Zwitterionic monomer graft copolymerization onto polyurethane surface through a PEG spacer

A new zwitterionic surface was obtained by a novel three-step grafting procedure. The zwitterionic monomer was introduced by cerium-induced graft copolymerization in the presence of N,N′-methylene bisacrylamide (MBAA) as cross-linking agent. Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) analysis confirmed the MBAA could stimulate zwitterionic monomer grafting onto the membrane surface. Surface properties were also determined by atomic force microscope (AFM) and water contact angle. The hemocompatibility of the modified PU membranes was evaluated by the activated partial thromboplastin time (APTT), thrombin time (TT) and prothrombin time (PT). The TT and APTT of PU were significantly prolonged by the zwitterion of sulfobetaine monomer grafting copolymerization. The new polyurethane membrane could have a great potential in biomedical applications.     

Chemically induced graft copolymerization of 2-hydroxyethyl methacrylate onto polyurethane surface for improving blood compatibility

To improve hydrophilicity and blood compatibility properties of polyurethane (PU) film, we chemically induced graft copolymerization of 2-hydroxyethyl methacrylate (HEMA) onto the surface of polyurethane film using benzoyl peroxide as an initiator. The effects of grafting temperature, grafting time, monomer and initiator concentrations on the grafting yields were studied. The maximum grafting yield value was obtained 0.0275 g/cm² for HEMA. Characterization of the films was carried out by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), water contact angle measurements. ATR-FTIR data showed that HEMA was successfully grafted onto the PU films surface. Water contact angle measurement demonstrated the grafted films possessed a relatively hydrophilic surface. The blood compatibility of the grafted films was preliminarily evaluated by a platelet-rich plasma adhesion test and hemolysis test. The results of platelet adhesion experiment showed that polyurethane grafted polymerization with monomer of 2-hydroxyethyl methacrylate had good blood compatibility featured by the low platelet adhesion. Hemolysis rate of the PU-g-PHEMA films was dramatically decreased than the ungrafted PU films. This kind of new biomaterials grafted with HEMA monomers might have a potential usage for biomedical applications.     

Polypropylene modified with 2-hydroxyethyl acrylate-g-2-methacryloyloxyethyl phosphorycholine and its hemocompatibility

Polypropylene (PP) was modified with 2-hydroxyethyl acrylate (HEA) by solution radical grafting to introduce active hydroxyl groups on polypropylene backbone (PP-g-HEA). Then the biomimic monomer, 2-methacryloyloxyethyl phosphorycholine (MPC), was grafted onto the surface of PP-g-HEA film (PP-g-HEA-g-MPC) by redox graft polymerizations with ceric(IV) ammonium nitrate as an initiator. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) showed that the HEA and MPC were introduced onto PP molecular chains and the copolymer, PP-g-HEA-g-MPC were formed. The water contact angle measurements demonstrated that the final modified PP film exhibited a better hydrophilic surface compared to the neat PP film. The platelets adhesion on the neat PP, PP-g-HEA and PP-g-HEA-g-MPC film was examined by scanning electron microscopy (SEM). It was found that a large number of platelets were adhered and activated on the surface of neat PP and PP-g-HEA films, while the number of platelets on PP-g-HEA-g-MPC surface was decreased remarkably. The result revealed that the introduction of poly(MPC) onto the PP surface improved the hemocompatibility of PP substantially.     

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.     

One-stage fabrication of sub-micron hydrophilic microchannels on PDMS

A sub-micron hydrophilic microchannel was fabricated on poly(dimethylsiloxane) (PDMS) in one step using vacuum ultraviolet light (VUV) lithography in vacuum. The topographies and properties of the irradiated PDMS surface were characterized and analyzed by atomic force microscopy (AFM), and the chemical composition changes on VUV-treated PDMS analyzed by X-ray photoelectron spectroscopy (XPS). The hydrophilic stability of irradiated PDMS surface was studied by static water contact angle. As demonstrated, the hydrophilicity on surface of PDMS microchannel can be kept for a longer term even three months after the treatment.     

Preparation and characterization of modified nano-porous PVDF membrane with high antifouling property using UV photo-grafting

In this study, the poly(vinylidene fluoride) (PVDF) membrane was prepared via immersion precipitation technique and modified by UV photo-grafting of hydrophilic monomers on the top membrane surface. Acrylic acid (AA) and 2-hydroxyethylmethacrylate (HEMA) as acrylic monomers and 2,4-phenylenediamine (PDA) and ethylene diamine (EDA) as amino monomers were used at different concentrations to modify the membrane and improve the hydrophilicity with less fouling tendency. Moreover the presence of benzophenon as photo-initiator for grafting the hydrophilic monomers onto PVDF membrane surface was elucidated. The virgin and modified PVDF membranes were characterized by contact angle, ATR-FTIR, SEM and cross-flow filtration. The contact angle measurements demonstrated that the hydrophilicities of the membranes were significantly enhanced by UV photo-grafting of hydrophilic monomers onto the membrane surface. The ATR-FTIR confirmed the occurrence of modification on PVDF membrane by UV photo-grafting. The pure water flux of membranes was declined by UV photo-grafting but the milk water permeation and protein rejection were slightly improved. Moreover the antifouling properties and flux recovery of PVDF membrane were improved by UV photo-grafting of hydrophilic monomers.     

Surface modification and characterization of magnesium hydroxide sulfate hydrate nanowhiskers

In order to enhance the compatibility with plastic polymers, magnesium hydroxide sulfate hydrate (MHSH) nanowhiskers were modified through grafting methyl methacrylate (MMA) on the surface of the nanowhiskers by emulsion polymerization. The influences of the reaction time, MMA monomer content, adding speed of monomer and the reaction temperature on the grafting ratio were investigated. Thermogravimetry (TG), Fourier transform infrared (FT-IR) spectroscopy, X-ray powder diffraction (XRD), scanning electron microscope (SEM), energy-dispersive X-ray (EDX) spectroscopy and surface contact angle measurement were used to characterize the effect of surface modification. The results showed that the MHSH nanowhiskers were uniformly coated by polymethyl methacrylate (PMMA), and a well-defined core-shell hybrid structure of MHSH/PMMA was obtained. The surface contact angle of the hybrid whiskers increased to 87.32° from 12.71° and the whiskers surface was changed from hydrophilic to lipophilic.     

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.     

Hydrophilic modification of polyethersulfone porous membranes via a thermal-induced surface crosslinking approach

A thermal-induced surface crosslinking process was employed to perform a hydrophilic surface modification of PES porous membranes. Difunctional poly(ethylene glycol) diacrylate (PEGDA) was used as the main crosslinking modifier. The addition of trifunctional trimethylolpropane trimethylacrylate (TMPTMA) into the reaction solutions accelerated the crosslinking progress of PEGDA on PES membranes. The membrane surface morphology and chemical composition were characterized by scanning electron microscopy (SEM) and FTIR-ATR spectroscopy. The mass gains (MG) of the modified membranes could be conveniently modulated by varying the PEGDA concentration and crosslinking time. The measurements of water contact angle showed that the hydrophilicity of PES membranes was remarkably enhanced by the coating of crosslinked PEGDA layer. When a moderate mass gain of about 150 μg/cm² was reached, both the permeability and anti-fouling ability of PES membranes could be significantly improved. Excessive mass gain not only contributed little to the anti-fouling ability, but also brought a deteriorated permeability to PES membranes.     

Surface modification of polystyrene with atomic oxygen radical anions-dissolved solution

A novel approach to surface modification of polystyrene (PS) polymer with atomic oxygen radical anions-dissolved solution (named as O⁻ water) has been investigated. The O⁻ water, generated by bubbling of the O⁻ (atomic oxygen radical anion) flux into the deionized water, was characterized by UV-absorption spectroscopy and electron paramagnetic resonance (EPR) spectroscopy. The O⁻ water treatments caused an obvious increase of the surface hydrophilicity, surface energy, surface roughness and also caused an alteration of the surface chemical composition for PS surfaces, which were indicated by the variety of contact angle and material characterization by atomic force microscope (AFM) imaging, field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), and attenuated total-reflection Fourier transform infrared (ATR-FTIR) measurements. Particularly, it was found that some hydrophilic groups such as hydroxyl (OH) and carbonyl (CO) groups were introduced onto the polystyrene surfaces via the O⁻ water treatment, leading to the increases of surface hydrophilicity and surface energy. The active oxygen species would react with the aromatic ring molecules on the PS surfaces and decompose the aromatic compounds to produce hydrophilic hydroxyl and carbonyl compounds. In addition, the O⁻ water is also considered as a “clean solution” without adding any toxic chemicals and it is easy to be handled at room temperature. Present method may suit to the surface modification of polymers and other heat-sensitive materials potentially.     

Synthesis of styrene-maleic anhydride copolymer esters and their surface enriched properties when blending with polyethylene

Three kinds of comb-like amphiphilic copolymers based on styrene-maleic anhydride copolymer (SMA) backbone and long fatty alcohol grafts were synthesized by esterification of SMA with octanol, tetradecanol and octadecanol, respectively. SMA and the esters were used as surface modifiers to blend with high density polyethylene (HDPE). The surface composition of the binary blends has been determined by Attenuated Total Reflection Fourier Transform infra-red (ATR-FT-IR) spectroscopy. It was found that grafting of alcohols onto SMA can promote the enrichment of the modifiers on the surface of the blending film, and that the enrichment effect enhances when using shorter fatty alcohols. The data of contact angle measurements and surface tension of the blend film show that the addition of SMA esters to HDPE can improve the hydrophilicity of the HDPE surface.     

Fabrication of a superhydrophobic ZnO nanorod array film on cotton fabrics via a wet chemical route and hydrophobic modification

A superhydrophobic ZnO nanorod array film on cotton substrate was fabricated via a wet chemical route and subsequent modification with a layer of n-dodecyltrimethoxysilane (DTMS). The as-obtained cotton sample was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), scanning probe microscope (SPM) and X-ray photoelectron spectroscopy (XPS), respectively. The wettability of the cotton fabric sample was also studied by contact angle measurements. The modified cotton fabrics exhibited superhydrophobicity with a contact angle of 161° for 8 μL water droplet and a roll-off angle of 9° for 40 μL water droplet. It was shown that the proper surface roughness and the lower surface energy both played important roles in creating the superhydrophobic surface, in which the Cassie state dominated.     

Modification of hydrophobic acrylic intraocular lens with poly(ethylene glycol) by atmospheric pressure glow discharge: A facile approach

To improve the anterior surface biocompatibility of hydrophobic acrylic intraocular lens (IOL) in a convenient and continuous way, poly(ethylene glycol)s (PEGs) were immobilized by atmospheric pressure glow discharge (APGD) treatment using argon as the discharge gas. The hydrophilicity and chemical changes on the IOL surface were characterized by static water contact angle and X-ray photoelectron spectroscopy to confirm the covalent binding of PEG. The morphology of the IOL surface was observed under field emission scanning electron microscopy and atomic force microscopy. The surface biocompatibility was evaluated by adhesion experiments with platelets, macrophages, and lens epithelial cells (LECs) in vitro. The results revealed that the anterior surface of the PEG-grafted IOL displayed significantly and permanently improved hydrophilicity. Cell repellency was observed, especially in the PEG-modified IOL group, which resisted the attachment of platelets, macrophages and LECs. Moreover, the spread and growth of cells were suppressed, which may be attributed to the steric stabilization force and chain mobility effect of the modified PEG. All of these results indicated that hydrophobic acrylic IOLs can be hydrophilic modified by PEG through APGD treatment in a convenient and continuous manner which will provide advantages for further industrial applications.     

Functionalization of PET and PA6.6 woven fabrics

In the present work as received woven fabrics of polyethylene terephthalate (PET) and polyamide 6.6 (PA6.6) were exposed to a continuous dielectric barrier discharge (DBD), in air at atmospheric pressure, at selected discharge power values and conveyor speeds. The chemical modification of the fabric surface was studied by contact angle analysis, attenuated total reflection (ATR)-FTIR spectroscopy and X-ray photoelectron spectroscopy (XPS). The results confirmed that the treatment changed the fabric surface chemistry, increasing its wettability by polar liquids and its oxygen content. Contact angle results showed different behaviour of the two polymer fabrics toward ageing effects; while PET showed a contact angle increase along the subsequent days of treatment, the PA6.6 fabric maintained its hydrophilicity even 15 days after treatment. The surface morphology analysed by scanning electron microscopy (SEM), did not show any significant difference before and after treatment.     

Preparation of superhydrophobic membranes by electrospinning of fluorinated silane functionalized poly(vinylidene fluoride)

Fluorinated silane functionalized poly(vinylidene fluoride) (PVDF) is synthesized by graft polymerization of 3-trimethoxylpropyl methylacrylate with PVDF followed by coupling of fluorinated silanes. Flat membrane prepared using this functionalized PVDF has a water contact angle of 140°. Superhydrophobic PVDF membrane with a contact angle larger than 150° is prepared by the electrospinning of the fluorinated silane functionalized PVDF. The morphologies of the membranes are characterized using scanning electron microscopy. The surface composition of the membranes is analyzed using FTIR and the contact angles and water drops on the surface of the membrane are measured using video microscopy.     

Novel strategy in increasing stability and corrosion resistance for super-hydrophobic coating on aluminum alloy surfaces

A novel super-hydrophobic coating was prepared by chemical modification on the anodized aluminum alloy surface. The surface structure was characterized by water contact angle measurement, scanning electron microscopy (SEM), and the composition was measured by X-ray photoelectron spectroscopy (XPS). The corrosion behavior of the super-hydrophobic coating was evaluated by the polarization curve and the electrochemical impedance spectroscopy (EIS). It was found that the static water contact angle on the surface of super-hydrophobic coating was as high as 167.7 ± 1.2°, and the sliding angle was 5°. The super-hydrophobic coating resulted in excellent corrosion resistance property and the super-hydrophobic coating showed a good stability.     

Mechanochemically conjugated PMHS/nano-SiO2 hybrid and subsequent optimum grafting density study

In this paper, we reported the preparation of poly(methylhydrosiloxane) (PMHS)/SiO₂ hybrid particles by mechanochemical method based on high energy ball milling (HEBM). The obtained hybrid particles were characterized by Fourier transform infrared (FT-IR) spectroscopy, ²⁹Si CP (cross-polarization) MAS NMR, viscosity measurement, particle size distribution, thermal analysis (TGA, DSC and DTG), static contact angle (CA), field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). FT-IR and ²⁹Si CP MAS NMR spectra indicate that PMHS is chemically anchored onto the surface of nano-SiO₂. Viscosity measurement, particle size distribution, FE-SEM and TEM demonstrate that an appropriate grafting density optimizes the dispersion of nanoparticles in poly(dimethylsiloxane) (PDMS) matrix, so lower viscosity can be achieved. Too high or too low grafting density may only achieve suboptimal and poor dispersions. The optimum grafting density of PMHS on nano-SiO₂ was determined by thermal analysis, with approximately 0.0531 PMHS/nm². Static contact angle measurement indicates that the water contact angle of hybrid particles is modulated by changing the grafting density of PMHS on nano-SiO₂. The CA value of PMHS/SiO₂ hybrid with optimum grafting density is 139.4°, and the highest CA value of PMHS/SiO₂ hybrid is approximately 158.2°.     

Modification of polysulfone membranes via surface-initiated atom transfer radical polymerization

Hydrophilic poly((poly(ethylene glycol) methyl ether methacrylate) (P(PEGMA)) and poly(glycidylmethacrylate) (PGMA) brushes were grafted from chloromethylated polysulfone (CMPSF) membrane surfaces via surface-initiated atom transfer radical polymerization (ATRP). Prior to ATRP, chloromethylation of PSF was performed beforehand and the obtained CMPSF was prepared into porous membranes by phase inversion process. It was demonstrated that the benzyl chloride groups on the CMPSF membrane surface afforded effective macroinitiators to graft the well-defined polymer brushes. ¹H NMR was employed to confirm the structure of CMPSF. The grafting yield of P(PEGMA) and PGMA was determined by weight gain measurement. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed the grafting of P(PEGMA) and PGMA chains. Water contact angle measurements indicated that the introduction of P(PEGMA) and PGMA graft chains promoted remarkably the surface hydrophilicity of PSF membranes. The effects of P(PEGMA) and PGMA immobilization on membrane morphology, permeability and fouling resistance were investigated. It was found that P(PEGMA) and PGMA grafts brought higher pure water flux, improved hydrophilic surface and better anti-protein absorption ability to PSF membranes after modification. And evidently, macromonomer P(PEGMA) brought much better properties to the PSF membranes than PGMA macromonomer.     

Surface modification of the nanoparticles by an atmospheric room-temperature plasma fluidized bed

Using hexamethyldisiloxane (HMDSO) monomer, the magnetic nanoparticles (NPs) of nickel oxide (NiO) were modified by using an atmospheric room-temperature plasma fluidized bed (ARPFB). The plasma gas temperature of the ARPFB was not higher than 325 K, which was favorable for organic polymerization. The plasma optical emission spectrum (OES) of the gas mixture consisting of argon (Ar) and HMDSO was recorded by a UV-visible monochromator. The as-treated NPs were characterized by means of scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The results show that the assembling NPs were isolated greatly after modified by the organosilicon polymer. Moreover, this treatment process changed the wettability of the NPs from super-hydrophilicity to super-hydrophobicity, and the contact angle (CA) of water on the modified NPs surface exceeded 150°. Therefore, the ARPFB is a prospective technology for the NPs surface modification according to the different requirements.     

FAS grafted superhydrophobic ceramic membrane

The hydrophobic properties of γ-Al₂O₃ membrane have been obtained by grafting fluoroalkylsilane (FAS) on the surface of the membrane. The following grafting parameters were studied: the eroding time of the original membrane, the grafting time, the concentration of FAS solution and the multiplicity of grafting. Hydrophobicity of the membranes was characterized by contact angle (CA) measurement. The thermogravimetric analysis (TGA) was used to investigate the weight loss process (25–800 °C) of the fluoroalkylsilane grafted on Al₂O₃ powders under different grafting conditions. The morphologies of the membranes modified under different parameters were examined by field emission scanning electron microscopy (FE-SEM) and the surface roughness (Ra) was measured using white light interferometers. A needle-like structure was observed on the membrane surface after modification, which causes the change of Ra. On the results above, we speculated a model to describe the reaction between FAS and γ-Al₂O₃ membrane surface as well as the formed surface morphology.