New insights into membrane fouling in coagulation-ultrafiltration by cake characteristics analysis: A case study with PACl-Al13 and PACl.

Membrane fouling is a bottleneck issue that hindered the further application of ultrafiltration technology. To alleviate membrane fouling, coagulation-ultrafiltration (C-UF) process using polyaluminum chloride (PACl) and PACl-Al13 with high proportion of Al13O4(OH)247+ as coagulants, respectively, were investigated at various pH conditions. Results indicated that an increase in solution pH contributed to larger floc size and looser floc structure for both PACl and PACl-Al13. It was conducive to the formation of more porous cake, as evidenced by mean pore area and pore area distribution of cake, leading to lower reversible fouling. Furthermore, humic acid (HA) removal presented a trend of first increasing and then decreasing with the increase of pH. The optimal HA removal was achieved at pH 6 regardless of coagulant type, suggesting that the slightest irreversible fouling should be occurred at this point. Interestingly, the irreversible fouling with PACl coagulant achieved a minimum value at pH 9, while the minimal irreversible fouling with PACl-Al13 was observed at pH 6. We speculated that the cake formed by PACl could further intercept HA prior to UF process at alkaline pH. Furthermore, compared with PACl, PACl-Al13 had a stronger charge neutralization ability, thus contributing to more compact floc structure and higher HA removal at various pH conditions. By UF fractionation measurement, higher HA removal for PACl-Al13 was due to higher removal of HA with molecular weight less than 50 kDa.

MXene Nanosheet Templated Nanofiltration Membranes toward Ultrahigh Water Transport.

The demand for thin-film composite (TFC) nanofiltration membranes with superior permeance and high rejection is gradually increasing for seawater desalination and brackish water softening. However, improving the membrane permeance remains a great challenge due to the formation of excrescent polyamide in the substrate pores and thick polyamide film. Herein, we fabricated a high-performance TFC nanofiltration membrane via a classical interfacial polymerization reaction on a two-dimensional lamellar layer of transition-metal carbides (MXene). The MXene layer promoted the absorption of the reactive monomer, and higher amine monomer concentration facilitated the self-sealing and self-termination of interfacial polymerization to generate a thinner outer polyamide film from 68 to 20 nm. The almost nonporous lamellar interface inhibited the formation of inner polyamide in the substrate pores. In addition, the MXene lamellar layer could be eliminated by mild oxidation after interfacial polymerization to avoid imparted additional hydraulic resistance. The resulting TFC membrane conferred a high rejection above 96% for Na2SO4 and excellent permeance of 45.7 L·m-2·h-1·bar-1, which was almost 4.5 times higher than that of the control membrane (10.2 L·m-2·h-1·bar-1). This research provides a feasible strategy for fabricating a high-performance nanofiltration membrane using two-dimensional nanosheets as a templated interface.

Ultrathin Thin-Film Composite Polyamide Membranes Constructed on Hydrophilic Poly(vinyl alcohol) Decorated Support Toward Enhanced Nanofiltration Performance.

Traditional polyamide-based interfacial polymerized nanofiltration (NF) membranes exhibit upper bound features between water permeance and salt selectivity. Breaking the limits of the permeability and rejections of these composite NF membranes are highly desirable for water desalination. Herein, a high-performance NF membrane (TFC-P) was fabricated via interfacial polymerization on the poly(vinyl alcohol) (PVA) interlayered poly(ether sulfone) (PES) ultrafiltration support. Owing to the large surface area, great hydrophilicity, and high porosity of the PES-PVA support, a highly cross-linked polyamide separating layer was formed with a thickness of 9.6 nm, which was almost 90% thinner than that of the control membrane (TFC-C). In addition, the TFC-P possessed lower ζ-potential, smaller pore size, and greater surface area compared to that of the TFC-C, achieving an ultrahigh water permeance of 31.4 L m-2 h-1 bar-1 and a 99.4% Na2SO4 rejection. Importantly, the PVA interlayer strategy was further applied to a pilot NF production line and the fabricated membranes presented stable water flux and salt rejections as comparable to the lab-scaled membranes. The outstanding properties of the PVA-interlayered NF membranes highlight the feasibility of the fabrication method for practical applications, which provides a new avenue to develop robust polyamide-based NF desalination membranes for environmental water treatment.

Incorporation of Cellulose Nanocrystals (CNCs) into the Polyamide Layer of Thin-Film Composite (TFC) Nanofiltration Membranes for Enhanced Separation Performance and Antifouling Properties.

To achieve greater separation performance and antifouling properties in a thin-film composite (TFC) nanofiltration membrane, cellulose nanocrystals (CNCs) were incorporated into the polyamide layer of a TFC membrane for the first time. The results of Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed the successful formation of the CNC-polyamide composite layer. Surface characterization results revealed differences in the morphologies of the CNC-TFC membranes compared with a control membrane (CNC-TFC-0). Streaming potential measurements and molecular weight cutoff (MWCO) characterizations showed that the CNC-TFC membranes exhibited a greater negative surface charge and a smaller MWCO as the CNC content increased. The CNC-TFC membranes showed enhanced hydrophilicity and increased permeability. With the incorporation of only 0.020 wt % CNCs, the permeability of the CNC-TFC membrane increased by 60.0% over that of the polyamide TFC without CNC. Rejection of Na2SO4 and MgSO4 by the CNC-TFC membranes was similar to that observed for the CNC-TFC-0 membrane, at values of approximately 98.7% and 98.8%, respectively, indicating that divalent salt rejection was not sacrificed. The monovalent ion rejection tended to increase as the CNC content increased. In addition, the CNC-TFC membranes exhibited enhanced antifouling properties due to their increased hydrophilicity and more negatively charged surfaces.

Electrical-based ultrafiltration processes enhanced by in-situ generation of Fe(III): Significance of permanganate oxidation.

In this study, a permanganate-assisted electrocoagulation-ultrafiltration (PEC-UF) process was proposed to control membrane fouling in the treatment of secondary effluent. Four comparable systems, i.e., UF, electro-UF (E-UF), electrocoagulation-UF (EC-UF), and PEC-UF, were investigated to systematically clarify the role of permanganate and electrocoagulation in mitigating membrane fouling. Results revealed that the formation of a dense cake layer containing concentrated solutes was the primary reason for membrane fouling. Electrocoagulation significantly mitigated membrane fouling and resulted in the reduction of the normalized transmembrane pressure of the EC-UF and PEC-UF systems by 35.0% and 44.6% compared with the UF control system, respectively. However, the retention of a considerable amount of iron oxyhydroxide precipitates on the membrane surface aggravated inorganic fouling in the in-situ EC-UF system. Furthermore, the enhanced formation of Fe(III) by oxidation of Fe(II) with permanganate promoted the coagulation process. Hence, increased generation of Fe(III) and enhanced coagulation promoted by formed MnOx accelerated the formation of a hydrophilic cake layer with high porosity and thereby reduced the occurrence of both organic and inorganic membrane fouling. These results demonstrated the potential application of permanganate-assisted in-situ electrical-based methods to control UF membrane fouling during advanced wastewater treatment.

A passive-active combined strategy for ultrafiltration membrane fouling control in continuous oily wastewater purification.

Membrane-based technology has been confirmed as an effective way to treat emulsified oily wastewater, however, membrane fouling is still one of practical challenges in long-term operation. Herein, a novel passive-active combined strategy was proposed to control membrane fouling in continuous oily wastewater purification, where the δ-MnO2 decoration layer helped to reduce the total fouling ratio (passive strategy for fouling mitigation) and the catalytic cleaning effectively removed the irreversible oil fouling (active strategy for fouling removal). The functional membrane was prepared via in-situ modification, referred to as δ-MnO2@TA-PES. The morphology, crystalline phase, chemical structure and surface properties of the membranes were systematically characterized. Compared with PES, the δ-MnO2@TA-PES possessed superhydrophilicity, enhanced electronegativity and narrowed pore size. The δ-MnO2@TA-PES achieved high water permeation flux of 723.9 L·m - 2·h - 1·bar-1, excellent oil rejection with separation efficiency above 98.5% for various emulsions, and durable anti-oil-fouling performance with FRRb of 98.0%. Notably, the oil cake layer fouling on δ-MnO2@TA-PES was greatly alleviated owing to its enhanced surface properties. In addition, δ-MnO2@TA-PES showed high cleaning efficiency in the peroxymonosulfate (PMS) cleaning process, where the radical and nonradical pathways occurred simultaneously. And the active substances generated in the nonradical process (especially 1O2) were considered as the main contributor to the reduction of irreversible fouling. Overall, the novel strategy of fouling control ensured the efficient operation of ultrafiltration membranes for the continuous oily wastewater purification.

Surface coating of UF membranes to improve antifouling properties: A comparison study between cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs).

The inherent properties of hydrophilicity and environmental preferability of cellulose nanocrystals (CNCs) and cellulose nanofibers (CNFs) make them great candidates for application in water-treatment membranes. In this study, the antifouling properties of CNCs and CNFs, modified ultrafiltration (UF) membranes, were directly compared. A facile modification method was conducted by coating CNCs and CNFs on the surface of polyethersulfone (PES) membranes to prepare CNC-coating membranes and the CNF-coating membranes. Membrane surface morphology was characterized by atomic force microscopy (AFM), and the results showed that the CNF-coating membranes exhibited greater surface roughness than the CNC-coating membranes. Pure water flux measurements demonstrated that the flux of the CNC-coating membranes was slightly lower than that of the CNF-coating membranes. Antifouling properties were evaluated and compared for the two types of membranes by filtration of NOM foulant models, humic acid (HA) and bovine serum albumin (BSA). The results showed that the antifouling properties of the modified membranes were enhanced through the coating of either CNCs or CNFs to a control PES membrane. The CNC-coating membranes outperformed the CNF-coating membranes in alleviating both reversible fouling and irreversible fouling caused by HA and BSA. In addition, the antifouling performance of the coating membranes was enhanced with increased coating content.

Adhesion forces between Staphylococcus epidermidis and surfaces bearing self-assembled monolayers in the presence of model proteins.

Self-assembled monolayers (SAMs) are being developed into coatings to reduce microbial biofilm formation on biomaterials. To test anti-adhesion properties, SAMs can be easily constructed on gold, and used to represent a coated biomaterial. However, coatings that prevent bacterial adhesion must also resist protein adsorption. We explored the competitive effects of bacteria and protein for adsorption to SAMs, choosing fetal bovine serum (FBS) to represent protein non-specific binding, and fibronectin (FN) to evaluate ligand/receptor binding. Staphylococcus epidermidis were immobilized on an atomic force microscope (AFM) tip and used as a force probe to detect the interaction forces between bacteria and gold-coated SAMs. The SAMs tested were alkanethiol molecules terminating in isophthalic acid (IPA) or isophthalic acid with silver (IAG). While S. epidermidis showed weak interactions with FBS, the bacteria showed strong adhesion with FN, due to ligand/receptor binding. Bacterial retention and viability experiments were correlated with the force measurements. S. epidermidis interacting with IAG SAMs showed a loss of viability, due to the mobility of silver ions. For most substrata, there was a link between high adhesion forces with bacteria and a high percentage of dead cells being retained on that substratum (even in the absence of a specific biocidal effect, such as silver). This may suggest that high adhesion forces can cause stress to the bacteria which contributed to their death. The relationship between highly adhesive SAMs and bacterial inactivation may be useful in future biomaterial design. When evaluating coatings for biomaterials, it is important to consider the interplay between bacteria, proteins, and the coating material.

Quantifying the adhesion and interaction forces between Pseudomonas aeruginosa and natural organic matter.

Atomic force microscopy (AFM) was used to characterize interactions between natural organic matter (NOM), and glass or bacteria. Poly(methacrylic acid) (PMA), soil humic Acid (SHA), and Suwannee River humic Acid (SRHA), were adsorbed to silica AFM probes. Adhesion forces (Fadh) for the interaction of organic-probes and glass slides correlated with organic molecular weight (MW), but not with radius of the organic aggregate (R), charge density (Q), or zeta potential (zeta). Two Pseudomonas aeruginosa strains with different lipopolysaccharides (LPS) were chosen: PAO1 (A+B+), whose LPS have common antigen (A-band) + O-antigen (B-band); and mutant AK1401 (A+B-). Fadh between bacteria and organics correlated with organic MW, R, and Q, but not zeta. PAO1 had lower Fadh with silica than NOM, which was attributed to negative charges from the B-band polymers causing electrostatic repulsion. AK1401 adhered stronger to silica than to the organics, perhaps because the absence of the B-band exposed underlying positively charged proteins. DLVO calculations could not explain the differences in the two bacteria or predict qualitative or quantitative trends in interaction forces in these systems. Molecular-level information from AFM studies can bring us closer to understanding the complex nature of bacterial-NOM interactions.