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.

Preparation of large,ultra-flexible and free-standing nanomembranes of metal oxide-polymer composite and their gas permeation properties

In this work,fabrication of free-standing nanomembranes of metal oxide(MO_(x))and polymers by simple spin-coating method is discussed.First,double-layer nanomembranes containing MO_(x) and epoxy resin of polyethyleneimine and poly[(o-cresyl glycidyl ether)-co-formaldehyde]were prepared.Free-standing nanomembranes were successfully prepared,but defects formed in the metal oxide nanolayer during sharp bending of the nanomembrane.To overcome fragility of MO_(x) nanolayer,poly(vinyl alcohol)nanolayers were introduced between MO_(x) nanolayers by layer-by-layer(LbL)assembly process.The LbL nanomembrane was also free-standing and was highly flexible during macroscopic membrane manipulations.Even after transfer of the LbL nanomembrane onto a porous support,it did not have apparent cracks,confirmed by scanning electron microscopy(SEM).The LbL nanomembrane sustained low gas permeance,confirming the absence of significant defects,although it shows excellent flexibility.We believe that the presented LbL nanomembrane could be a platform useful for the design of molecular nanochannels,which is the next challenge for efficient gas separation.

MORPHOLOGIES AND GAS SEPARATION PROPERTIES OF MELT-SPUN ASYMMETRIC POLY(4-METHYL-1-PENTENE)HOLLOW FIBER MEMBRANES

Poly(4-methyl-1-pentene) (PMP) hollow fiber membranes were prepared by the melt-spun and cold-stretch(MSCS) method. Scanning electronic microscopy (SEM) was used to characterize the section and surface structures of themembranes with special asymmetric structure. The preliminary results of gas permeation measurements indicated that the resultant hollow fiber membranes have the potential ability for oxygen/nitrogen separation.

PREPARATION OF ASYMMETRIC POLYETHERKETONE FLAT AND HOLLOW FIBER MEMBRANES FOR GAS SEPARATION USING ACETIC ACID BASED COAGULANTS

Membranes for gas separation have developed significantly in the last twenty years,however,there is still a need for high temperature and chemically resistant membranes that exhibit good selectivity and gas permeability.Our study examines the fundamental properties of polyetherketone (PEK,a thermally stable and chemically resistant polymer) membranes prepared using concentrated sulphuric acid (98% H_2SO_4) as the solvent.Non-solvents used in the work included acetic acid,ethanol,methanol,glycerol,and water....

GAS TRANSPORT PROPERTIES OF A POLYIMIDE BASED ON 2, 2-BIS (3, 4-DECARBOXYPHENYL) HEXAFLUOROPROPANE AND meta-PHENYLENEDIAMINE

By means of a vacuum time-lag method, gas transport properties of a polyimide based on 2,2-bis(3,4-decarboxyphenyl) hexafluoropropane dianhydride (6FDA) and meta-phenylenediamine (mPDA) have been measured as a function of upstream pressure and temperature. The results show that no gas-induced plasticization occurs for this polyimide in the upstream pressure range from 1 atm to 20 atm. The temperature dependence of P and D can be described by the Arrhenius equations. The activation energies of permeation and diffusion were obtained for the gas/polymer pair studied and correlated with the size of penetrant gas.

EXTREME PROPERTIES OF FIBER COMPOSITES AND THEIRCRYOGENIC APPLICATIONS

Fiber-polymer composites exhibit extraordianary and unusual properties. Depending on the fiber type and arrangementt the following can be achieved: a very high tensile strength and stiffness or fatigue strength, a zero or negative thermal expension, a rather high damping capability and a very high thermal and electrical insulating performance. But even carbon fibers can be converted into excellent electrical conductors when calined with fluorine. However, the shear properties of fiber composites with a polymeric matrix are medium. Extreme mechanical and thermal cryogenic properties will be discussed and compared to those of other material classes. Special emphasis is put on present and future cryogenic applications including storage and transportation of hydrogen or liquefied gases. Gas permeation through composites afier mechani-cal and thermal cycling and modifications for a better performance will be discassed.Further trends for getting advanced materials will finish the presentation.

STUDIES ON THE PERMEABILITY OF P VC/EBBA OVERLAPPED ULTRATHIN COMPOSITE MEMBRANES MODIFIED BY PLASMA-POLYMERIZATION WITH FLUOROCARBON MONOMERS

The PVC/EBBA ultrathin composite membranes with thickness of about 100 nm were prepared by spreading the solution on water surface. The overlapped composite membrane showed a characteristic aggregation structure in which the polymer matrix exists as a three-dimensional spongy network and the liquid crystal domains werc observed. Tne surface modification for the overlapped membranes was carried out by means of plasma-polymerization with the monomers of fluorocarbon compounds. Both Arrhenius plots of permeability coefficients for oxygen ((?)_O_2) in the membrane samples before and after modification showed significant increase in the vicinity of the T_(KN) of EBBA.

The effect of humidity on the CO_2/N_2 separation performance of copolymers based on hard polyimide segments and soft polyether chains:Experimental and modeling

In this work, we studied two copolymers formed by segments of a rubbery polyether（PPO or PEO） and of a glassy polyimide（BPDA-ODA or BKDA-ODA） suitable for gas separation and CO2 capture. Firstly, we assessed the absorption of water vapor in the materials, as a function of relative humidity（R.H.）, finding that the humidity uptake of the copolymers lies between that of the corresponding pure homopolymers values.Furthermore, we studied the effect of humidity on CO2 and N2 permeability, as well as on CO2/N2 selectivity, up to R.H. of 75%. The permeability decreases with increasing humidity, while the ideal selectivity remains approximately constant in the entire range of water activity investigated. The humidity-induced decrease of permeability in the copolymers is much smaller than the one observed in polyimides such as Matrimid? confirming the positive effect of the polyether phase on the membrane performance.Finally, we modeled the humidity-induced decrease of gas solubility, diffusivity and, consequently, permeability, using a suitable approach that considers the free volume theory for diffusion and LF model for solubility. Such model allows estimating the extent of competition that the gases undergo with water during sorption in the membranes, as a function of the relative humidity, as well as the expected reduction of free volume by means of water molecules occupation and consequent reduction of diffusivity.

Preparation and permeability of ZSM-35 zeolite membranes on porous stainless steel tubes

ZSM-35 zeolite membranes were prepared on porous stainless steel tubes with silica sol and tetraethoxysi-lane as silica source,and with 1-butylamine and ethylenedi-amine as templates,respectively.The characterization of X-ray diffraction(XRD)and scanning electron microscopy(SEM)showed that the membranes prepared with ethylene-diamine as the template displayed growth orientation with their crystal planes(h00)parallel to the support surface.The single-component permeability tests of H2,N2 and C3H8 showed that the membranes synthesized with ethylene-diamine as the template,compared with those with 1-butylamine as the template,showed relatively higher permeation rates and ideal separation factors,and above their corresponding ideal Knudsen diffusion factors,which might be attributed to the different growth orientation of zeolite membranes synthesized with different templates.