Corona-induced graft polymerization for surface modification of porous polyethersulfone membranes

Graft polymerization of acrylic acid (AA) onto porous polyethersulfone (PES) membrane surfaces was developed using corona discharge in atmospheric ambience as an activation process followed by polymerization of AA in aqueous solution. The effects of the corona parameters and graft polymerization conditions on grafting yield (GY) of AA were investigated. The grafting of AA on the PES membranes was confirmed by ATR-FTIR and X-ray photoelectron spectroscopy (XPS) analysis. Porosimetry measurements indicate the average pore diameters and porosities of the modified membranes decrease with the increase of the GY. The hydrophilicity and surface wetting properties of the original and modified membranes were evaluated by observing the dynamic changes of water contact angles. It is found that the grafting of AA occurs not only on the membrane surfaces, but also on the pore walls of the cells inside the membrane. The permeability experiments of protein solution reveal that the grafting of PAA endows the modified membranes with enhanced fluxes and anti-fouling properties. The optimized GY of AA is in the range of 150-200 μg/cm². In addition, the tensile experiments show the corona discharge treatment with the power lower than 150 W yields little damage to the mechanical strength of the membranes.     

The influence of sulfonated polyethersulfone (SPES) on surface nano-morphology and performance of polyethersulfone (PES) membrane

In this research, firstly sulfonation of polyethersulfone (PES) was carried out and then polyethersulfone (PES)/sulfonated polyethersulfone (SPES) blend membranes were prepared with phase inversion induced by immersion precipitation technique. polyvinylpyrrolidone (PVP, 2 wt% concentration) was added in the casting solution as pore former. SPES was characterized by FT-IR and UV-visible spectra, ion exchange capacity and swelling ratio. The characterization of SPES polymer indicates that the sulfonic acid groups were produced on PES polymer. Also, the prepared PES/SPES blend membranes were characterized by contact angle, AFM, SEM and cross-flow filtration for milk concentration. The contact angle measurements indicate that the hydrophilicity of PES membrane is enhanced by increasing the SPES content in the casting solution. The SEM and AFM images show that the addition of SPES in the casting solution results in a membrane with larger surface pore size and higher sub-layer porosity. The mean pore size of the membrane increased from 98 nm for PES membrane to 240 and 910 nm for 50/50 and 0/100 PES/SPES blend membranes, respectively. The pure water flux and milk water permeation through the prepared membranes are increased by blending PES with SPES. Moreover, the protein rejection of PES/SPES blend membranes was lower than PES membrane.     

ArF laser surface modification of polyethersulfone film: Effect of laser fluence in improving surface biocompatibility

ArF laser treatment of polyethersulfone (PES) films was performed to improve biocompatibility of surfaces. For this purpose, the threshold fluence for laser ablation of PES was obtained from experimental measurements and then samples were irradiated at 2 separate ranges of fluences, i.e. below and above the ablation threshold. In order to investigate the physico-chemical changes, the modified surfaces were characterized by attenuated total reflectance (ATR) infrared spectroscopy and contact-angle measurements. The biocompatibility of the treated samples in comparison to those untreated was examined in vitro using a platelet adhesion test. The number of adhered platelets was obtained using the lactate dehydrogenase (LDH) method. For surfaces irradiated below the ablation threshold, a high reduction in the number of the adhered platelets was observed; while this number increased in samples treated at the fluence above the ablation threshold. The change in platelet adhesion was attributed to the change in chemistry and roughness of the irradiated surfaces.     

Ultrasonically synthesized MOFs for modification of polymeric membranes: A critical review

Metal-organic framework (MOF) membranes hold the promise for energy-efficient separation processes. These nanocrystalline compounds can effectively separate materials with different sizes and shapes at a molecular level. Furthermore, MOFs are excellent candidates for improving membrane permeability and/or selectivity due to their unique properties, such as high specific area and special wettability. Generally, MOFs can be used as fillers in mixed matrix membranes (MMMs) or incorporated onto the membrane surface to modify the top layer. Characteristics of the MOFs, and correspondingly, the properties of the MOF-based membranes, are majorly affected by their production technique. This critical review discusses the sonication technique for MOF production and the opportunities and challenges of using MOF for making membranes. Effective parameters on the characteristics of the synthesized MOFs, such as sonication time and power, were discussed in detail. Although the ultrasonically synthesized MOFs have shown great potential in the fabrication/modification of membranes for gas and liquid separation/purification, so far, no comprehensive and critical review has been published to clarify such accomplishments and technological gaps for the future research direction. This paper aims to review the most recent research conducted on ultrasonically synthesized MOF for the modification of polymeric membranes. Recommendations are provided with the intent of identifying the potential future works to explore the influential sonication parameters.     

Organic light-emitting diode performance enhancement via indium tin oxide glass surface modification

A self-assembly monolayer (SAM), with phenyl-triethoxysilane (PTES), was used to modify the indium tin oxide anode for an organic light-emitting diode (OLED) in order to improve the OLED performance. The enhancement of OLED performance is attributed to the blockage of excessive hole injection by PTES, balancing the hole and electron injection numbers. The result indicates that the SAM process reaction time duration greatly affects the OLED performance outcomes. If the reaction time is too long, it will impact on the optical efficiency due to molecular aggregates accumulated on the SAM layers, thus reducing the performance of the OLEDs. The electrical and optical characteristics of the OLEDs are modeled by using the modified Shockley equation. Modified Shockley parameters are extracted to interpret the experimental data with excellent accuracy. Those parameters, both electrical and optical, can be used as the DC level modeling parameters for OLED product design simulations.     

Electroless deposition of silver on synthesized calcite via surface modification

Metallic silver was deposited on the surface of synthesized calcite via a simple electroless deposition method. Calcite with cubic morphology was prepared first by homogeneous precipitation and it was subsequently surface modified using ammonium oxalate. The electroless deposition was carried out using formaldehyde as the reducing agent and silver nitrate as the silver source. Both calcite and the silver deposited calcite were characterized by different techniques. Surface modification of calcite with ammonium oxalate is necessary for the deposition of silver and the size of the deposited silver particles could be controlled by changing the deposition parameters such as concentration of the reagents and the deposition time. Lower concentration of silver ions (e.g. 0.01 M AgNO₃) and shorter deposition times (e.g. 30 min) lead to the formation of silver nanoparticles on calcite.     

Development of high performance nano-porous polyethersulfone ultrafiltration membranes with hydrophilic surface and superior antifouling properties

Hydrophilic nano-porous polyethersulfone ultrafiltration membranes were developed for milk concentration. The membranes were prepared from new dope solution containing polyethersulfone (PES)/polyvinylpirrolidone (PVP)/polyethyleneglycole (PEG)/cellulose acetate phthalate (CAP)/acrylic acid/Triton X-100 using phase inversion induced by immersion precipitation technique. This casting solution leads to formation of new hydrophilic membranes. The morphological studies were investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). In addition, the hydrophilicity and performance of membranes were examined by contact angel measurements and cross-flow filtration (pure water flux, milk water permeation, protein rejection and antifouling measurements). The contact angle measurements indicate that a surface with superior hydrophilicity was obtained for PES membranes. Two concentrations of PES (16 and 14.4 wt.%) and two different non-solvents (pure water and mixtures of water and IPA) were used for preparation of membranes. The morphological studies showed that the higher concentration of PES and the presence of IPA in the gelation media results in formation of a membrane with a dense top and sub-layer with small pores on the surface. The pure water flux of membranes was decreased when higher polymer concentration and mixtures of water and IPA were employed for membrane formation. On the other hand, the milk water permeation and protein rejection were increased using mixtures of water and IPA as non-solvent. Furthermore, the fouling analysis of the membranes demonstrated that the membrane surface with fewer tendencies for fouling was obtained.     

Preparation of chitosan–ethylenediaminetetraacetate-enwrapped magnetic CoFe2O4 nanoparticles via zero-length emulsion crosslinking method

A kind of magnetic multiple functional groups nanocomposites, chitosan–ethylenediaminetetraacetate (EDTA)-enwrapped CoFe₂O₄ nanoparticles, i.e. CoFe₂O₄@chitosan–EDTA nanocomposites were synthesized by a facile zero-length emulsion crosslinking process. In this method, CoFe₂O₄ was used as magnetic core, and 1-ethyl-3-(3-dimethylminopropyl) carbodiimide hydrochloride (EDAC) was used as a crosslinker, integrating amino group of chitosan and carboxyl group of EDTA. Determination of amino groups in chitosan modified by EDAC-activated EDTA was carried out through the trinitrobenzenesulfonic acid (TNBS) method. The as-prepared magnetic nanocomposites were characterized by XRD, FT-IR, XPS, SEM, EDS, TEM, SAED and vibrating sample magnetometer (VSM), and the results showed that the as-prepared CoFe₂O₄@chitosan–EDTA nanocomposites have good dispersibility, spherical shape and enough magnetization. The method proposed can be extended to fabricate other magnetic nanocomposites possessed amino and carboxyl groups.     

Surface modification of porous poly(tetrafluoroethylene) film via cold plasma treatment

In this study, cold plasma technology was applied for the surface modification of porous polytetrafluoroethylene (PTFE) film to improve the hydrophilicity. The surface properties of PTFE, modified by air, helium (He) or acrylic acid (AAc), were investigated with scanning electron microscopy (SEM), scanning probe microscope (SPM), in situ X-ray photoelectron spectroscopy (XPS) and water contact angle measurements. The changes of the surface property before and after plasma treatment were discussed. According to SEM and SPM measurements, the surface roughness increased at different levels after plasma treatment. Compared to air and AAc plasma treatment, the He plasma treatment introduced large amounts of oxygen into the surface, as known from XPS results. Contact angle measurements revealed that the hydrophilicity of the PTFE film surface was greatly improved due to the surface roughness and changes of chemical elements on the PTFE surface.     

Surface modification of PVDF membrane via AGET ATRP directly from the membrane surface

This contribution demonstrates a method for PVDF microporous membrane modification via surface-initiated activators generated by electron transfer atom transfer radical polymerization (AGET ATRP) directly from the membrane surface. Three hydrophilic polymers, poly(2-(N,N-dimethylamino) ethyl methacrylate) (PDMAEMA), poly(2-oligo (ethylene glycol) monomethyl ether methacrylate) (POEGMA), and poly(2-hydroxyethyl methacrylate) (PHEMA), were grafted from the PVDF membrane surface in aqueous solution at room temperature. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed the successful covalent tethering of the polymer chains onto the PVDF membrane surface. The gravimetry results indicated an approximately linear increase of the graft yields, up to about 330 μg/cm² for DMAEMA and 470 μg/cm² for both HEMA and OEGMA, with the polymerization time. Block copolymer brushes were prepared by chain extension. Water contact angle decreased over 50% for high yields, indicating improved surface hydrophilicity. The effects of the graft polymerization on membrane surface morphology, pore structure and permeability were investigated. It was found that the surface roughness was decreased and the pore size distribution was narrowed. The membrane permeability increased at low graft yields due to the enhanced hydrophilicity and decreased at high graft yields due to the overall reduction of the pore diameters.     

Hydrophilic modification of microporous polysulfone membrane via surface-initiated atom transfer radical polymerization of acrylamide

Polyacrylamide (PAM) brushes were grafted from chloromethylated polysulfone (CMPSF) membrane surface by surface-initiated atom transfer radical polymerization (SI-ATRP) to improve the membrane's hydrophilic property. In order to anchor the initiator onto polysulfone (PSF) membrane surface, CMPSF was used to prepare the microporous membrane by phase-inversion process. Attachment of the PAM chains on membrane surface was confirmed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). The grafted density of PAM was calculated to be 0.08 chains nm⁻². Field emission scanning electron microscopy (FESEM) and atomic force microscope (AFM) were used to characterize the surface morphology of the CMPSF membrane and modified membrane. The number-average molecular weight (M_n) of PAM linearly increased with the polymerization time, while the static water contact angle (θ) of the membrane grafted with PAM linearly decreased. This indicated the hydrophilic property of the membrane was linearly correlated with the chain length of graft polymer. Therefore linear control of PSF membrane's hydrophilic property was realized through adjusting polymerization time.     

Laser-induced surface modification of polystyrene

The modification induced in polystyrene (PS) by the ArF excimer laser radiation has been investigated. Various numbers of the laser pulses of the energies below the material ablation threshold were applied. Changes in the chemical composition of the PS surface layer were studied by the X-ray photoelectron spectroscopy (XPS). Analysis of the morphological changes in the polymer surface layer was performed via the atomic force microscopy (AFM). The contact angles of test liquids (water and diiodomethane) were measured with use of a goniometer while the surface energy (SE) was calculated by the Owens-Wendt method. It was found that the surface energy change was mainly affected by surface roughness caused by the laser radiation and that surface oxidation had not considerably contributed to this change. The increase in the SE was mostly due to its disperse component.     

Introduction of amino groups on the surface of thin photo definable epoxy resin layers via chemical modification

The introduction of amine groups on the surface of dielectric resins improves the adhesion with electrochemically deposited metals. In this work, etched epoxy resin surfaces are modified with aliphatic amines via a two step wet chemical reaction approach. First, cyanuric chloride is introduced on the surface. Next, the remaining reactive sites of cyanuric chloride are used to couple an aliphatic polyamine. Both reaction steps are optimized by variation of reaction parameters such as concentration, chemicals, temperature and time. A detailed surface characterization after each reaction step is provided using following techniques: ATR-IR, SEM-EDS, XPS and AFM.     

Laser induced modification of surface structures

The results on surface modification of materials of different structures; morphology, grain sizes, density and porosity by exposure to nanosecond laser light are given. Laser induced changes in their surface characteristics are presented. Surface layers of Si₃N₄, SiC dense ceramics and BN graphite and turbostratic pressed powders are studied by scanning electron microscopy to reveal the new nanostructures (nanowires or nanotubes) and new morphologies. A pronounced evolution in structure and grain size of BN graphite powders was demonstrated in laser processing layers.     

Surface modification of polypropylene non-woven fabric using atmospheric nitrogen dielectric barrier discharge plasma

In this paper, a dielectric barrier discharge operating in nitrogen at atmospheric pressure has been used to improve the surface hydrophilic property of polypropylene (PP) non-woven fabric. The changes in the hydrophilic property of the modified PP samples are investigated by the contact angle measurements and the variation of water contact angle is obtained as a function of the energy density; micrographs of the PP before and after plasma treatment are observed by scanning electron microscopy (SEM) and the chemical composition of the PP surface before and after plasma treatment is also analyzed by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The results show that the surface hydrophilic property of the PP samples is greatly improved with plasma treatment for a few seconds, as evidenced by the fact that the contact angle of the treated PP samples significantly decreases after plasma treatment. The analysis of SEM shows that the surface roughness of the treated PP samples increases due to bonding and etching in plasma processing. The analyses of FTIR and the C1s peak in the high-resolution XPS indicate that oxygen-containing and nitrogen-containing polar functional groups are introduced into PP surface in plasma processing. It can be concluded that the surface hydrophilic property of the modified PP samples has been obviously improved due to the introduction of oxygen-containing and nitrogen-containing polar groups and the increase of the surface roughness on the PP surface.     

Surface modification of porous poly(tetrafluoraethylene) film by a simple chemical oxidation treatment

A simple, inexpensive and environmental chemical treatment process, i.e., treating porous poly(tetrafluoroethylene) (PTFE) films by a mixture of potassium permanganate solution and nitric acid, was proposed to improve the hydrophilicity of PTFE. To evaluate the effectiveness of this strong oxidation treatment, contact angle measurement was performed. The effects of treatment time and temperature on the contact angle of PTFE were studied as well. The results showed that the chemical modification decreased contact angle of as-received PTFE film from 133 ± 3° to 30 ± 4° treated at 100 °C for 3 h, effectively converting the hydrophobic PTFE to a hydrophilic PTFE matrix. The changes in chemical structure, surface compositions and crystal structure of PTFE were examined by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), environmental scanning electron microscopy (ESEM), X-ray diffraction (XRD), respectively. It was found that the F/C atomic ratio decreased from untreated 1.65-0.10 treated by the mixture at 100 °C for 3 h. Hydrophilic groups such as carbonyl (CO) and hydroxyl (OH) were introduced on the surface of PTFE after treatment. Furthermore, hydrophilic compounds K_0.27MnO₂·0.54H₂O was absorbed on the surface of porous PTFE film. Both the introduction of hydrophilic groups and absorption of hydrophilic compounds contribute to the significantly decreased contact angle of PTFE.     

Hydrophobic modification of wood via surface-initiated ARGET ATRP of MMA

To convert the hydrophilic surface of wood into a hydrophobic surface, the present study investigated activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP) as a method of grafting methyl methacrylate (MMA) onto the wood surface. The wood treated with 2-bromoisobutyryl bromide and with the subsequently attached MMA via ARGET ATRP under different polymerization times (2 h, 4 h, 6 h, 8 h) were examined using scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. All the analyses confirmed that PMMA had been grafted onto the wood surface. Water contact angle measurement proved that the covering layer of PMMA on wood made the surface hydrophobic. Polymerization time had a positive influence on the contact angle value and higher contact angle can be produced with the prolongation of the polymerization time. When the reaction time was extended to 8 h, the contact angle of treated wood surface reached 130° in the beginning, and remained at 116° after 60 s. The ARGET ATRP method may raise an alteration on the wood surface modification.     

Fatigue properties of a S45C steel subjected to ultrasonic nanocrystal surface modification

An ultrasonic nanocrystal surface modification (UNSM) technique, at 3 different vibration strike numbers (34,000 times/mm², 45,000 times/mm², 68,000 times/mm²) was used to modify the surface structure and properties of S45C. These three process conditions respectively produced 2 μm, 12 μm and 30 μm nanocrystal layers. UNSM technique improves the following mechanical properties: microhardness, surface roughness, and compressive residual stress. Also, fatigue life increased with the vibration strike number. UNSM C3 (with the vibration strike number of 68,000 times/mm²) has improved the fatigue strength by as much as 33% for S45C. Optical microscope pictures show that cracks usually initiate from intergranular microcracks on the surface and then extend along the tip traces of UNSM which are considered as process defects. A simple math model (tearing adhesive plaster model) has been made to analyze the initiation and growth of cracks. Though most of the cracks initiate at the surface of specimens, surface nanocrystal layers can help to retard crack initiation. In S45C, the efficiency of crack resistance is more than 48%.the vibration strike number     

Polymer surface modification and characterization of particulate calcium carbonate fillers

The efficacy of the surface treatment of particulate fillers depends on the chemical character of the components, on the method and conditions of the treatment, and on the amount of the treating agent. Here, the ultra-fine calcium carbonate is surface treated with 1, 2, 3 and 4 wt.% polyacrylic acid (PAA) synthesized by ourselves, which has strong ionic interaction and is an efficient surface modifier. The PAA coated filler is submitted to the measurement of the surface bonded amount, bonding efficacy, X-ray photoelectron spectroscopy (XPS) and inverse gas chromatography. Maximum efficacy is expected at the monolayer coverage of the surface, which is about 0.6 wt.% according to the calculation based on the way they are aligned and is basically in agreement with the “substrate overlayer” model based on the mole ratio of C²⁸⁶ and C²⁹⁰ taking no account of the possible underestimation because of the inaccuracy or because of the CH_x contamination present originally on the CaCO₃. The initial decrease of the mole ratio of C²⁹⁰/O and C²⁹⁰/Ca with the surface bonded PAA may indicate that the bonding interaction between the polymer and the filler surface is the leaving of one molecular carbon dioxide. The IGC measurement shows that there is a considerable surface tension falling in the case of the PAA modified filler compared with the reference. An abnormal high surface energy in the case of filler treated with 4% PAA is observed.     

Enhanced in vitro biocompatibility of ultrafine-grained titanium with hierarchical porous surface

Bulk ultrafine-grained Ti (UFG Ti) was successfully fabricated by equal-channel angular pressing (ECAP) technique in the present study, and to further improve its surface biocompatibility, surface modification techniques including sandblasting, acid etching and alkali treatment were employed to produce a hierarchical porous surface. The effect of the above surface treatments on the surface roughness, wettability, electrochemical corrosion behavior, apatite forming ability and cellular behavior of UFG Ti were systematically investigated with the coarse-grained Ti as control. Results show that UFG-Ti with surface modification had no pitting corrosion and presented low corrosion rate in simulated body fluids (SBF). The hierarchical porous surface yielded by surface modification enhanced the ability of UFG Ti to form a complete apatite layer when soaked in SBF and promoted osteoblast-like cells attachment and proliferation in vitro, which promises to have a significant impact on increasing bone-bonding ability and reducing healing time when implanted due to faster tissue integration.