Characterization of a Thermoresponsive Chitosan Derivative as a Potential Draw Solute for Forward Osmosis.

A thermoresponsive chitosan derivative was synthesized by reacting chitosan (CS) with butyl glycidyl ether (BGE) to break the inter- and intramolecular hydrogen bonds of the polymer. An aqueous solution of the thermoresponsive CS derivative exhibits a lower critical solution temperature (LCST) than CS, and it undergoes a phase transition separation when the temperature changes. Successful incorporation of BGE into the CS was confirmed by FTIR and XPS analyses. Varying the BGE content and the concentration of the aqueous solution produced different LCST ranges, as shown by transmittance vs temperature curves. The particle size was observed by scanning electron microscopy, which revealed that the particles were smaller and well dispersed at 15 °C, whereas the particles became larger and tended to aggregate at 60 °C. A similar trend was observed with the mean particle size measured using dynamic light scattering. Positron annihilation lifetime spectroscopy data also revealed the reversibility of the particle properties as a function of temperature. Microstructure analysis showed that the particles had larger free-volume sizes at 15 °C than at 60 °C. The particles were also found to be nontoxic with 92% cell survival. A simple forward osmosis (FO) test for dye dehydration revealed the potential use of the thermoresponsive chitosan derivative as a draw solute with a flux of 8.6 L/m2 h and rejection of 99.8%.

Membranes with fast and selective gas-transport channels of laminar graphene oxide for efficient CO2 capture.

Graphene oxide (GO) nanosheets were engineered to be assembled into laminar structures having fast and selective transport channels for gas separation. With molecular-sieving interlayer spaces and straight diffusion pathways, the GO laminates endowed as-prepared membranes with excellent preferential CO2 permeation performance (CO2 permeability: 100 Barrer, CO2/N2 selectivity: 91) and extraordinary operational stability (>6000 min), which are attractive for implementation of practical CO2 capture.

Using Tannic-Acid-Based Complex to Modify Polyacrylonitrile Hollow Fiber Membrane for Efficient Oil-In-Water Separation.

Separating oil from water allows us to reuse both fluids for various applications, leading to a more economical process. Membrane separation has been evidenced as a cost-effective process for wastewater treatment. A hollow fiber membrane made of polyacrylonitrile (PAN) is an excellent choice for separating oil from water because of its superior chemical resistance. Its low antifouling ability, however, reduces the effectiveness of its separation. Hence, in this study, we used tannic acid (TA) and FeIII complex to modify the surface of the PAN hollow fiber membrane. To improve membrane performance, different reaction times were investigated. The results demonstrate that even when the TA-FeIII covered the pores of the PAN membrane, the water flux remained constant. However, when an emulsion was fed to the feed solution, the flux increased from 50 to 66 LMH, indicating low oil adhesion on the surface of the modified membrane. When compared to the pristine membrane, the modified membrane had superior antifouling and reusability. As a result, the hydrophilic TA-FeIII complex on PAN surface improves overall membrane performance.

When self-assembly meets interfacial polymerization.

Interfacial polymerization (IP) and self-assembly are two thermodynamically different processes involving an interface in their systems. When the two systems are incorporated, the interface will exhibit extraordinary characteristics and generate structural and morphological transformation. In this work, an ultrapermeable polyamide (PA) reverse osmosis (RO) membrane with crumpled surface morphology and enlarged free volume was fabricated via IP reaction with the introduction of self-assembled surfactant micellar system. The mechanisms of the formation of crumpled nanostructures were elucidated via multiscale simulations. The electrostatic interactions among m-phenylenediamine (MPD) molecules, surfactant monolayer and micelles, lead to disruption of the monolayer at the interface, which in turn shapes the initial pattern formation of the PA layer. The interfacial instability brought about by these molecular interactions promotes the formation of crumpled PA layer with larger effective surface area, facilitating the enhanced water transport. This work provides valuable insights into the mechanisms of the IP process and is fundamental for exploring high-performance desalination membranes.

Hemocompatible control of sulfobetaine-grafted polypropylene fibrous membranes in human whole blood via plasma-induced surface zwitterionization.

In this work, the hemocompatibility of zwitterionic polypropylene (PP) fibrous membranes with varying grafting coverage of poly(sulfobetaine methacrylate) (PSBMA) via plasma-induced surface polymerization was studied. Charge neutrality of PSBMA-grafted layers on PP membrane surfaces was controlled by the low-pressure and atmospheric plasma treatment in this study. The effects of grafting composition, surface hydrophilicity, and hydration capability on blood compatibility of the membranes were determined. Protein adsorption onto the different PSBMA-grafted PP membranes from human fibrinogen solutions was measured by enzyme-linked immunosorbent assay (ELISA) with monoclonal antibodies. Blood platelet adhesion and plasma clotting time measurements from a recalcified platelet-rich plasma solution were used to determine if platelet activation depends on the charge bias of the grafted PSBMA layer. The charge bias of PSBMA layer deviated from the electrical balance of positively and negatively charged moieties can be well-controlled via atmospheric plasma-induced interfacial zwitterionization and was further tested with human whole blood. The optimized PSBMA surface graft layer in overall charge neutrality has a high hydration capability and keeps its original blood-inert property of antifouling, anticoagulant, and antithrmbogenic activities when it comes into contact with human blood. This work suggests that the hemocompatible nature of grafted PSBMA polymers by controlling grafting quality via atmospheric plasma treatment gives a great potential in the surface zwitterionization of hydrophobic membranes for use in human whole blood.

Evaluation of the Antibacterial Activity of Eco-Friendly Hybrid Composites on the Base of Oyster Shell Powder Modified by Metal Ions and LLDPE.

Transforming biological waste into high-value-added materials is currently attracting extensive research interest in the medical and industrial treatment fields. The design and use of new antibacterial systems are urgently needed. In this study, we used discarded oyster shell powder (OSP) to prepare calcium oxide (CaO). CaO was mixed with silver (Ag), zinc (Zn), and copper (Cu) ions as a controlled release and antibacterial system to test the antibacterial activity. The inhibition zones of various modified metals were between 22 and 29 mm for Escherichia coli (E. coli) and between 21 and 24 mm for Staphylococcus aureus (S. aureus). In addition, linear low-density polyethylene (LLDPE) combined with CaO and metal ion forms can be an excellent alternative to a hybrid composite. The strength modulus at 1% LLDPE to LLDPE/CaO Ag increased from 297 to 320 MPa. In addition, the antimicrobial activity of LLDPE/CaO/metal ions against E. coli had an antibacterial effect of about 99.9%. Therefore, this hybrid composite material has good potential as an antibacterial therapy and biomaterial suitable for many applications.

Vacuum-Assisted Interfacial Polymerization Technique for Enhanced Pervaporation Separation Performance of Thin-Film Composite Membranes.

In this work, thin-film composite polyamide membranes were fabricated using triethylenetetramine (TETA) and trimesoyl chloride (TMC) following the vacuum-assisted interfacial polymerization (VAIP) method for the pervaporation (PV) dehydration of aqueous isopropanol (IPA) solution. The physical and chemical properties as well as separation performance of the TFCVAIP membranes were compared with the membrane prepared using the traditional interfacial polymerization (TIP) technique (TFCTIP). Characterization results showed that the TFCVAIP membrane had a higher crosslinking degree, higher surface roughness, and denser structure than the TFCTIP membrane. As a result, the TFCVAIP membrane exhibited a higher separation performance in 70 wt.% aqueous IPA solution at 25 °C with permeation flux of 1504 ± 169 g∙m-2∙h-1, water concentration in permeate of 99.26 ± 0.53 wt%, and separation factor of 314 (five times higher than TFCTIP). Moreover, the optimization of IP parameters, such as variation of TETA and TMC concentrations as well as polymerization time for the TFCVAIP membrane, was carried out. The optimum condition in fabricating the TFCVAIP membrane was 0.05 wt.% TETA, 0.1 wt% TMC, and 60 s polymerization time.

Enhancing Performance of Thin-Film Nanocomposite Membranes by Embedding in Situ Silica Nanoparticles.

In this work, silica nanoparticles were produced in situ, to be embedded eventually in the polyamide layer formed during interfacial polymerization for fabricating thin-film nanocomposite membranes with enhanced performance for dehydrating isopropanol solution. The nanoparticles were synthesized through a sol-gel reaction between 3-aminopropyltrimethoxysilane (APTMOS) and 1,3-cyclohexanediamine (CHDA). Two monomers-CHDA (with APTMOS) and trimesoyl chloride-were reacted on a hydrolyzed polyacrylonitrile (hPAN) support. To obtain optimum fabricating conditions, the ratio of APTMOS to CHDA and reaction time were varied. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) were used to illustrate the change in morphology as a result of embedding silica nanoparticles. The optimal conditions for preparing the nanocomposite membrane turned out to be 0.15 (g/g) APTMOS/CHDA and 60 min mixing of APTMOS and CHDA, leading to the following membrane performance: flux = 1071 ± 79 g∙m-2∙h-1, water concentration in permeate = 97.34 ± 0.61%, and separation factor = 85.39. A stable performance was shown by the membrane under different operating conditions, where the water concentration in permeate was more than 90 wt%. Therefore, the embedment of silica nanoparticles generated in situ enhanced the separation efficiency of the membrane.

Nanofiltration Membranes Formed through Interfacial Polymerization Involving Cycloalkane Amine Monomer and Trimesoyl Chloride Showing Some Tolerance to Chlorine during Dye Desalination.

Wastewater effluents containing high concentrations of dyes are highly toxic to the environment and aquatic organisms. Recycle and reuse of both water and dye in textile industries can save energy and costs. Thus, new materials are being explored to fabricate highly efficient nanofiltration membranes for fulfilling industrial needs. In this work, three diamines, 1,4-cyclohexanediamine (CHD), ethylenediamine (EDA), and p-phenylenediamine (PPD), are reacted with TMC separately to fabricate a thin film composite polyamide membrane for dye desalination. Their chemical structures are different, with the difference located in the middle of two terminal amines. The surface morphology, roughness, and thickness of the polyamide layer are dependent on the reactivity of the diamines with TMC. EDA has a short linear alkane chain, which can easily react with TMC, forming a very dense selective layer. CHD has a cyclohexane ring, making it more sterically hindered than EDA. As such, CHD's reaction with TMC is slower than EDA's, leading to a thinner polyamide layer. PPD has a benzene ring, which should make it the most sterically hindered structure; however, its benzene ring has a pi-pi interaction with TMC that can facilitate a faster reaction between PPD and TMC, leading to a thicker polyamide layer. Among the TFC membranes, TFCCHD exhibited the highest separation efficiency (pure water flux = 192.13 ± 7.11 L∙m-2∙h-1, dye rejection = 99.92 ± 0.10%, and NaCl rejection = 15.46 ± 1.68% at 6 bar and 1000 ppm salt or 50 ppm of dye solution). After exposure at 12,000 ppm∙h of active chlorine, the flux of TFCCHD was enhanced with maintained high dye rejection. Therefore, the TFCCHD membrane has a potential application for dye desalination process.

Solving the charging effect in insulating materials probed by a variable monoenergy slow positron beam.

A variable monoenergy slow positron beam (VMSPB) operating at a high vacuum on insulating materials encounters a problem of significant surface charging effect with time. As a result, positronium formation is inhibited, and the positron annihilation radiation counting rate is reduced; these consequently distorted the experimental positron annihilation and results. To solve such problems, a technique of depositing an ultrathin layer of sputtering noble metals on insulators is developed. We report a successful method of sputtering a few atomic layers of platinum (∼1 nm) on a polyamide membrane to completely remove the charging effect for VMSPB applications in insulators.

Multilayered poly(vinylidene fluoride) composite membranes with improved interfacial compatibility: correlating pervaporation performance with free volume properties.

A spin-coating process integrated with an ozone-induced graft polymerization technique was applied in this study. The purpose was to improve the poor interfacial compatibility between a selective layer of poly(2-hydroxyethyl methacrylate) (PHEMA) and the surface of a poly(vinylidene fluoride) (PVDF) substrate. The composite membranes thus fabricated were tested for their pervaporation performance in dehydrating an ethyl acetate/water mixture. Furthermore, the composite membranes were characterized by field emission scanning electron microscopy (FE-SEM) for morphological change observation and by Fourier transform infrared spectroscopy equipped with attenuated total reflectance (ATR-FTIR) for surface chemical composition analysis. Effects of grafting density and spin-coating speed on pervaporation performance were examined. The composite membrane pervaporation performance was elucidated by means of free volume and depth profile data obtained with the use of a variable monoenergy slow positron beam (VMSPB). Results indicated that a smaller free volume was correlated with a higher pervaporation performance of a composite membrane consisting of a selective layer of spin-coated PHEMA on a PHEMA-grafted PVDF substrate (S-PHEMA/PHEMA-g-PVDF). The composite membrane depth profile illustrated that an S-PHEMA layer spin-coated at a higher revolutions per minute (rpm) was thinner and denser than that at a lower rpm.

Grape seed extract ameliorates tumor necrosis factor-α-induced inflammatory status of human umbilical vein endothelial cells.

BACKGROUND: Inflammation has played a key role in the causation of atherosclerosis. However, the effects of grape seed extract (GSE) on the pro-inflammatory intracellular signaling, enzyme activity, and inflammatory mediators of endothelial cells have not been sufficiently studied, and less information exists on the comparison between GSE and vitamin C, a well-known antioxidant compound, on their anti-inflammatory properties. PURPOSE: We investigated the effects of GSE and vitamin C on the cell viability, oxidative stress, monocyte adhesion, the expression of nuclear factor-κB inhibitor (IκB), intercellular adhesion molecule-1 (ICAM-1) and cyclooxygenase-2 (COX-2), and the production of prostaglandin E(2) (PG E(2)) in TNF-α-treated human umbilical vein endothelial cells (HUVECs). METHODS: Cell viability was measured by MTT assay. The adhesion of THP-1 to HUVECs was evaluated by cell adhesion assay. The oxidized nucleoside 8-hydroxydeoxyguanosine (8-OHdG) (an indicator of oxidative damage to DNA), ICAM-1, and PG E(2) were measured by ELISA. IκB and COX-2 expression were evaluated by western blot analysis. RESULTS: TNF-α (10, 20, and 50 ng/mL), GSE (50 and 200 µg/mL), or vitamin C (100 µM) did not affect cell viability. GSE (50-100 µg/mL) attenuated TNF-α (20 ng/mL)-induced 8-OHdG production, THP-1 adhesion, the expression of IκB degradation, ICAM-1 and COX-2, and the production of PGE(2) in a dose-dependent manner. Vitamin C (100 µM) also showed significant antioxidative and anti-inflammatory effects. CONCLUSIONS: GSE effectively ameliorates TNF-α-induced inflammatory status of HUVECs. The findings of the present study suggest that consumption of GSE may be beneficial to inflammatory atherosclerosis.

Optimal Performance of Thin-Film Composite Nanofiltration-Like Forward Osmosis Membranes Set Off by Changing the Chemical Structure of Diamine Reacted with Trimesoyl Chloride through Interfacial Polymerization.

Thin-film composite (TFC) polyamide membranes formed through interfacial polymerization can function more efficiently by tuning the chemical structure of participating monomers. Accordingly, three kinds of diamine monomers were considered to take part in interfacial polymerization. Each diamine was reacted with trimesoyl chloride (TMC) to manufacture TFC polyamide nanofiltration (NF)-like forward osmosis (FO) membranes. The diamines differed in chemical structure; the functional group present between the terminal amines was classified as follows: aliphatic group of 1,3-diaminopropane (DAPE); cyclohexane in 1,3-cyclohexanediamine (CHDA); and aromatic or benzene ring in m-phenylenediamine (MPD). For FO tests, deionized water and 1 M aqueous sodium sulfate solution were used as feed and draw solution, respectively. Interfacial polymerization conditions were also varied: concentrations of water and oil phases, time of contact between the water-phase solution and the membrane substrate, and polymerization reaction time. The resultant membranes were characterized using attenuated total reflectance-Fourier transform infrared spectroscopy, field emission scanning electron microscopy, atomic force microscopy, and surface contact angle measurement to identify the chemical structure, morphology, roughness, and hydrophilicity of the polyamide layer, respectively. The results of FO experiments revealed that among the three diamine monomers, CHDA turned out to be the most effective, as it led to the production of TFC NF-like FO membrane with optimal performance. Then, the following optimum conditions were established for the CHDA-based membrane: contact between 2.5 wt.% aqueous CHDA solution and polysulfone (PSf) substrate for 2 min, and polymerization reaction between 1 wt.% TMC solution and 2.5 wt.% CHDA solution for 30 s. The composite CHDA-TMC/PSf membrane delivered a water flux (Jw) of 18.24 ± 1.33 LMH and a reverse salt flux (Js) of 5.75 ± 1.12 gMH; therefore, Js/Jw was evaluated to be 0.32 ± 0.07 (g/L).

Cosolvent-Driven Interfacial Polymerization for Superior Separation Performance of Polyurea-Based Pervaporation Membrane.

A thin-film composite (TFC) polyurea membrane was fabricated for the dehydration of an aqueous tetrahydrofuran (THF) solution through interfacial polymerization, wherein polyethyleneimine (a water-soluble amine monomer) and m-xylene diisocyanate (an oil-soluble diisocyanate monomer) were reacted on the surface of a modified polyacrylonitrile (mPAN) substrate. Cosolvents were used to tailor the membrane properties and increase the membrane permeation flux. Four types of alcohols that differed in the number of carbon (methanol, ethanol, isopropanol, and tert-butanol) were added as cosolvents, serving as swelling agents, to the aqueous-phase monomer solution, and their effect on the membrane properties and pervaporation separation was discussed. Attenuated total reflection Fourier transform infrared spectroscopy confirmed the formation of a polyurea layer on mPAN. Field emission scanning electron microscopy and surface water contact angle analysis indicated no change in the membrane morphology and hydrophilicity, respectively, despite the addition of cosolvents for interfacial polymerization. The TFC membrane produced when ethanol was the cosolvent exhibited the highest separation performance (permeation flux = 1006 ± 103 g·m-2·h-1; water concentration in permeate = 98.8 ± 0.3 wt.%) for an aqueous feed solution containing 90 wt.% THF at 25 °C. During the membrane formation, ethanol caused the polyurea layer to loosen and to acquire a certain degree of cross-linking. The optimal fabrication conditions were as follows: 10 wt.% ethanol as cosolvent; membrane curing temperature = 50 °C; membrane curing time = 30 min.

Superfast Water Transport Zwitterionic Polymeric Nanofluidic Membrane Reinforced by Metal-Organic Frameworks.

Nanofluidics derived from low-dimensional nanosheets and protein nanochannels are crucial for advanced catalysis, sensing, and separation. However, polymer nanofluidics is halted by complicated preparation and miniaturized sizes. This work reports the bottom-up synthesis of modular nanofluidics by confined growth of ultrathin metal-organic frameworks (MOFs) in a polymer membrane consisting of zwitterionic dopamine nanoparticles (ZNPs). The confined growth of the MOFs on the ZNPs reduces the chain entanglement between the ZNPs, leading to stiff interfacial channels enhancing the nanofluidic transport of water molecules through the membrane. As such, the water permeability and solute selectivity of MOF@ZNPM are one magnitude improved, leading to a record-high performance among all polymer nanofiltration membranes. Both the experimental work and the molecular dynamics simulations confirm that the water transport is shifted from high-friction-resistance conventional viscous flow to ultrafast nanofluidic flow as a result of rigid and continuous nanochannels in MOF@ZNPM.

Modifying Cellulose Acetate Mixed-Matrix Membranes for Improved Oil-Water Separation: Comparison between Sodium and Organo-Montmorillonite as Particle Additives.

In this study, cellulose acetate (CA) mixed-matrix membranes were fabricated through the wet-phase inversion method. Two types of montmorillonite (MMT) nanoclay were embedded separately: sodium montmorillonite (Na-MMT) and organo-montmorillonite (O-MMT). Na-MMT was converted to O-MMT through ion exchange reaction using cationic surfactant (dialkyldimethyl ammonium chloride, DDAC). Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) compared the chemical structure and composition of the membranes. Embedding either Na-MMT and O-MMT did not change the crystallinity of the CA membrane, indicating that the nanoclays were dispersed in the CA matrix. Furthermore, nanoclays improved the membrane hydrophilicity. Compared with CANa-MMT membrane, CAO-MMT membrane had a higher separation efficiency and antifouling property. At the optimum concentration of O-MMT in the CA matrix, the pure water flux reaches up to 524.63 ± 48.96 L∙m-2∙h-1∙bar-1 with over 95% rejection for different oil-in-water emulsion (diesel, hexane, dodecane, and food-oil). Furthermore, the modified membrane delivered an excellent antifouling property.

Infusion of Silver-Polydopamine Particles into Polyethersulfone Matrix to Improve the Membrane's Dye Desalination Performance and Antibacterial Property.

The advancement in membrane science and technology, particularly in nanofiltration applications, involves the blending of functional nanocomposites into the membranes to improve the membrane property. In this study, Ag-polydopamine (Ag-PDA) particles were synthesized through in situ PDA-mediated reduction of AgNO3 to silver. Infusing Ag-PDA particles into polyethersulfone (PES) matrix affects the membrane property and performance. X-ray photoelectron spectroscopy (XPS) analyses confirmed the presence of Ag-PDA particles on the membrane surface. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) describe the morphology of the membranes. At an optimum concentration of Ag-PDA particles (0.3 wt % based on the concentration of PES), the modified membrane exhibited high water flux 13.33 L∙m-2∙h-1 at 4 bar with high rejection for various dyes of >99%. The PESAg-PDA0.3 membrane had a pure water flux more than 5.4 times higher than that of a pristine membrane. Furthermore, in bacterial attachment using Escherichia coli, the modified membrane displayed less bacterial attachment compared with the pristine membrane. Therefore, immobilizing Ag-PDA particles into the PES matrix enhanced the membrane performance and antibacterial property.

Microporous polymers with cascaded cavities for controlled transport of small gas molecules.

In membrane-based separation, molecular size differences relative to membrane pore sizes govern mass flux and separation efficiency. In applications requiring complex molecular differentiation, such as in natural gas processing, cascaded pore size distributions in membranes allow different permeate molecules to be separated without a reduction in throughput. Here, we report the decoration of microporous polymer membrane surfaces with molecular fluorine. Molecular fluorine penetrates through the microporous interface and reacts with rigid polymeric backbones, resulting in membrane micropores with multimodal pore size distributions. The fluorine acts as angstrom-scale apertures that can be controlled for molecular transport. We achieved a highly effective gas separation performance in several industrially relevant hollow-fibrous modular platform with stable responses over 1 year.

Effects of surface properties of different substrates on fine structure of plasma-polymerized SiOCH films prepared from hexamethyldisiloxane (HMDSO).

In this study, Doppler broadening energy spectroscopy (DBES) combined with slow positron beam was used to discuss the effect of substrate types on the fine structure of a plasma-polymerized SiOCH layer as a function of depth. From the SEM pictures, the SiOCH films formed on different substrates showed hemispherical macrostructures, and the deposition rate was dependent on the mean pore size. It appears that the morphology of the plasma-polymerized SiOCH films was associated with the porosity-related characteristics of the substrate such as the size/shape of pores. As deposited on the MCE-022 substrate (mixed cellulose esters membrane with a mean pore size of 0.22 µm) with a nodular structure, the SiOCH films had pillar-like structures and high gas permeabilities. DBES results showed that the SiOCH films deposited on different substrates were composed of three layers: the SiOCH bulk layer, the transition layer, and the substrate. It was observed that the microstructure of the SiOCH films was affected layer by layer; a higher surface pore size in the substrates induced thicker transition layers with higher microporosities and led to thinner bulk layers having higher S parameter values during the plasma polymerization. It was also observed that the change in O(2)/N(2) selectivity was consistent with the DBES analysis results. The gas separation performance and DBES analysis results agreed with each other.

Effect of UV-ozone treatment on poly(dimethylsiloxane) membranes: surface characterization and gas separation performance.

A thin SiO(x) selective surface layer was formed on a series of cross-linked poly(dimethylsiloxane) (PDMS) membranes by exposure to ultraviolet light at room temperature in the presence of ozone. The conversion of the cross-linked polysiloxane to SiO(x) was monitored by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray (EDX) microanalysis, contact angle analysis, and atomic force microscopy (AFM). The conversion of the cross-linked polysiloxane to SiO(x) increased with UV-ozone exposure time and cross-linking agent content, and the surface possesses highest conversion. The formation of a SiO(x) layer increased surface roughness, but it decreased water contact angle. Gas permeation measurements on the UV-ozone exposure PDMS membranes documented interesting gas separation properties: the O(2) permeability of the cross-linked PDMS membrane before UV-ozone exposure was 777 barrer, and the O(2)/N(2) selectivity was 1.9; after UV-ozone exposure, the permeability decreased to 127 barrer while the selectivity increased to 5.4. The free volume depth profile of the SiO(x) layer was investigated by novel slow positron beam. The results show that free volume size increased with the depth, yet the degree of siloxane conversion to SiO(x) does not affect the amount of free volume.