Second modification of a polyamide membrane surface

The aim of this study was to develop the water flux and antifouling properties of a polyamide (PA) nanofiltration membrane. A nascent PA membrane was prepared with an interfacial polymerization technique and modified with 2,5‐diaminobenzene sulfonic acid (2,5‐DABSA) as a second modification. The effects of the 2,5‐DABSA monomer concentration and the modification time on the membrane performance were investigated. The chemical structure, morphology, roughness, hydrophilicity, molecular weight cutoff, and antifouling properties of the membranes were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, atomic force spectroscopy, contact angle measurement, poly(ethylene glycol) tracers, and cetyl trimethyl ammonium bromide filtration, respectively. The PA membrane with optimized performance was shown to have a greater than 44% higher water permeate flux with a change in the salt rejection in the order RNa₂SO₄ > RCaCl₂ > RNaCl to RNa₂SO₄ > RNaCl > RCaCl₂. The improvement of the hydrophilicity led to excellent antifouling properties in the new PA membranes and illustrated a promising and simple method for the fabrication of high‐performance PA membranes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43583.     

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%).     

Nanofiltration and reverse osmosis thin film composite membrane module for the removal of dye and salts from the simulated mixtures

Nanofiltration (NF) and reverse osmosis (RO) thin film composite polyamide membrane modules were used to remove the color from the contaminated solution mixture. The feasibility of membrane processes for treating simulated mixture by varying the feed pressures (100-400 psi) and feed concentrations was studied to assess the separation performance of both NF and RO membranes. It was found that the efficiency of NF and RO membranes used in the treatment of colored water effluents was greatly affected by the presence of salts and dyes in the mixture. Color removal by NF with a high rejection of 99.80% and total dissolved solids (TDS) of 99.99% was achieved from RO by retaining significant flux rate compared to pure water flux, which suggested that membranes were not affected by fouling during the simulated wastewater process operation. The effect of varying concentrations of Na₂SO₄ salt and methyl orange (MO) dye on the performance of spiral wound membranes was determined. Increasing the dye concentration from 500 to 1000 mg/L resulted in a decrease of salt rejection at all operating pressures and for both concentrations of 5000 and 10,000 mg/L as the feed TDS. Increasing the salt concentration from 5000 to 10,000 mg/L resulted in a slight decrease in dye removal.     

Improved performance of polyamide nanofiltration membranes by incorporating reduced glutathione during interfacial polymerization

Inspired by the specific amino acid sequence Asn-Pro-Ala (NPA) of water channel aquaporins (AQPs), we fabricated polyamide (PA) nanofiltration (NF) membranes by introducing reduced glutathione (GSH) in interfacial polymerization (IP) method. Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectrometry (XPS), scanning electron microscope (SEM), atomic force microscopy (AFM), zeta potential and static water contact angle measurement were employed to characterize the chemical composition, morphology, electronegativity and hydrophilicity of the NF membranes. The water flux of GSH/PIP-TMC NF membrane reached 32.00 L m^-2 h^-1 at 0.2MPa, which was approximately twice than that of pristine PIP-TMC NF membrane when the ratio of GHS to piperazidine (PIP) was 40% during IP process. More water channels were built as GSH was embedded into PA layer. The fabricated NF membranes also took on potent rejection for dyes and Na₂SO₄. This study presents a simple and facile method to simulate water channels-based biological materials which may find potential application in water treatment.     

Preparation and properties of hollow fibre nanofiltration membrane with continuous coffee-ring structure

Polyamide(PA)hollow fibre composite nanofiltration(NF)membranes with a coffee-ring structure and beneficial properties were prepared by adding graphene oxide(GO)into the interfacial polymerization process.The presentation of the coffee-ring structure was attributed to the heterogeneous,finely dispersed multiphase reaction system and the“coffee-stain”effect of the GO solution.When the piperazine concentration was 0.4 wt-%,the trimesoyl chloride concentration was 0.3 wt-%,and the GO concentration was 0.025 wt-%,the prepared NF membranes showed the best separation properties.The permeate flux was 76 L·m^?2·h^?1,and the rejection rate for MgSO4 was 98.6%at 0.4 MPa.Scanning electron microscopy,atomic force microscopy,and attenuated total reflectance-Fourier transform infrared spectroscopy were used to characterize the chemical structure and morphology of the PA/GO NF membrane.The results showed that GO was successfully entrapped into the PA functional layer.Under neutral operating conditions,the PA/GO membrane showed typical negatively charged NF membrane separation characteristics,and the rejection rate decreased in the order of Na2SO₄>MgSO₄>MgCl₂>NaCl.The PA/GO NF membrane showed better antifouling performance than the PA membrane.     

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.     

纳滤和反渗透膜形貌结构与膜性能关系探索

纳滤和反渗透膜表面形貌结构、亲疏水性的性质与膜脱盐率、水通量等性能存在一定关系。对几款商用纳滤、反渗透膜进行表面形貌结构、表面粗糙度、亲水性表征。结果表明,纳滤膜表面平整粗糙度低、亲水性强、脱盐率较低,但水通量高。反渗透膜表面存在大量疏松的峰谷结构,比纳滤膜粗糙度更大、亲水性强。对比两款海水反渗透膜,推测调整反渗透膜"叶片"大小和数量可调节反渗透膜的脱盐率和水通量性能。     

Novel charged chitosan composite nanofiltration membranes containing chiral mesogenic group

To improve the performance of nanofiltration (NF) membranes, a chiral mesogenic compound, a positively charged compound, and a negatively charged compound were grafted to chitosan, respectively. Series of novel composite NF membranes were prepared by over‐coating the polysulfone ultrafiltration membrane with the mixture of chitosan and modified chitosan. The chiral mesogenic compound, the positively charged compound, the negatively compound and their chitosan derivatives were characterized by infrared spectrophotometer, differential scanning calorimetry, polarized optical microscope; the structure of the membrane was characterized by scanning electron microscopy. The performance of composite NF membranes was strictly related to the novel compounds grafted to chitosan and its composition. The rejection reached the maximum of 95.7% for CaCl₂ with P_2‐7 composite NF membrane, corresponding flux was 3155 Lm^?2h^?1. The rejection reached the maximum of 93% for Na₂SO₄ with P_3‐5 composite NF membrane, corresponding flux was 3879 Lm^?2h^?1. Comparing with conventional NF membranes, the membranes were used in low pressure with high flux, especially for the separation of high‐valence ions from solution. The membranes were typical charged NF membranes. POLYM. ENG. SCI., 57:22–30, 2017. © 2016 Society of Plastics Engineers     

Nanofiltration of Magnesium Chloride,Sodium Carbonate,and Calcium Sulphate in Salt Solutions

Abstract

Nanofiltration (NF) membranes have been employed in pre‐treatment unit operations in both thermal and membrane seawater desalination processes. This has resulted in reduction of chemicals used in pretreatment processes as well as lowering the energy consumption and water production cost and, therefore, has led to a more environmentally friendly processes. In order to predict NF membrane performance, a systematic study on the filtration performance of selected commercial NF membranes against brackish water and seawater is required. In this study, three commercial nanofiltration membranes (NF90, NF270, N30F) have been used to treat highly concentrated different salts solutions (MgCl₂, Na₂CO₃, and CaSO₄) at salinity level similar to that of brackish water and seawater. The main parameters studied in this paper are salt concentration and feed pressure. The experimental data were correlated and analysed using the Spiegler‐Kedem model. In particular, the reflection coefficient (σ) of all studied membranes and the solute permeability (P_s) have been determined for all membranes and at different salinity levels of studied salts. All the studied membranes fitted the model well for all investigated salts except the experimental data of MgCl₂ using N30F membrane, which did not fit well at low rejection. The results showed that NF90 produced a high rejection around 97% for all salts with medium permeate flux while NF270 gave a high flux with medium rejection and N30F gave low rejection and flux.     

Treatments of stainless steel wastewater containing a high concentration of nitrate using reverse osmosis and nanomembranes

A nanomembrane (NTR 729HF) and three different types of reverse osmosis (RO) membranes (CPA2, LFC1, and ESPA1) were tested for the treatment of high concentration of nitrate wastewater from stainless steel industry. All the tested RO membranes showed higher rejection rates (90–99% at 1000–60 mg/L of NO₃⁻ -N) than the NF membrane. The rejection rate and flux of RO membranes were not highly affected by pH variation and Ca²⁺ as co-existing ion. However, the rejection rate of NF, which was 67% at 60 mg/L of feed concentration, was decreased as pH decreased and Ca²⁺ concentration increased indicating that charge repulsion is one of the major rejection mechanisms. As nitrate concentration increased from 20 to 1000 mg/L in feed water, the removal rate decreased from 67 to 20% in NF membrane. The flux of RO was relatively high and ESPA1 (a low-pressure RO type) showed more than two times higher flux compared to the NF. ESPA1 was successfully tested for a longterm experiment with real stainless steel wastewater for 30 days of experimental period. Current study implicates that RO membranes could be an alternative for the treatment of stainless steel wastewater.     

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.     

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.     

Preparation of sulfonated polysulfone/polysulfone and aminated polysulfone/polysulfone blend membranes

Sulfonation and amination of polysulfone (PSf) were performed in this study to improve the hydrophilicity of PSf membranes. The sulfonated polysulfone (SPSf) and aminated polysulfone (APSf) membranes with a higher degree of reaction exhibited a higher water flux and worse mechanical strength than that of the original PSf membranes. Therefore, SPSf/PSf and APSf/PSf blended membranes were prepared in this study to improve their individual properties. By altering the formulations of casting solutions and forming conditions of the membranes (e.g., blending ratios of both polymers, additives, evaporation time, and gelation temperature), different SPSf/PSf and APSf/PSf blending membranes were prepared; and their performance in water flux and salt rejection were measured and are discussed. A difference in salt rejection was also observed between both SPSf/PSf and APSf/PSf blending membranes that rejected the various salts. Experimental results indicated that water flux increased and salt rejection decreased with an increase of the SPSf/PSf blending ratio from 1: 9 to 2: 1. The order of salt rejection, in which the SPSf/PSf blended membranes rejected four varieties of salts, was Na₂SO₄ > MgSO₄ > NaCl > MgCl₂. Furthermore, the opposite order was obtained by the APSf/PSf blended membranes. © 1996 John Wiley & Sons, Inc.     

Positively charged loose nanofiltration membrane grafted by diallyl dimethyl ammonium chloride (DADMAC) via UV for salt and dye removal

A novel positively charged loose nanofiltration (NF) membrane was fabricated feasibly by UV-induced photografting polymerization of diallyl dimethyl ammonium chloride (DADMAC) on Polysulfone ultrafiltration membrane. A possible reaction mechanism was proposed that a linear chain structure and/or pyrrole like five-membered nitrogen heterocycles structure on the side chain were grafted to form the active barrier layer. NF membrane demonstrated a looser average pore size of 8.6 nm and positive charges surface. Owing to the nanoscale ultrathin nanoscale barrier layer and the combination of Donnan exclusion and steric hindrance, NF membrane exhibited good hydrophilicity, a high pure flux of 60 L/m² h (0.5 MPa), a good salt rejection to Mg²⁺ (90.8%), Al³⁺ (94.0%), Ca²⁺ (91.5%), and a high dye rejection to methylene blue (99.4%) and congo red (100.0%) respectively. The salts rejection of NF membrane to different salts followed the order of AlCl₃ > CaCl₂ > MgCl₂ > NaCl > LiCl > MgSO₄ > Na₂SO_4. NF membrane showed certain fouling resistance to seawater and BSA solution. The grafting polymerization kinetics were comprehensively investigated including irradiation time, monomer concentration and irradiation intensity. X-ray Photoelectron Spectroscopy (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM) and contact angle measurement were employed to investigate membrane chemistry, morphologies, and hydrophilicity.     

Preparation and characterization of a composite nanofiltration membrane interfacially polymerized from cis,cis‐1,3,5‐triaminocyclohexane and trimesoyl chloride

cis,cis‐1,3,5‐Triaminocyclohexane (TAC) was synthesized and used to prepare composite nanofiltration (NF) membranes by interfacial polymerization with trimesoyl chloride (TMC). The surface elemental composition, morphology, and hydrophilicity of the prepared NF membranes were characterized. The separation performances were examined with various salts and polyethylene glycol (PEG400, PEG600) solutions. The effects of preparation conditions were also systematically studied. The NF membrane was negatively charged and exhibited a salt rejection in the order Na₂SO₄ (98.2%) > MgSO₄ (90.8%) > MgCl₂ (84.5%) > NaCl (54.6%). The water permeability was 1.56 L m^?2 h^?1 bar^?1, and the molecular weight cutoff was 600 Da. The TAC/TMC membrane exhibited some characteristics that were different from the ones made from common diamines such as m‐phenylenediamine: (1) the surface was smoother, without a ridge‐and‐valley structure; (2) there were two kinds of crosslinking points in the polyamide chains; (3) the active layer was formed faster (only 5 seconds was required to reach a Na₂SO₄ rejection of 98%). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43511.     

A melamine-based covalent organic framework nanomaterial as a nanofiller in polyethersulfone mixed matrix membranes to improve separation and antifouling performance

This research reported developing a polyethersulfone (PES) membrane using covalent organic frameworks (COFs) nanoparticle with a mean dimension of 30 nm. The SNW-1 (Schiff-based network) COF was synthesized using precursors of melamine and terephthalic acid and then characterized by XRD, SEM, TEM, and FTIR analyses. The influence of different loadings of the COF was evaluated on the permeability, antifouling behavior and dye/salt rejection. The addition of SNW-1 caused a reduction in surface roughness and an improvement in hydrophilicity of the nanocomposite membranes, which improved their flux and fouling resistance considerably. The improvement of water flux, 2.6 times, was observed by adding 0.5 wt% COF to the membrane matrix. The 0.5 wt% COF membrane presented the best water permeability, 38.9 L/m² h bar BSA solution flux, dye rejection of 98.7% for Reactive Green 19 and 62.6% for Reactive yellow 39, 52.9% Na₂SO₄ and 24.5% NaCl salt rejections. Zeta potential and salt rejection trend indicated a negative surface charge on the nanocomposite membrane. Fouling experiments by BSA protein solution exhibited that the FRR reached 88.9% for 2 wt% COF membrane. Thus, employing SNW-1 into PES matrix resulted in a promising nanofiltration membrane for dye separation and moderate salt separation with suitable antifouling properties.     

氧化石墨烯掺杂反渗透混合基质膜制备及性能

由于芳香族聚酰胺反渗透膜在抗污染性以及耐氯性方面存在不足,限制了其在海水淡化等方面的应用。采用往油相中添加氧化石墨烯（GO）的二次界面聚合法改性了商业反渗透膜,评价了GO掺杂反渗透混合基质膜的分离性能和耐氯性能,并用接触角仪、Zeta电位仪、扫描电镜和原子力显微镜等仪器表征了膜的亲水性能、荷电性能以及膜表面形貌。结果表明,GO的添加提高了膜的分离性能、耐氯性能和亲水性能;当GO添加量为30 mg·L^-1时,膜的通量为（77.7±0.9） L·m^-2·h^-1,膜的截留率为97.6%±0.5%,相比商业膜分别提高了38.4%和4.5%。当氯化强度低于4800 mg·L^-1·h时,膜的水通量和盐截留率变化不明显。     

High‐performance composite nanofiltration membranes fabricated via ternary mixture: Complementary preponderance of the fluorine‐containing monomer 2,2′‐bis(1‐hydroxyl‐1‐trifluoromethyl‐2,2,2‐triflutoethyl)‐4,4′‐methylene dianiline and the rigid monomer bisphenol F

In a previous study, we proved that tailoring the polyamide backbone stiffness is an effective way to fabricate high‐performance polyamide nanofiltration (NF) membranes. However, in the previous study, we mainly focused on the flat membrane and did not consider its chlorine tolerance. In this study, by regulating the aqueous‐phase compositions in the interfacial polymerization process, chlorine tolerance on NF hollow‐fiber membranes was endowed while the membrane performance stayed high. The experimental results show that when the ratio of Piperazine (PIP)–bisphenol F (BPF)/2,2′‐bis(1‐hydroxyl‐1‐trifluoromethyl‐2,2,2‐triflutoethyl)‐4,4′‐methylene dianiline (BHTTM) was 5:1:4, the NF membrane possessed a permeate flux of 21.0 L m^?2 h^?1 bar^?1 and an Na₂SO₄ rejection up to 90.0%. X‐ray photoelectron spectroscopy analysis also confirmed that the polymerization degree of the PIP–BPF–BHTTM NF membrane was the highest. Moreover, the NF membrane could tolerate active chlorine to over 10,000 ppm h Cl. After the active chlorine treatment, the permeate flux increased over 30.0 L m^?2 h^?1 bar^?1, and the Na₂SO₄ rejection was about 90.0%. Although the PIP–BHTTM NF membrane also possessed good chlorine tolerance, its permeate flux (after active chlorine treatment) was only 60% of that of the PIP–BPF–BHTTM NF membrane. Therefore, the PIP–BPF–BHTTM NF membrane possessed a combination of high flux and high chlorine tolerance and showed good potential in water treatment in rigorous environments. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46482.     

纳滤/反渗透膜处理重金属废水的性能

The performance of different nanofiltration （NF） and reverse osmosis （RO） membranes was studied in treating the toxic metal effluent from metallurgical industry. The characteristics and filtration behavior of the processes including the wastewater flux, salt rejection and ion rejection versus operating pressure were evaluated. Then the wastewater flux of RO membrane was compared with theoretical calculation using mass transfer models, and good consistency was observed. It was found that a high rejection rate more than 95% of metal ions and a low Chemical Oxygen Demand （COD） value of 10 mg·L^-1 in permeate could be achieved using the RO composite membrane, while the NF rejection of the salt could be up to 78.9% and the COD value in the permeate was 35 mg·L^-1. The results showed that the product water by both NF and RO desalination satisfied the State Reutilization Qualification, but NF would be more suitable for large-scale industrial practice, which offered significantly higher permeate flux at low operating pressure.     

Influence of polyethyleneimine layer and zinc nitrate on morphology and structure of PES-based membranes with highly selective properties

In this paper, nanofiltration (NF) polymer membranes based on polyestersulphone (PES) were prepared by the phase inversion method. Polyethyleneimine (PEI) and zinc nitrate (Zn(NO₃)₂) as a surface modifier and glutealdehyde (GA) as cross-linker was used. Fourier transform infrared spectroscopy analysis (FTIR) was used to confirm the chemical composition on the membrane surface. Membranes were also characterized using field emission scanning electron microscopy (FESEM) and 3D surface images. Water contact angle, average pore size and porosity measurements, water flux, salt rejection, and membrane anti-fouling ability were discussed. Modified membranes showed a smoother surface than the original membrane. The amount of pure water flux decreased with increasing the concentration of modifiers at the surface, but the yield of Na₂SO₄ salt increased, 53% in virgin membrane and 83% in M3 membrane. Modified membranes had better anti-fouling and hydrophilicity properties than primary membranes. The lowest contact angle value was 26.2° for M4. Also, the best anti-clogging comparable properties were for the M3 membrane with FRR = 63.37%, R_r = 10.69%, R_ir = 36.6%, and R_t = 47.3%. By increasing the concentration of modifiers, the removal of CuNO₃⁻ and CuSO₄ improved that the M1 membrane (97.59%) had the highest Cu(NO₃)₂ separation and the M4 membrane (87.5%) had the most increased CuSO₄ separation.