The effect of photodegradation of polystyrene on its permeability characteristics

The diffusion (D) and permeability (P) coefficients for ¹⁴CO₂ in polystyrene films which had been irradiated by short-wave ultraviolet (253.7 nm) radiation under vacuum and in oxygen were determined in the temperature range of 20° to 55°C. Both D and P decreased with increasing exposure, the vacuum-irradiated sample showing significantly greater decreases, presumably on account of a larger extent of crosslinking which was possible in the absence of oxidation. A good correlation was observed between crosslinking and decreasing P and D values. The solubility coefficients for all irradiated samples increase with increasing dose. Activation energies for diffusion increase with increasing irradiation, particularly for the vacuum-irradiated samples. Reductions in P and D values are interpreted in terms of free-volume decreases due to crosslinking and other modifications, while the increasing activation energies are attributed to the increasing energy requirements for creation of free volume in modified polymers.     

Permeation of gases through modified polymer films. V. Permeation and diffusion of helium,nitrogen, methane,ethane, and propane through γ-ray crosslinked polyethylene

The permeation and diffusion of helium, nitrogen, methane, ethane, and propane through γ-irradiated polyethylene films were investigated. These studies were carried out with two objectives in mind: (1) to determine the effect of crosslinking by γ irradiation on permeability and diffusivity using the gas molecules as molecular probes; and (2) to study the plasticizing effects of the low hydrocarbons on the polyethylene film. The γ-ray-induced crosslinking efficiency of polyethylene was investigated in the following irradiation atmospheres: vacuum, acetylene, and nitrogen–acetylene mixtures. Results showed that irradiation in acetylene decreased the crosslinking efficiency while an acetylene–nitrogen atmosphere increased the efficiency compared to irradiation in vacuum. Both the permeation constants and the diffusion coefficients were found to decrease with increasing irradiation dose while the activation energies increased. The permeation constants of the organic gases through polyethylene increased with molecular diameter while the diffusion coefficients decreased. This increase in permeability was attributed to an increase in the solubility due to solubilization of the membrane by the penetrant. For example, the molecular diameter of propane is 4.397 Å compared with 2.807 Å for methane; however, propane permeated the polyethylene film at a rate twice that of methane. Nitrogen and methane have approximately the same molecular diameters—2.7085 and 2.807 Å, respectively—but owing to the plasticizing effect of methane, it permeated the film at a rate three times greater than that of nitrogen. It is interesting to note that the stronger the plasticizing ability of the penetrant, the greater the effect of the irradiation dose. The permeability of propane decreased by 40.7%, while the permeability of helium decreased by 6.4% after an irradiation dose of 50 Mrad.     

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.     

Selective permeation of hydrocarbon gases in poly(tetrafluoroethylene) and poly(fluoroethylene–propylene) copolymer

The permeabilities and diffusivities of methane, ethane, propane, n-butane, and isobutane in commercially available poly(tetrafluoroethylene) (TFE) and poly(fluoroethylene–propylene) (FEP) Teflon have been measured in a Pasternak-type permeation cell. Experiments were carried out at upstream hydrocarbon partial pressures up to 50 torr (1000–60,000 ppm gas phase concentration) and temperatures from 40 to 195°C with films of 0.0508 and 0.127 mm thickness using nitrogen as carrier gas on the upstream and downstream sides of the membrane. The transient and steady-state permeation data are described well by a combination of Henry's law and Fick's law with a concentration-independent diffusion coefficient. Linear Arrhenius plots of both permeabilities and diffusivities were obtained. Linear correlations were found both between the activation energy for diffusion and the square of the gas molecule diameter, and between the logarithm of solubility at 90°C and the penetrant boiling point. Separation factors for binary mixtures of hydrocarbons were measured for TFE at 140°C and found to be similar to those predicted by individual permeabilities in most cases. Measurements with mixed gases were not made for FEP Teflon, but selectivities of FEP are expected to be similarly well described by the ratios of the pure gas permeabilities at the low partial pressures studied. The effect of annealing FEP Teflon for 24 hr at 200°C was found to produce an average of 20–30% reduction in solubility as well as a 9% increase in the activation energy for diffusion compared to as-received films. These effects are believed to be due to increased crystallinity in the sample upon annealing.     

Gas permeability of copolypeptide membranes composed of γ-methyl L-glutamate and γ-benzyl L-glutamate

Membranes of copoly(γ-methyl L -glutamate, γ-benzyl L -glutamate) (PMBLG) as well as the related homopolymer membranes were prepared, and permeabilities of oxygen, nitrogen, argon, and carbon dioxide were measured in the 0–70°C temperature range. The values of permeability coefficients and solubility coefficients of the copolymers were smaller than those of permeability coefficients and solubility coefficients of the two homopolymers for every gas studied. The diffusion coefficients of the gases showed a minimum at around 25 mole % benzyl glutamate. The temperature at a maximum of tan δ spectra for the membranes showed a maximum at around 25 mole % benzyl glutamate. The Arrhenius plots of diffusion coefficients and solubility coefficients for PMBLG, which contained 50 and 71 mole % benzyl glutamate, showed a break at about 50 and 40°C, respectively. This permeation behavior is explained by assuming a unique interaction between methyl glutamate and benzyl glutamate side chains.     

Molecular dynamics simulation of diffusion and permeation of gases in polystyrene

Molecular dynamics simulations are performed to study the diffusion and permeation of gases, including argon, nitrogen, methane, carbon dioxide, and propane, in polystyrene over a wide range of temperatures. A jumping mechanism is observed for the diffusion of diffusants in polymer. The calculated diffusion coefficients agree well with the experimental data and with the results of former simulation studies. The relation between the diffusion coefficient and the molecular diameter is confirmed by the results. Our calculated results on the temperature-dependence of diffusion coefficients show that for some gases a break is seen, at the glass transition temperature, in the Arrhenius plot of ln (D) versus 1/T, while for some other light gases, argon and nitrogen, the plot is linear over the whole temperature range. We have also calculated the permeability coefficients, using the diffusion coefficients calculated in this work and our recently published solubility coefficients [Eslami and Müller-Plathe, Macromolecules 2007; 40:6413]. Our results show that the calculated permeability coefficients are higher than the experimental data by almost the same trend observed in the solubility calculations, but the ratios of calculated permeabilities are in a very good agreement with experiment.     

Gas transport properties of polyaniline membranes

The transport properties of He, H₂, CO₂, O₂, N₂, and CH₄ gases in solvent cast, HCl doped, and undoped polyaniline (PANi) membranes were determined. Measurements were carried out at 40 psi pressure from 19°C to 60°C. An excellent correlation was found between the diffusion coefficients and the molecular diameters of gases. The solubility coefficients of gases were found to correlate with their boiling points or critical temperatures. The sepa-ration factors for CO₂/N₂ and CO₂/CH₄ are dominated by the high solubility of CO₂. These correlations enable us to predict the permeability, diffusion, and solubility coefficients of other gases. After the doping-undoping process, the fluxes of gases with kinetic diameters smaller than 3.5 Å increased but those of larger gases decreased. This results in a higher separation factor for a gas pair involving a small gas molecule and a larger one. © 1996 John Wiley & Sons, Inc.     

Effects of wide‐range γ‐irradiation doses on the structures and properties of 4,4′‐dicyclohexyl methane diisocyanate based poly(carbonate urethane)s

For medical applications, 4,4′‐dicyclohexyl methane diisocyanate (HMDI)‐based poly(carbonate urethane)s were synthesized from HMDI and 1,4‐butanediol as hard segments and poly(carbonate diol) (number‐average molecular weight = 2000 g/mol) as soft segments. The effects of wide‐range γ irradiation on the samples were examined through a series of analytical techniques. Scanning electron microscopy revealed that γ irradiation etched and roughened the surfaces of the irradiated samples. The gel content and crosslinking density measurements confirmed that crosslinking occurred along with degradation at all of the investigated irradiation doses and the degree of both crosslinking and degradation increased with increasing irradiation dose. Fourier transform infrared spectroscopy demonstrated that chain scission in the γ‐irradiated samples occurred at the carbonate and urethane bonds. The decreasing molecular weight and tensile strength indicated that the degradation increased with the γ‐irradiation dose. Differential scanning calorimetry and dynamic mechanical thermal analysis indicated that γ irradiation had no significant effect on the phase‐separation structures. There was a slight reduction in the contact angle. An evaluation of the cytotoxicity demonstrated the nontoxicity of the nonirradiated and irradiated polyurethanes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41049.     

Radiation crosslinking of polyethylene with electron beam at different temperatures

The effect of temperature over the range ?196 to 150°C on the crosslinking of polyethylenes irradiated by electron beam has been investigated on the basis of gel content determination and Fourier transform infra-red (FTIR) spectroscopy. The crosslinking efficiency increases significantly with increasing irradiation does and at elevated irradiation temperature. The crosslinking rates of high density polyethylene (HDPE) and low density polyethylene (LDPE) samples above the melting point (T_M) are much higher than those below T_m. The FTIR data give positive evidence: (i) that trans-vinylene double bonds in cross linked HDPE and LDPE samples increase with increasing irradiation dose temperature (ii) that vinyl double bonds in HDPE decrease rapidly with increasing irradiation dose and temperature, and (iii) vinylidene groups in LDPE decrease slowly with increasing temperature at the lower dose and are almost independent of the irradiation temperature at above room temperature and the higher dose of more than 100 kGy. Gas bubbles are observed in LDPE samples irradiated at 100 and 150°C with high dose (200 to 250 kGy). The size of the bubbles increases gradually at high temperatures.     

Water‐transport properties in polyetherimide blends with a liquid crystal polymer

The effect of the addition of a liquid crystal polymer (Rodrun^®) on the sorption and transport properties of water through films of a polyetherimide (PEI, Ultem 1000) was investigated. A Cahn electrobalance was employed for measuring the water uptake by the polymer samples. Sorption measurements were made with films of PEI, Rodrun, and heterogeneous PEI/Rodrun blends at different water activities at 30°C. In all cases, diffusion and sorption coefficients decreased when the amount of Rodrun increased. Values of the water‐sorption isotherms were adjusted to different models. Permeabilities for the different samples were indirectly obtained using experimental values of the solubility and diffusion coefficients described above. Furthermore, permeabilities of the binary composite material were calculated on the basis of those of the pure components and some theoretical assumptions concerning blend morphology. Results were consistent with a Rodrun structure in the composite intermediate between a fibrillar and a laminar morphology. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 323–332, 1999     

The solubility of methane in aqueous solutions of monoethanolamine,diethanolamine and triethanolamine

The solubility of methane in 3 kmol/m³ solutions of monoethanolamine, diethanolamine, and triethanolamine was measured from 25° to 125°C and pressures up to about 13 MPa. Measurements were also made for the solubility of methane in water at 25° to 125°C and pressures up to 18 MPa in order to confirm the accuracy of the experimental technique. It is demonstrated that methane is more soluble (in terms of mole fraction) in the amine solution than in pure water. Furthermore, the solubility is an increasing function of the size of the alkanolamine. The solubility data were modeled using a Henry's-law approach and the results summarized in terms of salting-in coefficients.     

Studies on the radiation stability of ion exchange membranes

This article deals with some aspects of γ-radiation stability of (phenolsulfonic acid, PSA) cation exchange membranes synthesized in the laboratory. The changes in cation exchange capacity, moisture content, coion sorption, concentration potential, area resistance, counterion transference number, and solute flux of the membranes were evaluated before and after irradiation. The membrane samples were irradiated under wet conditions using a ⁶⁰Co source up to a total dose of 18.65 Mrads. The experimental data point out the possibility of degradation of PSA membranes beyond a dose of 9.78 Mrads, resulting in the loss of functional groups from membrane matrix.     

Impact of H+ ion beam irradiation on Matrimid®. II. Evolution in gas transport properties

Ion beam irradiation is an easily controlled method to modify the chemical structure and microstructure of polymers including the fractional free volume, free volume distribution and chain mobility, thus altering the gas transport properties of the irradiated polymers. The previous paper focused on the impact of H⁺ ion beam irradiation on chemical structural evolution of the polyimide Matrimid®. This paper focuses on the impact of H⁺ ion beam irradiation on microstructure and gas permeation properties of Matrimid®. Irradiation at low ion fluence resulted in slight decreases in permeabilities for five gases (i.e., He, CO₂, O₂, N₂, and CH₄) with increases in permselectivities for some gas pairs (e.g., He/CH₄ and He/N₂). In contrast, irradiation at relatively high ion fluences resulted in simultaneous increases in permeabilities and permselectivities for most gas pairs (e.g., He/CH₄, He/N₂, O₂/N₂, and CO₂/CH₄). While Matrimid® has bulk gas permeation properties that are below the range of commercially interesting polymers, samples irradiated at high ion fluences exhibited significant improvement in gas separation performances. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1670–1680, 2007     

Effects of radiation on mechanical properties of polybutadiene/polystyrene blends

Blends containing 3 wt % low molecular weight polybutadiene (PB) in a polystyrene (PS) matrix were prepared via a precipitation technique that yielded spherical, submicron pools of PB. Tensile specimens made from these blends were then irradiated with high energy electrons in air at dose levels from 0 to 70 Mrads. The blends, which previously showed high levels of toughness approaching that of high impact PS, lost all enhanced toughness when irradiated above 10 Mrads. Analysis of pure PS specimens irradiated over the dose range from 0 to 45 Mrads showed no appreciable dependence of mechanical behavior on dose level. Molecular weight studies of the polybutadiene demonstrated only a very modest increase in molecular weight in the dose range studied here; therefore, reduced mobility of the PB in the blends was not the reason for the dramatic drop in toughness with radiation dose. It was concluded that radiation-induced scission of the PS near the surface of the blends resulted in a significant local reduction in molecular weight. This degraded layer led to premature craze failure and hence a low level of toughness. It was demonstrated that the absence of oxygen during the irradiation process or the removal of the scissioned surface layer via mechanical abrasion resulted in a recovery of toughness. © 1995 John Wiley & Sons, Inc.     

Properties of positive resists. I. irradiation-induced degradation and sensitivity of certain methyl methacrylate copolymers

Poly(methyl methacrylate), poly(methyl methacrylate-co-2-hydroxyethyl methacrylate), poly(methyl methacrylate-co-itaconic acid), poly(methyl methacrylate-co-maleic anhydride), poly(methacrylic acid-co-itaconic acid), poly(methacrylic acid-co-maleic anhydride), and poly(itaconic acid) were prepared by copolymerization of the appropriate amounts of the two monomers at 50°C for 24–40 h using benzoyl peroxide as initiator. Selected samples were γ-irradiated with a total dose ranging from 2 to 12 Mrad. The unexposed and degraded polymers were dissolved in tetrahydrofuran and their molecular weight distribution was determined by gel permeation chromatography. It was found that M?_n decreased drastically with increasing irradiation dose. The presence of various functional groups in both unexposed and irradiated samples was confirmed by infrared spectroscopy. The copolymer thermodynamic compatibility with various solvents was evaluated on the basis of their fractional solubility parameters. The G_s values of these copolymers were determined using the gel permeation chromatography data. It was established that, among those studied, poly(methyl methacrylate-co-maleic anhydride) is the best material for positive resist application based on a G_s value of 8 9 scissions per 100eV.     

Direct measurement of gas solubilities in polymers with a high‐pressure microbalance

Solubility and diffusion data are presented for methane and carbon dioxide gases in high‐density polyethylene. The polymer was cut from extruded piping intended for use in offshore oil and gas applications. The measurements were carried out with a high‐pressure microbalance. The properties were determined from 25 to 50°C and from 50 to 150 bar for methane and from 20 to 40 bar for carbon dioxide. In general, a good agreement was obtained with similar measurements reported in the literature. The solubility followed Henry's law (linear) dependence with pressure, except at high pressures for methane, for which negative deviations from Henry's law behavior were observed. The diffusion coefficients for each of the gases in the polymer were also measured with the balance, although the uncertainty was greater than for the solubility measurements. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1476–1488, 2004     

Effect of Carrier Gas Species on Ferroelectric Properties of PZT/Stainless-Steel Fabricated by CO2 Laser-Assisted Aerosol Deposition

Pb(Zr,Ti)O₃ (PZT) thick films were deposited onto stainless-steel substrates by aerosol deposition using different kinds of carrier gases and were irradiated by CO₂ laser both during and after deposition, for the recovery of ferroelectricity. The ferroelectric and dielectric properties of PZT films deposited using oxygen and nitrogen gases and irradiated by CO₂ laser were superior to those of films deposited using He gas and irradiated by the laser. Some kinds of defects within the film were relaxed by CO₂ laser irradiation during deposition, and grain growth in the film was promoted by post-annealing using laser irradiation.     

Microstructural evolution,swelling and hardening of CVD-SiC induced by He ions irradiation at 650 °C

In the present study, chemical vapor deposited (CVD) SiC samples were irradiated by 500 keV He ions to different doses at 650 °C. The microstructural evolution, surface swelling and nanohardness change caused by irradiation versus He ion dose were investigated using TEM, AFM and nanoindentation. Results showed that a high number density of He bubbles and dislocation loops were formed in the sample irradiated to the high dose, resulting in a swelling of 1.53%. Meanwhile, the hardness of the samples increased after He ions irradiation, which was attributed to the pinning effect of the irradiation induced defects and bubbles. The irradiation hardening degree increased and tended to be saturated with the increasing He ion dose.     

Preparation and characterization of polyethylene oxide (PEO)/gelatin blend for biomedical application: Effect of gamma radiation

polyethylene oxide (PEO)/gelatin blend membranes of four different compositions (w/w) (5/95, 10/90, 20/80, and 30/70) were prepared by solution casting. The films were irradiated by gamma radiation at a total dose of 250 krad (dose rate of 321 krad/h). The X‐ray diffractograms demonstrate both the PEO and radiation influences on the blend thus enhancing crystallinity of gelatin. X‐ray diffractograms of irradiated blend films containing 30% PEO showed highest integrated intensity. The DTA and TGA study showed that the irradiated blend films are more thermally stable than the non‐irradiated films. TMA study showed that the incorporation of PEO into gelatin increased melting point of the blend films. The melting point for irradiated gelatin film changes from 52.9°C to 75.6°C and the glass point changes from 60.3°C to 90.6°C. The phase separation and compatibility of the PEO/gelatin blend films were studied by scanning electron microscopy (SEM). The experimental results showed that the blend films exhibit higher thermal stability and improved mechanical properties in dry state, which suggests the occurrence of interaction detected by XRD and DTA among gelatin, PEO, and water molecules in the films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of electron beam radiation on the mechanical and thermal properties of poly(4-methylpentene-1)

The changes in the mechanical and thermal properties of electron-beam-irradiated PMP of two different molecular weights (〈M_w〉 = 9.2 × 10⁵, 〈M_w〉 = 1.8 × 10⁶) have been studied. Electron beam (EB) irradiation was performed either in a nitrogen or air atmosphere to a maximum dosage of 40 Mrad. Stress–strain behavior of the irradiated materials show that the lower molecular weight polymer is more affected within this dose range than the higher molecular weight material. The modulus of both PMP materials (at 23°C), however, was not affected by EB. Moreover, it was observed that by increasing radiation dose up to 10 Mrad the occurrence of yielding disappeared in the case of the lower molecular weight system but was still found in the high molecular weight material up to 20 Mrad. The elongation at break of both PMP materials was systematically decreased by increasing the dose level. The rate of stress–relaxation of irradiated samples increased as dosage increased. It is believed that oxidative degradation is promoted as a result of irradiation which induces chain scission. This result was confirmed by GPC analysis which showed that, by increasing radiation dose, the molecular weight systematically decreased. DSC measurements used to investigate the changes in thermal properties showed that the melting temperature and heat of fusion decreased as the dose increased. An interesting feature of the DSC studies was the presence of an endothermic doublet in the melting behavior that transformed into a single peak following irradiation.