Suppression of radiation‐induced oxidation of polymers by sputtered silicon oxide coating

Oxygen barrier coating on polymers was attempted to obtain polymeric composite materials with improved radiation resistance. Silicon oxide (SiO_1.6) films ranging from 120 to 240 nm thick were formed on polypropylene (PP) and polyethylene (PE) by radio frequency (RF) magnetron sputtering. Oxygen permeability after SiO_1.6 deposition was reduced significantly in all samples studied, indicating that silicon oxide is a useful gas barrier. The oxygen permeability coefficient of deposited films for PP was 1.7–2.2 × 10^?14 cm³‐cm/cm²/s/cmHg and that for PE was 2.8–4.8 × 10^?13 cm³‐cm/cm²/s/cmHg. We studied the effect of such films on the radiation resistance of polymers in the presence of oxygen by microscopic infrared (IR) absorption spectroscopy. Silicon oxide films 180 nm thick were deposited on the surfaces of PP and PE, and the formation of carbonyl groups after irradiation in air was measured as a function of depth from the surface. Results compared with those for uncoated PE and PP showed that the radiation‐induced polymer oxidation is dramatically suppressed by silicon oxide coating. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 186–190, 2002     

Preparation of oxygen gas barrier poly(ethylene terephthalate) films by deposition of silicon oxide films plasma‐polymerized from a mixture of tetramethoxysilane and oxygen

To prepare silicon oxide (SiOx)‐deposited poly(ethylene terephthalate) films with high oxygen gas barrier capability, SiOx deposition by plasma polymerization has been investigated from the viewpoint of chemical composition. Tetramethoxysilane (TMOS) is suitable as a starting material for the synthesis of the SiOx films. The SiOx deposition under self‐bias, where the etching action occurs around an electrode surface, is effective in eliminating carbonaceous compounds from the deposited SiOx films. There is no difference in the chemical composition between the SiOx films deposited under self‐bias and under no self‐bias. The SiOx films are composed of a main component of Si O Si networks and a minor component of carbonized carbons. The SiOx films deposited under no self‐bias from the TMOS/O₂ mixture show good oxygen gas barrier capability, but the SiOx films deposited under the self‐bias show poor capability. The minimum oxygen permeation rate for poly(ethylene terephthalate) films deposited SiOx film is 0.10 cm³ m⁻² day⁻¹ atm⁻¹, which corresponds to an oxygen permeability coefficient of 1.4 × 10⁻¹⁷ cm³‐cm cm⁻² s⁻¹ cm⁻¹ Hg for the SiOx film itself. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2091–2100, 1999     

Plasma polymerized membranes and gas permeability. II

Thin films were deposited onto porous substrates by plasma polymerization using three kinds of organosilicic compounds, tetramethylsilane (TMS), hexamethyldisiloxane (M₂), and octamethylcyclotetrasiloxane (D₄). Those composite membranes showed different characteristics of gas permeability. When D₄ was plasma-deposited onto a porous substrate, the composites membrane showed the highest oxygen permeability and the lowest oxygen-to-nitrogen permeability ratio. The composite membrane prepared from TMS showed the permeability characteristics opposite to the membrane obtained from D₄. Infrared spectrum of the polymer from D₄ resembles that of dimethylpolysiloxane. The plasma polymers from TMS and M₂ showed different profiles in Si? O absorption bands in the range 1100–1000 cm^-1 or in absorption bands of SiCH₃ groups in the range 850–750 cm^-1 from respective monomers. X-ray photoelectron spectroscopic observation indicated that all the plasma polymers contained more than two species of Si atom with different oxidation states. The greater part of Si atoms in plasma polymers took the same oxidation states in corresponding monomer. The gas permeability characteristics were closely related to the oxidation states of Si atom in the plasma polymers.     

Isobaric measurement of gas permeability of polymers

The principles and design of a gas permeability measuring instrument based on thermal conductivity measurement are described. Since the thermal conductivity of a gas mixture is dependent upon the partial pressure fraction rather than absolute partial pressure of sample gas, and the permeation rate of reference and sample gases through polymer films differe considerably, a pressure-equalizing device is necessary for the accurate measurement of gas permeability. The three types of measurements—integral, differential (flow method), and decay rate measurements—can be used with the instrument. The results of permeability constants and diffusion constants obtained with the methods showed good agreement with the conventional vacuum-type method. With proper selection of methods, the instrument can measure the gas flux through the range of 10^?10 to 10^?3 cm³ (STP)/cm² sec cm Hg. Some advantages of the methods are discussed.     

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.     

Electrical Properties of B-doped homoepitaxial diamond films grown from UHP gas sources

It is confirmed that a small amount of nitrogen incorporated into chemical vapor deposited diamond films dramatically affects their electrical properties. Nitrogen can be incorporated into diamond films through the leak of vacuum system and/or from the impurity in source gases. Because a nitrogen atom can be a deep donor in diamond crystal, the p-type semiconducting properties of boron doped diamond films can be degraded even by the small amount of nitrogen. The small amount of nitrogen in chemical vapor deposited diamond films was measured by cathodoluminescence spectroscopy. For the detection of nitrogen, the N–V center was intentionally induced by defect formation through ion beam irradiation and subsequent annealing. The luminescence intensity of the N–V center was decreased by reducing the leak of the vacuum system and by upgrading the purity of the source gases. Both the carrier density and the Hall mobility of the boron doped diamond films were successfully improved by the control of nitrogen contamination. Using extremely high pure CH₄, H₂ and B₂H₆ in a tightly sealed vacuum system, the total amount of nitrogen impurity in the source gas was controlled to <80 ppm in the N/C atomic ratio resulting in a Hall mobility of 1600 cm²/Vs with a hole concentration of >10¹⁴ cm⁻³ at the room temperature in a 10-ppm-boron doped homoepitaxial diamond film.     

Preparation of oxygen gas barrier polypropylene films by deposition of SiOx films plasma‐polymerized from mixture of tetramethoxysilane and oxygen

Silicon oxide (SiOx) film deposition on the surface of oriented poly(propylene) (OPP) films was done to form a new oxygen gas barrier material using plasma polymerization of the tetramethoxysilane (TMOS)/O₂ mixture. The SiOx film deposition on OPP films never improved oxygen gas barrier properties. The inefficacy of the SiOx deposition was due to poor adhesion at the interface between the deposited SiOx and OPP films and also to the formation of cracks in the deposited SiOx film. If prior to the SiOx film deposition surface modification of OPP films was done by a combination of the argon plasma treatment and TMOS coupling treatment, this contributed effectively to strong adhesion leading to success in the SiOx deposition on the OPP film surface, and then the oxygen gas barrier ability was improved. The oxygen permeation rate through the SiOx‐deposited OPP film was decreased from 2230 to 37–52 cm³/m²/day/atm, which was comparable to that of poly(vinylidene chloride), 55 cm³/m²/day/atm at a film thickness of 11 μm. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2389–2397, 2000     

LIGASE: An Automated Apparatus for Gas Permeability and Separation Measurements

Abstract

An automated computer-controlled apparatus for gas permeability measurements through polymeric membranes is described in detail. The apparatus was specifically designed to operate with hydrocarbon streams and acid gases (CO², H²S) and therefore special care was devoted to the control devices. The maximum capacity of the apparatus in 100 L/h at temperatures up to 70°C and pressures in the 0–15 atm range. Permeability measurements of biogas components (CH⁴, CO², H²S) and their separation factors through experimental hollow fiber membranes are presented as typical data of the equipment described.     

Effect of doping treatment on gas transport properties and on separation factors of polyaniline memebranes

Gas permeation experiments of H₂, O₂, CO₂, N₂, and CH₂ were carried out with freestanding films of the conjugated polymer polyaniline (PANi). At first annealed to remove residual solvent, PANi membranes were doped (i.e., protonated) in a strongly acidic medium (HCl 4M), undoped in a basic medium (NH₄OH 1M), and redoped in a slightly acidic medium (HCl 10^?2M). Protonation and deprotonation kinetics were studied by elementary analysis Gas permeation experiments were performed with the annealed, doped, undoped, and redoped PANi films. The gas transport mechanism was clearly influenced by the diffusivity factor and it obeyed a Fickian diffusion model. From the variations in permeability coefficients with the doping treatment, gases could be divided in two subgroups comprising H₂, O₂, and CO₂ on one hand and N₂ and CH₄ on the other. After the doping–undoping–redoping process, gas fluxes were increased by 15% for the smaller gases and were decreased by 45% for the larger gases. As a consequence gas separation factors were approximately doubled for a gas pair involving the two subgroups and these were unchanged for a gas pair involving only one subgroup. The highest O₂/N₂ and CO₂/CH₄ selectivity coefficients were, respectively, equal to 14 and 78. © 1995 John Wiley & Sons, Inc.     

Dry etching properties of methyl-BCN film with C4F8 gas for Cu/low-k interconnection

Methyl-BCN is an attractive low-k material for the fabrication of next generation LSI device system. This paper describes dry etching of methyl-BCN film in order to develop interconnections for future devices. The methyl-BCN films were deposited by plasma-assisted chemical-vapor deposition (PACVD) using tris(dimethylamino)boron (TMAB) gas at 350 °C. We have investigated dry etching properties and mechanism of the methyl-BCN film using C₄F₈ gas with induced coupling plasma (ICP) etching equipment. In this study we used C₄F₈ gas whose atmospheric lifetime is less than one-sixteenth of the conventional CF₄ gas for suppression greenhouse gases. It was found that methyl bonds in the methyl-BCN film can be kept after dry etching, because the peak of C–H (2962 cm^?1) in Fourier transform infrared absorption (FTIR) spectra didn't significantly change after dry etching. X-ray photoelectron spectroscopy (XPS) analysis shows the presence of C–F₂ and C–F₃ bonds just on the methyl-BCN surface after dry etching and no traces of these bonds inside the film. It is observed that intensities of B–N and B–C bonds decrease after dry etching. This suggests that the etching of methyl-BCN films by C₄F₈ gas mainly involves boron desorption.     

Studies on the preparation and properties of conductive polymers. IV. Novel method to prepare metallized plastics from metal chelates of polymides–imides

A new type of polyamide–imides (PAI) was synthesized by direct polycondensation. A series of polyamide–imide metal chelate films was prepared by the transition-metal salts (AgNO₃, CuCl₂, and CoCl₂) mixed with the polyamide–imides in NMP solution. These polyamide–imide metal chelate films were reduced by various reducing agents, and the reduced films exhibited low surface resistivity around 10⁰?10¹ Ω/cm². The surfaces of these conductive films were proved to be metallized by means of X-ray analysis. The metal adhered on the film was believed to be responsible for the improvement of electrical conductivity. The effects of kinds and concentrations of metal salts, kinds and concentrations of reducing agents, and reduction time on the conductivity of metallized films were investigated. The IR spectra and SEM observations of unreduced and reduced polymer chelate films were also studied.     

Gas transport in poly(alkoxyphosphazenes)

The permeability of four structurally related poly(alkoxyphosphazenes), three isomers of poly(dibutoxyphosphazenes) (PBuP), and poly(di-neopentyloxyphosphazene) (Pneo-PeP), to 13 gases has been determined by the time-lag method. Systematic variations in chemical structure have shown a large effect of side chains on permeabilities and permselectivities. The permeability of poly(di-n-butoxyphosphazene) (Pn-BuP) is of the order of 10^?8 cm³ (STP) cm/(cm² s cmHg) for many gases, and the value for a large gas is higher than that for a smaller one. For small gases such as He and H₂, poly(di-sec-butoxyphosphazene) (Ps-BuP) is as permeable as Pn-BuP, but its diffusivities for larger gases such as Xe and C₃H₈ are about one order lower than those of Pn-BuP. While the permselectivity of Pn-BuP is determined by the solubility, that of Ps-BuP depends on both the diffusivity and solubility factors. The property of poly(diisobutoxyphosphazene) (Pi-BuP) is intermediate between them. These polymers are constitutionally identical, and the only difference is the arrangements of carbons in the side groups. As the side chains become bulky, the permeability decreases, whereas the permselectivity increases. Further decreases of diffusivity and then permeability are observed for Pneo-PeP, whose side groups have one more methyl group than does Pi-BuP. But the solubility data are not much different from other three polymers and the diffusivity factor becomes more significant in permselectivity. The diffusivity depends on the polymer structure much more than does the solubility. The relationships between chemical structure and gas diffusivity and solubility are discussed.     

Experimental measurement of gas permeability through bitumen: results for H2, N2 and O2

This study reports experimental results concerning the transport of permanent gases (H₂, O₂, N₂) through bitumen between 15 and 25 °C. A pressure differential technique, already used in membrane science in order to determine the permeability of gases through dense polymeric films, has been attempted with bitumen samples. It is shown that reproducible permeability data can be obtained thanks to this strategy, providing that bitumen mechanical resistance is improved by a support paper and a low leak module is used. Experimental results are analyzed in terms of permeability value and temperature dependency (activation energy) in comparison with other dense and permeable organic solids (polymers). The limitations of the technique as well as its potential extension to diffusion coefficient determination are discussed.     

Plasma polymer deposition from mixture of tetramethoxysilane and oxygen on PET films and their oxygen gas barrier properties

Plasma polymerization of silane compounds has been discussed for deposition of SiOx positron emission tomography (PET) films at room temperature. A mixture of tetramethoxysilane (TMOS) and oxygen containing 60 mol % O₂ is a preferable raw material for SiOx formation by plasma polymerization. The deposited plasma polymers consist mainly of Si(SINGLE BOND)O networks with small amount of Si(SINGLE BOND)OH and Si(SINGLE BOND)C groups. A part of Si(SINGLE BOND)O networks in the plasma polymers is distorted by the Si(SINGLE BOND)OH and Si(SINGLE BOND)C groups. The oxygen permeability coefficient for the plasma polymer itself is 2.1 × 10⁻¹⁵ (STP) cm³/cm/cm²/s/cm Hg, which is lower than that for hydrolyzed ethylene-vinylacetate copolymer (Eval) and poly(vinylidene chloride) (Saran). Conclusively, the plasma polymer deposited from the mixture of TMOS and oxygen containing 60 mol % O₂ is a material with good oxygen barrier properties. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1031–1039, 1997     

The interaction of hydrogen sulfide with lead- and barium–cadmium–zinc-stabilized poly(vinyl chloride)

Poly(vinyl chloride) polymers stabilized with tribasic lead sulfate discolor upon exposure to hydrogen sulfide gas as a result of lead sulfide formation. The discoloration occurs for samples in both cord and sheet forms and is shown to be a function of total H₂S exposure, reaching a limiting value that is determined by the amount of lead stabilizer used in the polymer formulation. The permeation and diffusion constants for H₂S through PVC stabilized with tribasic lead sulfate and with a liquid Ba–Cd–Zn formulation are found to be P_Pb = (6.0 ± 0.2) × 10^?9, P_BaCdZn = (5.2 ± 0.2) × 10^?9 (both in cm³ gas?cm film/cm² area?sec?cm Hg), D_Pb = (1.3 ± 0.2) × 10^?7 cm²/sec, and D_BaCdZn = (6.4 ± 0.6) × 10^?8 cm²/sec, all measured at 21°C. The stabilizing efficiencies of the formulations were assessed by HCl evolution measurements, which show that exposure to H₂S decreases the initial polymer stability for both Pb-stabilized and Ba–Ca–Zn-stabilized formulations. Protection of stabilized PVC formulations from diffusing hydrogen sulfide is thus advisable for long-term stability as well as for color integrity.     

Preparation of water‐swollen hydrogel membranes for gas separation

Water‐swollen hydrogel (WSH) membranes for gas separation were prepared by the dip‐coating of asymmetric porous polyetherimide (PEI) membrane supports with poly(vinyl alcohol) (PVA)–glutaraldehyde (GA), followed by the crosslinking of the active layer by a solution method. Crosslinked PVA/GA film of different blend compositions (PVA/GA = 1/0.04, 0.06, 0.08, 0.10, 0.12 mol %) were characterized by differential scanning calorimetry (DSC) and their water‐swelling ratio. The swelling behavior of PVA/GA films of different blend compositions was dependent on the crosslinking density and chemical functional groups created by the reaction between PVA and GA, such as the acetal group, ether linkage, and unreacted pendent aldehydes in PVA. The permeation performances of the membranes swollen by the water vapor contained in a feed gas were investigated. The behavior of gas permeation through a WSH membrane was parallel to the swelling behavior of the PVA/GA film in water. The permeation rate of carbon dioxide through the WSH membranes was 10⁵ (cm³ cm^?2 s^?1 cmHg) and a CO₂/N₂ separation factor was about 80 at room temperature. The effect of the additive (potassium bicarbonate, KHCO₃) and catalyst (sodium arsenite, NaASO₂) on the permeation of gases through these WSH membranes was also studied. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1785–1791, 2001     

Ultraviolet‐ray treatment of polysulfone membranes on the O2/N2 and CO2/CH4 separation performance

UV irradiation on polysulfone (PSF) membranes was studied to improve their gas‐separation properties. Membranes with 19–25% PSF contents were prepared by the phase‐inversion method, and the membrane surface was modified with UV rays with a wavelength of 312 nm and a power of 360 µw/cm². Measurements of gas permeation were conducted with pure carbon dioxide (CO₂), methane (CH₄), oxygen (O₂), and nitrogen (N₂) gases under 3–8 bar pressure at 25°C. Fourier transform infrared spectrometry revealed that the polar functional groups of hydroxyl and carbonyl were introduced by UV irradiation. The water contact angle of the treated membrane was reduced from 70–75° to 10–12° after 12 h of UV exposure. Scanning electron microscopy observation showed that the dense skin layer increased as the polymer concentration increased. After UV treatment, the permeation of O₂ decreased from 0.4–3.4 to 0.2–2.3 m³ m^?2 h^?1 bar^?1, whereas that of N₂, CO₂, and CH₄ increased for all of the pressures used from 0.1–1.7 m³ m^?2 h^?1 bar^?1 to about 0.1–3.4 m³ m^?2 h^?1 bar^?1; this depended on the applied pressure and the PSF content. As a result, the selectivity ratio of O₂/N₂ decreased from 1.9–7.8 to 0.6–1.5, whereas that of CO₂/CH₄ increased from 0.9–2.6 to 1.1–6.1. Moreover, the O₂/N₂ and CO₂/CH₄ of the untreated and the treated membranes decreased with increasing pressure and increased with increasing polymer concentration. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42074.     

Gas transport properties of siloxane polyurethanes

Polyurethanes (PUs) were synthesized from toluenediisocyanates (TDIs) and a polymeric diol having polydimethylsiloxane and polyoxyethylene blocks of the ABA type, ended with OH groups. Prepolymers, prepared in toluene solution using ratios [NCO]/[OH] ≥ 2, were crosslinked with triisopropanolamine (TIPA) (ratio [OH]/[NCO] = 1.1) (two-step process). PUs were also obtained with a one-step process using, contemporaneously, TDI, block copolymer, and, as crosslinking agent, TIPA or the glyceride of ε-hydroxyhexanoic acid. Polydimethylsiloxane (PDMSO) was prepared as a reference material. The course of the reaction between block copolymer and TDI was studied by differential scanning calorimetry in the absence and presence of benzoyl chloride (BzCl). Without BzCl, with ratios [NCO]/[OH] > 2, uncontrolled crosslinking side reactions occur. The properties of the PU films obtained with the two methods were studied both for the density of crosslinking and for gas transport properties. The two-step polymers are less crosslinked than the others and are characterized by higher diffusion coefficients and by higher permeability to gases. The permeability order is 10^?9 (N cm³ cm^?1 cm^?1 cm Hg^?1 s^?1) for CH₄, O₂, CO, and N₂ and is 10 times higher for CO₂. The selectivity for the couple O₂/N₂ is higher than that obtained with PDMSO films. Considerable selectivities are shown for the couples CO₂/N₂ and CO₂/CO. © 1995 John Wiley & Sons, Inc.     

Measurement of gas permeability of polymers. I. Permeabilities in constant volume/variable pressure apparatus

A constant volume/variable pressure gas permeability apparatus is described that provides accurate determination of permeabilities ranging from less than 10^?1 to 10⁶ centibarrers. Metal construction, variable temperature control, adjustable downstream pressure and constant volume, and a differential pressure transducer with automatic recording are design features that permit detailed permeability studies under a variety of environmental conditions. Pressure effects on polymer films have been investigated up to 1000 psi, and the relation of gas concentration to permeability has been studied by varying the downstream pressure and volume conditions. The high feed pressures have significantly shortened the time required to obtain meaningful data on low-permeability materials after steady-state conditions are achieved, and the variable-temperature control has permitted evaluation of temperature-related phenomena.     

MMA/TPX homograft membrane for oxygen enrichment

Utilizing the factors of degradation and crosslinking of TPX polymer and high O₂/N₂ selectivity of MMA, the performances of MMA homografted TPX membrane are efficiently improved compared to those of pure TPX membrane. The degradation and crosslinking of TPX polymer solution with or without dissolved oxygen during irradiation were observed and proved in existence by the gas permeability, mechanical, and viscosity change study. High O₂/N₂ permeability ratio of 7.6 and fairly high oxygen permeability of 28 × 10^?10 cm³ cm/cm² s cm Hg of the membrane which was cast from the degassing polymer solution, with 20% degree of MMA grafting, can be obtained. Also the membrane for high oxygen permeability of 63 × 10^?10 cm³ cm/cm² s cm Hg with an O₂/N₂ permeability ratio of 4.5, which was cast from the polymer solution with dissolved oxygen, can be obtained under the condition of 60 h irradiation time and about 7% degree of grafting. O₂/N₂ selectivity of TPX membrane can be improved by homografting method with lower MMA grafting degree than that of heterografting method.