GAS PERMEATION OF SEGMENTED POLYURETHANES AND THEIR BLENDS WITH PVC

Film specimens of four segmented polyurethanes with different soft segments, namely polycaprolactone, polytetramethylene adipate, polytetramethylene oxide and polypropylene oxide, and their blends with PVC of different compositions were obtained by solution cast. The permeability of these films to O_2, N_2 and H_2 and their density were measured by using gas chromatography and technique of density gradient column. The polyether polyurethanes were found to have higher permeability than the polyester ones due to their low glass transition temperature and /or the low density value. The blends of PVC and polyether polyurethanes, especially the PPO-based polyurethane, are incompatible, and their permeability coefficient-composition dependence has the typical S-shaped curves. PVC is well compatible with the soft segments in its blends with polyester polyurethanes. For these blends the composition dependence of permeability is characterized by a negative deviation from the semilogarithmic additivity rule, and it is possible to prepare blends having T_g 20℃lower than that of PVC, but retaining its low permeability almost unchanged, results were discussed in according with the different approaches for the permeation behavior of compatible and incompatible blends.     

Oxygen permeability, thermal expansion and mixed conductivity of GdxCe0.8−xPr0.2O2−δ, x=0, 0.15, 0.2

The non-linear thermal expansion behaviour observed in Ce_1−yPr_yO_2−δ materials can be substantially controlled by Gd substitution. Coulometric titration shows that the charge compensation mechanism changes with increasing x, in the system Gd_xCe_0.8−xPr_0.2O_2−δ. For x=0.15, charge compensation is by vacancy formation and destabilises the presence of Pr⁴⁺. At x=0.2, further Gd substitution is charge compensated by additionally raising the oxidation state of Pr rather than solely the creation of further oxygen ion vacancies. Oxygen concentration cell e.m.f. measurements in an oxygen/air potential gradient show that increasing Gd content decreases ionic and electronic conductivities. Ion transference numbers measured under these conditions show a positive temperature dependence, with typical values t_o=0.90,0.98 and 0.80 for x=0,0.15 and 0.2, respectively, at 950 °C. These observations are discussed in terms of defect association. Oxygen permeation fluxes are limited by both bulk ambipolar conductivity and surface exchange. However, the composition dependent trends in permeability are shown to be dominated by ambipolar conductivities, and limited by the level of electronic conductivity. At the highest temperatures, oxygen permeability of composition x=0.2 approaches that of composition x=0, Ce_0.8Pr_0.2O_2−δ, with specific oxygen permeability values approximately 2×10⁻⁹ mol s⁻¹ cm⁻¹ at 950 °C, but offering much better thermal expansion properties.     

A dense oxygen separation membrane with a layered morphologic structure

A configuration of dense mixed ionic and electronic conducting (MIEC) membrane with layered morphological structure for oxygen separation, which combines the benefits of high oxygen permeation flux of cobalt-based membrane, high chemical stability of iron-based perovskite and high mechanical strength of thick membrane, was studied. The membrane is normally composed of two layers; each layer is a dense MIEC oxide. The substrate layer is a thick dense membrane with high oxygen permeability but relatively lower chemical stability. The feasibility of dense thick Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF5582) membrane as the substrate layer and Ba_0.5Sr_0.5Co_0.2Fe_0.8O_3−δ (BSCF5528) as the thin-film layer was mainly experimentally investigated. Both the BSCF5582 and the BSCF5528 show the same cubic perovskite structure and the similar lattice constant with no detrimental reaction products formed. By optimizing fabrication parameters of a simple dry pressing process, dual-layered membrane, free of cracks, was successfully fabricated. The oxygen permeation flux of a dual-layered membrane with the thin-film BSCF5528 layer facing to the sweep gas reached 2.1 mL cm⁻² min⁻¹ [STP] (1.56 × 10⁻⁶ mol cm⁻² s⁻¹) at 900 °C, which is about 3.5 times higher than that of the BSCF5528 membrane (0.6 mL cm⁻² min⁻¹, [STP] (4.46 × 10⁻⁷ mol cm⁻² s⁻¹) under the same conditions.     

Extraction of humic acids and their fractions in poly(ethylene glycol)-based aqueous biphasic systems

The possibility of extraction and fractionation of humic acid (HA) in the aqueous biphasic systems (ABS) was shown for the first time. The 10% PEG-10% (NH₄)₂SO₄-H₂O and 5% PEG-7.5% dextran (or dextran sulphate, sodium salt)-H₂O systems were used. HA originated from peat, soddy-podzolic soil and chernozem were studied. The distribution coefficients were measured for HA of different origin, size of the molecules, molecular weights (MW) of the polymers and pH of the system. The PEG-(NH₄)₂SO₄-H₂O system was found to be better for preconcentration and isolation of HA, whereas the PEG-dextran-H₂O system is preferable for HA fractionation. The extractability of HA in ABS increases with increasing the MW of HA molecules. Peat HA are extracted in ABS with higher distribution coefficients compared with chernozem and soddy-podzolic soil HA. It is consistent with higher hydrophobicity of peat HA revealed by hydrophobic interaction chromatography. ABS are promising for HA separation into fractions that differ in their hydrophobic/hydrophilic properties as well as for comparing HA of different origin by their relative hydrophobicity.     

Star polymer synthesis using trithiocarbonate functional β‐cyclodextrin cores (reversible addition–fragmentation chain‐transfer polymerization)

Polystyrene stars were synthesized with reversible addition–fragmentation chain‐transfer (RAFT) polymerization. The core of the stars comprised a trithiocarbonate heptafunctional β‐cyclodextrin ring. Polymerizations were performed at 100 and 120 °C in the absence of an extraneous initiator and at 60 °C in the presence of a radical initiator. Monofunctional trithiocarbonate was also synthesized and used to make linear polystyrene to allow direct a comparison with the star synthesis. In all cases, the polymerization kinetics conformed to pseudo‐first‐order behavior. The measured molecular weights of the stars were found to deviate from those predicted on the basis of the monomer/trithiocarbonate group ratio. The extent of this deviation was dependent on the polymerization temperature, RAFT agent concentration, and conversion. Despite the low radical concentrations, termination reactions are suggested to play a significant role in the seven‐arm polystyrene star syntheses. The synthetic method was found to be suitable for generating star block structures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4498–4512, 2002     

An observation of palladium membrane formation on a porous stainless steel substrate by electroless deposition

The membranes made of palladium and its alloys are used for the extraction of high quality hydrogen from a mixture of gases. Most of recent research is focused on the development technologies for depositing a durable ultra-thin palladium membrane on a porous substrate in order to assure a good mechanical support and maximize the flux of hydrogen permeation. The formation of a palladium membrane deposited on a porous stainless steel substrate by an electroless process is recorded and described in this paper. The palladium deposition progress around the pore area at the surface of the substrate in the initial stages is illustrated. A bridge model is presented to describe the membrane formation around the pore area of the substrate. This model, together with the micrographs showing the deposition progress on the pore areas, will lead to the control of the deposition process for a membrane fabrication as well as the design and modification of a substrate.     

Differential permeation — Part I: A method for the study of solvent diffusion through membranes

We describe the differential permeation method for the study of the diffusion of solvents from a liquid (or liquid mixture) through flat or tubular membranes. This method consists of measuring the transient permeation rates through the membrane when one of its faces is suddenly put into contact with the liquid medium. The change in the transient rate with time is analyzed by numerical best fitting methods to determine the Fickian diffusion coefficient. A simplified equation is proposed for the fitting of the response of a tubular membrane. Deviations from the Fickian transport mechanism with concentration-independent diffusion coefficient can be evidenced and eventually analyzed by using other mechanistic models.     

GEL PERMEATION CHROMATOGRAPHIC ANALYSIS OF LACQUER POLYSACCHARIDE

Ten fractionated samples of Chinese lacquer polysaccharide in aqueous 0.1M NaC1 solution were studied by aqueous-phase gel permeation chromatography (GPC). The universal calibration, broad MWD calibration and corrected column dispersion were adopted to the analysis of GPC chromatograms of the polysaccharide. The molecular weights M_w, M_n and polydispersity index M_w/M_n obtained from GPC are in good agreement with the results of light scattering and membrane osmometry. It is verified that the universal calibration concept is applicable to the lacquer polysaccharide having a number of side chains.     

Dehydration of water-alcohol mixtures by pervaporation and vapor permeation through surface resintering expanded poly(tetrafluoroethylene) membranes

For the purpose of separating aqueous alcohol mixtures by the use of the pervaporation and vapor permeation techniques, a surface resintering expanded poly(tetrafluoroethylene) (e-PTFE), membrane was investigated. The surface properties of the modified e-PTFE membranes were characterized by atomic force microscopy, scanning electron microscopy, and contact angle meter. The X-ray diffraction measurements show that the crystallinity of the e-PTFE membrane decreases with increasing the surface resintering temperature. The surface roughness decreases with the surface resintering temperature increases. The membrane exhibited water selectivity during all process runs. The effects of feed composition, surface resintering temperature, and molar volume of the alcohols on pervaporation and vapor permeation were investigated. Compared with the e-PTFE membrane without surface modified, the e-PTFE membrane with surface resintering treatment effectively improve the separation factor for pervaporation of aqueous alcohol mixtures. The separation performances of e-PTFE membranes in vapor permeation are higher than that in pervaporation.     

Transport of organic vapors through poly(1-trimethylsilyl-1-propyne)

Poly(1-trimethylsilyl-1-propyne) [PTMSP], a high-free-volume glassy polymer, has the highest gas permeability of any known synthetic polymer. In contrast to conventional, low-free-volume, glassy polymers, PTMSP is more permeable to large, condensable organic vapors than to permanent gases. The organic-vapor/permanent-gas selectivity of PTMSP based on pure gas measurements is low. In organic-vapor/permanent-gas mixtures, however, the selectivity of PTMSP is much higher because the permeability of the permanent gas is reduced dramatically by the presence of the organic vapor. For example, in n-butane/methane mixtures, as little as 2 mol% n-butane (relative n-butane pressure 0.16) lowers the methane permeability 10-fold from the pure methane permeability. The result is that PTMSP shows a mixed-gas n-butane/methane selectivity of 30. This selectivity is the highest ever observed for this mixture and is completely unexpected for a glassy polymer. In addition, the gas mixture n-butane permeability of PTMSP is considerably higher than that of any known polymer, including polydimethylsiloxane, the most vapor-permeable rubber known. PTMSP also shows high mixed-gas selectivities and vapor permeabilities for the separation of chlorofluorocarbons from nitrogen. The unusual vapor permeation properties of PTMSP result from its very high free volume - more than 20% of the total volume of the material. The free volume elements appear to be connected, forming the equivalent of a finely microporous material. The large amount of condensable organic vapor sorbed into this finely porous structure causes partial blocking of the small free-volume elements, reducing the permeabilities of the noncondensable permanent gases from their pure gas values.