Effect of additives concentration on the surface properties and performance of PVDF ultrafiltration membranes for refinery produced wastewater treatment

The aim of this study was to investigate the effect of pore-forming hydrophilic additives on the porous asymmetric polyvinylideneflouride (PVDF) ultrafiltration (UF) membrane morphology and transport properties for refinery produced wastewater treatment. PVDF ultrafiltration membranes were prepared via a phase inversion method by dispersing lithium chloride monohydrate (LiCl·H₂O) and titanium dioxide (TiO₂) nanoparticles in the spinning dope. The morphological and performance tests were conducted on PVDF ultrafiltration membranes prepared from a different additive content. The top surface and cross-sectional area of the membranes were observed using a field emission scanning electron microscope (FESEM) and energy dispersive X-ray (EDX) analysis. The surface wettability of porous membranes was determined by the measurement of a contact angle. The mean pore size and surface porosity were calculated based on the permeate flux. The results indicated that the PVDF/LiCl/TiO₂ membranes with lower TiO₂ nanoparticles loading possessed smaller mean pore size, more apertures inside the membrane with enhanced membrane hydrophilicity. LiCl·H₂O has been employed particularly to reduce the thermodynamic miscibility of dope which resulted in increasing the rate of liquid–liquid demixing process. The maximum flux and rejection of refinery wastewater using PVDF ultrafiltration membrane achieved were 82.50 L/m² h and 98.83% respectively at 1.95 wt.% TiO₂ concentration.     

Preparation and characterization of dimethyldichlorosilane modified SiO2/PSf nanocomposite membrane

Investigations on nanocomposite membranes imply that these hybrid materials recommend promising newgeneration membranes for gas separation in future. In this study, to investigate the effects of preparation parameters on the morphology and gas transport, various parameters including nanofiller content, surface modification and polymer concentration were considered. Two types of fumed silica nanoparticles (nonmodified and modified) were used to study the surface modification effect on agglomeration, void formation and gas separation properties of prepared membranes. Prepared nanocomposite membranes were characterized by scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) and tensile strength techniques. The gas permeabilities of hydrogen, methane, and carbon dioxide through pure PSf and nanocomposites were measured as a function of silica volume fraction, and permeability coefficients were determined using a variable pressure/constant volume experimental setup. Results showed that gas permeabilities increase with silica content, and proper H₂/CH₄ and H₂/CO₂ selectivities can be achieved with modified type of silica nanoparticles due to inhibition of particle agglomeration and bonding with polymer network. Hydrogen selectivity was improved by using 15 wt% polymer content instead of 9 wt% in preparation of nanocomposite membrane with same silica content. Gas permeation results indicated that increasing of feed pressure from 3 bar to 6 bar has a positive effect on selectivity of H₂/CH₄ but negligible effect on that of H₂/CO₂ for modified silica/PSf membrane.     

Magnetic electrospun fluorescent polyvinylpyrrolidone nanocomposite fibers

Magnetic nanoparticles (MNPs) were synthesized from facile thermodecomposition of iron pentacarbonyl and the subsequent silica coating on the MNP surface was achieved via a modified Stöber process to obtain the core–shell composite structured particles (MNPs-SiO₂). MNPs-SiO₂ were then incorporated into polyvinylpyrrolidone (PVP) to form nanocomposite fibers via an electrospinning process with optimized operational parameters such as polymer concentration, applied electrical voltage, feed rate and tip-to-collector distance. All these parameters show an unusual effect on the produced fiber diameter. Contrary to the conventional observation, i.e., increasing the applied voltage and feed rate or decreasing the distance could increase the fiber diameter; a reduced average fiber diameter was observed in this study and could be explained from the stretching and contraction force balance within the fiber during electrospinning. The size of the resulting PVP fibers is correlated to the corresponding rheological behaviors of the PVP solutions with different concentrations. The MNPs-SiO₂/PVP nanocomposite fibers exhibit a similar thermal decomposition temperature (386.3 °C) as that (387.8 °C) of pure PVP. Meanwhile, unique fluorescent and magnetic properties have been incorporated simultaneously in the nanocomposite fibers with the addition of small amount of MNPs-SiO₂ nanoparticles.     

Preparation and characterization of ZrO2/PES hybrid ultrafiltration membrane with uniform ZrO2 nanoparticles

In current or next-generation reuse systems, the development of new classes of antifouling membranes is needed before viable membrane-based approaches for wastewater reclamation can be achieved. In this study, ZrO₂/PES hybrid ultrafiltration membranes with uniform ZrO₂ nanoparticles were prepared by combining an ion-exchange process with a traditional immersion precipitation process. Hydrous ZrO₂ sol was synthesized by addition of anion-exchange resin in N,N-dimethylformamide solvent containing zirconyl chloride. Homogeneous ZrO₂/PES casting solution was then obtained by dissolving PES polymer in the ZrO₂ sol. The existence and dispersion states of ZrO₂ nanoparticles in the resultant membrane matrix were examined by X-ray photoelectron spectrometer, thermogravimetric analysis, scanning electron microscope and transmission electron microscope. The results indicate that the ZrO₂ nanoparticles were well dispersed throughout the PES matrix and the diameter of the formed nanoparticles was about 5–10 nm. The hydrophilicity of the membranes was determined by measuring the contact angles. The antifouling property was determined by antifouling experiments and atomic force microscopy. The results confirm that the existence of ZrO₂ nanoparticles improves the hydrophilicity and reduces protein adsorption of membranes.     

Inorganic nanoparticles incorporated in polyacrylonitrile-based mixed matrix membranes for hydrophilic,ultrafast, and fouling-resistant ultrafiltration

Mixed matrix membrane (MMM) structures and performances are greatly affected by the distribution of nanoparticles in the polymeric matrix. Until now, there has been little research on the effects of nanoparticle distribution states on polyacrylonitrile (PAN)-based MMM structures and performances. In this paper, different intermolecular interactions between nanoparticles and PAN molecules were generated by in situ fabricated amino-functionalized SiO₂ and TiO₂ nanoparticles to create absolutely different distribution states of nanoparticles in a PAN matrix. The results indicated that, due to the strong interactions between amino and cyano groups, SiO₂ is distributed in the PAN membranes homogeneously, while most of the TiO₂ migrates to the membrane's top surfaces or the walls of pores or even escape from the membranes during the nonsolvent index phase separation (NIPS) process. PAN-TiO₂ MMMs have more hydrophilic top surfaces, higher porosity, larger mean pore size, and stronger antifouling performances than pure PAN and PAN-SiO₂ membranes. The PAN-TiO₂ MMMs have an ultrahigh water flux of 1204.6 L/(m² h), which is more than 44 times that of PAN membranes. And the good pore structures and hydrophilicity of the membranes derived from special interactions between in situ TiO₂ nanoparticles and PAN molecules can give high-performance PAN-based ultrafiltration membranes a bright future. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47902.     

Paraffin wax emulsions stabilized with polymers,surfactants, and nanoparticles

Problems preparing paraffin wax emulsions stabilized by different types of emulsifiers have been discussed. The effect of the preparation conditions and stabilizers, such as polyethylene glycol and cetyl/oleyl alcohol ether (Eumulgin O10), polyvinyl alcohol, and SiO₂@Al₂O₃ nanoparticles (20 nm in diameter) on the dispersion of paraffin wax emulsions has been demonstrated. It has been noted that, in order to obtain paraffin wax particles with an average diameter of 400–500 nm, the concentration of PVA, Eumulgin O10, and SiO₂@Al₂O₃ nanoparticles must be equal to 0.5, 0.5, and 1.0 wt %, respectively.     

Composite membranes from polyacrylonitrile with poly(N,N-dimethylaminoethyl methacrylate)-grafted silica nanoparticles as additives

Polyacrylonitrile (PAN)-based composite membranes were prepared by immersion precipitation method by using poly(N,N-dimethylaminoethyl methacrylate)-grafted silica (PDMAEMA@SiO₂) nanoparticles as hydrophilic additives. The molecular weight of PDMAEMA were controlled by the surface initiated atom transfer radical polymerization of N,N-dimethylaminoethyl methacrylate on SiO₂ nanoparticles. The synthesized nanoparticles have a typical core–shell structure as characterized in detail by FT-IR, TEM, DLS and GPC. The prepared PAN-based composite membranes have higher porosity and water permeation flux than those of the pure PAN membranes. They also show high rejection (⩾90%) to bovine serum albumin and high flux recovery ratio (⩾90%) to water permeation. These improved performances are attributed to the good hydrophilicity of PDMAEMA@SiO₂ nanoparticles. The results suggest that PDMAEMA@SiO₂ nanoparticles are suitable for the property optimization of PAN-based composite membranes.     

Poly(vinylidene fluoride) ultrafiltration membranes containing hybrid silica nanoparticles: Preparation,characterization and performance

Poly(vinylidene fluoride) (PVDF) ultrafiltration membranes were prepared by immersion precipitation method using poly(hydroxyethyl methacrylate)-block-poly(methyl methacrylate) grafted silica (PHEMA-b-PMMA@SiO₂) nanoparticles as additives. The hybrid nanoparticles were synthesized by the surface initiated atom transfer radical polymerization (SI-ATRP), and they were characterized in detail by FT-IR, TEM, DLS and GPC. Results confirm that core–shell structure is formed after grafting PHEMA-b-PMMA brushes on the silica nanoparticles. Their average hydrodynamic diameter also increases with the prolongation of grafting time. After blending PVDF with the hybrid silica nanoparticles, the composite PVDF membranes exhibit high porosity and improved water permeation. Especially, when the molecular weight is 1.73 × 10⁵ g/mol for PHEMA-b-PMMA on the hybrid nanoparticles, the water flux of the PVDF composite membrane is 2.5 times than that of the control PVDF membrane, while the rejection to bovine serum albumin (BSA) remains at a high level (>90%). In addition, all the composite PVDF membranes show lower BSA adsorption and larger water flux recovery ratio than the control PVDF membrane. The improvement of membrane performance is attributed to the good hydrophilicity of PHEMA-b-PMMA@SiO₂ nanoparticles. Our results suggest that PHEMA-b-PMMA@SiO₂ nanoparticles with moderate molecular weight of PHEMA-b-PMMA are suitable for the property optimization of PVDF-based composite membranes.     

New versatile synthesis for low dimension superparamagnetic YBa2Cu3O7−x nanoparticles

This paper describes the synthesis and characterization of YBa₂Cu₃O_7−x (YBCO) nanoparticles obtained through an environmentally friendly chemistry approach. Y-, Cu- acetates and Ba trifluoroacetate were used for the synthesis of the precursor gel. Moreover, sucrose and pectin reagents were added as chelating agents inducing the formation of small size oxide nanoparticles. The thermal decomposition process of the precursor powder was investigated by thermal analysis correlated with mass spectrometry. The chemical nature, structure and morphology of the particles were investigated by X-Ray diffraction (XRD), Transmission Electron Microscopy (TEM) and Fourier Transform Infrared Spectroscopy. According to XRD analysis the nanoparticles have an orthorhombic structure and the average diameter between 18–30 nm, additionally confirmed by TEM measurements. The superparamagnetic behavior at room temperature of the YBCO nanoparticles has been clearly evidenced by magnetization measurements. Furthermore, the effect of the annealing atmosphere on the magnetic properties has been studied.     

Immobilization of Metalloporphyrin on Functionalized Magnetic Nanoparticles as a Catalyst in Oxidation of Cyclohexene: Novel Modified Fe3O4 Nanoparticles with Triethoxysilane Agent

Magnetic nanoparticles, Fe₃O₄, have been prepared and functionalized by (N-(3-(triethoxysilyl)propyl)isonicotinamide) and characterized by infrared spectroscopy, thermal analysis (TGA/DTA), X-ray powder diffraction, scanning electron microscopy, elemental analysis and BET surface area measurement. The functionalized Fe₃O₄ nanoparticles were used as a support to anchor metalloporphyrin. Application of immobilized metalloporphyrin as a heterogeneous catalyst in the oxidation of cyclohexene was explored. Effect of various parameters such as solvent and temperature on immobilization process and also various parameters (solvent, time, oxidant and axial group effect) on oxidation of cyclohexene has been investigated. The result showed that the immobilized metalloporphyrin on functionalized magnetic nanoparticles is an efficient and reusable catalyst for oxidation of cyclohexene.     

Influence of solvent and nanoparticles on the morphology and gas separation properties of copolyimide membranes

In this study, the effect of solvent type and nanoparticles of silica and zeolite 4A on the gas separation properties of polyimide (PI) membranes were investigated. Gas separation of the membranes based on pure solvents of dimethylformamide (DMF), n-methyl-2-pirrolidone (NMP), dimethylacetamide (DMAc), and dimethylsulfoxide (DMSO) were studied. The prepared PI membranes using DMAc and DMSO showed the highest selectivity and permeability, respectively. In this regard, the influence of their mixing on transport properties of the PI was evaluated. The prepared membrane using the mixture of DMSO/DMAc with the volume ratio of 1:3 showed the best gas separation performance in comparison to the Robeson's upper bound. Incorporation of 20 wt% of silica and zeolite 4A nanoparticles into the PI membrane indicated that the selectivity of CO₂/CH₄ increased from 39.4 to 57.6 and 68.5, respectively. Besides, gas transport properties of the PI-based mixed matrix membranes were satisfactory predicted by modified Maxwell model. Furthermore, characteristic parameters of the encapsulated particles by interfacial layer were determined.     

Poly(arylene sulfide sulfone) hybrid ultrafiltration membrane with TiO2‐g‐PAA nanoparticles: Preparation and antifouling performance

Poly(arylene sulfide sulfone) (PASS) is a kind of newly developed polymeric membrane material which has excellent mechanical strength, thermal stability, and solvent resistance. And, it would be a potential material for high temperature ultrafiltration and organic solvent filtration. In this article, PASS hybrid ultrafiltration membrane with improved antifouling property was prepared by mixing TiO₂ nanoparticles which were grafted with polyacrylic acid (PAA). These membranes were prepared by a phase inversion technique and their separation performance and antifouling property of the prepared membranes were investigated in detail by SEM, FTIR, EDS, contact angle goniometry, filtration experiments of water, and BSA solution. The results shown that the TiO₂‐g‐PAA nanoparticles dispersed well in membrane matrix, the hydrophilicity of the membranes prepared within TiO₂‐g‐PAA nanoparticles have been improved and these membranes exhibited excellent water flux and antifouling performance in separation than that of the pure PASS membranes and PASS membranes with TiO₂ nanoparticles. More specifically, among membrane sample M0, M1.5, and MP1.5, MP1.5 which contained 1.5 wt% TiO₂‐g‐PAA exhibited the highest water permeation (190.4 L/m² h at 100 kPa), flux recovery ratio, and the lowest BSA adsorption amount. POLYM. ENG. SCI., 55:2829–2837, 2015. © 2015 Society of Plastics Engineers     

Salt-assisted solution combustion synthesis of NiFe2O4: Effect of salt type

The effects of three types of salt including NaF, KCl, and NaCl on the properties of NiFe₂O₄ nanoparticles using salt-assisted solution combustion synthesis (SSCS) have been investigated. The synthesized powders were evaluated by SEM, TEM, FTIR, XRD, and VSM analysis. Also, the specific surface area (SSA), as well as size distribution and volume of the porosities of NiFe₂O₄ powders were determined by the BET apparatus. The visual observations showed that the intensity and time of combustion synthesis of nanoparticles have been severely influenced by the type of salt. The highest crystallinity was observed in the synthesized powder using NaCl. The SSA has also been correlated completely to the type of salt. The quantities of SSA was achieved about 91.62, 64.88, and 47.22 m²g^-1 for the powders synthesized by KCl, NaCl, and NaF respectively. Although the magnetic hysteresis loops showed the soft ferromagnetic behavior of the NiFe₂O₄ nanoparticles in all conditions, KCl salt could produce the particles with the least coercivity and remanent magnetization. Based on the present study, the salt type is a key parameter in the SSCS process for the preparation of spinel ferrites. Thermodynamic evaluation also showed that the melting point and heat capacity are important parameters for the proper selection of the salt.     

The Role of Solution and Coagulation Temperatures in Crystalline Structure,Morphology, Roughness,Pore Diameter Distribution,and Separation Properties of Nanoporous Membranes Fabricated Via Phase Inversion

In this study, fabrication of poly(vinylidene fluoride) (PVDF) flat sheet membranes and correlation of membrane morphology, roughness, crystalline structure, and pore diameter distribution as functions of coagulant temperature (T_C) and precursor-solution preparation temperature (T_S) in the phase inversion (PI) process of PVDF-DMF-H₂O mixture with 20%wt of PVDF concentration was investigated. The results demonstrated that membranes have a typical asymmetric structure with a dense skin top layer and a porous substructure. An increasing amount of macrovoids was observed in the membrane substructure when T_S is decreased. It was found that at lower T_C, the membrane solution precipitated into a uniform morphology composed of spherical crystallites that exhibited the β-form crystal structure. By contrast, when PVDF was precipitated at higher temperatures, the formed membrane became largely in the α-form crystal structure. The pore size was estimated by Barett-Joyner-Halenda (BJH) method, ranging from 15 nm to tenth of hundred nm, depending on T_C. The performance of the prepared membranes has been tested by the measure the effects of T_C and T_S on the separation characteristic of nanoporous PVDF membranes. We observed that the removal of Acid Yellow 23 (AY23) decreases as T_S increases and extremely high dye removal efficiency of 99.37% was achieved.     

Hydrophilic modification of polypropylene microporous membranes by grafting TiO2 nanoparticles with acrylic acid groups on the surface

Hydrophilic microporous membranes were prepared based on polypropylene (PP) cast films blended with a commercial acrylic acid grafted polypropylene (PP-g-AA) via melt extrusion followed by grafting titanium dioxide (TiO₂) nanoparticles on its surface, annealing and stretching. ATR-FTIR, XPS and EDS analyses showed that the hydrophilic segments of an amphiphilic modifier (PP-g-AA) acted as surface functional groups on the film surface. The results indicated that the presence of the modifier was very important for grafting TiO₂ nanoparticles on the film surface. Compared to PP and PP/PP-g-AA blend films, the water contact angle decreased by a factor of 2.5 after grafting TiO₂ on the surface of the films, meanwhile the water vapor permeability of the microporous membranes prepared from those films increased by a factor of 1.5. All these results indicated that the hydrophilicity of the modified PP membranes was improved.     

Techniques to manage geometry characteristics of hollow-fiber membranes

The process of the dry-wet spinning of asymmetric hollow-fiber membranes has been studied. The set of the parameters of spinning process, which allows the preparation of the smooth, round, and symmetric cross section of a fiber and the given inner and outer diameter so that the hollow-fiber membrane would finally appear as a smooth hollow cylinder, has been determined. The procedure was carried out using the fabrication of hollow fibers from poly(2,6-dimethyl-1,4-phenylene oxide) as an example. The samples with the oxygen permeance Λ/δ (O₂) = 400 L/(m² h bar) and the separation factor corresponding to the properties of material, α(O₂/N₂) = 4.5, have been obtained. The effective thickness of the selective layer of this membrane is 100 nm. The maximum diameter ratio that has been attained upon dry-wet spinning is 1.4 for the studied polymer solution–internal coagulant system.     

State-of-the-art membrane based CO2 separation using mixed matrix membranes (MMMs): An overview on current status and future directions

The main purpose of research in membrane gas separation is to develop membranes with high permeability and selectivity. Historically, the gas separation performance of polymeric membranes has been constrained to an upper performance limit. Hence, different methods have been investigated to prepare membranes that can exceed this limitation including the incorporation of inorganic materials into polymer matrices. Membranes formed by this method are called mixed matrix membranes (MMMs). The major challenge is to prepare a defect-free polymer/inorganic nanoparticles interfaces with enhanced separation performance and mechanical and thermal stability. For this purpose, various types of nanoparticles have been proposed and examined experimentally. This review is especially devoted to summarize the fundamental concepts that have to be considered to prepare various types of MMMs, including considerations for the design novel MMMs that will eventually surpass the Robeson's trade-off upper bound. In addition, it provides the pros and cons of various factors that affect the MMM preparation especially for CO₂ separation processes.     

Fe3O4 nanoparticle-coated boron nitride nanospheres: Synthesis,magnetic property and biocompatibility study

Hybrid nanocomposites consisting of uniform Fe₃O₄ nanoparticles and boron nitride (BN) nanospheres were synthesized via an ethanol-thermal reaction method. The spherical BN nanoparticles (BNNSs) with average diameter 150 nm have been uniformly coated with dense ultra-small Fe₃O₄ nanoparticles (with average diameter of 10 nm), forming novel Fe₃O₄@BNNS nanocomposites. Magnetic measurement by using vibrating sample magnetometer (VSM) indicates that the Fe₃O₄ coating is superparamagnetic, and the nanocomposites can be physically manipulated at a low magnetic field. Preliminary biocompatibility study has also been performed to evaluate the toxicity of the nanocomposites. The nanocomposites show cytocompatibility at low concentration and have little effect on cell viability of MCF-7, MCF-10 and Hela cell lines. The Fe₃O₄@BNNS nanocomposites may find a wide range of potential applications including water treatment, catalysts, carriers for boron neutron capture therapy and magnetic-targeted drug delivery.     

Chitosan- and dehydroascorbic acid-coated Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles: preparation,characterization and their potential as draw solute in forward osmosis process

Forward osmosis (FO) is a natural osmosis process that has attracted a significant attention due to its many advantages. However, the development of FO process depends on the development of proper draw solutions. In this work, chitosan (CS)-coated Fe₃O₄ nanoparticles and dehydroascorbic acid (DHAA)-coated Fe₃O₄ nanoparticles were successfully synthesized by co-precipitation method and their performance as draw solutes was investigated for application in FO systems. CS and DHAA could improve the surface hydrophilicity of the Fe₃O₄ nanoparticles. The synthesized nanoparticles were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometry (VSM) which the results presented a small size, crystalline morphology and high magnetization value for their structure as well as a good dispersion in water. Cellulose triacetate/cellulose acetate (CTA/CA)-based membranes were also prepared by immersion precipitation and used as FO membranes. The synthesized FO membranes were characterized by FESEM. The performance evaluation of synthesized nanoparticles revealed that the water flux of Fe₃O₄ nanoparticles capped with DHAA was higher than that of the chitosan-coated Fe₃O₄ nanoparticles. At the end of the process, the Fe₃O₄ nanoparticles were easily separated from the diluted draw solution by applying the magnetic field.     

Effect of SiO2 nanoparticle addition on the characteristics of a new organic-inorganic hybrid membrane

Poly(vinylidene fluoride) composite membranes filled with different weight fractions of SiO₂ nanoparticles have been prepared by a blending method. Cation-exchange groups were introduced by the copolymerization of glycidyl methacrylate with divinylbenzene and subsequent sulfonation. These hybrid membranes have been characterized by Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and water uptake and ion-exchange capacity measurements. Membrane potential and membrane conductivity measurements have been carried out with different counter ions to investigate the relationship between ionic migration and the SiO₂ nanoparticle content. The counter-ion transport number and permselectivity of these membranes are found to be highly dependent on the SiO₂ content in the membrane phase and the nature of the counter ion. Membrane conductance was analyzed in terms of phenomenological coefficients using non-equilibrium thermodynamic principles. It can be concluded that these hybrid membranes exhibit high thermal stability, improved selectivity, and moderate membrane conductivity, and may be suitable for use in the electro-driven separation processes.