Preparation,characterisation and gas transport properties of trifluoroacetylated ethyl cellulose

A mixed ester of ethyl cellulose (EC) has been prepared by reaction of trifluoroacetic anhydride with the residual hydroxy groups of ethyl cellulose. The mixed ester is soluble in tetrahydrofuran, dichloromethane, chloroform, benzene and pyridine. FTIR and NMR spectra show that hydroxy groups of ethyl cellulose were replaced by trifluoroacetoxy groups. The trifluoroacetyl ethyl cellulose (TFAEC) has higher selectivity for oxygen relative to nitrogen, in gas transport, than unmodified EC. Annealing at an elevated temperature further improves selectivity for oxygen, whilst subsequent ageing at ambient temperature partially reduces oxygen selectivity. The tensile strength of TFAEC is virtually the same as that of unmodified EC, but the elongation to break is 200% higher than for EC.     

Permeation,sorption, and diffusion of water in ethyl cellulose

The permeability of ethyl cellulose to water vapor and liquid water was measured as a function of temperature. A change of slope was found in the Arrhenius plots at about 50°C., close to the glass transition. The sorption isotherms showed essentially zero heat of mixing in agreement with other workers. The diffusion constants were measured in four ways, viz., sorption, desorption, time lag, and by dividing the permeability constants by the equilibrium solubility coefficients. The time lag method gave diffusion constants which were independent of concentration, whereas the other three methods led to diffusion constants which steadily decreased with concentration. All the methods, however, extrapolated to about the same value at zero concentration. The decreasing diffusivities are believed to be due to the clustering of water molecules in the polymer. However, no clustering appeared to take place under the conditions of the time lag measurements.     

Analysis of gas sorption in glassy polymers with the GAB model: An alternative to the dual mode sorption model

The suitability of the Guggenheim–Anderson–De Boer (GAB) model for the parameterization of gas sorption isotherms and their dependences on temperature is explored. The GAB model implies that molecules adsorb on inner surfaces of the polymer in multilayers, which contrasts with the assumptions of the classical Dual Mode Sorption (DMS) model which implies the simultaneous occurrence of Henry‐like dissolution and Langmuir's case I adsorption. The GAB model shows similar efficacy of the parameterization of the gas sorption isotherms in polymers as the DMS model. The isosteric heat of adsorption shows clear dependence on relative surface coverage for carbon dioxide sorption in cellulose acetate, polyethylene terephthalate, and the first polymer of intrinsic microporosity (PIM‐1), thus allowing for the occurrence of adsorption multilayers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1490–1495     

Combined sorption/transport of sodium dodecyl sulfate and hydrochloric acid in a blend of cellulose acetate butyrate with cellulose acetate hydrogen phthalate

The transport of hydrochloric acid (0.001-0.1 M) and sodium dodecyl sulfate (0.001-0.1 M) has been measured through a membrane consisting of a blend of cellulose acetate butyrate and cellulose acetate hydrogen phthalate. The cellulose derivative blend is suggested to suffer an alteration in the degree of hydrophobicity when in equilibrium with sodium dodecyl sulfate (SDS) through hemimicelle formation. An increase in surface hydrophobicity of the blend when in equilibrium with SDS solution was observed by fluorescence measurements using the vibronic bands of the probe pyrene, as well as by water desorption kinetics; a decrease of the effective diffusion coefficients from 1.2 × 10⁻¹¹ m² s⁻¹ in the absence of SDS to approximately 2 × 10⁻¹³ m² s⁻¹ in its presence was found. The value obtained for the mutual diffusion coefficient of HCl in the concentration range 0.001-0.1 M (D=4.2×10⁻¹⁴ m² s⁻¹) shows also that the membrane presents hydrophobic features. The flux of SDS in the blend membrane at different pH values shows two distinct permeation rates depending on the cmc. However, from the calculation of permeability coefficients at SDS concentrations below the cmc a clear decrease in P is found, whilst, at concentrations above the cmc the permeability coefficients are nearly constant, only showing a slightly increase. The diffusion coefficients of SDS in the blend increase over the whole SDS concentration range analysed and show an effective diffusion coefficient 2-3 orders of magnitude below the diffusion coefficients of SDS in aqueous solutions. This fact suggests that the only diffusing species are SDS unimers. The presence of HCl in the SDS bulk solution has the effect of increasing the permeability and diffusion coefficients. Mutual analysis of permeation and diffusion coefficients and sorption isotherms shows that, on decreasing the pH, the interactions between SDS and the polymer network decrease. This is also reflected in a clear decrease of the hydrophobic interactions between the diffusing and polymeric species, provoked by a decrease in the unimer-unimer association.     

Detailed elucidation of hydrocarbon contamination in food products by using solid-phase extraction and comprehensive gas chromatography with dual detection

The present work is focused on the development/optimization of a comprehensive two-dimensional gas chromatography method, with dual detection [flame ionization (FID) and mass spectrometric], for the simultaneous identification and quantification of mineral-oil contaminants in a variety of food products. The two main classes of contaminants, namely saturated and aromatic hydrocarbons, were previously fractionated on a manually-packed silver silica solid-phase extraction (SPE) cartridge. The quantitative results were compared with those obtained by performing a large volume injection, in a GC-FID system, after the same SPE process and by an on-line liquid–gas chromatography method, with very similar results observed. The presence of a series of unknown compounds, that appeared when using the off-line methods, was investigated using the mass spectrometric data, and were tentatively-identified as esterified fatty acids, most probably derived from vegetable oil based ink.     

Refractometry of lyotropic mesophase systems: Ethyl cellulose/m-cresol and ethyl cellulose/acetic acid

An Abbé refractometer with a rotatable polarizer mounted on the eyepiece is used for determining the two principal refractive indices of birefringent concentrated solutions of ethyl cellulose in m-cresol and in acetic acid. At a certain concentration, birefringence appears for both systems, and the concentration agrees with that for the onset of iridescence (here defined as the critical concentration C_a for formation of the liquid-crystalline phase). The birefringence of concentrated solutions depends strongly on concentration and temperature and can be generalized by a master curve. The refractive index increments for both systems are almost independent of temperature at high concentrations.     

Argon sorption and partial molar volume in poly(ethyl methacrylate) above and below the glass transition temperature

Sorption and dilation isotherms for argon in poly(ethyl methacrylate) (PEMA) are reported for pressures up to 50 atm over the temperature range 5–85°C. At temperatures below the glass transition (T_g=61°C), sorption isotherms are well described by the dual-mode sorption model; and isotherms above T_g follow Henry's law. However, isotherms for dilation due to sorption are linear in pressure at all temperatures over the range investigated. Partial molar volumes of Ar in PEMA are obtained from these isotherms. The volumes are approximately constant above T_g (about 40 cm³/mol), whereas the volumes below T_g are smaller and dependent on both temperature and concentration (19–26 cm³/mol). By analyzing the experimental data according to the dual-mode sorption and dilation model, the volume occupied by a dissolved Ar molecule and the mean size of microvoid in the glass are estimated to be 67 129 ų, respectively. The cohesive energy density of the polymer is also estimated as 61 cal/cm³ from the temperature dependence of the dual-mode parameters.     

Effect of antiplasticization on gas sorption and transport. I. Polysulfone

The addition of tricresyl phosphate, N-phenyl-2-naphthylamine, and 4,4′-dichlorodiphenyl sulfone to polysulfone causes changes in thermal and mechanical properties of the glassy mixtures associated with antiplasticization, i.e., reduction in glass transition temperature and increase in stiffness. These changes are also found to be accompanied by reductions in sorption of carbon dioxide and the permeability coefficients for helium, carbon dioxide, and methane at low diluent concentrations with reversal of these trends at higher levels as also occurs for the mechanical properties. Detailed analyses of data for carbon dioxide are given in terms of the dual sorption and mobility models often used for glassy polymers. The mobility for gas transport was found to decrease with diluent addition. The major cause for the decreased sorption is the reduction in glass transition temperature accompanying addition of the diluents. The changes in transport behavior approximately parallel the changes in mechanical behavior. These trends are not even qualitatively correlated with estimates of the excess volume changes associated with addition of the diluents to polysulfone.     

Polypyrrolones for membrane gas separations. I. Structural comparison of gas transport and sorption properties

Despite efforts by the membrane community to develop polymeric materials with improved O₂/N₂ separation performance, limited progress has occurred for almost a decade. Molecular sieving media, which can exhibit gas separation properties superior to polymers, tend to be brittle and uneconomical to produce for large‐scale membrane separation processes. Considering this, the polymer structures investigated in this work were designed to mimic aspects of the structure of molecular sieving media such as zeolites and carbon molecular sieves while maintaining the processability associated with polymers. Significantly attractive gas separation material properties were obtained using hyper rigid polypyrrolone copolymers with controlled packing disruptions between flat, packable segments. The gas transport properties in the materials changed dramatically as a result of different average interchain spacing. Moreover, all of the polypyrrolones studied in this work exhibited performance lying on or above the existing O₂/N₂ upper bound trade‐off line between permselectivity and permeability. These results, therefore, may point the way to a new cycle of membrane materials improvements for gas separations. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1235–1249, 1999     

Concentration-dependent transport of gases and vapors in glassy polymers: II. Organic vapors in ethyl cellulose

The solution (sorption) and transport of acetone, benzene, and methanol vapors in ethyl cellulose have been studied by Barrer, Barrie and Slater [5, 6] over a range of temperatures and penetrant concentrations. The solubility isotherms for the three penetrants as well as the diffusivity and permeability data for acetone reported by these investigators are analyzed in terms of a “dual-sorption” model with partial penetrant immobilization [3], assuming that the diffusion coefficient is concentration dependent [4].     

Effect of structure on the temperature dependence of gas transport and sorption in a series of polycarbonates

The permeabilities and solubilities of five gases are reported for bisphenol-A polycarbonate (PC), tetramethyl polycarbonate (TMPC), and tetramethyl hexafluoro polycarbonate (TMHFPC) at temperatures up to 200°C. The temperature dependence of permselectivity is discussed in terms of solubility and diffusivity selectivity changes with temperature for CO₂/CH₄ and He/N₂ gas separations. The activation energies for permeation and diffusion and the heats of sorption are also reported for each gas in the three polycarbonates. Analysis of these values provides a better fundamental understanding of the effect of polymer-penetrant interactions and polymer backbone structure on the temperature dependence of the transport and sorption properties of gases in membrane separation processes. Important factors affecting the solubility and diffusivity selectivity losses or gains with increased temperature are also identified through correlation of these data with physical properties of the gases and polymers. These conclusions provide a framework for choosing the most promising membrane materials for particular gas separations at elevated temperatures. © 1994 John Wiley & Sons, Inc.     

Effect of antiplasticization on gas sorption and transport. III. Free volume interpretation

Previous papers have shown that antiplasticization of polysulfone and poly(phenylene oxide) by low molecular weight diluents is accompanied by substantial reductions in permeability to gases like helium, carbon dioxide, and methane because of reduced mobility in the glass. These effects are not explained even qualitatively by the extent of volume contraction on mixing for these mixtures. However, as shown here, a simple free volume treatment provides an excellent correlation of these effects. Free volume was computed from measured specific volume and an estimate of the volume at the absolute zero of temperature of the material from a group contribution method. Application of this approach to the mechanical stiffening associated with antiplasticization is suggested. The basis and limitations of this analysis are discussed.     

Effects of hydrocarbon quenching in gas chromatography when using the flame photometric detector

Summary The long time retardation of the main hydrocarbon peak in the chimney of the flame photometric detector greatly reduces the responses of later-eluting sulfur compounds. In the absence of hydrocarbons in the flame, the slope (s) of the log I vs. log [S] plot (where I is the sulfur response and [S] is the sulfur concentration in the sample) is of the highest value and is constant for all experimental conditions tested. Flame hydrocarbons cause the s value to decrease, and this is dependent on the oxygen to hydrogen ratio in the flame (O/H) and, under certain conditions, also on the sulfur to carbon ratio (S/C) of the sample. The abnormalities observed in the determination of methyl thiol in natural gas are explained on the basis of the present study.     

Molecular mass distribution analysis of ethyl(hydroxyethyl)cellulose by size-exclusion chromatography with dual light-scattering and refractometric detection

Dual low-angle light scattering and refractometric detection coupled to size-exclusion chromatography provided proof for the presence of a low amount of stable aggregates/particles in ethyl(hydroxyethyl)cellulose. Unlike the correct size-exclusion chromatographic behavior of the parent polysaccharide itself, the aggregates exhibit variable size-dependent weak retention as a function of flow-rate and of ionic strength of the aqueous mobile phase. Therefore, determination of the molecular mass of non-aggregated polymer is possible in aqueous mobile phase containing 0.1 M NaCl under conditions at which aggregates are completely adsorbed on the column packing irrespective of the flow-rate used. Flow-rate and ionic strength-dependent variations of aggregate behavior as well as model size-exclusion experiments with latex particles indicate that they partly carry a minute charge and have a compact structure. Their weak retention under the separation conditions used suggests a difference in their surface chemistry when compared with the dissolved polymer coils which exhibit a correct size-exclusion behavior.     

Features of the sorption of water vapor and nitrogen on cellulose

Molecular-kinetic parameters of adsorptives, i.e., water (at 300 K) and nitrogen (at 77 K) vapors, are calculated and compared at the initial steps of their adsorption by cellulose. The role of the dipole structure of water molecules is considered upon their interaction with active centers of cellulose, forming heterogeneous electric fields in its pores. The effect of the temperature of the adsorptive and the sizes of its molecules on activation penetration through narrowings of the micropores dominant in absolutely dry cellulose due to the mobility of its structure is determined. The development of a porous system upon water adsorption is demonstrated according to ¹H NMR. It is concluded that low-temperature nitrogen adsorption on cellulose yields rather limited information on its structure and adsorption properties.     

全二维气相色谱-质谱分析煤油基吸热型碳氢燃料烃族组成

采用全二维气相色谱-质谱联用（GC×GC-MS）考察了色谱柱系统、程序升温条件和调制周期3个主要因素对样品组分分离结果的影响,建立了煤油基吸热型碳氢燃料烃族组成的定性分析方法,并利用GC×GC-FID通过有效碳数校正因子对烃族组成进行定量。对选取的9种燃料的分析结果表明,该方法对链烷烃和环烷烃的定量结果与标准方法ASTM D2425的结果高度一致,相对误差基本均在±10%以内。利用该方法计算的碳含量结果与元素分析法相比误差均在0.5%以下。该方法无需复杂的前处理,稀释后可直接进样分析,操作简单,而且可直观地看出不同样品之间的差异,为改进燃料的性能提供了必要的分析手段。     

Miscibility and interfacial property studies of the blends of ethyl cellulose with copolyamide6/66/1010

Interfacial properties governing reverse osmosis separations were studied by using liquid chromatography data with respect to ethyl cellulose/copolyamide6/66/1010 (EC/PA-130) blends. The miscibility of ethyl cellulose/copolyamide6/66/1010 (EC/PA-130) blends was investigated by using differential scanning calorimetry (DSC) and Fourier transform infrared, while the interfacial properties of the blends, including the interfacial adsorption, hydrophobicity, polar and non-polar parameters and β-parameters, were studied by using liquid chromatography. The results show that EC and PA-130 are miscible at compositions of (80/20), (70/30) and (50/50). The hydrophobicity of EC/PA-130 increases with the of PA-130 content. The EC/PA-130(70/30) is superior to the other blends for separating non-dissociable polar organic solute and is more suitable for use as desalting membrane material. It seems that liquid chromatography is an effective tool for studying the interfacial properties of polymer blend materials and selecting high performance of membrane materials.     

Evaluation of gas sorption parameters and prediction of sorption isotherms in glassy polymers

A model of continuous‐site distribution for gas sorption in glassy polymers is examined with sorption data of CO₂ and Ar in polycarbonate. A procedure is presented for determining from a measured isotherm the number of sorption sites in a polymer, an important parameter that previously had to be assumed. With this parameter value and solubility data obtained at zero pressure, the model can reasonably predict sorption isotherms of CO₂ in glassy polycarbonate for a wide temperature range. The number of sorption sites and the average site volume evaluated from CO₂ sorption isotherms are employed for the prediction of Ar sorption isotherms with zero‐pressure solubility data and the independently measured partial molar volume of Ar. A reasonable fit to the measured isotherms of Ar is achieved. With the proposed procedure, the continuous‐site model shows several advantages over the conventional dual‐mode sorption model. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 883–888, 2000