Improvement of filtration performance of polyvinyl chloride/cellulose acetate blend membrane via acid hydrolysis

Based on the hydrophilicity and biodegradability of cellulose acetate (CA), polyvinyl chloride (PVC)/CA blend membrane was prepared by solution comixing and phase transformation method. Then the CA in the blend membrane was partially hydrolyzed under acidic conditions to improve the hydrophilicity of the blend membrane, so as to improve the filtration performance of the PVC/CA blend membrane. The properties of the membranes were systematically characterized by Fourier transform infrared spectroscopy, differential scanning calorimeter, and scanning electron microscopy (SEM). The porosity, water contact angle, pure water flux (PWF), protein retention rate, and mechanical properties of the membrane were measured, and the effect of hydrolysis on the filtration performance of the blend membrane was analyzed. The results showed that the hydrophilicity and porosity of the blend membrane increased, the PWF and protein rejection rate enhanced after acid catalyzed hydrolysis, while the mechanical properties of PVC membrane were maintained. This simple preparation method endows PVC/CA blend membrane with desirable filtration performance, and also helps to overcome the disadvantages of poor hydrophilicity and easy pollution of pure PVC membrane.     

Cellulose acetate ultrafiltration membranes reinforced by cellulose nanocrystals: Preparation and characterization

Cellulose nanocrystals (CNCs) were used as a sustainable additive to improve the hydrophilicity, permeability, antifouling, and mechanical properties of blend membranes. Different CNC loadings (0–1.2 wt %) in cellulose acetate (CA) membranes were studied. The blend membranes were prepared by a phase‐inversion process, and their chemical structure and morphological properties were characterized by attenuated total reflectance–Fourier transform infrared spectroscopy, scanning electron microscopy, porosity, and mean pore size and contact angle measurement. The blend membranes became more porous and more interconnected after the addition of CNCs. The thickness of the top layer decreased and a few large holes in the porous substrate appeared with increasing CNC loading. In comparison with the pure CA membranes, the pure water flux of the blend membranes increased with increasing CNC loading. It reaches a maximum value of 76 L m^?2 h^?1 when the CNC loading was 0.5 wt %. The antifouling properties of the CA membrane were significantly improved after the addition of CNCs, and the flux recovery ratio value increased to 68% with the addition of 0.5 wt % CNCs. In comparison with that of the pure CA membranes, the tensile strength of the composite membranes increased by 47%. This study demonstrated the importance of using sustainable CNCs to achieve great improvements in the physical and chemical performance of CA ultrafiltration membranes and provided an efficient method for preparing high‐performance membranes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43946.     

Interfacial Properties of Ethyl Cellulose/Cellulose Acetate Blends by HPLC

The high performance liquid chromatography method (HPLC) with ethyl cellulose/cellulose acetate (EC/CA) blends and EC as column packing material, and small molecular weight compound as probe molecules was employed to measure the retention volume (VR) and equilibrium distribution coefficient (K) of both inorganic and organic solutes. The interfacial separation properties of EC/CA blends were characterized by the HPLC data. The effects of the blends on the interfacial adsorption properties, hydrophilicity, affinity, polar and non-polar parameters of EC membrane materials were studied subsequently. The research results indicate that the interfacial adsorption properties and hydrophilicity of EC have been improved by solution blending with CA. The alloys are superior to EC in the separation efficiency for non-dissociable polar organic solute. The EC/CA alloy (80:20, w) is suitable for desalting and desaccharifying.     

High performance forward osmosis cellulose acetate (CA) membrane modified by polyvinyl alcohol and polydopamine

Cellulose acetate (CA) is a low cost and readily available material widely used in forward osmosis (FO) membranes. However, the performance of pure CA membranes is not good enough in salt separation and the traditional modification methods are generally multistep and difficult to control. In this paper, we reported high performance cellulose acetate (CA) composite forward osmosis (FO) membranes modified with polyvinyl alcohol (PVA) and polydopamine (PDA). PVA was first cross-linked onto the surface of CA membranes, and then PDA was coated with a rapid deposition method. The membranes were characterized with respect to membrane chemistry (FTIR and XPS), surface properties comprising wettability (by water contact angle), and osmosis performance. The modified membrane coated by PVA and PDA shown better hydrophilicity and exhibited 16.72 LMH osmotic water flux and 0.14 mMH reverse solute flux with DI water as feed solution and 2.0 M NaCl as draw solution and active layer facing the feed solution. This simple and highly effective modification method makes it as an excellent candidate for further exploration for FO.     

Cellulose acetate ultrafiltration membranes customized with copper oxide nanoparticles for efficient separation with antifouling behavior

Cellulose acetate (CA) nanocomposite ultrafiltration membranes are fabricated with copper oxide (CuO) nanoparticles with the aim of improving efficient protein separation and antifouling performance. CuO nanoparticles are synthesized from cupric nitrate using a wet precipitation method and characterized by FTIR and XRD. CA/CuO nanocomposite membranes fabricated using 0.5, 1.0, and 1.5 wt% of CuO nanoparticles individually by simple phase inversion technique. The CA nanocomposite membrane with 0.5 wt% of hydrophilic CuO exhibited enhanced PWF of 118.6 Lm⁻² h⁻¹ due to the improvement in porosity and water uptake. This is in good agreement with the enhanced hydrophilicity of the CA/CuO nanocomposite membranes results observed in surface contact angle and morphological investigations. Further, 95.5% of BSA separation and 94.7% of flux recovery ratio (FRR) indicates its superior antifouling potential caused due to the presence of the hydration layer at the CA/CuO membrane surface. Among all the fabricated membranes, the CA-0.5 nanocomposite membrane with 0.5 wt% of CuO exhibited superiorly improved hydrophilicity, water permeation, BSA separation, and antifouling performance indicates its potential use in water and wastewater treatment applications.     

Preparation of high‐flux ultrafiltration membranes by blending strongly charged polymer

Three kinds of high‐flux ultrafiltration membranes were fabricated by blending strongly charged polymer [sulfonated poly(phenylene oxide) (SPPO)] with neutral polymer [cellulose acetate (CA), polyethersulfone (PES), or polyvinylidene fluoride (PVDF)]. After blending with SPPO, the pure water flux of CA‐SPPO, PES‐SPPO, and PVDF‐SPPO membrane increase by 3, 76, and 30 times at a transmembrane pressure of 100 kPa. Compared with the unblended membranes, the pore radius of CA‐SPPO, PES‐SPPO, and PVDF‐SPPO membrane increased from 31.9 to 33.2 nm, 26.1 to 28.6 nm, and 19.8 to 25.7 nm, respectively. The addition of strongly charged polymer decreased the thermodynamic stability of casting solutions, promoting the phase inversion process and resulting in highly porous structure. The charged groups and hydrophilicity of the polymer facilitate the formation of an additive concentration gradient (more additive in the active layer), endowing the blend membrane with better hydrophilicity and greater wettability gradient. The high porosity, good hydrophilicity, and larger wettability gradient enable the high permeation of blend membranes. This work shows how the strongly charged polymer affects the formation and performance of blend membrane, which will be useful for designing high‐performance membrane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44570.     

Preparation,characterization and performance of cellulose acetate ultrafiltration membranes modified by charged surface modifying macromolecule

A charged surface modifying macromolecule (cSMM) was synthesized, characterized by FT-IR spectroscopy and blended into the casting solution of cellulose acetate (CA) to prepare surface modified UF membranes by phase inversion technique. With an increasing cSMM additive content from 1 to 4 wt%, pure water flux (PWF) and water content (WC) were increases whereas the hydraulic resistance decreases. Surface characteristic study reveals that the surface hydrophilicity increased in cSMM modified CA membranes. The pore size and surface porosity of the 4 wt% cSMM blend CA membranes increases to 41.26 Å and 0.015%, respectively. Similarly, the molecular weight cut-off (MWCO) of the membranes ranged from 20 to 45 kDa, depending on the various compositions of the prepared membranes. Lower flux decline rate (47.2%) and higher flux recovery ratio (FRR) (89.0%), exhibited by 4 wt% cSMM blend membranes demonstrated its fouling resistant characteristic compared to pristine CA membrane.     

Preparation of blend polyethersulfone/cellulose acetate/polyethylene glycol asymmetric membranes for oil–water separation

Blend PES/CA hydrophilic membranes were prepared via a phase-inversion process for oil–water separation. PEG-400 was introduced into the polymer solution in order to enhance phase-inversion and produce high permeability membranes. A gas permeation test was conducted to estimate mean pore size and surface porosity of the membranes. The membranes were characterized in terms of morphology, overall porosity, water contact angle, water flux and hydraulic resistance. A cross-flow separation system was used to evaluate oil–water separation performance of the membranes. From FESEM examination, the prepared PES/CA membrane presented thinner outer skin layer, higher surface porosity with larger pore sizes. The outer surface water contact angle of the prepared membrane significantly decreased when CA was added into the polymer solution. The higher water flux of the PES/CA membrane was related to the higher hydrophilicity and larger pore sizes of the membrane. From oil–water separation test, the PES/CA membrane showed stable oil rejection of 88 % and water flux of 27 l/m² s after 150 min of the operation. In conclusion, by controlling fabrication parameters a developed membrane structure with high hydrophilicity, high surface porosity and low resistance can be achieved to improve oil rejection and water productivity.     

Preparation and characterization of PES/CA microporous membranes via reverse thermally induced phase separation process

The blend polyethersulfone (PES)/cellulose acetate (CA) flat‐sheet microporous membranes were prepared by reverse thermally induced phase separation (RTIPS) process. The effects of CA content and coagulation bath temperature on membrane structures and properties were investigated in terms of membrane morphology, water contact angle, permeation performance, and mechanical properties. The cloud point results indicated that the cloud point decreased with the increasing content of CA. When the coagulation bath temperature was lower than the cloud point, the membrane formation process underwent nonsolvent induced phase separation (NIPS) process and dense skin layer and finger‐like structure were formed in membranes. These membranes had lower pure water flux and poor mechanical properties. But when the coagulation bath temperature was higher than the cloud point, the membrane formation process underwent RTIPS process. The porous top surface as well as porous cross‐section of the membranes were formed. Therefore, high pure water flux and good mechanical properties were obtained. The contact angles results indicated that the hydrophilicity of the prepared membranes improved obviously with the addition of CA. When the content of CA was 0.5 wt% and the membrane formation temperature was 323K, the PES/CA microporous membrane which was prepared via the RTIPS process displayed a optimal permeability of the pure water flux of 816 L m^?2 h^?1 and the BSA rejection rate of 49.5%, which showed an increase of 48.9% and 23.6% than that of pure PES membrane, respectively. Moreover, the mechanical strengths of the membranes obtained by RTIPS process were better than those membranes prepared by NIPS process. POLYM. ENG. SCI., 58:180–191, 2018. © 2017 Society of Plastics Engineers     

Synthesis,characterization, and anti-fouling properties of cellulose acetate/polyethylene glycol-grafted nanodiamond nanocomposite membranes for humic acid removal from contaminated water

Polyethylene glycol-grafted nanodiamond (ND-PEG) was synthesized from pristine detonation NDs and utilized to prepare novel cellulose acetate/polyethylene glycol-grafted nanodiamond(CA/ND-PEG)nanocomposite membranes. Due to unique thermal, mechanical, and antibacterial properties and very easy cleaning of fouled ND-embedded CA nanocomposite membranes, we tried to investigate the performance of CA/ND-PEG membrane for humic acid (HA) removal from contaminated water. Surface functionalization was confirmed by Fourier transform infrared spectroscopy and thermogravimetry analysis. Pristine and functionalized ND with different concentration was added in the casting solution containing CA. The prepared membranes were characterized using contact angle, mechanical strength, scanning electron microscopy (SEM), transmission electron microscopy, and permeation tests. SEM micrographs of the surface of the membranes depicted the increase in the number of pores by the addition of ND and especially ND-PEG into polymer matrix. The results indicated that the nanocomposite membrane with 0.5 wt% ND-PEG exhibited excellent hydrophilicity, mechanical properties, permeability, high rejection, high abrasion resistance, and good anti-fouling performance. The HA adsorption on the membrane surface decreased from 2.85 to 2.15 mg cm^?2 when the ND-PEG content increased from 0 to 0.5 wt%. Most importantly, the HA filtration experiments revealed that the incorporation of ND and especially ND-PEG particles reduced membrane irreversible fouling, dramatically. Meanwhile, the analysis of the fouling mechanism based on Hermia’s model revealed that cake formation is a prevailing mechanism for all membranes.     

Performance adjustable porous polylactic acid-based membranes for controlled release fertilizers

Here, the phase inversion method using a mixture of chloroform and acetone as a solvent was adopted to fabricate a series of porous polylactic acid (PLA)-based membranes for controlled release fertilizers (CRFs). Cellulose acetate (CA) was used as an additive; polyethylene glycol (PEG) and nano-SiO₂ were used as porogens. Our first interest is to investigate effects of the amount of additive and porogen and type of porogens on the resulting membranes' performance. Results show the dialysis coefficient for membrane M1-3 (CA content of 2%) is nearly 20 times higher than that for M0-1 (CA content of 0%), suggesting that the addition of CA can promote the membrane's permeability. Porogens can increase membranes' hydrophilicity, dialysis coefficient and nutrient release rate. However, there is no obvious performance difference between membranes with different porogens. Secondly, M1-2 (no porogen), M2-2 (nano-SiO₂ content of 0.5%) and M3-2 (PEG content of 0.5%) were selected to coat urea granules. Results show the nutrient release rate of urea coated by M2-2, M3-2 is much higher than that of urea coated by M1-2. This research suggests the resulting membranes' performance is easily adjustive and they can be applied to prepare various CRFs to fertilize various crops.     

Cellulose membranes for reverse osmosis Part I. RO cellulose acetate membranes including a composite with polypropylene

With the aim of obtaining RO membranes for brackish water desalination from purified celluloses (cotton linters and bleached bagasse pulp), two reactions (heterogeneous and homogeneous) were applied for the synthesis of cellulose acetate (CA). The efficiency of the membranes was measured and compared with those prepared from purchased CA and prepared CA by acetylation of imported high-grade viscose wood pulp. The effect of blending CA with polypropylene (PP), on the efficiency of the prepared RO membranes was also studied. Results showed that the method of preparation of CA plays a profound effect on the salt rejection and water flux of the RO membranes. The efficiencies of RO membranes formed from heterogeneously acetylated celluloses are higher than those prepared from homogeneous ones. Blending the acetylated cellulose with 9% PP wastes improves the efficiency of membranes prepared from the homogeneously acetylated celluloses.     

Poly(vinylidene fluoride)–polyacrylonitrile blend flat‐sheet membranes reinforced with carbon nanotubes for wastewater treatment

In this reported study, poly(vinylidene fluoride) (PVDF) and polyacrylonitrile (PAN) blend flat‐sheet membranes were prepared via a phase‐inversion method with various loadings of multiwalled carbon nanotubes. The effects of the carbon nanotubes (CNTs) on the performance and morphology of the PVDF–PAN composites were investigated via tests of the pure water flux and rejection of bovine serum albumin, scanning electron microscopy, atomic force microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, thermogravimetric analysis, and contact angle (CA) analysis. The experimental results demonstrate that the CNTs contributed to the improvement of the flux and hydrophilicity of the membranes. The maximum value of the flux was 398.1 L m^?2 h^?1, and the value of CA for the composite membranes was found to be 48°. In addition, the results of the mechanical properties tests illustrate that the brittleness and plasticity of the hybrid membranes were greatly improved by the presence of the CNTs. The flux recovery ratio was maintained at 75%; this demonstrated that the PVDF–PAN membranes enhanced with the CNTs possessed good antifouling performance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46155.     

Development of a novel graphene oxide-blended polysulfone mixed matrix membrane with improved hydrophilicity and evaluation of nitrate removal from aqueous solutions

In this study, four types of mixed matrix membranes were fabricated using polysulfone (as the base polymer) and different contents of graphene oxide (GO) nanosheets (as modifier) through wet phase inversion method. Based on the amounts of GO (0, 0.5, 1, and 2?wt%), the synthesized membranes named as M1, M2, M3, and M4, respectively. The membranes characteristics were evaluated using FE-SEM, FT-IR, and water contact angle measurements. In addition, the performance of the prepared membranes was investigated in terms of basic parameters: filtrate water flux, nitrate removal efficiency, and antifouling properties. Results showed significant improvements of the characteristics of modified membranes with GO. Accordingly, the permeability and hydrophilicity were enhanced and water flux was considerably improved. At operating pressure of 4?bar and nitrate concentration of 110?mg/L, the removal efficiency for unmodified membrane (M1) was 15.5% and for modified M2, M3, and M4 membranes were 22.78%, 39.12%, and 41.37%, respectively. In addition, the results of flux recovery ratio (FRR) showed that the anti-fouling properties of the GO modified membranes were improved due to the increase in membrane surface hydrophilicity.     

Fabrication and characterization of high flux poly(vinylidene fluoride) electrospun nanofibrous membrane using amphiphilic polyethylene-block-poly(ethylene glycol) copolymer

Electrospun nanofiber membranes (ENM) made of polymers such as polysulfone and poly(vinylidene fluoride) (PVDF) have a much higher contact angle (CA) and also more hydrophobic when compared to the virgin polymers. For water treatment applications, membranes with hydrophilic nature are highly desirable in order to achieve high flux and less fouling potentials. Hence, in the present study, highly hydrophilic electrospun nanofiber membranes (ENMs) were prepared by blending PVDF polymer with amphiphilic polyethylene-block-poly (ethylene glycol) (PE-b-PEG) copolymer. Resulting amphiphilic ENMs were highly porous (77%–92%) and the breaking elongation of 140% with a young's modulus of 2.55 MPa was observed. When compared with the control PVDF membrane, PE-b-PEG blended ENMs revealed higher water permeation flux owing to the enrichment of the hydrophilic PEG segments at the membrane surface, which was confirmed by using X-ray photoelectric spectroscopy and Energy-dispersive spectroscopy measurements. When compared to the phase inversion process (CA of 97.3°) blended ENM had CA of 0°, which indicates that besides hydrophilic block copolymer segments, the nature of membrane formation also contributes its role in influencing the hydrophilicity of the membrane. This improved hydrophilicity in combination with larger pore sizes of the PVDF/ PE-b-PEG membranes have contributed to enhancement of pure water flux, protein solution permeability and water flux recovery, which can be applied potentially for water treatment applications.     

用于油水分离的非化学计量掺杂Ce纳米SiO_2聚砜复合膜的研究

为提高膜分离法对油水分离的效果,减小油质对膜的污染,采用非化学计量掺杂Ce纳米SiO2聚砜(PSF)复合膜对油田回注水进行处理.通过对复合膜的拉伸强度、亲水性和ESEM性能测试并将其应用于油水分离试验可知,纳米SiO2复合粒子添加量为PSF质量的10%时,复合膜的机械强度最大,接触角为最小值41.7°.以此含量制得的复合膜的渗透通量最大,且随着操作时间的进行该复合膜的渗透通量下降的最慢,表明复合膜的耐污染能力得到增强;同时此复合膜对油的截留率高于98%,处理后的水样符合国家水质排放标准.     

Clay-hyperbranched epoxy/polyphenylsulfone nanocomposite membranes

Nanocomposite membranes containing polyphenylsulfone (PPSU) and a clay modified with a hyperbranched epoxy (HBE) were prepared by blending of modified montmorillonite (m-MMT) with a polymer solution using phase inversion method. The hyperbranched epoxy synthesized by polycondensation reaction of bisphenol A and triethanolamine with epichlorohydrin was grafted to amine-functionalized MMT by reaction between the epoxy groups of hyperbranched epoxy and the amine groups on the MMT surface. In this way, the m-MMT was exfoliated into single layers of nanoparticles in a solvent medium and the polymer chains were intercalated into m-MMT layers. The aim was to study the effect of this additive on the membrane separation efficiency. For this purpose, pure water flux, fouling, and pigment and heavy metal rejection were measured by a home-made dead end filtration cell and the performance of the prepared membranes was investigated. Hydrophilicity of the nanocomposite membranes was specified by water contact angle measurements. Degree of dispersion of additive into the polymer matrix and membrane morphology were studied by FESEM. Membrane surface area, pore size, and volume were evaluated by BET. The results indicated that the surface hydrophilicity increased after incorporation of m-MMT. Furthermore, the water permeability, salt rejection, and antifouling resistance of PPSU membranes were improved significantly. Membrane with 3 wt% m-MMT showed the best performance compared to other membranes.     

Effects of Gelatin and Nano-ZnO on the Performance and Properties of Cellulose Acetate Water Membranes

Biodegradable cellulose acetate (CA) membranes were prepared via phase inversion induced by immersion precipitation method. Acetic acid and deionized water were used as solvent and non-solvent, respectively. The modifying effect of gelatin and zinc oxide (ZnO) nanoparticles additives was investigated on the membranes in terms of water flux, protein rejection percentage, and fouling ability during two hours of bovine serum albumin separation from aqueous solution. Specimens were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), tensile test, contact angle technique, and porosity measurement. The incorporation of gelatin and ZnO nanoparticles into the CA matrix increased the porosity coefficient and hydrophilicity. Moreover, gelatin improved the tensile properties of the membrane.     

Preparation and characterization of modified ultrafiltration nylon 6 membrane modified by poly (acrylamide-co-maleic anhydride)

In attempt to prepare modified ultrafiltration (UF) Nylon 6 membrane and improve its hydrophilicity and anti-fouling performance, poly (acrylamide-co-maleic anhydride)(AM-MA) was utilized as hydrophilic copolymer additive in the dope solution. The UF Nylon 6/AM-MA membranes were synthesized through blending Nylon 6 with poly(AM-MA) using a phase inversion process. Characterization of the prepared membranes for morphological studies and thermal behavior was carried out by SEM and DSC instruments respectively. The SEM photos demonstrated that by increasing the copolymer density in the dope solution, the morphology was changed from spongy to bi-continuous, composed of small interlocked and stick-like crystallites. FTIR/ATR and water contact angle data also confirmed the existence of AM-MA copolymer on the blend membranes surface. Furthermore, the effect of different molecular weights and concentration of hydrophilic copolymer on filtration performance and antifouling properties were experimentally studied. The results exhibited that the blend UF membranes possessed better water flux permeability than pure Nylon 6 membrane due to the increased surface hydrophilicity and porosity. Fouling resistance experiments revealed that the surface anti-fouling ability of the blend membranes was improved via the addition of AM-MA copolymer with lower MW (co1) to the cast solution, while this parameter was weakened in higher MW of copolymer (co2).     

Facile surface modification of PVDF microfiltration membrane by strong physical adsorption of amphiphilic copolymers

To endow the surface of poly(vinylidene fluoride) (PVDF) microfiltration (MF) membranes with hydrophilicity and antifouling property, physical adsorption of amphiphilic random copolymers of poly(ethylene glycol) methacrylate (PEGMA) and poly(methyl methacrylate) (PMMA) (P(PEGMA‐r‐MMA)) onto the PVDF membrane was performed. Scanning electron microscopy (SEM) images showed that the adsorption process had no influence on the membrane structure. Operation parameters including adsorption time, polymer concentration, and composition were explored in detail through X‐ray photoelectron spectroscopy (XPS), static water contact angle (CA), and water flux measurements. The results demonstrated that P(PEGMA‐r‐MMA) copolymers adsorbed successfully onto the membrane surface, and hydrophilicity of the PVDF MF membrane was greatly enhanced. The antifouling performance and adsorption stability were also characterized, respectively. It was notable that PVDF MF membranes modified by facile physical adsorption of P(PEGMA₅₈‐r‐MMA₃₃) even showed higher water flux and better antifouling property than the commercial hydrophilic PVDF MF membranes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3112–3121, 2013