The permeability coefficients of gases through glassy polymers have been correlated with the fractional free volume (FFV) of the polymers. In general, polymers with high fractional free volumes have high permeabilities while those with low FFV have low permeabilities. This observation is valid for many, but not all materials. This study evaluates the impact of the average size of a free volume element on the permeability of gases through the polymer.

Evaluation of the influence of average free volume element size is only possible by employing model systems in which the chemistry and the total free volume are essentially equivalent. In this study, two stereochemical forms of a methyl-substituted polynorbornene were employed. The isomers are chemically equivalent, with similar total free volumes (0.181 versus 0.188). The average defect size was probed using positron annihilation lifetime spectroscopy. The ortho-positronium lifetimes were measured and it was determined that the difference between the two isomers was approximately 10% with the lower-FFV isomer having the larger average lifetime. For simplicity, the two isomers will be termed Pd and Ni (in reference to the catalysts used in their preparation). The Pd isomer has a slightly lower FFV, but larger average defect size. The Ni isomer has a higher FFV, but smaller average defect size.

Transport evaluation indicates that the Pd-isomer has gas permeabilities two to three times those of the Ni-isomer. In depth analysis indicates that the increase in permeability is a result of an increase in both the diffusivity of gases through the polymer and gas solubility.

Bilayer nickel membranes have been prepared using electrodeposition to grow polycrystalline nickel on a nanocrystalline nickel substrate. When hydrogen is charged from the nano-Ni side of the nano-Ni and poly-Ni composite membrane, the permeation current increases rapidly, then the membrane releases hydrogen faster during decay. When hydrogen is charged from the poly-Ni side of the same composite membrane, the permeation current rises gradually and takes a longer time to reach steady state. Also the permeability of nano-poly-Ni membrane is eight times higher than that of poly-nano-Ni membrane. The diffusivity for the nano-Ni side charging in a nano-poly-Ni membrane is two times higher than that of poly-Ni side charging of the same membrane. The diffusivity and permeability of nano-poly-Ni membranes are smaller than those for nano-Ni membranes, but larger than those for poly-Ni membranes. Using this anisotropic behavior, one can manipulate hydrogen permeation through composite membranes. A hydrogen permeation model for bilayer membranes is proposed to simulate diffusion in a nano-Ni and poly-Ni bilayer membrane in two-directions of charging. The experimental data is in good qualitative agreement with the model.

Asymmetric membranes were prepared from modified poly(ether ether ketone), PEEKWC, by the nonsolvent induced phase separation (NIPS) technique. The influence of the type of solvent and polymer concentration in the casting solution on the morphology, bubble point and on the gas and water transport properties of the membranes were studied.

A variety of plasma treatments have been employed to achieve permanent hydrophilic surfaces throughout the membrane structure. Specifically, we have modified microporous polyethersulfone (PES) membranes using H2O, CO2, and N2 plasma treatments to implant polar functional groups; alternatively, Ar-plasma treatment followed by grafting of hydrophilic monomers (acrylic acid and acrylamide) in the vapor phase has also been successful at modifying PES membranes. PES membranes treated with H2O and CO2 plasmas as well as the grafted membranes are found to be permanently hydrophilic (for a minimum of six months), and the entire membrane cross-section is modified. Chemical changes to the modified PES membranes were determined with FTIR and XPS measurements. Furthermore, water bubble point measurements and electron microscopy results reveal that pore sizes of the modified membranes are only slightly affected, depending on the treatment. Incorporation of polar functionalities results in an increase in the glass transition temperature (Tg) and a moderate change in tensile strength of the modified membranes. Most importantly, the surfaces of the modified membrane are less susceptible to absorption by bovine serum albumin (BSA) proteins.

We have employed mesoporous molecular sieves in polymer membranes in an effort to enhance the permselectivity. The principal advantage of these materials is that the polymer chains can penetrate the pores reducing the nonselective voids that are often observed with inorganic additives. In this study, we have prepared Matrimid® membranes with various loadings of the all silica molecular sieve DAM-1 (Dallas Amorphous Material) as well as DAM-1 functionalized with amines in the channel wall, to enhance the gas permeability characteristics of a high performance polymer. For all gases tested (N2, O2, CO2, CH4), the permeability increased in proportion to the wt % of the amine DAM-1 present in the membrane. The addition of the amine DAM-1 resulted in modest ideal O2/N2 permselectivity, while the ideal CO2/CH4 permselectivity values were >100, depending upon the moisture content of the feed. The ideal CO2/CH4 permselectivity values are among the highest for this type of composite membrane. Details of membrane fabrication as well as permeability and permselectivity results will be presented for a range of Matrimid®/molecular sieve composites.

Pd-Cu alloys are being considered for hydrogen membrane applications because of their resistance to sulfur poisoning. Therefore the permeance of Pd-Cu alloys containing 53, 60, and 80 wt% Pd has been determined over the 623 – 1173 K temperature range for H2 partial pressure drops as great as 2.75 MPa. The results indicate that Pd-Cu alloy composition and thermal history influence membrane permeance. The 60%Pd-40%Cu alloy exhibited very high permeance at 623 K, although both the 53%Pd and 60% Pd alloys exhibited a distinct drop in permeability at higher temperatures due to the transition of the Pd-Cu crystal structure from bcc to fcc. Upon cooling the membrane back to 623 K, the permeability of the 60%Pd alloy was initially an order-of-magnitude less than its initial value, but the permeance increased steadily with time as the Pd – Cu crystal structure slowly reverted to bcc. The fcc 80%Pd alloy was less permeable than the bcc 60% Pd alloy at 623 K, but the 80% Pd alloy was more permeable than the fcc 60%Pd alloy at elevated temperatures.

Protein binding studies reveal increased levels of protein adsorbed to thermally treated poly-acrylamide-modified PVDF microporous membranes in comparison to polyacrylate-modified membranes. Application of XPS, ToF-SIMS, densitometry and μthermal AFM indicate poly-acryamide-PVDF mixing as the primary cause of the increased protein binding.

Silica/zirconia (SZ; Si/ Zr molar ratio = 9/1) membranes having pore sizes in the range of 1∼ 3 nm were prepared by the sol-gel process. Organic/ inorganic hybrid membranes were developed by modifying the surface of the silica-zirconia porous membranes via a gas-phase reaction with trimethylchlorosilane (TMCS) to give a surface that was modified with a monolayer of TMCS. Using nanopermporometry, it was found that the inner surface of membrane pores with diameters larger than several nms were successfully modified with TMCS. TMCS-modified membranes showed approximately the same permeability, Lp, irrespective of water concentration (10 and 100 ppm) in hexane. In contrast, an unmodified membrane, showed a decrease in Lp with increasing water concentration, which was pronounced at low permeation temperatures. This suggests that small amounts of water adsorbed to the inner surface of unmodified silica-zirconia membranes and blocked the permeation of hexane.

The Advanced Technology Program (ATP) is a unique partnership between government and private industry designed to accelerate the development of innovative, high-risk technologies for broad national benefit. Topics for ATP projects are proposed by industry, and awards are made on the basis of announced competitions that consider both the technical and business merits of the proposed work. Companies of any size may apply, and universities or governmental research institutions may partner with industry in ATP projects. Between 1990 and September, 2002, ATP provided a total of $2.0 billion in funding across all technology areas for 642 high-risk, industrial R&D projects. Approximately equivalent matching funds have been provided by the industry partners for a total investment of $3.9 billion. Small businesses are thriving; more than 60% of all projects are led by small businesses. On average, more than half of all ATP projects include university participation, with more than 160 universities participating. Over 25 national laboratories participate.

Matrimid® is a widely used polyimide that has both attractive thermal and gas transport properties. In addition, it has been used as a precursor polymer for production of carbon molecular sieving membranes with commercially interesting gas separations. Ion beam irradiation over a wide range of doses was used to modify a series of Matrimid® membranes. A combined analysis of impact of ion irradiation on the chemical structure, microstructure and gas transport properties of Matrimid® will be presented. Specifically, the evolution in gas permeation properties following irradiation over a wide range of doses will be discussed. Ion irradiation resulted in combined increased permeability and permselectivity for several gas pairs of interest.

Composite membranes of titanium oxide and phosphorus oxide (TiP) were prepared by the sol-gel method and evaluated for use as proton conductive materials at intermediate temperatures. Titanium phosphorus oxide sol solutions were prepared by the hydrolysis of titanium isopropoxide (TTIP) using hydrochloric acid as a catalyst in isopropanol solutions, and the addition of an appropriate amount of phosphoric acid (H3PO4). A new concept for structurally composite membranes is proposed for proton conductive membranes. A composite membrane, Ti/TiP, where the pores of a porous titanium oxide layer are filled with titanium phosphorus oxide, was found to be effective for high electrical conductivity as well as mechanical strength. Electrical conductivities as high as 0.1 and 0.06 S cm−1 at 100 and 300 °C, respectively, under a partial pressure of water of 50 kPa, was achieved for the Ti/ TiP membranes.

Thin films of zeolites including silicalite-1, mordenite and UTD-18 have been prepared on stainless steel foil via pulsed laser deposition (PLD). Laser ablation of as-synthesized zeolite targets onto stainless steel foil followed by a post hydrothermal treatment results in partially oriented zeolite thin films. SEM, XRD were used to characterize the zeolite thin films. Preliminary results for multilayercoatings of different zeolites will also be presented.

A ceramic membrane with an ordered mesoporous top layer has been developed. The active layer possesses a close-packed hexagonal network of spherical pores. Results on permeation of helium and argon through the membrane are presented and correlated with the structural and textural properties of the top layer. New insights are given on the porosity of this close-packed hexagonal structure.

Polyacrylonitrile copolymer having amphiphilic octyl-dimetyl quarternized ammonium moiety was used as imprint scaffolding media for Theophylline (THO) adsorbent. The THO imprinted membranes were prepared by phase inversion technique; The polymer dimethylsulfoxide (DMSO) solution containing THO was cast and then phase-inversed in water to prepare THO imprinted membranes. After template extraction, adsorbent properties of THO were studied by heterogeneous binding experiments of THO and analogs such as caffeine, uracil, and theobromine. Results showed that imprinting effect was appeared in copolymer containing both octyl-hydrophobic group and positively charged ammonium groups.

Materials research involves many areas for which a proper understanding of multi-component mass transport is essential. Examples include sintering and transport-limited reaction in syntheses. In addition, materials may be principally designed for direct manipulation of mass transport, as in membrane materials. Macroscopic descriptions for mass transport are available, but physical interpretation of related transport parameters is generally not straightforward and often relies on microscopic considerations. We will show that, even for diffusion in a simple ideal Langmuir type lattice, macroscopic theories should be used with caution. Differences in mobilities of dissimilar species can set off percolation behavior, causing the flux of the more mobile species to vanish. Such behavior is, for instance, observed for zeolite membranes and cannot be predicted by commonly accepted macroscopic transport theories. Correlations between successive movements of molecules cause a decrease in the self-diffusion coefficient, DS. For non-equilibrium transport it can be shown that correlation effects in most cases disappear in which case non-equilibrium transport becomes related to the component diffusion coefficient D, instead of the smaller DS.

In order to improve the stability of silica membranes against water (vapor) some metal oxides were added to silica to obtain composite silica-metal oxide membranes by the sol-gel techniques. A Ni-doped silica membrane (Ni/Si=1/2) fired at 500°C showed a relatively large permeance of 1.5×10−5 [m3(STP)/(m2skPa)] with selectivity of 350 (H2/CH4), 4200 (H2/SF6) at 200°C and 100 (CO2/CH4) at 35 °C. After leaving the membrane in humid air (RH: 60%, 40°C) for 70 days, the permeance of H2 decreased by about 50% but the selectivity was improved to 930 for H2/CH4. And little change was observed in the activation energy for H2 permeation, while under the same conditions a silica membrane showed a quite large change in the activation energy from 3.1kJ/mol to 14kJ/mol. There is a possibility that metal oxides added to silica help prevent the densification of silica networks through which hydrogen and helium molecules can permeate.

Advances in biotechnology in the past decade have raised the possibility of fabricating biocompatible, porous membranes for molecular sieving and dialysis separations of particles sized 20–50 nm or less. As a prerequisite for such applications, we demonstrate that thin films (∼ 400 nm) of monomeric bovine dermal collagen spin-deposited on a silicon substrate are patternable using standard semiconductor microlithographic processing techniques. Patterning via liftoff has reliably produced square features as small as 10–25 μm laterally, and 50 nm thick, in initial experiments.

HVEM (high vacuum electron microscope) images of these collagen membranes have revealed typical pore sizes ranging from 1–100 nm. Through-membrane diffusion of chromophores spanning this size range was quantified via UV/vis spectrometry. These studies revealed that a 400 nm thick collagen membrane crosslinked with 0.02% glutaraldehyde rejected detectable quantities of methyl orange dye (MW 327) for at least 48 hours, while a 100 nm thick layer admitted methyl orange in under 30 minutes. DNA has been demonstrated to pass through a 100 nm thick collagen layer more slowly than through a bare through-etched control wafer.

In this work, the dehydration of an industrial ketonic solvent used in the chemical industry is investigated by means of pervaporation (PV) using commercially available silica membranes (from Sulzer Chemtech and Pervatech BV). The solvent used is an industrial acetone-water mixture, with minor quantities of other reaction products. The initial water content is 30wt.%. The removal of water by PV has been previously experimentally studied using a polymeric Symplex membrane (GKSS), with relative success though the selectivity was low. Recent developments in the inorganic membrane field have led to the commercial availability of silica microporous membrane materials, like those used in this study. The performance of these ceramic membranes is compared, regarding their fluxes and selectivities. A simplified mathematical model is applied in order to be able to predict the pervaporation flux through pervaporation membranes.

The paper deals with important differences in the distribution of free volume in high and low free volume polymers as indicated by a joint investigation utilizing molecular modeling and positron annihilation lifetime (PALS) studies. The main focus of this paper is on the molecular modeling approach. The first set of polymers in question are the ultra-high free volume polymer poly(1–(trimethylsilyl)-1-propyne) (PTMSP) and two polystyrene derivatives containing Si and F. Extended equilibration procedures were necessary to obtain reasonable packing models for the polymers. The transition state Gusev-Suter Monte Carlo method was utilized to prove a reasonable agreement between simulated and measured diffusivity and solubility values for the model structures. The free volume distribution was analyzed for the validated packing models and compared with respective PALS data. In both cases a bimodal distribution of free volume was observed for PTMSP while the polystyrene derivatives as other conventional glassy polymers showed a more or less monomodal behavior. Good qualitative agreement is demonstrated between size distributions of free volume elements in these polymers obtained via molecular computer modeling and PALS experiments. In addition a series of conventional and high performance polyimides was considered. There a major result is that polyimides with conventional permeabilities for small molecules always show just a monomodal distribution of free volume element sizes in the radius range up to about 5 Å, while all polyimides with high permeabilities have a wider, often bimodal, distribution extending up to a radius between 6 and about 8 Å.

Macroporous silicon is a type of porous silicon that has ordered arrays of channels with high aspect ratio. Macroporous silicon with ordered 3-D structures have a variety of applications such as filters for a particle separation, photonic crystals and optical shortpass filters because of their spatially periodic structures [1–3]. These structures can be prepared by the electrochemical etching (ECE) of silicon wafers in hydrofluoric acid (HF). We report here a way to fabricate macroporous silicon membranes with ordered 3D structures that have controlled periodicity and dimensions appropriate for cell sorting. The silicon 3D structures have pores with variable diameters to modulate the flow behavior and optimize cell sorting efficiency. The silicon membranes were fabricated by wet etching of n-type (100) silicon substrate (40–60 W cm) in potassium hydroxide (KOH) solution with isopropyl alcohol at 80 °C. The 3-D structures were prepared by the electrochemical etching (ECE) of the membranes in diluted HF using the backside illumination with modulated intensity. The thickness of the fabricated membrane has been varied from 20 to 200 mm to optimize filtration of the cells by MEMS (Micro-ElectroMechanical Systems) chips designed for biological cell sorting and cell positioning. The software packages IntelliSuite and ANSYS FLOWTRAN were used to study the mechanical strength of the membrane as well as the velocity profile and flow behavior of Newtonian fluids inside the macroporous silicon membrane.