Lewis acid–base properties of cellulose acetate phthalate‐polycaprolactonediol blend by inverse gas chromatography

The net retention volumes, V_N, of n‐alkanes and five polar probes are determined on cellulose acetate phthalate–polycaprolactonediol blend column by inverse gas chromatography in the temperature range 323.15–363.15 K. The dispersive surface energy, $\gamma _{\bf S}^{\bf d}$ , of the blend has been calculated using the V_N values of n‐alkanes and the $\gamma _{\bf S}^{\bf d}$ at 333.15 K is 12.6 mJ/m². The $\gamma _{\bf S}^{\bf d}$ values are decreasing linearly with increase of temperature. The V_N values of the five polar solutes are used to calculate the specific component of the enthalpy of adsorption, ${\Delta }{H}_{\bf a}^{\bf S}$ . The Lewis acid–base parameters, K_a and K_b, are derived using ${\bf \Delta }{H}_{\bf a}^{\bf S}$ values and are found to be 0.019 and 0.403, respectively. The K_a and K_b values indicate that the blend surface contain more basic sites and interact strongly with the acidic probes. The acid–base parameters have been used to analyze the preferential interaction of the solid surface with acidic and basic probes. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Tailoring the Degree of Polymerization of Low Molecular Weight Cellulose

The degradation of cellulose to lmw samples with $\overline {DP} _{{\rm w}} $ varying from 15 to 130 is investigated. Cellulose samples prepared from the hydrolysis of regenerated cellulose fibers in dilute HCl possess $\overline {DP} _{{\rm w}} $ = 50. Applying homogenous degradation of microcrystalline cellulose in H₃PO₄ at RT for 3 weeks, samples with $\overline {DP} _{{\rm w}} $ = 35 and a PDI of 1.58 are obtained. Decreasing the hydrolysis temperature to 8 °C results in lmw cellulose with $\overline {DP} _{{\rm w}} $ > 70. Fractionation in DMA/LiCl provides samples with $\overline {DP} _{{\rm w}} $ = 12 to 130, together with a narrow molecular weight distribution. Detailed structural analysis by 2D NMR spectroscopy reveals that the prepared lmw celluloses are suitable as mimics for cellulose.

     

Versatility of a succinimidyl‐ester functional alkoxyamine for controlling acrylonitrile copolymerizations

Styrene/acrylonitrile (S/AN) and tert‐butyl methacrylate/acrylonitrile (tBMA/AN) copolymers were synthesized in a controlled manner (low polydispersity $ {{\overline M _w } / {\overline M _n }} $ with linear growth of number average molecular weight $ \overline M _n $ vs. conversion X) by nitroxide mediated polymerization (NMP) with a succinimidyl ester (NHS) terminated form of BlocBuilder unimolecular initiator (NHS‐BlocBuilder) in dioxane solution. No additional free nitroxide (SG1) was required to control the tBMA‐rich copolymerizations with NHS‐BlocBuilder, a feature previously required for methacrylate polymerizations with BlocBuilder initiators. Copolymers from S/AN mixtures (AN molar initial fractions f_AN,0 = 0.13–0.86, T = 115°C) had $ {{\overline M _w } / {\overline M _n }} $ = 1.14–1.26 and linear $ \overline M _n $ versus conversion X up to X ≈ 0.6. tBMA/AN copolymers (f_AN,0 = 0.10–0.81, T = 90°C) possessed slightly broader molecular weight distributions ( $ {{\overline M _w } / {\overline M _n }} $ = 1.23–1.50), particularly as the initial composition became richer in tBMA, but still exhibited linear plots of $ \overline M _n $ versus conversion X up to X ≈ 0.6. A S/AN/tBMA terpolymerization (f_AN,0 = 0.50, f_S,0 = 0.40) was also conducted at 90°C and revealed excellent control with $ \overline M _n $ = 13.6 kg/mol, $ {{\overline M _w } / {\overline M _n }} $ = 1.19, and linear $ \overline M _n $ versus conversion X up to X = 0.54. Incorporation of AN and tBMA in the final copolymer (molar composition F_AN = 0.47, F_tBMA = 0.11) was similar to the initial composition and represents initial designs to make tailored, acid functional AN copolymers by NMP for barrier materials. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Oxygen permeability,electron spin resonance,differential scanning calorimetry and positron annihilation lifetime spectroscopy studies of uniaxially deformed linear low‐density polyethylene film

Linear low‐density polyethylene (PE‐LLD) films were mechanically deformed at room temperature in both parallel and perpendicular directions to their initial orientation obtained during the manufacturing process. The degree of deformation ${\lambda}$ , defined as ${\lambda} = l/l_{0}, l$ and l₀ being the length of the deformed and relaxed samples, respectively, was varied from 1.0 to 2.0. Oxygen transport was investigated by a manometric method and the results were correlated with differential scanning calorimetry and positron annihilation lifetime spectroscopy measurements in order to investigate the contribution of various factors that influence the permeability of deformed PE‐LLD films. An electron spin resonance spin‐probe method was employed to determine the influence of uniaxial deformation on the chain segmental mobility in the amorphous phase. The results show that the deformation process reduces oxygen permeability and diffusion coefficients. It was found that the reduction is a combined effect of an increased crystallinity and reduced fractional free volume. The decrease of the chain segmental mobility with deformation plays an important role in the gas diffusion mechanism. © 2012 Society of Chemical Industry     

Influence of uric acid amendment on the in‐vessel process of composting composite food waste

BACKGROUND: The food waste produced in small cities, rural areas and small communities often coexists with agroindustrial waste, such as livestock and poultry manure, which include high levels of uric acid (UA). This study investigated the influence of UA on the composting of food waste in an in‐vessel system. RESULTS: Results showed that the performance of food waste composting was significantly different in systems with UA amendment and without UA amendment. Treatment with UA addition was the first to reach the thermophilic phase. More intensive mass reduction took place in the UA‐amended treatments at an early stage. The variations of pH and O₂ uptake were also correlated with the added UA. A decreasing trend in C/N ratio and a general increasing trend for NH$_{4}^{+}$ ‐N concentration were observed when UA was added. CONCLUSIONS: The overall effect of UA can be assumed to be the sum of a large number of individual events with different mechanisms. Appropriate strategies could be applied to adjust the composting process, mediating both positive and negative effects of the coexistence of food waste and UA as well as manure. The results from this study may have important implications for composting technologies used to treat food waste. Copyright © 2012 Society of Chemical Industry     

Correlation of Sequence Block Lengths and Degree of Randomness with Melt Rheological Properties in PET/PEN Blends

PET/PEN blends were prepared over the full composition range via a melt mixing process under various processing conditions. This resulted in transesterification reactions and formation of copolymer structures with various average sequence block lengths and degree of randomness (RD) determined by ¹H NMR. It was seen that with an increase in time and temperature of mixing copolymer content (TEN%) and RD increased, whereas the , values were decreased. The differences in the extent of transreactions arising from different processing histories showed their systematic influence on rheological characteristics. Moreover due to progress of transreactions during the rheological measurements, convergence was seen in all the rheological characteristics at terminal zones in the high frequency regions. Similar convergence in the copolymer structural parameters was also obtained by NMR analysis. An increase in TEN% led to a systematic increase in viscosity of the blends. A decrease in the , values results in an increase in elasticity and relaxation time due to improvement of blend interface with increase in extent of copolymer formation.

     

Adsorptive removal of nitrate and phosphate anions from aqueous solutions using functionalised SBA‐15: Effects of the organic functional group

Adsorption of nitrate and monovalent phosphate anions from aqueous solutions on mono, di‐ and tri‐ammonium‐functionalised mesoporous SBA‐15 silica was investigated. The adsorbents were prepared via a post‐synthesis grafting method, using either 3‐aminopropyltrimethoxysilane (N‐silane) or [1‐(2‐aminoethyl)‐3‐aminopropyl]trimethoxysilane (NN‐silane) or 1‐[3‐(trimethoxysilyl)‐propyl]‐diethylenetriamine (NNN‐silane), followed by acidification in HCl solution to convert the attached surface amino groups to positively charged ammonium moieties. The nominal loading of amino moieties on the SBA‐15 surface was varied from 5% to 20% as organoalkoxysilane/silica molar ratio. The adsorption experiments were conducted batchwise at room temperature. Results showed that adsorption capacity increased with increasing the concentration of monoammonium groups on the SBA‐15 adsorbent. Nitrate adsorption capacity increased from 0.34 to 0.66 mmol ${\rm NO}_{3}^{{-} } /{\rm g}$ adsorbent while phosphate adsorption capacity increased from 0.34 to 0.63 mmol ${\rm H}_{2} {\rm PO}_{4}^{{-} } /{\rm g}$ adsorbent when the molar ratio organoalkoxysilane/silica was varied from 5% to 20%, respectively. Also, for the same organoalkoxysilane/silica molar ratio of 10%, the adsorption capacity increased with the increase of the number of protonated amines in the functional groups. Therefore, maximum adsorption capacities of 0.80, 1.16 and 1.38 mmol ${\rm NO}_{3}^{{-} } /{\rm g}$ adsorbent and 0.72, 0.82 and 1.17 mmol ${\rm H}_{2} {\rm PO}_{4}^{{-} } /{\rm g}$ adsorbent were obtained using mono‐, di‐ and triammonium functionalised SBA‐15 adsorbents, respectively. © 2011 Canadian Society for Chemical Engineering     

Transfer RNA Misidentification Scrambles Sense Codon Recoding

Sense codon recoding is the basis for genetic code expansion with more than two different noncanonical amino acids. It requires an unused (or rarely used) codon, and an orthogonal tRNA synthetase:tRNA pair with the complementary anticodon. The Mycoplasma capricolum genome contains just six CGG arginine codons, without a dedicated tRNA^Arg. We wanted to reassign this codon to pyrrolysine by providing M. capricolum with pyrrolysyl‐tRNA synthetase, a synthetic tRNA with a CCG anticodon (${{\rm tRNA}{{{\rm Pyl}\hfill \atop {\rm CCG}\hfill}}}$ ), and the genes for pyrrolysine biosynthesis. Here we show that ${{\rm tRNA}{{{\rm Pyl}\hfill \atop {\rm CCG}\hfill}}}$ is efficiently recognized by the endogenous arginyl‐tRNA synthetase, presumably at the anticodon. Mass spectrometry revealed that in the presence of ${{\rm tRNA}{{{\rm Pyl}\hfill \atop {\rm CCG}\hfill}}}$ , CGG codons are translated as arginine. This result is not unexpected as most tRNA synthetases use the anticodon as a recognition element. The data suggest that tRNA misidentification by endogenous aminoacyl‐tRNA synthetases needs to be overcome for sense codon recoding.     

MHD flow and heat transfer over stretching/shrinking sheets with external magnetic field,viscous dissipation and Joule effects

The present article considers the steady magnetohydrodynamic (MHD) laminar boundary layer flow of a viscous and incompressible electrically conducting fluid near the stagnation point on a horizontal stretching or shrinking surface, with variable surface temperature and a constant magnetic field applied normal to the surface of the sheet. The governing system of partial differential equations is first transformed into a system of ordinary differential equations by introducing an appropriate similarity transformation, which is then solved numerically using a finite‐difference scheme known as the Keller‐box method. The effects of the governing parameters on the skin friction coefficient, the local Nusselt number as well as the velocity and temperature profiles are determined and discussed. Results indicate that for the stretching sheet, solution exists and is unique for all values of the stretching/shrinking parameter $\lambda $ , while for the shrinking sheet, solutions only exist up to some critical values $\lambda = \lambda _{{\rm c}} $ , and these solutions may be unique, dual and sometimes triple. © 2011 Canadian Society for Chemical Engineering     

Preparation and characterization of polystyrene modified single‐walled carbon nanotube

A halogen atom terminated Polystyrene (PSt) was prepared by means of atom transfer radical polymerization. Then, the halogen atom was converted into ‐N₃ group and a ‐N₃ terminated PSt was obtained. Finally PSt was grafted onto the surface of single walled carbon nanotube (SWNT) by the reaction of azide group with SWNT. Comparison of X‐ray photoelectron spectrometer of N1s electron belonging to ‐N₃ and the surface of SWNT demonstrated that three‐membered rings were formed by releasing N₂ from ‐N₃ during the reaction. The structure of PSt modified SWNT was characterized by FTIR, UV, Raman spectrum, and TEM. The experimental results showed that the PSt was connected assuredly to SWNT by the covalent bond. TGA data showed that the amount of PSt on the surface of SWNT firstly increased with growing of PSt and then decrease when continues to grow. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Tailored Media for Homogeneous Cellulose Chemistry: Ionic Liquid/Co‐Solvent Mixtures

Co‐solvents can minimize two of the major problems associated with the use of ionic liquids (ILs) as solvents for homogeneous derivatization of cellulose: high viscosity and limited miscibility with non‐polar reagents or reaction products. Thus, the effects of 18 solvents and 3 binary solvent mixtures on cellulose solutions in three ILs were systematically studied with respect to the solution phase behavior. The applicable limits of these mixtures were evaluated and general guidelines for the use of co‐solvents in cellulose chemistry could be advanced: Appropriate co‐solvents should have $E_{{\rm T}}^{{\rm N}} $ values (normalized empirical polarity) > 0.3, very low “acidity” (α < 0.5), and relatively high “basicity” (β ≥ 0.4). Moreover, novel promising co‐solvents and binary co‐solvent mixtures were identified.

     

Effect of Processing Variables on the Morphology of Electrospun Poly[(lactic acid)‐co‐(glycolic acid)] Nanofibers

A systematic study of the effects of , flow rate, voltage, and composition on the morphology of electrospun PLGA nanofibers is reported. It is shown that changes of voltage and flow rate do not appreciably affect the morphology. However, the of PLGA predominantly determines the formation of bead structures. Uniform electrospun PLGA nanofibers with controllable diameters can be formed through optimization. Further, multi‐walled carbon nanotubes can be incorporated into the PLGA nanofibers, significantly enhancing their tensile strength and elasticity without compromising the uniform morphology. The variable size, porosity, and composition of the nanofibers are essential for their applications in regenerative medicine.

     

Dielectric properties of high coercivity barium ferrite–natural rubber composites

The effect of frequency, temperature, and BaFe₁₂O₁₉ (BF) content on the dielectric constant $ \acute\varepsilon $ , dielectric loss ε″, and tan δ were studied for barium ferrite—natural rubber composites (RFC). The dielectric constant for barium ferrite was related to the preparation method, meanwhile the dielectric constant of natural rubber (NR) is relatively large compared to the theoretical value. The results showed that $ \acute\varepsilon $ , ε″, and tan δ for RFC decrease as the frequency increases, however, at higher frequencies, the effect significantly weakens. At low ferrite loading, the dielectric properties are strongly influenced by BF content. Strong correlation between magnetic initial permeability and dielectric constant for hard magnetic material polymer composites was also observed. Increasing the content of barium ferrite in NR matrix enhances both ε″ and tan δ. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Nanostructured Polymer Blends: From Core/Shell Nanoobjects to Continuous Three‐Phase Morphologies

A PS‐b‐PIP‐b‐PMMA copolymer has been melt‐blended with homo‐PMMA with a similar molecular weight as the PMMA block. For a 50:50 wt.‐% mixture, the components form 3D bicontinuous lamellae. Upon annealing at 190 °C, a more regular network is observed, which consists of PMMA and 55 nm‐thick bilayered lamellae of triblock copolymer, both being continuous. This co‐continuity persists even when $\overline {M} _{{\rm n}} $ of the homo‐PMMA is twice that of the PMMA block in the copolymer. For 30:70 and 20:80 wt.‐% copolymer/homopolymer pair, the copolymer forms cylindrical and spherical phases, respectively. Blends have also been prepared by solvent casting. Large domains of copolymer interconnected by few lamellae are observed in the 50:50 blend that reorganize into a bicontinuous network upon annealing.

     

Mass Transfer Simulation of Gold Extraction in Membrane Extractors

The extraction of gold in membrane extractors was theoretically investigated. Extraction of gold in the form of $ {\rm Au(CN)}_2^- $ in a solution of n‐heptane and synergistic extractants of LIX79+TOPO was studied. The membrane extractor consists of three sections: the tube side, the membrane, and the shell side. Conservation equations were derived for $ {\rm Au(CN)}_2^- $ in the membrane module and were numerically solved based on finite element method. Simulations were conducted through solving the momentum and mass transfer equations simultaneously. It was indicated that as the feed flows within the tube side, it moves into the membrane due to the concentration difference, and then gets swept by the moving extractants within the shell side. The distribution of solute concentration in the membrane contactor was obtained. Simulation results showed increasing the feed flow rate reduces the extraction efficiency, while doing the same for the organic phase flow rate does not change the extraction efficiency.     

Solvent effects in the hydrodechlorination of 2,4‐dichlorophenol over Pd/Al2O3

Solvent effects in the liquid phase (0.1 MPa; 303 K) hydrodechlorination (HDC) of 2,4‐dichlorophenol have been established over Pd/Al₂O₃. In the absence of secondary reactions, catalyst deactivation, and transport limitations, a stepwise HDC yields 2‐chlorophenol and phenol, where product selectivity was insensitive to the nature of the solvent. In contrast, the initial HDC rates exhibited a marked dependence on the reaction medium and increased in the order: benzene < THF < n‐hexane < cyclohexane < alcohols < water. Higher rates result from the concomitant effect of an increase in the dielectric constant (ε) and a decrease in the molar volume ( $\overline {\nu}$ ) of the solvent, where the major (ca. 80%) contribution is due to ε. We attribute this response to the increased solvent capacity to stabilize the arenium intermediate at higher/lower ε/$\overline {\nu}$ , an effect that extends to reaction in water + organic combinations. We provide, for the first time, a reliable quantification of solvent effects that can be potentially applied to other catalytic hydrogenolysis systems. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Ring‐opening metathesis polymerization of bicyclo[2.2.1]hepta‐2,5‐diene (norbornadiene) initiated by new ruthenium(II) complex

The polymerization of norbornadiene (NBD) initiated by a novel ruthenium (Ru)(II) complex ( 3 ) containing 1,1′‐pyridine‐2,6‐diylbis[3‐(dimethylamino)prop‐2‐en‐1‐one] ( 1 ) as ligand has been investigated. Ru complexes exhibit more catalytic activity in the ring‐opening metathesis polymerization (ROMP) of NBD when activated with trimethylsilyldiazomethane (TMSD). The influence of the various experimental parameters such as reaction time and temperature, nature of the solvent and catalyst, ratio of the NBD/Ru, and TMSD addition has been investigated. The polymers have been obtained in high yields with a relatively low polydispersity index for ROMP and a high $ \bar M_n $ and $ \bar M_w $ values in a monomodal distribution. Their structures have been determined by means of FTIR and ¹H‐NMR spectroscopy. Thermal properties have been determined via thermogravimetric analysis and DTG methods. The NBD polymerization results that initiated by Ru‐based catalyst coordinated to amine ligand have been compared to initiated by [RuCl₂(p‐cymene)]₂. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Diffusion of semi‐flexible polyelectrolyte through nanochannels

The diffusion of sodium polystyrene sulfonate through polycarbonate nanochanels was studied in salt‐free dilute aqueous solution. A stronger molecular weight dependence of diffusion was observed compared to free diffusion in dilute solution. Scaling exponentials relating polymer size to diffusivity were between Flory's theory (D_eff ∝ N^?0.6) and Rouse's model (D_eff ∝ N^?1), revealing a crossover regime from 3‐D diffusion to 1‐D diffusion. Diffusion was less hindered for the polyelectrolyte (D_eff/D₀), than for a rigid sphere, when the polymer/channel size ratio exceeded 0.2. This is attributed to elongated chains with reduced frictional hindrance. Simulation of the confined diffusion based on an elongated cigar model gave D ∝ N^?1 ${R_{\rm t}^{2/3}}$ while the experimental results agree with D ∝ N^?0.94${R_{\rm t}^{ 2/3}}$ . For charged polyelectrolytes, the transition to 1‐D diffusion therefore begins before the polymer radius of gyration exceeds the channel size contrary to model assumptions. We attribute this to the charged nature of the polyelectrolytes causing extended chain conformations. © 2009 American Institute of Chemical Engineers AIChE J, 2010