for selection of a ST technique of CF to design the desired performance of a composite. The composites with polyetherimide and treated CF (including untreated) were developed and evaluated for various properties including tribological one. Treated CF based composites exhibited excellent mechanical and tribological properties (under harsh operative conditions with wear rates ≈ 1 × 10^?15 m³/Nm and μ ≈ 0.09). It was concluded that for strength and tribo‐performance, different treatments and doses are to be employed. Overall nanosized‐YbF₃ treatment of CF proved to be the most promising ST method. Copyright © 2013 John Wiley & Sons, Ltd.     

A correlation between the variable melt flow index and the molecular mass distribution of virgin and recycled polypropylene used in the manufacturing of battery cases

This study looked at establishing a correlation between the variable melt flow index (VMFI) values of molten polypropylene (PP) with different piston-load masses using a standard MFI analyser. The study was done using virgin PP and recycled PP obtained from recycling Pb-acid batteries. The study showed that the results would fit a suitable power function equation where the size of the exponent reflects the increase in flow characteristics of the polymer with increased piston-load mass. The established correlation was then compared to the average molecular weight distribution of virgin PP determined by gel permeation chromatography (GPC). Good agreement was obtained for the range of grades of virgin PP samples that correlated well with the Mark-Houwink power law where the inverse of the MFI (1/MFI) would be proportional to the average molecular weight to the power of 3.4 (Mw^3.4). GPC analysis cannot be effectively used to study recycled PP, where a number of factors can influence the melt flow properties such as fillers, impurities and the presence of polyethylene in the polymer matrix. Instead, a comparative understanding of the flow behaviour of recycled PP to that of virgin PP was done by using the VMFI method to possibly show the dissimilar polymer melt flow behaviour of using virgin and recycled PP material in injection moulding of new battery cases and lids, or when attempting to seal the lid to the battery case during manufacturing.     

New basis sets for the evaluation of interaction‐induced electric properties in hydrogen‐bonded complexes

Interaction‐induced static electric properties, that is, dipole moment, polarizability, and first hyperpolarizability, of the CO? (HF)_n and N₂? (HF)_n, n = 1–9 hydrogen‐bonded complexes are evaluated within the finite field approach using the Hartree–Fock, density functional theory, Møller–Plesset second‐order perturbation theory, and coupled cluster methods, and the LPol‐n (n = ds, dl, fs, fl) basis sets. To compare the performance of the different methods with respect to the increase of the complex size, we consider as model systems linear chains of the complexes. We analyze the results in terms of the many‐body and cooperative effects. © 2012 Wiley Periodicals, Inc.     

Scaling in Electrical Conductivity Measurements and Rheological Measurements of Monarch 700 Dispersions Stabilized by Polymers

For making stable dispersions of graphitic carbon black (Monarch 700), the effectiveness of three dispersants/polymers (hypermer LP1, hypermer B246, and OLOA 11000) in xylene is investigated. Hypermer LP1 (polyhydroxystearic acid) is a homopolymer and hypermer B246 (PEG 30-dipolyhydroxystearate) is a polyhydroxystearic acid/polyethylene oxide/polyhydroxystearic acid ABA block copolymer, while OLOA 11000 (polyisobutylene succinimide) has a polar head group (polyamine) attached to a hydrocarbon chain (polyisobutylene). Well-dispersed graphitic carbon black dispersions were prepared using dispersants at optimum concentrations. Percolation threshold and rheological threshold were determined by analyzing the variations in electrical conductivity and elastic modulus with concentration of carbon black. Above threshold concentration, scaling law was applied to experimental data of rheology (dynamic measurements) and electrical conductivity measurements to evaluate quality of the system. Effectiveness of polymers was investigated on the basis of value of critical exponent (t and t′, respectively) in scaling power law. Hypermer LP1 was proved to be a poor dispersant for Monarch 700 dispersions while other two polymers were found to be effective stabilizers.     

Removal of Cyanide from Aqueous Solutions by Adsorption on Activated Carbon Prepared from Lignocellulosic By-products

Cyanide is considered one of the most dangerous compounds for the environment. They are discharged by various industries: chemical and metallurgical processes (extraction of gold and silver) and food industries. Adsorption is among the most used processes for elimination of cyanides particularly for the low concentrations. In this work, the cyanide removal is carried out by adsorption onto activated carbons prepared from olive stones and coffee ground. So we can promote this by-product as an inexpensive adsorbent. The prepared activated carbons are characterized by scanning electron micrograph and by determination of the physicochemical properties and specific surface area. All the adsorption experiments were performed in batch mode on synthetic water cyanide (KCN) at pH 10.8–11.0 to avoid volatilization of very toxic HCN. To describe the adsorption kinetics, the kinetic models of pseudo-first-order, pseudo-second-order, and intra-particle diffusion were applied. The experimental equilibrium data for adsorption of free cyanide were analyzed by the Langmuir, Freundlich, and Temkin isotherm models.     

Fractal Aperture Distribution of Activated Carbon Fiber and Adsorption Behavior to Low‐Density Benzene Steam

Based on the J(x) fractal distribution function of aperture given by Jaroniec, this article suggests another function K(x), a variant of J(x) but offering new insight. We then use these two functions to characterize three kinds of activated carbon fiber (ACF) of different specific areas. This article also provides the fractal distribution of the aperture and the isotherm of nonpolarity benzene steam on the ACF specimens and the relationship between them.