Surface Modification of Polyvinylidene Fluoride (PVDF) Membranes by Low-Temperature Plasma with Grafting Styrene

In order to control the surface pore sizes of polyvinylidene fluoride membranes and their distribution, low temperature plasma-induced grafting modifications of PVDF were studied to prepare hydrophobe membranes. By argon （Ar） treating and subsequent grafting reaction, a hydrophobe monomer, styrene, was introduced into the PVDF membrane. Fourier transform infrared attenuated total reflection （FTIR-ATR） was utilized to characterize the chemical and physical changes in the Ar plasma modified membrane. The surface modifications of PVDF membranes were investigated by using scanning electron microscopy （SEM）, atomic force microscopy （AFM） and differential scanning calorimeter （DSC）. The water permeability and the solute rejection were measured by PVDF membrane modified in different graft conditions. Results demonstrated that the pores in the modified membranes get smaller and the distribution of pores gets narrowed with the increase in grafting reaction duration. Longer graft time caused the water flux of PVDF membrane to decrease from 578 kg/（m^2· h） to 23 kg/（m^2· h） and the solute rejection to increase from 73% to 92%.

Insight into fouling behavior of poly(vinylidene fluoride)(PVDF)hollow fiber membranes caused by dextran with different pore size distributions

Membrane fouling is the key problem that occurs in membrane process for water treatment. However, how membrane microstructure influences the fouling behavior is still not clear. In this study, fouling behavior caused by dextran was deeply and systematically investigated by employing four poly（vinylidene fluoride） （PVDF） membranes with different pore sizes, ranging from 24 to 94 nm. The extent of fouling by dextran was accurately characterized by pore reduction, flux decline, and the change of critical flux. The result shows that membrane with the smallest pore size of 24 nm experienced the smallest fouling rate and the lowest fouling extent. As the membrane pore size increased, the critical flux ranges were 105-114, 63-73, 38-44 and 34- 43 L. m 2. h t, respectively. The critical flux and fouling resistances indicated that the fouling propensity in- creases with the increase of membrane pore size. Two pilot membrane modules with mean pore size of 25 nm and 60 nm were applied in membrane filtration of surface water treatment. The results showed that serious ir- reversible membrane fouling occurred on the membrane with pore size of 60 nm at the permeate flux of 40.5 L.m 2.h 1. On the other hand, membrane with pore size of 25 nm exhibited much better anti-fouling per- formance when permeate flux was set to 40.5, 48 and 60 L-m 2-h- 1.

Synthesis of Membrane Adsorbers via Surface Initiated ATRP of 2-Dimethylaminoethyl Methacrylate from Microporous PVDF Membranes

Surface-initiated atom transfer radical polymerization （SI-ATRP） was used to tether poly（2-dimethylaminoethyl methacrylate） （PDMAEMA） onto microporous PVDF membranes in order to synthesize membrane adsorbers for protein adsorption. The alkaline treatment and bromine addition reaction were used to anchor ATRP initiators on membrane surface. Then PDMAEMA was grafted from the membrane surface via SI-ATRP. Fourier transform infrared spectroscopy （FTIR）, X-ray photoelectron spectroscopy （XPS） and scanning electron microscopy （SEM） revealed the chemical composition and surface topography of the PVDF-g-PDMAEMA membrane surfaces. These results showed that PDMAEMA was grafted from the membrane surface successfully and a grafting yield as high as 1500 ~g/cm2 was achieved. The effects of the grafting time and the density of initiators on the static and dynamic binding capacity of bovine serum albumin （BSA） were systematically investigated. Both the static and dynamic binding capacities increase with the bromination and polymerization time. However, the benefits of the initiator density on binding capacities are limited by the graft density of PDMAEMA chains.

Two-Dimensional Graphitic Carbon-Nitride(g-C_(3)N_(4))-Coated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)Cathodes for High-Energy-Density and Long-Life Lithium Batteries

High-capacity nickel-rich layered oxides are promising cathode materials for high-energy-density lithium batteries.However,the poor structural stability and severe side reactions at the electrode/electrolyte interface result in unsatisfactory cycle performance.Herein,the thin layer of two-dimensional(2D)graphitic carbon-nitride(g-C_(3)N_(4))is uniformly coated on the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(denoted as NCM811@CN)using a facile chemical vaporization-assisted synthesis method.As an ideal protective layer,the g-C_(3)N_(4)layer effectively avoids direct contact between the NCM811 cathode and the electrolyte,preventing harmful side reactions and inhibiting secondary crystal cracking.Moreover,the unique nanopore structure and abundant nitrogen vacancy edges in g-C_(3)N_(4)facilitate the adsorption and diffusion of lithium ions,which enhances the lithium deintercalation/intercalation kinetics of the NCM811 cathode.As a result,the NCM811@CN-3wt%cathode exhibits 161.3 mAh g^(−1)and capacity retention of 84.6%at 0.5 C and 55°C after 400 cycles and 95.7 mAh g^(−1)at 10 C,which is greatly superior to the uncoated NCM811(i.e.129.3 mAh g^(−1)and capacity retention of 67.4%at 0.5 C and 55°C after 220 cycles and 28.8 mAh g^(−1)at 10 C).The improved cycle performance of the NCM811@CN-3wt%cathode is also applicable to solid–liquid-hybrid cells composed of PVDF:LLZTO electrolyte membranes,which show 163.8 mAh g^(−1)and the capacity retention of 88.1%at 0.1 C and 30°C after 200 cycles and 95.3 mAh g^(−1)at 1 C.

Fouling behavior of poly(vinylidene fluoride)(PVDF)ultrafiltration membrane by polyvinyl alcohol(PVA)and chemical cleaning method

Severe fouling to poly(vinylidene fluoride)(PVDF)membrane is usually caused as filtrating the papermaking wastewater in the ultrafiltration(UF)process.In the paper,fouling behavior and mechanism were investigated,and the low-concentration polyvinyl alcohol(PVA)contained in the sedimentation tank wastewater was found as the main foulant.Consequently,the corresponding cleaning approach was proposed.The experiment and modeling results elaborated that the fouling mode developed from pore blockage to cake layer along with filtration time.Chemical cleaning conditions including the composition and concentration of reagents,cleaning duration and trans-membrane pressure were investigated for their effect on cleaning efficiency.Pure water flux was recovered by over 95% after cleaning the PVDF membrane using the optimal conditions 0.5 wt% NaClO(as oxidant)and 0.1 wt% sodiumdodecyl benzene sulfonate(SDBS,as surfactant)at 0.04MPa for 100 min.In the chemical cleaning method,hypochlorite(ClO−)could first chain-scissor PVA macromolecules to small molecules and SDBS could wrap the fragments in micelles,so that the foulants were removed from the pores and surface of membrane.After eight cycling tests,pure water flux recovery maintained above 95% and the reused membrane was found intact without defects.

Polymerizable Ionic Liquid Copolymer P(MMA-co-BVIm-Br) and Its Effect on the Surface Wettability of PVDF Blend Membranes

Polymerizable ionic liquid copolymer P（MMA-co-BVIm-Br） was synthesized by radical polymerization technique, and characterized by Fourier transform infrared spectrometry （FTIR）, 1H Nuclear magnetic resonance （1H-NMR） and gel permeation chromatography （GPC）. The resulting copolymer was used to prepare poly（vinylidene fluoride） （PVDF） blend membranes via a phase inversion method. The effects of the copolymer on the polymorphism, surface wettability and zeta potential （0 of the blend membranes were investigated by ATR-FTIR, contact angle instrument and zeta potential analyzer. Scanning electron microscopy （SEM and SEM-EDS） was also applied to investigate the morphology and the surface element changes of the fabricated membranes. The results indicated that P（MMA-co-BVIm-Br） copolymer existed on the surface of the membrane which made the blend membrane have a positive surface during the experimental pH range. The copolymer was also in favor of the formation of βcrystal phase in PVDF membranes. The contact angle experiment indicated that P（MMA-co-BVIm-Br） copolymer could switch the wettability of the blend membranes from hydrophilic to hydrophobic by exchanging Br- anion with PF6-. Compared with pure PVDF membranes, the water flux and water recovery flux of the blend membranes were enhanced obviously. The results from the flux recovery ratio （FR） and total fouling ratio （Rt） all suggested that the blend membranes had good anti-fouling properties.

Thermo-responsive and Antifouling PVDF Nanocomposited Membranes Based on PNIPAAm Modified TiO_2 Nanoparticles

A novel hydrophilic nanocomposite additive （TiO2-g-PNIPAAm） was synthesized by the surface modification of titanium dioxide （TiO2） with N-isopropylacrylamide （NIPAAm） via ＂graft-from＂ technique. And the nanocomposite membrane of poly（vinylidene fluoride） （PVDF）/TiO2-g-PNIPAAm was fabricated by wet phase inversion. The graft degree was obtained by thermo-gravimetric analysis （TGA）. Fourier transform infrared attenuated reflection spectroscopy （FTIR-ATR） and X-ray photoelectronic spectroscopy （XPS） characterization results suggested that TiO2-g-PNIPAAm nanoparticles segregated on membrane surface during the phase separation process. Scanning electron microscopy （SEM） was conducted to investigate the surface and cross-section of the modified membranes. The water contact angle measurements confirmed that TiO2-g-PNIPAAm nanoparticles endowed PVDF membranes better hydrophlilicity and thermo-responsive properties compared with those of the pristine PVDF membrane. The water contact angle decreased from 92.8~ of the PVDF membrane to 61.2~ of the nanocompostie membrane. Bovine serum albumin （BSA） static and dynamic adsorption experiments suggested that excellent antifouling properties of membranes was acquired after adding TiO2-g- PNIPAAm. The maximum BSA adsorption at 40℃ was about 3 times than that at 23 ℃. The permeation experiments indicated the water flux recover ratio and BSA rejection ratio were improved at different temperatures.

SURFACE MODIFICATION OF PVDF POROUS MEMBRANES

A novel method for the surface modification of PVDF porous membranes was introduced. Styrene-（N-（4- hydroxyphenyl） maleimide） alternating copolymer SHMI-Br was blended with PVDF to fabricate SHMI-Br/PVDF membranes. The C-Br bond on the SHMI-Br/PVDF membrane was served as initial site of ATRP, and P（PEGMA） brush was grafted on the PVDF membrane. Attenuated total reflectance-Fourier transform infrared spectroscopy （ATR/FTIR） was used to prove the P（PEGMA） brushes were successfully grafted onto the SHMI-Br/PVDF membrane surface. Introduction of P（PEGMA） brushes on the PVDF membrane surface enhanced the hydrophilicity effectively. When the PEGMA degree of grafting was 16.7 wt%, the initial contact angle of PVDF membrane decreased from 98° to 42°. The anti-fouling ability of PVDF membrane was improved significantly after P（PEGMA） brush was ~afted. Taking the PEGMA degree of grafting 16.7 wt% as an example, the flux of protein solution was about 151.21 L/（m h） when the pH value of the BSA solution was 4.9. As the pH value was increased to 7.4, the flux was changed to 180.06 L/（m2 h）. However, the protein solution flux of membrane M3 （PEGMA： 0 wt%） was only 73.84 L/（m2 h） and 113.52 L/（m2 h） at pH 4.9 and 7.4, respectively.

Amino Acids Functionalized Graphene Oxide for Enhanced Hydrophilicity and Antifouling Property of Poly(vinylidene fluoride) Membranes

Herein, functionalized graphene oxide（GO） was prepared by the covalent functionalization with amino acids（lysine, glycine, glutamic acid and tyrosine） in this study. Zeta potential results demonstrated that covalent functionalization of GO with amino acids was favourable for their homogeneous dispersion in water and organic solvents. Based on the higher absolute value of zeta potential and the better dipersion stability of GO-lysine, the PVDF/GO-lysine hybrid membranes were then prepared via the phase inversion induced by immersion precipitation technique. SEM images showed a better pore diameter and porosity distribution on the PVDF/GO-lysine membrane surface. The zeta potential absolute value of the PVDF/GO-lysine membrane surface was higher than that of the virgin PVDF membrane. Furthermore, the PVDF/GO-lysine membranes surface exhibited good hydrophilicity. The water flux of PVDF/GO-lysine membranes can reach two times of that of the virgin PVDF membrane. And the BSA adsorbed amount on PVDF/GO-lysine surface was decreased to 0.82 mg/cm^2 for PVDF/GO-lysine-8% membrane. Filtration experiment results indicated that the fouling resistance was significantly improved for the PVDF/GO-lysine membranes. As a result, lysine functionalized GO will provide a promising method to fabricate graphene oxide based hybrid membranes with effective antifouling property and hydrophilicity.

Excellent Hydrophilic and Anti-bacterial Fouling PVDF Membrane Based on Ag Nanoparticle Self-assembled PCBMA Polymer Brush

A silver nanoparticles-poly（carboxybetaine methacrylate） （AgNPs-PCBMA） nanocomposite was prepared on poly（vinylidene fluoride） （PVDF） membrane surface to improve its hydrophilicity and antifouling properties. Firstly, the PVDF membranes were grafted by PCBMA via physisorbed free radical grafting technique. Then Ag＋ coordinated to the carbonyl group on PCBMA and subsequently was reduced to silver nanoparticles. The hydrophilicity of the PVDF-g- PCBMA/Ag membrane was enhanced with the increasing fixed degree （FD） of AgNPs, and the original water contact angle of membrane was reduced to 33.97°. Additionally, water flux recovery ratio （FRR） and bovine serum albumin （BSA） rejection ratio of PVDF-g-PCBMA/AgNPs membrane were improved from 52% to 93.32% and 28.12% to 91.12%, respectively. Further, the PVDF-g-PCBMA/AgNPs membranes exhibited the more pronounced inhibition zone. The study demonstrated that compared with pure AgNPs or the PCBMA polymer brush, the synergistic effect of PCBMA and AgNPs made PVDF membranes have better hydrophilicity and anti-bacterial performances.

Preparation and characterization of poly （vinylidene fluoride）/ Ti02 hybrid membranes

Poly（vinylidene fluoride） （PVDF）/titanium dioxide （TiO2） hybrid membranes were prepared using nano-TiO2 as the modifier, and characterized by Transmis- sion Electron Microscope （TEM）, Fourier transform infrared spectroscopy （FT-IR）, scanning electron micro- scope （SEM）, atomic force microscope （AFM）, X-ray diffraction （XRD） and X-ray photoelectron spectroscopy （XPS）. The characterization results demonstrated that nano-sized TiO2 particles dispersed homogeneously within the PVDF matrix, contributing to more hydroxyls and smoother surfaces. Moreover, permeate flux, retention factor, porosity, contact angle and anti-fouling tests were carried out to evaluate the effect of TiO2 concentration on the performance of PVDF membranes. Among all the prepared membranes, PVDF/TiO2 membrane containing 10 vol.% TiO2 exhibited the best hydrophilicity with an average pure water flux up to 237 L.mE.h1, higher than that of unmodified PVDF membranes （155L.m2.h ）. Besides, the bovine serum albumin rejection of the hybrid membrane was improved evidently from 52.3% to 70.6%, and the contact angle was significantly lowered from 83° to 60°, while the average pore size and its distribution became smaller and narrower.

Effect of protein on PVDF ultrafiltration membrane fouling behavior under different pH conditions： interface adhesion force and XDLVO theory analysis

To further detem3ine the fouling behavior of bovine serum albumin （BSA） on different hydrophilic PVDF ultrafiltration （UF） membranes over a range of pH values, self-made atomic force microscopy （AFM） colloidal probes were used to detect the adhesion forces of membrane-BSA and BSA BSA, respectively. Results showed that the membrane-BSA adhesion interaction was stronger than the BSA-BSA adhesion interaction, and the adhesion force between BSA-BSA-fouled PVDF/PVA membranes was similar to that between BSA-BSA-fouled PVDF/PVP membranes, which indicated that the fouling was mainly caused by the adhesion interaction between membrane and BSA. At the same pH condition, the PVDF/PVA membrane-BSA adhesion force was smaller than that of PVDF/ PVP membrane-BSA, which illustrated that the more hydrophilic the membrane was, the better antifouling ability it had. The extended Derjaguin-Landau-Verwey Overbeek （XDLVO） theory predicts that the polar or Lewis acid-base （AB） interaction played a dominant role in the interracial free energy ofmcmbrane-BSA and BSA BSA that can be affected by pH. For the same membrane, the pH values of a BSA solution can have a significant impact on the process of membrane fouling by changing the AB component of free energy.

Preparation and characterization of Pd/Fe bimetallic nanoparticles immobilized on Al_2O_3/PVDF membrane:Parameter optimization and dechlorination of dichloroacetic acid

Using a liquid-solid phase inversion method, a hybrid matrix poly（vinylidene fluoride）（PVDF） membrane was prepared with alumina（Al2O3） nanoparticle addition. Pd/Fe nanoparticles（NPs） were successfully immobilized on the Al2O3/PVDF membrane, which was characterized by Scanning Electron Microscopy（SEM） and Transmission Electron Microscopy（TEM）. The micrographs showed that the Pd/Fe NPs were dispersed homogeneously. Several important experimental parameters were optimized, including the mechanical properties, contact angle and surface area of Al2O3/PVDF composite membranes with different Al2O3 contents. At the same time, the ferrous ion concentration and the effect of hydrophilization were studied. The results showed that the modified Al2O3/PVDF membrane functioned well as a support. The Al2O3/PVDF membrane with immobilized Pd/Fe NPs exhibited high efficiency in terms of dichloroacetic acid（DCAA） dechlorination. Additionally, a reaction pathway for DCAA dechlorination by Pd/Fe NPs immobilized on the Al2O3/PVDF membrane system was proposed.

Fabrication of Cu(OH)_2 Nanowires Blended Poly(vinylidene fluoride) Ultrafiltration Membranes for Oil-Water Separation

Cu（OH）2 nanowires were prepared and incorporated into poly（vinylidene fluoride）（PVDF） to fabricate Cu（OH）2-PVDF ultrafiltration（UF） membrane via immersion precipitation phase inversion process. The effect of Cu（OH）2 nanowires on the morphology of membranes was investigated by X-ray photoelectron spectroscopy（XPS）, Fourier transform infrared（FTIR） spectroscopy, atomic force microscopy（AFM）, scanning electron microscopy（SEM） and X-ray diffraction（XRD） measurements. The results showed that all the Cu（OH）2-PVDF membranes had wider fingerlike pore structure and better hydrophilicity, smoother surface than pristine PVDF membrane due to the incorporation of Cu（OH）2 nanowires. In addition, water flux and bovine serum albumin（BSA） rejection were also measured to investigate the filtration performance of membranes. The results indicated that all the Cu（OH）2-PVDF membranes had high water flux, outstanding BSA rejection and excellent antifouling properties. It is worth mentioning that the optimized performance could be obtained when the Cu（OH）2 nanowires content reached 1.2 wt%. Furthermore, the membrane with 1.2 wt% Cu（OH）2 nanowires showed outstanding oil-water emulsion separation capability.

Urimem,a membrane that can store urinary proteins simply and economically,makes the large-scale storage of clinical samples possible

By nature,biomarker is the measurable change associated with a physiological or pathophysiological process.Unlike blood which has mechanisms to minimize changes and to keep the internal environment homeostatic,urine is more likely to reflect changes of the body and is a better biomarker source.Because of its potential in biomarker discovery,urinary proteins should be preserved comprehensively as the duration of the patients’corresponding medical records.Here,we propose a method to adsorb urinary proteins onto a membrane we named Urimem.This simple and inexpensive method requires minimal sample handling,uses no organic solvents,and is environmentally friendly.Urine samples were filtered through the membrane,and urinary proteins were adsorbed onto the membrane.The proteins on the membrane were dried and stored in a vacuum bag,which keeps the protein pattern faithfully preserved.The membrane may even permit storage at room temperature for weeks.Using this simple and inexpensive method,it is possible to begin preserving urine samples from all consenting people.Thus,medical research especially biomarker research can be conducted more economically.Even more objective large-scale prospective studies will be possible.This method has the potential to change the landscape of medical research and medical practice.

Preparation of high concentration polyaluminum chloride by chemical synthesis-membrane distillation method with self-made hollow fiber membrane

A method of direct contact membrane distillation （DCMD） with a self-made hollow polyvinylidene fluoride membrane was applied to prepare high concentration polyaluminum chloride （PACl） with high Alb content based on chemical synthesis. The permeate flux and Al species distribution were investigated. The experimental results showed that the permeate flux decreased from 14 to 6 kg/（m2·hr） at the end of the DCMD process, which can be mainly attributed to the formation of NaCl deposits on the membrane surface. The Alb content decreased slightly, only from 86.3% to 84.4%, when the DCMD experiment finished, correspondingly the Alc content increased slightly from 7.2% to 8.5%, and the Ala content remained at 7% during the whole DCMD process. A PACl with Alb content of 84% at total aluminum concentration 2.2 mol/L was successfully prepared by the chemical synthesis-DCMD method.

CoFe_(2)O_(4)nanoparticles anchored on waste eggshell for catalytic oxidation of florfenicol via activating peroxymonosulfate

Eggshell-loaded CoFe_(2)O_(4) catalyst was synthesized via a convenient hydrothermal method during our work,then the surface morphology and elemental composition of the composites were systematically investigated.Performance of CoFe_(2)O_(4)/eggshell-activated peroxymonosulfate(PMS)system was evaluated by selecting florfenicol(FF)as the model pollutant,and effects of operating parameters and water matrices on the FF removal efficiency in this system were investigated.In addition,main radicals involved in FF degradation were identified by EPR tests and radical quenching experiments,and possible mechanism was proposed.The reduction of toxicity during FF degradation was confirmed,and in combination with HP-LC tests,it was found that dehalogenation and defluorination were effectively carried out during FF degradation.In addition,the prepared CoFe_(2)O_(4)polyvinylidene fluoride(PVDF)membrane effectively improved the stability of the material and reduced the precipitation of metals.