A Vycor® Membrane with Reduced Size Surface Pores I. Preparation and Characterization

Vycor® membranes are surface-modified by a crosslinked commercial silicone which is subsequently subjected to oxygen plasma and converted to silica dioxide. Samples are examined by integral gas permeability of helium, nitrogen, methane and carbon dioxide, differential permeability of carbon dioxide and relative permeability of helium gas vs. water vapor. The modified surface is found to contain large micropores as well as a population of small nanopores. The new membrane may be appropriate for applications such as gas/vapor separations, reverse osmosis and the low molecular weight end of nanofiltration.     

SURFACE MODIFICATIONS AND ADHESION OF VULCANIZED SBR RUBBER TREATED WITH RF PLASMAS OF DIFFERENT GASES

The surface modifications produced by treatment of a synthetic vulcanized styrene-butadiene rubber (R1) with oxidizing (oxygen, air, carbon dioxide) and nonoxidizing (nitrogen, argon) RF plasmas have been assessed by ATR-IR and XPS spectroscopy, SEM, and contact angle measurements. The effectiveness of the treatment depended on the gas atmosphere used to generate the RF plasma. In general, acceptable adhesion values of treated R1 rubber were obtained for all plasmas, except for the nitrogen plasma treatment during 15?min, due to the creation of weak layers of low molecular weight moieties on the outermost R1 rubber layer. A toluene wiping of the 15?min N₂-plasma–treated R1 rubber surface removed those moieties, and increased adhesion was obtained. On the other hand, the air, carbon dioxide, and oxygen plasmas produced ablation of the R1 rubber surface, whereas mechanical degradation was not produced by treatment with the Ar plasma.     

SURFACE MODIFICATIONS AND ADHESION OF VULCANIZED SBR RUBBER TREATED WITH RF PLASMAS OF DIFFERENT GASES

The surface modifications produced by treatment of a synthetic vulcanized styrene-butadiene rubber (R1) with oxidizing (oxygen, air, carbon dioxide) and nonoxidizing (nitrogen, argon) RF plasmas have been assessed by ATR-IR and XPS spectroscopy, SEM, and contact angle measurements. The effectiveness of the treatment depended on the gas atmosphere used to generate the RF plasma. In general, acceptable adhesion values of treated R1 rubber were obtained for all plasmas, except for the nitrogen plasma treatment during 15 min, due to the creation of weak layers of low molecular weight moieties on the outermost R1 rubber layer. A toluene wiping of the 15 min N₂-plasma-treated R1 rubber surface removed those moieties, and increased adhesion was obtained. On the other hand, the air, carbon dioxide, and oxygen plasmas produced ablation of the R1 rubber surface, whereas mechanical degradation was not produced by treatment with the Ar plasma.     

Plasma‐induced surface modification and adhesion enhancement of polypropylene surface

Unoriented (UPP) and biaxially oriented (BOPP) polypropylene films were treated under radio frequency plasma of air, nitrogen, oxygen, and ammonia. Surface modification of polypropylene films was investigated by using surface energy measurement and attenuated total reflection (ATR)‐FTIR spectroscopy. Surface energy of air and nitrogen plasma‐treated polypropylene film increased for shorter treatment time and then decreased and attained an equilibrium value. Such changes in surface energy were not observed for oxygen and ammonia plasma‐treated polypropylene film, which increased to an equilibrium value. ATR‐FTIR studies revealed characteristic differences in the absorption spectra for short‐duration and long‐duration treatments. From the relative intensity change in the C—H stretching vibration, the mechanism of surface chemical reaction could be inferred. Studies regarding the durability of surface modification due to plasma treatment were evaluated by investigating surface energy of samples aged for 2 months. Treated films subjected to peel strength measurement showed improvement in bondability for UPP and BOPP film by hydrophilic surface modification accompanied by surface crosslinking. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 925–936, 2002     

Functional finishing of nonwoven fabrics. I. Accessibility of surface modified PET spunbond by atmospheric pressure He/O2 plasma treatment

The surface of a polyethylene terephthalate (PET) spunbond nonwoven was modified by using atmospheric pressure He/O₂ plasma treatment. Accessibility of the modified PET nonwoven has been investigated in terms of crystallinity, surface chemical composition, hydrophilicity, and dye uptake. Differential scanning calorimetry (DSC) for crystallinity measurement and X‐ray photoelectron spectroscopy (XPS) for chemical composition measurement were used. Surface morphology was studied by using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Percentage crystallinity increased due to the depletion of amorphous region by plasma etching. Redeposition of etched particles was observed. Oxygen‐based functional groups on the surface of PET increase from 27 to about 32% after 90 s exposure. Wettability increases by more than 10 times and moisture regain increases by three times, compared with the untreated sample. Dye uptake was not changed significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4306–4310, 2006     

Plasma etching and plasma polymerization coating of carbon fibers. Part 2. Characterization of plasma polymer coated carbon fibers

Unsized AS-4 carbon fibers were subjected to RF plasma etching and/or plasma polymerization coating in order to enhance their adhesion to vinyl ester resin. Ar, N₂ and O₂ were utilized for plasma etching, and acetylene, butadiene and acrylonitrile were used for plasma polymerization coating. Etching and coating conditions were optimized in terms of plasma power, treatment time, and gas (or monomer) pressure by measuring the interfacial adhesion strength. Interfacial adhesion was evaluated using micro-droplet specimens prepared with vinyl ester resin and plasma etched and/or plasma polymer coated carbon fibers. Surface modified fibers were characterized by SEM, XPS, FT-IR, α-Step, dynamic contact angle analyzer (DCA) and tensile strength measurements. Interfacial adhesion between plasma etched and/or plasma polymer coated carbon fibers and vinyl ester resin was reported previously (Part 1), and characterization results are discussed is this paper (Part 2). Gas plasma etching resulted in preferential etching of the fiber surface along the draw direction and decreased the tensile strength, while plasma polymer coatings altered neither the surface topography of fibers nor the tensile strength. Water contact angle decreased with plasma etching, as well as with acrylonitrile and acetylene plasma polymer coatings, but did not change with butadiene plasma polymer coating. FT-IR and XPS analyses revealed the presence of functional groups in plasma polymer coatings.     

Hydrophobic recovery of repeatedly plasma-treated silicone rubber. Part 2. A comparison of the hydrophobic recovery in air,water, or liquid nitrogen

Surfaces of medical grade silicone rubber (Q7-4750, Dow Corning) were modified by repeated (six times) RF plasma treatments using various discharge gases: oxygen, argon, carbon dioxide, and ammonia. The treated samples were stored for a period of 3 months in ambient air, water, or liquid nitrogen. Subsequently, the temporal behavior of the effects of the plasma treatment on the physicochemical surface properties of the silicone rubber was investigated using water contact angle measurements and X-ray photoelectron spectroscopy (XPS). Hydrophobic recovery during 3 months storage in ambient air was considerable and nearly complete for all four plasmas used. Hydrophobic recovery was almost completely suppressed during storage in liquid nitrogen, and only a minor increase of around 10° in advancing water contact angle was observed for all four plasma treatments. Also during storage of treated samples in water, hydrophobic recovery was minimal and initiated again by returning the treated samples to ambient air. XPS analyses showed that argon, carbon dioxide, and ammonia plasma-treated silicone rubber all had increased carbon percentages at the expense of oxygen and silicon after storage in water, or in liquid nitrogen, compared with after storage in ambient air. Interestingly, the carbon content of oxygen plasma-treated silicone rubber decreased during storage in water, or in liquid nitrogen, compared with storage in ambient air, while its oxygen and silicon percentages increased.     

Plasma surface treatment of PCL/PC blend sheets

Surface treatments using glow discharge plasmas from O₂ and Ar were applied to blend sheets of poly(?‐caprolactone)‐polycarbonate (PCL/PC), which had been produced by extrusion from melts of the mixture at various blend ratios. As to the reactivity of these two plasmas, O₂‐plasma forms the oxidative species to be reactive in general, while Ar‐plasma is non‐oxidative. Weight loss by the oxidative O₂‐plasma etching increased with the content of PCL in the polymer blends. The surface became hydrophilic by plasma treatment, and the changes were affected also by the blend ratio. PC and the PC‐rich blend sheets became more hydrophilic than the PCL‐rich blends after plasma treatments. The O₂‐plasma treatments were more effective than non‐oxidative Ar‐plasma treatment in increasing the hydrophilicity. Hydrophilic change was related to the increase in the polar contribution of surface energy.     

Effect of surface treatment on electrical conductivity of carbon black filled conductive polymer composites

Two different types of surface modifiers, 3‐aminopropyltriethoxysilane and formamide, were applied to carbon black (CB) particles to lower electrical resistivity of polymer composites prepared by treated CB. Two different matrices, low‐density polyethylene and nylon 6, were chosen to compound with surface modified CB. Surface energy of CB was increased by adding amine or amide functional groups during surface treatment of CB. According to electron spectroscopy for chemical analysis (ESCA), chemical modification in surface chemistry of CB was obtained with the chemicals used for the treatment due to the nitrogen atoms in their structures, which may act as dopant atom. As a result of this, electrical resistivity of composites prepared by treated CB decreased. In addition, there was not any significant change in tensile strength and tensile modulus of the composites with the surface treatment. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

A study of the effect of oxygen plasma treatment on the interfacial properties of carbon fiber/epoxy composites

In this work, effects of the interface modification on the carbon fiber‐reinforced epoxy composites were studied. For this purpose, the surface of carbon fibers were modified by oxygen plasma treatment. The surface characteristics of carbon fibers were studied by X‐ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), dynamic contact angle analysis (DCAA), and dynamic mechanical thermal analysis (DMTA), respectively. The interlaminar shear strength (ILSS) was also measured. XPS and AFM analyses indicated that the oxygen plasma treatment successfully increased some oxygen‐containing functional groups concentration on the carbon fiber surfaces, the surface roughness of carbon fibers was enhanced by plasma etching and oxidative reactions. DCAA and DMTA analyses show that the surface energy of carbon fibers increased 44.9% after plasma treatment for 3 min and the interfacial bonding intensities A and α also reached minimum and maximum value respectively. The composites exhibited the highest value of ILSS after oxgen plasma treated for 3 min. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of low‐temperature plasma conditions on wicking properties of PA/PU knitted fabric

Plasma surface treatment has been extensively applied in the textile industry for the modification of polymer materials. In this study low‐temperature plasma (LTP) is used for surface treatment of polyamide/polyurethane (PA/PU) knitted fabric. The envisaged plasma effect is an increase in the surface energy of the treated textile, leading toward improved hydrophilic properties. The knitted fabric was treated by LTP using three non polymerizing gases: oxygen, air, and carbon dioxide. After plasma treatment, wettability of samples was tested through their wicking properties measuring capillary rise after water bath contact. The PA/PU knitted fabric samples treated with different plasma gases exhibited different hydrophilic performances. The influence of plasma variables (discharge power, time, pressure) was investigated. Although the chemical characteristics of elastan (PU) and nylon (PA) threads are different, the study has demonstrated that plasma treatment can in the same time alter the surface‐wetting behavior of both the components of the knitted fabric. It was also shown how these treatments can be regulated to produce the desired level of hydrophilicity dependently on the request application. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Interaction of different types of cells on physicochemically treated poly(L‐lactide‐co‐glycolide) surfaces

To improve the cell compatibility of poly(L ‐lactide‐co‐glycolide) (PLGA; 75/25 molar ratio of lactide to glycolide) surfaces, we experimented with physicochemical treatments. Chemical treatments employed 70% chloric acid, 50% sulfuric acid, and 0.5N sodium hydroxide solutions, and physical methods included corona and plasma treatments. The water contact angle of surface‐treated PLGA decreased from 73 to 50–60°; that is, the hydrophilicity increased because of the introduction of oxygen‐containing functional groups onto the PLGA backbone according to electron spectroscopy for chemical analysis. The physicochemically modified PLGA surfaces were used to investigate the interaction of four different types of cells—hepatoma (Hep G2), osteoblast (MG 63), bovine aortic endothelial (CPAE), and fibroblast (NIH/3T3) cells—in terms of the surface hydrophilicity and hydrophobicity of PLGA. The cells that adhered and grew on the physicochemically modified PLGA surfaces were counted and observed with scanning electron microscopy. The adhesion and growth of Hep G2, MG 63, CPAE, and NIH/3T3 cells on physicochemically treated PLGA surfaces, especially on chloric acid‐treated PLGA surfaces, were more active than on the control. This result seems closely related to the serum protein adsorption on the surface; the serum proteins were also adsorbed more on the hydrophilic surface. Surface hydrophilicity apparently plays an important role in cell adhesion, spreading, and growth on PLGA surfaces. The surface modification technique used in this study may be applicable to tissue engineering for the improvement of tissue compatibility of film‐ and scaffold‐type substrates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1253–1262, 2002     

Gas barrier and wetting properties of whey protein isolate‐based emulsion films

The aim of this research was to investigate the effect of rapeseed oil concentration (1–3% w/w) on the water vapor, oxygen and carbon dioxide permeability, water vapor sorption and surface properties of whey protein isolate emulsion‐based films. The water contact angle as affected by oil content, film side and time was analyzed. The effect of temperature (5 and 25°C) on the water vapor permeability (WVP), water vapor sorption kinetics and diffusion coefficient was also studied. The results showed that the incorporation of a lipid phase to whey protein film‐forming solutions was able to decrease the WVP, water hydrophilicity (increasing water contact angle) and water transfer of whey protein films. However, the films containing oil were more permeable to oxygen and carbon dioxide. Significantly higher values of WVP and diffusion coefficient were obtained at 5°C than at 25°C, indicating that storage temperature should be taken into account when designing the composition of edible films and coatings for food applications. POLYM. ENG. SCI., 59:E375–E383, 2019. © 2018 Society of Plastics Engineers     

Enhancement of the monovalent cation perm-selectivity of Nafion by plasma-induced surface modification

In this paper, we focus on improvement of the monovalent cation perm-selectivity of a perfluorinated cation-exchange membrane, Nafion 117, by depositing an anion-exchange layer using a plasma surface modification process. The anion-exchange layer was deposited from 4-vinylpyridine monomer vapor followed by quaternization with 1-bromopropane. The transference number of divalent cation (Fe²⁺) through the membrane, t_Fe, decreased with increasing thickness of the plasma polymer layer at the expense of enhanced membrane resistance. A large interfacial resistance was observed between Nafion and the plasma polymer layer which was ascribed to the implantation of cationic species containing nitrogen. To avoid the formation of an interfacial layer, a novel method of plasma-induced surface modification was devised. After a Nafion 117 sheet was placed on an RF (radio-frequency) electrode and sputtered with an oxygen or argon plasma in order to produce active sites on the Nafion, 4-vinylpyridine or 3-(2-aminoethyl)aminopropyltrimethoxysilane vapor was introduced into the reactor to react with radical sites. t_Fe decreased with increasing RF power. t_Fe through Nafion modified with 3-(2-aminoethyl)aminopropyltrimethoxysilane was lower than that for Nafion modified with 4-vinylpyridine, probably due to its weak Si-C bond. Nafion treated by the plasma surface modification method exhibited a very high monovalent cation perm-selectivity compared with Nafion treated by the plasma polymerization method.     

Separation of CO2/N2 Gas Mixture through Carbon Membranes: Monte Carlo Simulation

Abstract

Monte Carlo simulation method is employed to investigate separation behavior of gas mixture composed of carbon dioxide and nitrogen through a model carbon membrane under the different conditions. The simulation gives insight into the separation mechanism to a certain extent, which is based on the loading and diffusion of carbon dioxide and nitrogen in the carbon membrane with different pore size. The simulation results indicate that the carbon dioxide can be adsorbed on the surface of membrane wall more strongly, whereas the diffusion rate of nitrogen is more prominent. When the separation condition alters, the influence of the two main factors mentioned above on transport of gas molecules in membranes becomes different. Therefore, the equilibrium selectivity of nitrogen and carbon dioxide changes correspondingly.     

Enhanced Cell Adhesion to Helium Plasma-Treated Polypropylene

Materials used for biomedical applications are required to have suitable surface properties since they depend more on the surface properties than on the bulk properties. Surface properties greatly influence the cell adhesion and its behavior either directly by guiding cell spreading or indirectly by controlling proteins adsorption and their structural rearrangement on the material. Modulation of physical and chemical properties of polymers by various treatments can render the substrates adhesive for cells in a culture. In the present study, polypropylene surface was modified using helium plasma to enhance cell adhesion to its surface. The experiments were run according to the central composite design of response surface methodology to optimize the process conditions. The effects of the process variables, namely, RF power, pressure, flowrate and treatment time on surface energy and percentage weight loss were studied through central composite design (CCD). A statistical model relating the process variables and the responses was developed. The improved hydrophilicity of polypropylene through helium plasma treatment was observed from its surface energy data. Changes in surface chemistry and surface morphology were studied by Fourier transform infrared spectroscopy and scanning electron microscopy, respectively. Enhanced cell adhesion to polypropylene treated with helium plasma at the optimum conditions, obtained from the statistical design, was observed from cell adhesion test and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay with L929 mouse fibroblast cells.     

Ionic liquid-induced deep grafting of polyelectrolyte to reform polyamide layer for antifouling nanofiltration membrane

Surface grafting has been widely used to tune hydrophilicity and chargeability of nanofiltration membranes for reducing membrane fouling potential. However, surface grafting typically leads to a significant pore narrowing and resultant permeability loss, and monocharged surface still struggles to resist mixed foulants with different charges. Herein, ionic liquid (IL)-ethanol (EtOH) solution containing polyethyleneimine (PEI) is used to rearrange the nascent polyamide layer. The high affinity of IL to the PA layer and the low diffusion steric hindrance of EtOH contribute to the polyamide swelling and PEI deep grafting, during which the “self-regulation” effect (larger pores would be filled with more PEI molecules) narrows the pore size distribution and enhances hydrophilicity. The nearly charge-neutral and smooth separation layer shows impressive antifouling capacity to hydrophobic macromolecules and mixed charged molecules, along with long-term operating stability for real wastewater treatment. This study emphasizes the importance of solvent properties on the membrane grafting behavior.     

Hydrophobic recovery of repeatedly plasma-treated silicone rubber. Part 1. Storage in air

Silicone rubber is used for a wide variety of biomedical and industrial applications due to its good mechanical properties, combined with a hydrophobic surface. Frequently, however, it is desirable to alter the surface hydrophobicity of silicone rubber. Often this is done by plasma treatments but the effects are usually transient. In this study, surfaces of medical grade silicone rubber have been repeatedly modified by means of oxygen, argon, carbon dioxide, and ammonia RF plasma treatments with a 24 h time interval in between treatments. Treated samples were stored in air prior to surface characterization by water contact angle measurements, X-ray photoelectron spectroscopy (XPS), streaming potential measurements, and profilometry for surface roughness. The carbon percentage of the surfaces decreased after plasma treatment, while the silicon and oxygen percentages increased irrespective of the plasma used. The formation of Si-O-Si bridges between siloxane chains after plasma treatment was demonstrated by the appearance of a new component in the Si_2p peak but the degree to which this occurred differed per gas. Streaming potential measurements in a 10 mM potassium phosphate buffer indicated a more negatively charged surface for treated samples compared to untreated samples (-23.3 mV at pH 7.0). Surface roughness increased slightly for repeatedly plasma-treated samples from R_A = 0.35 μm to R_A = 0.46 μm, while scanning electron microscopy showed the presence of several 'cracks' spanning the surface after repeated treatment. Argon, carbon dioxide, and ammonia plasmas significantly reduced the advancing water contact angle from 115° to 58°, 72°, and 85°, respectively, on a more permanent basis (especially when the treatments were repeated after recovery). Oxygen plasma effects on water contact angles generally disappeared within 5 h, also after repeated treatment.     

活性炭孔结构及电化学性能协同优化

以马尾藻为原料,采用KOH活化法制备了高微孔率马尾藻基活性炭,结合二氧化碳与碳反应动力学机理,对马尾藻基活性炭进行二氧化碳扩孔改性,研究了二氧化碳改性对高微孔率马尾藻基活性炭孔结构特性和电化学性能的影响。研究表明：二氧化碳改性后马尾藻基活性炭的比表面积明显减小,由3155m²/g减小至2776m²/g,但是改性后活性炭中孔比表面积明显增大,由181m²/g增大至538m²/g,活性炭孔径介于2~8nm的中孔含量明显增多,比表面积的减少是由于微孔比表面积的减少导致的。改性后活性炭微孔含量降低,孔径介于0.4~0.6nm的微孔结构基本消失,但是孔径介于0.6~1nm的微孔结构却有所增加,活性炭微孔平均孔径增大。改性后马尾藻基活性炭的比电容性能以及倍率性能得到明显提升。经过二氧化碳改性后,马尾藻基活性炭的孔结构和电化学性能得到协同优化。     

Chemical structure and surface morphology of plasma polymerized-allylamine film

In this study, we conducted the plasma polymerization of allylamine using radio frequency (RF) glow discharge with continuous wave (CW) in order to make an organic thin film with an amine functional group retained. Allylamine as a monomer was deposited on a glass in a bell-jar type plasma reactor and polymerized to plasma-polymerized allylamine (PPAa). The parameter to control the property of plasma polymer was input power at other conditions remaining constant. The chemical structure and the surface morphology of plasma-polymerized allylamine (PPAa) film were characterized by contact angle measurement, Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR), X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM). The property of PPAa film was highly dependent upon the plasma input power. The input power, which determines the plasma density, results in a property of PPAa thin film such as hydrophilicity, high retention of functionality of PPAa’s surface. Surface energy calculated by contact angle measurement indicated that increasing input power (from 30W to 90W) decreased the hydrophilic property of PPAa due to loss of amine functional group and high cross-linking. The increase of the energy causes the films to be harder. ATR-FTIR and XPS results showed that high input energy fragmented the amine group from monomer with increasing nitrogen atomic content and nitrile group. The high retention of amine groups seems mainly favored by low input power (<30 W). From thickness measurement usingα-stepper, the deposition rates were 0.43, 0.83, 1.11, 1.37 nm/s at 30, 50, 70, 90W, respectively. The change of surface morphology of plasma-polymerized thin films was investigated after soaking the PPAa film into ethanol. Due to weak adhesion with substrate and internal stress in plasma polymer film, the surface morphology of PPAa film revealed some irregular network pattern.