Gas-phase photoinduced graft polymerization of acrylic acid onto polyacrylonitrile ultrafiltration membranes

Heterogeneous surface modification of polyacrylonitrile (PAN) ultrafiltration (UF) membranes is realized with UV irradiation-initiated graft polymerization of acrylic acid (AA) from the gas phase onto photoinitiator (benzophenone, BP)-coated samples. In the absence of monomer, PAN functionalization by ketyl radicals dominates after UV excitation of sorbed BP. With AA, graft and total polymer yield increase with BP loading and UV irradiation time. Average molecular weight and distribution of PAA homopolymer—formed in parallel during graft polymerization—are analyzed with gel permeation chromatography. Morphology of PAN-gr-AA UF membranes is checked with scanning electron micrographs (SEMs) and atomic force microscopy. Chemical changes are characterized with FTIR-ATR spectroscopy and SEM/EDX analyses, indicating a pronounced surface selctivity of the graft polymer modification (localized in the upper 5-μm membrane thickness). The amount of grafted PAA systematically reduces membrane permeability and increases dextrane retention, as verified in UF experiments. Photo graft polymer modificationof UF membranes will be applied to adjust membrane performance by controlling surface hydrophilicity and permeability using other monomers and/or further graft polymer functionalization. © 1995 John Wiley & Sons, Inc.     

紫外键联马来酸酐表面改性聚丙烯腈超滤膜

采用紫外光法将马来酸酐（MAH）单体键联到聚丙烯腈（PAN）超滤膜表面,考察了紫外光强度、辐射时间、光敏剂浓度以及单体浓度对MAH反应率的影响。采用衰减全反射-傅里叶红外光谱（ATR /FT-IR）、扫描电镜（SEM）和水接触角（CA）对改性膜和原膜进行表征,结果表明单体MAH已成功键联到PAN膜表面,膜表面的亲水性得到提高。蛋白质静态污染以及超滤实验表明马来酸酐键联改性对PAN膜水通量影响不大,但抗污染性能得到明显提高,且由于MAH含有酸酐基团,使PAN膜的可反应性大大提高,使PAN膜易于进一步改性。     

Nanoparticles modified Polyacrylonitrile/Polyacrylonitrile – Polyvinylidenefluoride blends as substrate of high flux anti-fouling nanofiltration membranes

Thin-film composite nanofiltration membranes were prepared by interfacial polymerization reaction of piperazine and trimesoylchloride on virgin and nanoparticles (SiO₂/TiO₂) modified Polyacrylonitrile/70:30 and 30:70 Polyacrylonitrile – Polyvinylidenefluoride blend ultrafiltration substrates. The membranes were characterized for surface hydrophilicity and potential, surface and cross-sectional morphology and equilibrium water content. Pure water permeability and differential rejection of multi (MgSO₄) and monovalent salts (NaCl) of the membranes were studied. Nanofiltration (NF) membranes prepared on nanoparticle modified UF substrates exhibit higher flux than the membranes prepared on virgin UF substrates. NF membranes prepared on TiO₂ modified substrates are exhibiting higher flux than the other membranes. Membrane prepared on TiO₂ modified 70:30 blend substrate exhibits the highest rejection ratio (4.63) of divalent to monovalent salts. Nanofiltration membranes prepared on nanoparticle modified substrates are displaying comparatively higher flux recovery ratio (FRR) and lower total fouling ratio (TFR) values than the NF membranes prepared on virgin ultrafiltration substrates.     

Flux,antifouling and separation characteristics enhancement of nanocomposite polyethersulfone mixed-matrix membrane by embedding synthesized hydrophilic adipate ferroxane nanoparticles

Polyethersulfone (PES) nanofiltration (NF) membranes were prepared by blending of synthesized hydrophilic adipate ferroxane nanoparticles (AFNPs) as a novel multifunctional nanofiller via the phase inversion method. The water contact angle measurement indicated the higher hydrophilicity of the NF membranes. The water flux of the membranes improved significantly after the addition of AFNPs, from 10.4 to 32.2 kg/m²h. Antifouling characteristics of AFNPs/PES membranes were improved by increased hydrophilicity and decreased membrane surface roughness. The 0.6 wt% AFNPs/PES membrane exhibited the highest FRR (96%) and the lowest irreversible fouling resistance (6%). The nanofiltration performance of the prepared membranes was evaluated by dye removal and salt retention. The results proved the high dye removal capability of modified membranes (98% rejection) compared with the unfilled PES membrane (89% rejection). The salt retention sequence for membrane with 0.2 wt% of nanoparticles was Na₂SO₄ (70%)>MgSO₄ (60%)>NaCl (18%).     

New polymeric membrane nanofiltration for succinate recovery: a comparative study

Bio-based succinic acid recovery from fermentation broth has remained a challenge in the separation industry due the presence of by-products with similar physicochemical properties. In this work, the selective separation of succinate from succinate model solutions and the actual fermentation broth were investigated using newly fabricated polyimide P84 (PI) nanofiltration (NF) membrane and compared with three types of commercial pressure filtration membranes namely NF1, NF2 and NF270. Results show that PI membrane demonstrated comparable inorganic salt rejections performance as the commercial NF membranes of 86% and 99% for NaCl and Na₂SO₄, respectively. However PI shows much lower surface roughness, beneficial in reducing the fouling effect. PI also demonstrated equivalent performance for succinate permeation flux and retention at high concentration as the commercial membranes. PI exhibited high succinate retention (95%) in actual fermentation broth, equivalent to the commercial membranes (92–99%) and also higher selectivity factor (SF) < 0.14 compared to the NF1 membrane, SF < 0.19. Thus the PI membrane could give better succinate recovery against other carboxylates in the fermentation broth than the commercial membranes.     

Evaluation of a modified spray-applied interfacial polymerization method for preparation of nanofiltration membranes

Nanofiltration (NF) membranes were fabricated by using piperazine (PIP) and trimesoyl chloride (TMC) by conventional and spray-applied interfacial polymerization methods, studying the effect of the application method for both phases, the number of applied layers, and the displacement speed for the spray application. A polysulfone ultrafiltration membrane was used as support. NF membranes were characterized by different spectroscopic, microscopic, and physicochemical techniques. Rejection capacity was evaluated for sodium chloride (NaCl), sodium sulfate (Na₂SO₄), and magnesium sulfate (MgSO₄) salts; the decreasing rejection order was Na₂SO₄ > MgSO₄ > NaCl for each NF membrane. NF membrane prepared with one layer of the sprayed out TMC solution and conventional application of PIP solution exhibited the highest salt rejection (99% for 1000 ppm Na₂SO₄) and a permeated flux of 10.28 L m⁻² h⁻¹ at 0.55 MPa. The modified method is a facile-reproducible preparation methodology that reduces the consumption of time, effort, and reagents leading to a scalable manufacturing process for separation technology. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48129.     

Green lignin-based polyester nanofiltration membranes with ethanol and chlorine resistance

As the main water treatment material, polymeric membranes inevitably suffer from membrane fouling. In this work, novel lignin-based polyester composite nanofiltration membranes (NFM) with ethanol and chlorine resistance were fabricated via interfacial polymerization. Lignin alkali (LA), a green lignin derivative, typically treated as chemical waste in the paper industry, was employed as the aqueous monomer, trimesoyl chloride (TMC) is served as the organic monomer. The structure and separation properties of the lignin-based NFM were studied, revealing that the dense polyester separation layer may show good performance for dye removal. The rejections of the optimized LA/TMC-3 membrane with an excellent permeation flux of 13.9 kg m^?2?h^?1 for rose Bengal sodium salt, brilliant blue, congo red, rhodamine B, MgSO₄, and NaCl are 97.6%, 97.3%, 97.8%, 71.34%, 51.4%, and 31.8%, respectively. Moreover, the LA/TMC-3 membrane also shows long-term tolerance in ethanol and sodium hypochlorite solution; the rejection of LA/TMC-3 to dye only decreases 8% after 8 days when immersed in alcohol, while the normalized rejection maintains 94% after 4000 ppm-hours of continuous exposure to chlorine. This lignin-based polyester membrane may broaden the sustainable utilization sphere of lignin derivatives, at that provide a referable direction for the development of membrane materials.     

Separation performance of thin-film composite nanofiltration membrane through interfacial polymerization using different amine monomers

Four kinds of thin-film composite (TFC) membranes were prepared via interfacial polymerization using diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and piperazidine (PIP) as water-soluble monomer, and trimesoyl chloride (TMC) as organic-soluble monomer. The surface chemical features of the resultant membranes were confirmed by contact angle measurement and Fourier transform infrared spectroscopy (FTIR). The membrane morphology and surface charges were investigated through Scanning electronic microscopy (SEM) and Zeta potential, respectively. Salt rejection was used to evaluate the separation performance of the four kinds of TFC membranes. The results showed that all the four kinds of TFC membranes exhibited typical negatively charged nanofiltration membrane characteristics. The salt rejections followed the sequence: Na₂SO₄ > MgSO₄ > MgCl₂ and the rejection of Na₂SO₄ was all over 80%. It was also found that the solubility of water-soluble monomer in organic solvent played an important role in manipulating the membrane structure, charge properties and thus the separation performance.     

Enhanced desalination performance and arsenate removal using semi-aromatic polyamide-based pervaporation membranes by modifying with amino-acids via interfacial polymerization

In this study, the semi-aromatic polyamide membranes were synthesized by the interfacial polymerization between piperazine (PIP) monomers in the water phase and Benzene-1,3,5-tricarbonyl chloride in the organic phase. To further modify the semi-aromatic pervaporation membrane, the two amino acids, glycine, and l -lysine, were mixed with PIP monomers for interfacial polymerization. The morphology and physicochemical properties of the synthesized membranes were analyzed using Fourier transform infrared (FTIR), field emission scanning electron microscope (FE-SEM), atomic force microscope (AFM), and contact angle measurements. The results show that the semi-aromatic polyamide membranes modified by the two amino acids possess a higher hydrophilic surface and lower thickness compared to the unmodified membrane. Additionally, the permeation flux of the semi-aromatic polyamide membranes was improved by 18.6% and 38.5% as modified with glycine and l -lysine, respectively, at the operating temperature of 70°C when the rejection of both NaCl and arsenic are higher than 99.8%. Furthermore, the operating temperature significantly influenced the permeation flux, while the salt rejections were insignificantly affected. The permeation flux increases by 3.2- and 4.0-folds for glycine and lysine-modified membranes, respectively, when elevating the feed temperature from 40°C to 70°C. The highest permeation flux of 29.5 kg m⁻² h⁻¹ with a 5 wt% NaCl rejection of 99.8% was obtained at 70°C by using 0.3 wt% l -lysine modified polyamide (PA) membrane. For elimination of 1.5 mg L⁻¹ As solution at the feed temperature of 70°C, such l -lysine modified PA membrane exhibited the permeation flux of 30.5 kg m⁻² h⁻¹ and As rejection of 99.6%, respectively. This work provides a cost-saving, facile, and eco-friendly preparation method for effectively improving the permeation flux while not sacrificing the high rejection of salts of the modified membranes.     

Novel thin-film composite nanofiltration membranes fabricated via the incorporation of ssDNA for highly efficient desalination

In this work, the biomacromolecule, single-stranded deoxyribonucleic acid (ssDNA) was innovatively incorporated into the polyamide layer to tailor the permeate flux and antifouling performance of the nanofiltration (NF) membranes. With active amines groups, the ssDNA was as the aqueous phase monomers along with piperazine (PIP), and reacted with trimesoyl chloride on polyethersulfone substrate to fabricate thin-film composite (TFC) NF membranes. The NF membrane prepared under optimal ratio of ssDNA/PIP had a pure water permeability of 75.8 L m⁻² h⁻¹ (improved 58% compared to PIP NF membrane) and Na₂SO₄ rejection of 98.0% at 6.0 bar. The rejections for different inorganic salts were the order: Na₂SO₄ (98.0%) > MgSO₄ (89.2%) > MgCl₂ (72.8%) > NaCl (23.0%). Furthermore, the TFC NF membranes showed good antifouling performance in long-term running with 300 ppm bovine serum albumin and humic acid solution. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 47102.     

紫外辐照接枝制备荷正电纳滤膜

通过在PEK-C微孔膜表面紫外辐照接枝甲基丙烯酰氧乙基三甲基氯化铵（DMC）制备了一种表面荷正电的纳滤膜。通过测定膜的纯水通量和对不同盐溶液截留率的变化,系统研究了接枝条件对膜分离性能的影响。结果表明,采用该方法制成的纳滤膜对高价阳离子盐溶液MgCl2的截留率和渗透通量都较高。     

Preparation and characterization of a novel positively charged nanofiltration membrane based on polysulfone

The goal of this study was to prepare positively charged nanofiltration (NF) membranes to remove cations from aqueous solutions. A composite NF membrane was fabricated by the modification of a polysulfone ultrafiltration support. The active top layer was formed by the interfacial crosslinking polymerization of poly(ethylene imine) (PEI) with p‐xylene dichloride (XDC). Then, it was quaternized by methyl iodide (MI) to form a perpetually positively charged layer. The chemical and morphological changes of the membrane surfaces were studied by Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy. To optimize the membrane operation, the PEI solution concentration, PEI coating time, XDC concentration, crosslinking time, and MI concentration were optimized. Consequently, high water flux (5.4 L m^?2 h^?1 bar^?1) and CaCl₂ rejection (94%) values were obtained for the composite membranes at 4 bars and 30°C. The rejections of the NF membrane for different salt solutions, obtained from pH testing, followed the order Na₂SO₄ < MgSO₄ < NaCl < CaCl₂. The molecular weight cutoff was calculated by the retention of poly(ethylene glycol) solutions with different molecular weights, and finally, the stoke radius was calculated as 1.47 nm. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41988.     

Comparative impact of SiO2 and TiO2 nanofillers on the performance of thin-film nanocomposite membranes

Nanoparticle (NP) additions can substantially improve the performance of reverse osmosis and nanofiltration polyamide (PA) membranes. However, the relative impacts of leading additives are poorly understood. In this study, we compare the effects of TiO₂ and SiO₂ NPs as nanofillers in PA membranes with respect to permeate flux and the rejection of organic matter (OM) and salts. Thin-film nanocomposite (TFN) PA membranes were fabricated using similarly sized TiO₂ 15 nm and SiO₂ (10 – 20 nm) NPs, introduced at four different NP concentrations (0.01, 0.05, 0.2, and 0.5% w/v). Compared with PA membranes fabricated without NPs, membranes fabricated with nanofillers improved membranes hydrophilicity, membrane porosity, and consequently the permeability. Permeability was increased by 24 and 58% with the addition of TiO₂ and SiO₂ , respectively. Rejection performance and fouling behavior of the membranes were examined with salt (MgSO₄ and NaCl ) and OM (humic acid [HA] and tannic acid [TA]). The addition of TiO₂ and SiO₂ nanofillers to the PA membranes improved the permeability of these membranes and also increased the rejection of MgSO₄ , especially for TiO₂ membranes. The addition of TiO₂ and SiO₂ to the membranes exhibited a higher flux and lower flux decline ratio than the control membrane in OM solution filtration. TFN membranes' HA and TA rejections were at least 77 and 71%, respectively. The surface change properties of NPs appear to play a dominant role in determining their effects as nanofillers in the composite membrane matrix through a balance of changes produced in membrane pore size and membrane hydrophilicity.     

Preparation and modification of thin film composite membrane using a bulky dianhydride monomer

One of the most effective methods to modify thin film composite (TFC) membranes is changing the chemistry of top selective layer by different monomers and different monomer concentrations. Herein, we report the preparation of modified TFC membranes using a pyromellitic dianhydride (PMDA) mixed with organic phase (trimesoyl chloride) and meta phenylene diamine (MPD). By manipulating the PMDA amount in organic phase, the structures and chemical compositions of polyamide selective layer could be modified. It was realized that the presence of PMDA could result in a modified membrane with higher surface roughness, less dense selective layer, more surface charge density, and better hydrophilic properties and consequently less fouling. The optimum PMDA concentration was found 0.05 wt%, such that the obtained membrane had 35.6 L m⁻² h⁻¹ pure water flux, about 1.6-fold higher than the reference membrane with similar salt rejection. Fouling intensity for the reference membrane was 38.1%, while for the modified membranes it decreased to 16.7%.     

Fouling control in sugarcane juice ultrafiltration with surface modified polysulfone and polyethersulfone membranes

Commercial 50 and 100 kD polyethersulfone (PES) and polysulfone (PS) ultrafiltration membranes were surface modified by UV photografting of poly(ethylene glycol) methacrylate (PEGMA) monomer. The modified membranes were characterized by the degree of grafting, water flux and molecular weight cutoff (MWCO) rating. The flux and fouling of the modified and unmodified membranes were examined with sugarcane juice and its polysaccharide fraction. Under the conditions of this study, the modified membranes displayed a low degree of grafting (26-36 μg/cm²), which was independent of the UV exposure duration; however, both membrane water flux and MWCO rating were affected by the irradiation time. In the best case, the modified membranes exhibited lower fouling with sugarcane juice; furthermore, the propensity to foul also decreased. More significantly, juice flux recovery was almost complete for successive UF-cleaning cycles.     

Synthesis of 4-Aminobenzoylpiperazine for Preparing the Thin Film Composite Nanofiltration Membrane by Interfacial Polymerization with TMC

A new synthesis method of aromatic diamine, 4-aminobenzoylpiperazine (4-ABP), was studied from 4-aminobenzoic acid and 1-formyl piperazine for the preparation of nanofiltration membrane. The structure of 4-ABP was identified by FT-IR spectra and ¹H NMR spectra. The resulting 4-ABP was used as aqueous monomer to fabricate a thin film on porous polyethersulfone (PES) ultra filtration membranes by interfacial polymerization (IP) with trimesoyl chloride (TMC) as organic monomer. The salt rejection order of these thin film composite (TFC) nanofiltration(NF) membranes is Na₂SO₄>MgSO₄>MgCl₂>NaCl. This sequence indicated that the membranes were negatively charged.     

Modification of PES Membrane: Reduction of Biofouling and Improved Flux Recovery

A 0.22 µm polyethersulfone microfiltration membrane was modified using acrylic acid irradiated with UV light. The degree of grafting (DG) was confirmed by FTIR spectroscopy, which varied from 21 to 568 µg/cm² for differing irradiation times and initial monomer concentrations. The contact angle of the modified membranes was at least 10° less than the unmodified PES membrane. Modification filled the pores with copolymer, and decreased the permeability of the membrane. However, following the filtration of E. coli, and membrane cleaning, the flux recovery was 100% for the modified membranes and only 50% for the unmodified membranes. Thus, the modification helped in showing reversible biofouling and higher flux recovery.     

Surface modification and preparation of nanofiltration membrane from polyethersulfone/polyimide blend—Use of a new material (polyethyleneglycol‐triazine)

Blends of polyethersulfone/polyimide (PES/PI) were prepared by dissolving in dimethylformamide/dioxane (DMF/DO) to manufacture nanofiltration membranes by using polyvinylpirrolidone (PVP) as a pore former. The membrane modification was carried out by adding ethylenediamine (EDA) to open the imide group ring of PI and by using polyethyleneglycol (PEG)‐triazine, as a new modifier material, that was produced in the laboratory. This modification involves the formation of a covalence ‐C‐N‐ bound between PEG‐triazine and amine groups (according to addition‐elimination reactions) at different temperatures. After functionalizing the membranes, diethanolamine (DA) was utilized as a hydrophilic modifier to change the membranes properties. SEM, AFM, FTIR‐ATR, EDS (X‐ray analysis) and contact angle tests were carried out to characterize modified membranes. The hydrophilicity of PES/PI membranes was improved by modification. An increase in pure water flux (up to 195 kg/m² h) and a decline in NaCl rejection (from 25 to 16%) are largely influenced by diminishing the PES/PI ratio in L₁‐L₅ membranes (Category 1). In L₆, L₇, and L₈ membranes (Category 2), by introducing PEG‐triazine into the membrane recipe, salt rejection increased from 75 to 80%. Addition of DA further enhances the salt rejection up to 93%. Fluxes were approximately similar for membranes in Category 2. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of adsorption and concentration polarisation on membrane performance during ultrafiltration of a non-ionic surfactant

Surfactants are present in almost all aqueous solutions — either as additives for different purposes, or because they occur naturally. Because of the common occurrence of surfactants in process water it is important to know how they behave in membrane processes. Ultrafiltration membranes allow almost complete passage of surfactant monomers, but reject micelles almost completely. Concentration polarisation during ultrafiltration of surfactant solutions is therefore mainly influenced by the presence of micelles. Operating parameters, e.g. the transmembrane pressure and the concentration of surfactant, as well as the pure water flux of the membrane, have a marked influence on the performance of hydrophilic membranes, as shown in this investigation. A distinct difference between the interaction of a non-ionic surfactant with hydrophilic and hydrophobic membranes was observed. The hydrophobic membrane showed a flux reduction already at concentrations below the critical micelle concentration (CMC), whereas no flux reduction was observed for a hydrophilic membrane with the same nominal molecular weight cut-off, below the CMC.     

Reinforced thin-film composite nanofiltration membranes: Fabrication,characterization, and performance testing

Hollow-fiber (HF) membranes have the advantage of a higher packing density compared to flat-sheet and spiral-wound configurations. However, the low pressure tolerance of HF membranes limits their applications in nanofiltration (NF). In this study, reinforced thin-film composite (r-TFC) HF NF membranes were fabricated and evaluated in tests with water containing different salts and organic matter. Reinforced polysulfone ultrafiltration membranes were used as a support for a polyamide layer prepared from piperazine and trimesoyl chloride monomers. The interfacial polymerization conditions were optimized via selection of the trimesoyl chloride reaction time that gave the highest membrane performance. A specific permeate flux of 5.1 L m^–2 h^–1 bar^–1, an MgSO₄ rejection of 69%, and an NaCl rejection of 26% at a transmembrane pressure of 6 bars were obtained with the optimized r-TFC membranes. Performance studies with water characterized by synthetic solution demonstrated removals of the total organic carbon, ultraviolet absorbance at 254 nm, and turbidity in excess of 65, 80, and 90%, respectively. The results of this study illustrate the feasibility of manufacturing r-TFC HFs and using them in water-treatment applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48001.