Impact of TiO2 nanoparticles on morphology and performance of crosslinked polyimide organic solvent nanofiltration (OSN) membranes

Chemically crosslinked polyimide organic–inorganic composite nanofiltration membranes suitable for application in harsh organic solvents were successfully prepared by phase inversion of dope solutions. TiO₂ nanoparticles were dispersed in these dope solutions, comprising polyimide (PI) in N,N-dimethylformamide/1,4-dioxane. The impact of TiO₂ on the resulting PI membranes was investigated using SEM, TGA, water contact angle, dope viscosity measurements and mechanical strength. The presence of TiO₂ nanoparticles within the membrane matrix was proved by the detection of a peak characteristic of TiO₂ in the WAXS pattern. SEM pictures of the cross-section of the PI/TiO₂ membranes showed dramatically changed morphology compared to reference membranes with no TiO₂ addition. Macrovoids present in reference membranes were suppressed by increasing loading of TiO₂ nanoparticles, and eventually disappeared completely at a TiO₂ loading above 3 wt.%. Decreasing water contact angle and an increase in ethanol flux indicated that hydrophilicity increased as nanoparticle loading increased. The effect of TiO₂ on the functional performance of the membranes was evaluated by measuring flux and rejection using cross-flow filtration. Perhaps surprisingly, the presence of TiO₂ improved the compaction resistance of the membranes, whereas rejection and steady flux were almost unaltered.     

Effect of membrane pretreatment on performance of solvent resistant nanofiltration membranes in methanol solutions

This paper reports the effect of membrane pretreatment using different organic solvents on the performance of polyamide, polyimide and polydimethylsiloxane (PDMS) membranes in methanol solutions. Membrane pretreatment using acetone, methanol and toluene results in significant changes of membrane flux and rejection for polyamide- and polyimide-based membranes (Desal-DK and STARMEM 228) due to membrane swelling. The Performance of a polydimethylsiloxane (PDMS)-based membrane (MPF-50) in methanol solutions was not significantly affected by membrane pretreatment.     

Cross-linked polyimide membranes for solvent resistant nanofiltration in aprotic solvents

Solvent stable nanofiltration membranes were prepared through the chemical cross-linking of asymmetric Matrimid^®-based polyimide membranes with p-xylylenediamine. The influence of this straightforward post-treatment on membrane stability, morphology and performance in dimethylformamide (DMF), N-methylpyrrolidinone (NMP), dimethylacetamide (DMAc) and dimethylsulfoxide (DMSO) was thoroughly investigated. With permeabilities up to 5.4 l/m² bar h and rejections up to 98% for low molecular weight dyes in these demanding solvents, optimally performing, truly solvent resistant nanofiltration membranes were obtained. Nanozeolite-filled membranes were prepared in parallel to study the effect of an inorganic filler on the cross-linking reaction and performance in aprotic solvents. The outstanding stability and performance of these membranes and their easy preparation clearly offer vast potential for applications in harsh solvent environments.     

Solute molecular transport through polyimide asymmetric organic solvent nanofiltration (OSN) membranes and the effect of membrane-formation parameters on mass transfer

This work studies the effect of two membrane-formation parameters, evaporation time and casting thickness, on the diffusive mass transport of organic solutes through an organic solvent nanofiltration (OSN) membrane. These parameters showed a coupled effect on the final membrane thickness, which was explained in terms of top-layer formation. In a concentration-driven dialysis, both parameters, as well as the resulting membrane thickness, had a significant effect on mass transport. Casting thickness had the greatest effect on membrane mass transport rates. Multivariate regression was used to model the dialysis process with acceptable fit. A representation of the membrane morphology was obtained from SEM pictures and used to formulate an alternative mechanistic mass-transport model. A resistance-circuit analogy was used to describe transport through the top and microporous layers, which also considered diffusion through the pores and the polymer for each layer. From the analyses of the models and considering that no differences in top-layer thickness were observed by SEM, it is concluded that membrane asymmetry, determined by the formation parameters, controls mass transport, rather than top-layer thickness.     

Asymmetric layer-by-layer polyelectrolyte nanofiltration membranes with tunable retention

Nanofiltration (NF) membrane processes are attractive to remove multivalent ions. As ion retention in NF membranes is determined by both size and charge exclusion, negatively charged membranes are required to reject negatively charged ions. Layer-by-layer assembly of alternating polycation (PC) and polyanion layers on top of a support is a versatile method to produce membranes. Especially the polyelectrolyte (PE) couple polydiallyldimethylammoniumchloride and poly(sodium-4-styrenesulfonate) (PDADMAC/PSS) is extensively investigated. This PE couple cannot form highly negatively charged membrane surfaces, due to interdiffusion and charge overcompensation of PDADMAC into the PSS layers, which limits the operational window to tailor membrane properties. We propose the use of asymmetric layer formation and show how combining two charge densities of one PC can produce negatively charged NF membranes. Starting from hollow fiber ultrafiltration supports coated with base layers of PDADMAC/PSS, they are coated with PDADMAC/PSS or poly(acrylamide-co-diallyldimethylammoniumchloride), P(AM-co-DADMAC)/PSS layers. P(AM-co-DADMAC) has a charge density of only 32% compared to 100% for PDADMAC. The particular novel membranes coated with P(AM-co-DADMAC) have a highly negatively charged surface and high permeabilities (7–19 L/[m²hbar]), with high retentions for Na₂SO₄ of up to 95%. These values position the developed membranes in the top range compared to commercial and other layer-by-layer membranes.     

Experimental contribution to the understanding of transport through polydimethylsiloxanenanofiltration membranes: Influence of swelling,compaction and solvent on permeation properties

This study aims to better understand the permeation properties of polydimethylsiloxane (PDMS) membranes. The compressibility and nanofiltration fluxes were measured for swollen PDMS films using several solvents at applied pressures ranging from 5 to 50 bar. The degree of swelling varied according to the solvent and the pressure applied. To show the correlation between the behaviour of the swollen PDMS under pressure and its permeation performance, the thickness reduction of the membrane was mimicked using uniaxial compression tests. The evolution of the nanofiltration flux as a function of the transmembrane pressure proved to be non-linear. Linearization was achieved by taking into account both the swelling and the thickness reduction previously measured, confirming that these phenomena may have occurred during the nanofiltration experiments. Moreover, the solvents' viscosity and affinity for the polymer were confirmed to have a great influence on their ability to permeate the membrane. Finally, employing the most commonly used models, a study of transport through the membrane led to the conclusion that the experimental results were in agreement with the hydraulic theory of transport.     

Composite nanofiltration membrane comprising one-dimensional erdite,two-dimensional reduced graphene oxide,and silkworm pupae binder

Composite nanofiltration membranes offer advantages because of synergetic effects among the constituent materials’ properties. However, the sustainability of both the membrane fabrication and the raw materials has been a drawback of this energy-efficient separation technology. We report the facile fabrication of a nanocomposite membrane composed of a two-dimensional (2D) material of reduced graphene oxide (rGO) combined with a one-dimensional (1D) material of a ternary metal-based chalcogenide (NaFeS₂ or NFS) using silkworm pupae protein as a natural binder. All the source materials can be derived from either nature or waste, ensuring the sustainability of the membrane and its production method. The structural characteristics of the synthesized membranes were analyzed, and the morphology of the composite membranes was studied thoroughly. Thermogravimetric analysis, differential scanning calorimetry, and nanoindentation characterizations indicated that the composite membranes were mechanically and thermally stable. The water and acetone fluxes; salt, dye, and pollutant rejections; and long-term membrane performance were evaluated using a cross-flow filtration system. Solute rejection was observed to increase (up to 98%, 94%, 95%, and 78% for Rhodamine B, 2,4-dichlorophenol, MgCl₂, and NaCl, respectively) with increasing concentration of the nanomaterials in the membrane. The fine-tuning of the molecular weight cutoff from 794 to 600 g mol^?1 was achieved by varying the concentration of the nanomaterials from 1 to 3 mg mL^?1. Our research findings demonstrate the synergetic effects of combining 1D and 2D materials using silkworm pupae binder. The composite membrane was stable in different classes of organic solvents, including hydrocarbons, alcohols, esters, ethers, polar aprotic solvents, halogenated solvents, and ketones. This first use of natural pupae binder in constructing membrane materials paves the way toward the development of more sustainable membranes.     

纳米复合膜在膜分离领域的研究进展

基于纳米材料的独特性质,将其引入高分子膜所制得的纳米复合滤膜有望解决目前制约膜技术发展的“上限平衡”问题。 本文综述了碳纳米管、石墨烯、SiO2、TiO2、分子筛、ZrO2以及纳米银颗粒等纳米复合膜在膜分离领域的研究进展。 这些纳米材料对于提高复合膜的机械稳定性、亲水性、选择性、渗透性及抗污染能力等有显著的效果。 此外,对纳米复合膜的发展与应用做了展望,也对其研究中存在的问题和解决方法进行了阐述。     

Polyurethane‐mesoporous silica gas separation membranes

The concept of mixed matrix membrane comprising dispersed inorganic fillers into a polymer media has revealed appealing to tune the gas separation performance. In this work, the membranes were prepared by incorporation of mesoporous silica into polyurethane (PU). Mesoporous silica particles with different pore size and structures, MCM‐41, cubic MCM‐48 and SBA‐16, were synthesized by templating method and functionalized with 3‐aminopropyltriethoxysilane (APTES). High porosity and aminated surface of the mesoporous silica enhance the adhesion of the particles to the PU matrix. The SEM and FTIR results showed strong interactions between the particles and the PU chains. Moreover, the thermal stability of the hybrid PUs improved compared to the pure polymer. Gas transport properties of the membranes were measured for pure CO₂, CH₄, O₂, and N₂ gases at 10 bar and 25°C. The results showed that the gas permeabilities enhanced with increasing in the loading of modified mesoporous silica particles. High porosity and amine‐functionalized particles render opportunities to enhance the gas diffusivity and solubility through the membranes. The enhanced gas transport properties of the mixed matrix membranes reveal the advantages of mesoporous silica to improve the gas permeability (CO₂ permeability up to ~70) without scarifying the gas selectivity (α(CO₂/N₂)~ 30 for 5 wt% SBA‐16 content).     

Effect of aqueous and organic solutions on the performance of polyamide thin‐film‐composite nanofiltration membranes

Polyamide/polyacrylonitrile thin‐film‐composite (TFC) nanofiltration (NF) membranes for the separation of oleic acid dissolved in organic solvents (methanol and acetone) were interfacially prepared by the reaction of trimesoyl chloride in an organic phase with an aqueous phase containing piperazine and m‐phenylene diamine. The interfacial reaction was confirmed by an investigation of the attenuated total reflection infrared spectrum. The surface morphology of the polyamide TFC membranes was examined with scanning electron microscopy. The hydrophilic properties of the membrane surfaces were conjectured on the basis of the ζ potential and contact angle. The effects of the monomer concentrations of the monomer blends (aliphatic and aromatic diamines) and drying times on various aspects of membrane performance, such as the solvents (water, alcohols, ketones, and hexane), permeation rates, and organic solute [poly(ethylene glycol) 200 and oleic acid] rejection rates, were investigated. All the membranes showed good solvent resistance. The polar solvent flux for water and methanol was higher than that for a nonpolar solvent (hexane). The membranes gave good rejection rates of oleic acid dissolved in methanol and acetone. The NF membranes were compared with various commercial membranes. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2151–2163, 2002     

Physico-chemical characterization of nanofiltration membranes.

This study presents a methodology for an in-depth characterization of six representative commercial nanofiltration membranes. Laboratory-made polyethersulfone membranes are included for reference. Besides the physical characterization [molecular weight cut-off (MWCO), surface charge, roughness and hydrophobicity], the membranes are also studied for their chemical composition [attenuated total reflectance Fourier spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS)] and porosity [positron annihilation spectroscopy (PAS)]. The chemical characterization indicates that all membranes are composed of at least two different layers. The presence of an additional third layer is proved and studied for membranes with a polyamide top layer. PAS experiments, in combination with FIB (focused ion beam) images, show that these membranes also have a thinner and a less porous skin layer (upper part of the top layer). In the skin layer, two different pore sizes are observed for all commercial membranes: a pore size of 1.25-1.55 angstroms as well as a pore size of 3.20-3.95 angstroms (both depending on the membrane type). Thus, the pore size distribution in nanofiltration membranes is bimodal, in contrast to the generally accepted log-normal distribution. Although the pore sizes are rather similar for all commercial membranes, their pore volume fraction and hence their porosity differ significantly.     

Polypyrrole modified solvent resistant nanofiltration membranes

New solvent resistant nanofiltration (SRNF) membranes with polypyrrole (PPy) modified toplayer were prepared on different types support by in situ pyrrole polymerization. The morphology of the membranes was studied by SEM. The PPy modified membranes were applied in the filtration of organic solvents. All the PPy modified membranes showed a very high retention of the negatively charged RB in different solvent systems, comparable to those of the MPF-50 and STARMEM 122 commercial membranes, but at much higher flux. The extended filtration experiment in strong aprotic DMF of PPy modified membranes showed a clearly stable permeability and retention over 30 h. In addition, the PPy modified membranes showed a much higher flux in THF systems than for earlier reported crosslinked poly(imide) membranes.     

Fabrication of the polyethersulfone/functionalized mesoporous carbon nanocomposite nanofiltration membrane for dyes and heavy metal ions removal: Experimental and quantum mechanical simulation method

The presence of industrial pollutants, especially salts, heavy metals ions, and dyes in water and wastewater is considered a serious environmental issue. To eliminate these pollutants, a high-performing nanofiltration (NF) membrane was prepared by blending the functionalized mesoporous carbon CMK-5 (F-CMK-5) nanofiller. This membrane was synthesized by introducing the active groups of sulfonyl and amide to the surface of mesoporous carbon CMK-5 through covalent functionalization. Characterizations were conducted to study the membranes' physical properties and separation performance in terms of antifouling properties and rejection of salts, heavy metal ions, and dyes. The interactions between the active sites of the nanocomposite membrane and the studied solutes, including dyes and heavy metal ions in aqueous solutions, were studied by the density functional based tight binding method and structural optimization was carried out. Insertion of the F-CMK-5 nanofiller was eventuated in a remarkable increase in surface hydrophilicity, pure water flux, and antifouling properties. For all membranes, the lowest and the highest salt rejection was obtained for NaCl and Na₂SO₄, respectively, exhibiting the characteristics of NF membranes. Moreover, M_0.3 with 0.3 wt% nanofiller showed the highest rejection for heavy metal ions (Fe²⁺ = 99.9%, Zn²⁺ = 99.9%, Cu²⁺ = 99.7%, and Pb²⁺ = 99.2%) and dyes (RB5 = 99.21, DR16 = 98.87, and MB = 98.12%), as well as high separation performance for filtration of multipollutant solutions. The reusability and 144 h uninterrupted filtration experiments for M_0.3 confirmed the stability of the membrane. The findings suggest that the PES/F-CMK-5 nanocomposite NF membrane is a promising candidate for water and wastewater treatment.     

Lactic acid recovery from cheese whey fermentation broth using combined ultrafiltration and nanofiltration membranes

The separation of lactic acid from lactose in the ultrafiltration permeate of cheese whey broth was studied using a cross-flow nanofiltration membrane unit. Experiments to test lactic acid recovery were conducted at three levels of pressure (1.4, 2.1, and 2.8 MPa), two levels of initial lactic acid concentration (18.6 and 27 g/L), and two types of nanofiltration membranes (DS-5DK and DS-5HL). Higher pressure caused significantly higher permeate flux and higher lactose and lactic acid retention (p<0.0001). Higher initial lactic acid concentrations also caused significantly higher permeate flux, but significantly lower lactose and lactic acid retention (p<0.0001). The two tested membranes demonstrated significant differences on the permeate flux and lactose and lactic acid retention. Membrane DS-5DK was found to retain 100% of lactose at an initial lactic acid concentration of 18.6 g/L for all the tested pressures, and had a retention level of 99.5% of lactose at initial lactic acid concentration of 27 g/L when the pressure reached 2.8 MPa. For all the test when lactose retention reached 99–100%, as much as 64% of the lactic acid could be recovered in the permeate.     

Interfacially polymerized thin film composite membranes on microporous polypropylene supports for solvent-resistant nanofiltration

Interfacial polymerization (IP) is a powerful technique for fabrication of thin film composite (TFC) membranes. The polymers used most often as support are polysulfone (PS) or polyethersulfone (PES). These supports have limited stability in organic solvents. In this work, microporous polypropylene (PP) flat film and hollow fiber membranes were used as a support to fabricate TFC membranes for nanofiltration by the IP technique. Porous polypropylene membranes can provide substantial chemical, pH, and solvent resistance and are therefore suitable as supports for fabricating TFC membranes functioning as solvent-stable nanofiltration membranes. The surface and the pore interior of polypropylene flat sheet and hollow fiber membranes were hydrophilized first by pre-wetting with acetone followed by oxidation with chromic acid solution. A standard procedure to successfully coat the hydrophilized flat film and hollow fiber membranes was developed next. The monomeric system chosen for IP was poly(ethyleneimine) and isophthaloyl dichloride. The TFC hollow fiber membranes were characterized by nanofiltration of safranin O (MW 351) and brilliant blue R (MW 826) dyes in methanol. Rejection values of 88% and 43% were achieved for brilliant blue R and safranin O, respectively at a transmembrane pressure of 413 kPa in the TFC hollow fiber membranes. Pressure dependences of the solvent flux and solute rejection of the TFC membranes were studied using the modified flat sheet membranes up to a pressure of 965–1241 kPa. Solvent flux increased linearly with an increase in the transmembrane pressure. Solute rejection also increased with an increase in the transmembrane pressure. All modified membranes were also characterized using scanning electron microscopy. Extended-term solvent stability of the fabricated membranes was studied in toluene; the membranes demonstrated substantial solvent stability in toluene.     

二胺结构对聚酰胺复合纳滤膜性能的影响

分别以邻苯二胺、间苯二胺、对苯二胺为水相单体,均苯三甲酰氯(TMC)为油相单体,聚醚砜超滤膜为基膜,界面聚合法制备了复合纳滤膜.在纳滤膜对Na<,2>SO<,4>,MgSO<,4>,MgCl<,2>和NaCl四种盐的脱盐率中,间苯二胺膜最高,对苯二胺膜居中,邻苯二胺膜最差;在纳滤膜耐氯性能方面,对苯二胺最佳,邻苯二胺居...     

Modeling of the adsorption of organic compounds on polymeric nanofiltration membranes in solutions containing two compounds.

The adsorption of organic compounds in aqueous solution on polymeric nanofiltration membranes is studied; this process is one of the most important fouling mechanisms influencing the flux and retention behavior of nanofiltration membranes. It is shown that the adsorption of dissolved organic compounds on polymeric nanofiltration membranes is comparable to that on activated carbon. Freundlich and Langmuir isotherms are used to describe the relation between the adsorbed mass on the membrane and the equilibrium concentration of the organic compound in a single-compound solution. Based on these results, three models for the adsorption of solutions containing several compounds [i.e., the simple competitive adsorption model (SCAM), the model of Jain-Snoeyinck, and the model of Butler-Ockrent] were used to predict the adsorption behavior of an organic compound in an aqueous solution containing two compounds. The results of the three models were compared to experimental observations. It is shown that the SCAM allows a good prediction of the adsorption behavior.     

Surfactant fouling of nanofiltration membranes: measurements and mechanisms.

Fouling of nanofiltration membranes is studied during filtration of aqueous surfactant solutions under different conditions. To this purpose, four typical nanofiltration membranes (Desal51HL, NF270, NTR7450 and NFPES10) and three typical surfactants (nonionic neodol, anionic SDBS and cationic cetrimide) are selected. Fouling is studied as a function of the surfactant concentration, with and without addition of an electrolyte (NaCl), at different pH and when filtering a mixture of surfactants. Adsorption experiments and hydrophobicity measurements (to study the orientation of the surfactants on the membrane surface) are also performed under the different conditions. The least membrane fouling is found for the anionic surfactant SDBS, while for the cationic surfactant cetrimide very low relative fluxes are observed. Neodol shows an intermediate degree of fouling. Both hydrophobic and electrostatic interactions (in the case of ionic surfactants) between the membrane surface and the surfactant explain the degree of adsorption and hence fouling, as membrane fouling is correlated with the amount of adsorbed surfactant. The difference between cetrimide and SDBS becomes especially visible when changing the pH: increasing the pH leads not only to an opposite orientation of the adsorbed surfactants, but also to an opposite trend in adsorbed amount and membrane fouling. This study permits selection of an optimal nanofiltration membrane to recycle wastewater containing surfactants in the carwash industry. The optimal choice would be a hydrophilic membrane with a low molecular weight cut-off and a small negative surface charge at neutral pH. Cationic surfactants in the wastewater should also be avoided as much as possible.     

Microwave-assisted solvent elution technique for the extraction of organic pollutants in water

Solid phase extraction (SPE) with appropriate solid sorbents has been commonly used in the routine extraction of organic pollutants in water. The elution of analytes from the solid sorbents normally takes place by organic solvents under an applied vacuum. In this study, a microwave-assisted solvent elution technique was developed for the elution of analytes from C₁₈ membrane disks during microwave irradiation from a microwave extraction system (MES). Several parameters, namely, elution solvent, elution temperature, duration of elution and the volume of solvent which may affect the elution efficiency of microwave-assisted solvent elution (MASE) technique towards organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), phthalate esters (PAEs), organophosphorus pesticides (OPs), fungicides, herbicides and insecticides from the membrane disk were investigated. Good recoveries above 75% were obtained for most of the organic pollutants using the optimum SPE-MASE technique. The effect of sodium chloride and humic acid on the recoveries on the target analytes were also investigated.