Effect of styrene grafting on diffusion and solubility of gases in polyethylene

Diffusion and solubility coefficient data of gases for styrene-grafted high-density polyethylene obtained by γ-irradiation are reported. Diffusion coefficients were determined by the time lag method. Solubility coefficients were determined by a new, more accurate static method. Densities and volume fractions of grafted polystyrene were calculated from the observed values of extent of grafting and density of the graft copolymer films. The solubility coefficients obey simple additivity in terms of volume fraction of side-chain polystyrene and amorphous polyethylene. However, behavior of the diffusion coefficients is more complex. Inasmuch as diffusion is a kinetic process, it is influenced by morphology. The experimental results reported here, together with x-ray diffraction and DSC data, provide a basis for discussing the morphology of the graft copolymers.     

The desorption of ethane–butane mixtures from polyethylene

The desorption of mixtures of ethane and butane at atmospheric pressure from low-density polyethylene was investigated over the temperature range from 20 to 60°C. Desorbed penetrants were continuously trapped in glass tubes immersed in liquid nitrogen, and composition was determined as a function of time by means of gas chromatography. The ratio of the quantity of desorbed gas at any time t, q_t, to the quantity at complete desorption, q_∞, was used to determine diffusion coefficients and solubility constants. The diffusion coefficients for both ethane and butane increase with increasing butane concentration in the temperature interval investigated. The solubility of both penetrants can be correlated by Henry's law at 40, 50, and 60°C. However, at 20 and 30°C. the solubility constant for both penetrants increases with increasing butane concentration. This trend is consistent with experimental observations for single-component diffusion and solubility of several hydrocarbons in polyethylene, where increasing concentration of penetrant plasticizes the polymer, resulting in increasing diffusion coefficients and solubility constants.     

The permeation of gases through modified polymer films. IV. Gas permeability and separation characteristics of graft copolymers of polyethylene and teflon FEP films

The effects of grafting styrene and acrylonitrile onto polyethylene and Teflon FEP films on their gas permeation and separation properties were investigated. The time-lag method was used to determine the permeability, diffusion, and solubility coefficients of nitrogen and methane gases in the grafted films. The separation factors of nitrogen—methane gas mixtures were measured by gas chromatography. Structural and morphologic changes in the modified films were examined by density, differential scanning calorimetry, and infrared measurements. Attempts were made to relate these changes to the gas permeation and separation characteristics of the films. Modification by graft copolymerization resulted in slightly improved separation factors; however, the permeability and diffusion coefficients decreased. The experimental permeability and diffusion coefficients for gas mixtures were in good agreement with those of the pure components and could be predicted by single gas permeability and diffusion coefficients.     

Measurement and prediction of diffusion coefficients of supercritical CO2 in molten polymers

The solubility and diffusivity of supercritical carbon dioxide (sc‐CO₂) in low‐density polyethylene (LDPE), high‐density polyethylene (HDPE), polypropylene (PP), ethylene‐ethylacrylate copolymer (EEA) and polystyrene (PS) were measured at temperatures from 150°C to 200°C and pressures up to 12 MPa by using the Magnetic Suspension Balance (MSB), a gravimetric technique for gas sorption measurements. The solubility of CO₂ in each polymer was expressed by Henry's constant. The interaction parameter between CO₂ and polymer could be obtained from the solubility data, and it was used to estimate the Pressure‐Volume‐Temperature relationship and the specific free volume of polymer/CO₂ mixtures. The diffusion coefficients were also measured by the MSB for each polymer. The resulting diffusion coefficients were correlated with the estimated free volume of polymer/CO₂ mixture. Combining Fujita's and Maeda and Paul's diffusion models, a model was newly developed in order to predict diffusion coefficients for the polymers studied. Polym. Eng. Sci. 44:1915–1924, 2004. © 2004 Society of Plastics Engineers.     

Measurement of solubility and diffusion coefficients of ethylene in solid and molten low-density polyethylene with different melt indices

The diffusion behavior of ethylene in polyethylene is of great importance for the polymerization and degassing of polyethylene (PE) industry. Based on the gravimetric sorption and desorption measurement approach, an intelligent gravimetric analyzer is applied to obtain the solubility and diffusion coefficients of ethylene in solid low-density PE (LDPE) with different melt indices at 30°C to 70°C, 0 to 4 atm and in molten LDPE at 160°C to 230°C, 0 to 4 atm, respectively. Results indicate that both the solubility and diffusion coefficients of ethylene in solid LDPE are smaller than those in molten LDPE, while the dissolution enthalpy and diffusion activation energy of ethylene in solid LDPE are higher. In addition, one- and two-dimensional diffusion models are built and the effects of particle size, polymer properties, and operation conditions are systematically investigated on the diffusion behaviors of ethylene in solid and molten LDPE.     

Acrylonitrile copolymer films: Influence of modification by reaction with ethylene oxide on biological degradation

The biological degradation of acrylonitrile–dimethylaminoethyl methacrylate and acrylonitrile–acrylic acid copolymers has been studied by evaluating copolymer films in a continuous in vitro rumen system. The copolymer films were examined before and after modification by reaction with ethylene oxide gas. The degradation of the acrylonitrile–dimethylaminoethyl methacrylate copolymer followed a pattern similar to that occurring on thermal degradation. Modification by reaction with ethylene oxide gas, which induces C?N conjugation, did not improve the resistance to degradation. The acrylonitrile–acrylic acid copolymer films disintegrated, but on prior modification by reaction with ethylene oxide they remained virtually unaltered. Modification of the acrylonitrile–acrylic acid copolymer results in crosslinking with an absence of C?N conjugation, leading to improved resistance to biological degradation.     

Single and mixed gas diffusion through polyethylene films

In this paper, the results of using a mass spectrometer technique to measure mixed-gas diffusion through polymer films are presented. Mixtures of oxygen, carbon dioxide and nitrogen are diffused through films of polyethylene with different degrees and type of chain branching. It is shown that in the case of pure gases Henry's law applies; the gas concentration is proportional to the partial pressure of gas. It is also demonstrated that there is a reasonable correlation between gas solubilities and the Lennard-Jones force constants, although detailed departures from this behaviour are observed for the different materials.The results show that, in general, the presence of one gas can affect the diffusion and solubility of another, although the solubility and diffusion of carbon dioxide were found to be independent of other gases. In particular, an apparent competition is observed between nitrogen and oxygen in terms of solubility. Moreover, the nature of the interaction between gases depends on the degree of branching and the state of annealing of the polyethylene. Contrary to expectation, it is shown that annealing, whilst increasing the crystallinity, increases the permeability of all gases for the only two samples studied in this regard.     

Permeation of Phenol through Ethylene Copolymer Hollow Fibers

Abstract

Hollow fibers were spun from low-density polyethylene, an ethylene/propylene copolymer, ethylene/vinyl acetate copolymers, and ethylene/ethyl acrylate copolymers. The phenol permeation rates through these hollow fibers by reactive dialysis were measured over a range of temperatures, allowing the calculation of the apparent activation energies for transport. The permeation rates for phenol transport were found to be dependent upon the degree of crystallinity in the hollow fiber and the increased solubility of phenol in the hollow fiber due to the presence of the polar ethyl acrylate and vinyl acetate groups in the amorphous phase.     

Experimental and theoretical investigation of solubility and diffusion of ethylene in semicrystalline PE at elevated pressures and temperatures

The solubility and diffusivity of ethylene in semicrystalline polyethylene were experimentally measured using a magnetic suspension microbalance. The sorption measurements were carried out at temperatures up to 80°C and pressures up to 66 atm. The experimentally measured solubilities were found to decrease with increasing temperature and increased with ethylene pressure in good agreement with the predictions of the Sanchez–Lacombe lattice‐fluid model. The diffusivity of ethylene in semicrystalline polyethylene films was estimated from the reduced sorption curves using the half‐time method. The experimentally determined diffusivities were compared with theoretical values predicted by a new molecular hybrid model, which combines the characteristic features of the Pace–Datyner diffusion model with those of the Kulkarni–Stern free‐volume model. The ethylene diffusion coefficient was found to increase with temperature and/or the ethylene‐sorbed concentration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 953–966, 2003     

Oxygen and carbon dioxide transport through high barrier polyester blends

The transport of oxygen and carbon dioxide through a set of random copolymer films based on poly(ethylene terephthalate) (PET) and poly(ethylene 2,6‐naphthalate) (PEN) were explored. Diffusivity and permeability of both gases decreased with increasing PEN content. The oxygen and carbon dioxide diffusion coefficients decreased 74 and 82% from pure PET to pure PEN, respectively. The presence of stiffer PEN moieties had an effect on the glass transition temperature (T_g) of PET/PEN blends and gas barrier. In the complete range of tested blends, the differential scanner calorimeter analysis displayed a single value of thermal glass transition temperature. As the PEN content was increased, the fractional free volume (FFV) and the diffusion coefficients of the blends were decreased. The Doolittle equation provided the best fit for diffusivity and FFV and showed that the gas transport behavior was better understood when it was taken into consideration the cohesive energy of blends. As the PEN content in films was increased, their rigidity and the glass/rubber transition temperature were increased, and their capacity to be penetrated by small molecules like O₂ and CO₂ was decreased. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Relationship between gas transport properties and fractional free volume determined from dielectric constant in polyimide films containing the hexafluoroisopropylidene group

The dielectric constant and gas transport properties (i.e., permeability, diffusivity, and solubility) in 2,2′‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride (6FDA)‐based polyimides were systematically investigated in terms of their polymer fractional free volumes (FFVs) at 30°C. The permeability and diffusion coefficients of the 6FDA‐based polyimide films to hydrogen, oxygen, nitrogen, methane, and carbon dioxide were correlated with their FFVs estimated using van Krevelen's group contribution method. There appeared, however, small linear correlation coefficients. Linear correlations were also observed between the gas transport properties and dielectric constant of these polyimides. This study described FFVas a function of the dielectric constant based on the Clausius‐Mossotti equation. It was found that the gas permeability and diffusion coefficients of these 6FDA‐based polyimide films increased as their dielectric constant‐based FFV increased. A better linear relationship was observed between the gas transport properties and the FFV determined from the polymer dielectric constant in comparison to that estimated using the group contribution method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Diffusion of some dyes in aqueous polymer solutions

The diffusion of both Direct Blue 76 and acid orange dyes in aqueous dilute polymer solutions was studied using the capillary method. The polymer systems studied included dilute solutions of carboxymethyl cellulose, polyethylene oxide and polyacrylamide. It was found that the diffusion coefficients of the two dyestuffs in carboxymethyl cellulose solutions are higher than that in pure water, while in polyacrylamide solutions the values of the coefficients are lower than that in pure water. In case of polyethylene oxide solutions, the diffusion coefficient of Direct Blue 76 was found to be lower than that in pure water, whereas that of acid orange was found to be higher than that in pure water. The diffusion coefficients of both dyes were found to decrease with increasing polymer concentration in the case of polyethylene oxide and polyacrylamide, whereas in the case of carboxymethyl cellulose the diffusion coefficients increased with polymer concentration. With change of temperature, the diffusion coefficients of both dyes in the three polymer solutions were found to obey the Arrhenius equation. The activation energy for diffusion of the two dyes was calculated in pure water, as well as in the different polymer solutions.     

The permeation of gases through modified polymer films. II. Gas permeability and separation characteristics of gamma ray-irradiated polyethylene

A study has been made of the diffusion, solubility, and separation of nitrogen and methane gases in a series of air-and vacuum-irradiated polyethylene films in the temperature range of 15° to 50°C. Samples were air irradiated to 90 Mrads and vacuum irradiated to 80 Mrads. The major structural differences between the modified films were the presence of oxygenated species in the air-irradiated samples. The oxidation of these samples reduced the amount of crosslinking normally found in vacuum-irradiated samples. Diffusion and permeability coefficients for both gases decreased with irradiation dose. The solubility coefficients for the air-irradiated samples increased with increasing irradiation dose while little change was observed for vacuum-irradiated film. The gas mixture permeabilities could be predicted from the pure component permeabilities, and the methane–nitrogen separation factor decreased with increasing irradiation dose.     

The barrier properties of polyethylene terephthalate to mixtures of oxygen, carbon dioxide and nitrogen

The diffusion and solubility of oxygen, nitrogen and carbon dioxide have been studied in amorphous and biaxially oriented films of polyethylene terephthalate (PET). To measure the sorption and desorption of each gas simultaneously in cases where mixtures of gases were studied, a mass spectrometer was used as a detector. It was found that the solubility and diffusion of nitrogen in PET were markedly affected by the presence of the other gases, oxygen and carbon dioxide with differences in detail between results for the amorphous and biaxially oriented films. It is of particular interest that the presence of oxygen reduces the solubility and increases the diffusivity of nitrogen.     

Gas permeation resistance of a perfluoroalkoxy‐tetrafluoroethylene copolymer

The permeation resistance of perfluoroalkoxy (PFA), a polytetrafluoroethylene (PTFE) copolymer, to various gases was explored. The diffusion and permeability coefficients for hydrogen, oxygen, nitrogen, and air were measured with extruded films using standard manometric techniques. For thicker films, transport properties were independent of film thickness. For the thinnest films, the diffusivity and permeability coefficients were slightly higher because of reduced crystallinity. The solubility of these apolar permeants in PFA was quite low and behaved ideally. Therefore, the permeation characteristics of air could be calculated from those of nitrogen and oxygen. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2122–2125, 2006     

Measurement of gas permeability of polymers. II. Apparatus for determination of permeabilities of mixed gases and vapors

A gas permeability apparatus has been constructed to facilitate the study of permeation of mixtures of gases and vapors. The apparatus utilizes the carrier gas method with gas-chromatographic analysis to determine individual permeation values and in-line thermal conductivity detectors to provide simultaneous overall diffusion and permeability data. The effects of film type, structure, and morphology on permeability may be studied from atmospheric to 100 psi feed pressure and from ambient to 300°C. Feed stocks may be custom mixed, and a vaporizing bath permits introduction of vapors either as contaminants or as primary permeants in an inert carrier. The experiments which illustrate the use of the equipment suggest that the noninteracting gases H₂ and CH₄ permeate a number of polymer films independently over a wide concentration range and that water vapor retards their permeation in polyimide films.     

Magnetic Mixed Matrix Membranes Consisting of PPO Matrix and Magnetic Filler in Gas Separation

Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and magnetic neodymium powder particles MQP-14-12 have been used for the preparation of magnetic mixed matrix membranes. Permeability diffusion and sorption coefficients of O₂, N₂, and synthetic air components were estimated for homogeneous and heterogeneous membranes using the Time Lag method based on dynamic experiments in a constant pressure system. The influence of magnetic field and magnetic powder particles on the gas transport properties of MMMs was studied. The results showed that the membrane permeation properties were improved with the magnetic neodymium particle filling. It was observed that the magnetic ethylcellulose and poly(2,6-dimethyl-1,4-phenylene oxide) membranes showed higher gas permeability, while their permselectivity and solubility were rather maintained or slightly increased. The results also showed that the magnetic powder addition enhanced gas diffusivity significantly in EC and PPO membranes.     

Association properties of a high molecular weight poly(propylene oxide–b–ethylene oxide) diblock copolymer in aqueous solution

Summary Summary A high molecular weight poly(propylene oxide–b–ethylene oxide) diblock copolymer was prepared via sequential anionic suspension polymerization using a calcium amidealkoxide initiating system. ¹H nuclear magnetic resonance, viscometry and static and dynamic light scattering have been used to characterize the copolymer and to examine its self–assembly in aqueous solution. The copolymer was found to self–associate in a narrow concentration range above a certain critical aggregation concentration. The weight–average molecular weight, the radii of gyration, the second virial coefficients, the diffusion coefficients, and the hydrodynamic radii of the particles in both unimer and aggregate regions were determined. Aggregates of low aggregation number (2–3) were formed. Dynamic light scattering measurements performed in a wide concentration range revealed an enhanced aggregate stability towards dissociation upon dilution.     

Solubility and diffusion coefficient of antioxidants in polyethylene

As an aid in assessing the ability of antioxidant additives to persist in polymers and thus remain effective in protecting against oxidation, the solubility and diffusion coefficient of two antioxidants in branched polyethylene have been determined in this work. A method was developed for this purpose by which the diffusion coefficient and solubility could be determined simultaneously. The method consists of analyzing the concentration profile across a stack of polyethylene sheets through which the antioxidant was allowed to diffuse. The concentration of antioxidants in polyethylene was determined by a thermogravimetric technique which relies directly on the ability of the additives to suppress oxidation reaction. The diffusion coefficients determined showed excellent agreement with values in the literature which were obtained by a radiotracer method. The solubility of the antioxidants in three normal hydrocarbon solvents of varying molecular sizes was also determined by a conventional technique at various temperatures and found to correlate well with their solubility in polyethylene determined by the diffusion method. In particular, the dependence of the solubility on the size of solvent molecules and on temperature agrees well with an equation derived on the basis of the regular solution theory of liquid mixtures.     

Molecular simulations of small gas diffusion and solubility in copolymers of styrene

The objective of this study is to investigate the relationship between gas permeability and the chemical structure and conformational properties for copolymers of styrene and its homopolymer. The diffusion and the solubility coefficients of small gas molecules (He, H₂, Ne, O₂, N₂, CH₄, Ar, CO₂) in amorphous structures of poly (styrene-alt-maleic anhydride) copolymer (SMA), poly (styrene-stat-butadiene) rubber (SBR), and atactic polystyrene (PS) are investigated by the transition state approach. Simulation results are found to be in good agreement with the experimentally measured values. The transport behavior of H₂O molecules is also studied in the same bulk structures by fully atomistic molecular dynamics simulations. In general, the diffusion coefficients of the gases in these matrices decrease in the following order: SBR>PS>SMA, whereas the solubility coefficients follow the reverse order. The differences in the mobility of the matrices seem to be the dominant determining factor for diffusion. And the solubility coefficients depend on the free volume distribution of the matrices.