Dynamic Fouling Experiments Research Articles

Comparison of organic fouling resistance of thin-film composite membranes modified by hydrophilic silica nanoparticles and zwitterionic polymer brushes

We conducted a comparative study to investigate the efficacies of two different types of highly hydrophilic materials (i.e., silica nanoparticles (SiNPs) and zwitterionic polymers) for antifouling surface modification of polyamide thin-film composite (TFC) membranes. Dense layers of SiNPs and zwitterionic polymer brushes were grafted on the membrane surfaces via dip-coating with aminosilane-functionalized SiNPs (i.e., SiNP-TFC membrane) and surface-initiated atom-transfer radical-polymerization of sulfobetaine methacrylate (i.e., PSBMA-TFC membrane), respectively. With the same degree of enhancement of surface hydrophilicity and identical surface roughness, the PSBMA-TFC membrane exhibited significantly higher fouling resistance than the SiNP-TFC membrane in adsorption tests of proteins and bacteria as well as in forward osmosis (FO) dynamic fouling experiments using alginate as a model organic foulant. Chemical force microscopy measurements revealed that membrane-foulant electrostatic attraction aggravates organic fouling of the SiNP-TFC membrane to a certain degree, but the primary fouling mechanism is the complexation of organic foulants with carboxylic groups on the polyamide membrane surface. We attribute the lower fouling resistance of the SiNP-TFC membrane to the high density of surface carboxylic groups that may still be accessible to foulants as well as to membrane-foulant electrostatic interaction. On the contrary, the zwitterionic polymer brushes effectively shield the surface carboxylic groups and provide steric hindrance against foulant adsorption due to significant hydration of the zwitterionic brushes.

Efficacy of antifouling modification of ultrafiltration membranes by grafting zwitterionic polymer brushes

Abstract We studied the efficacy of grafting zwitterionic polymer brushes for the antifouling modification of ultrafiltration (UF) membranes. Poly(vinylidene fluoride) (PVDF) UF membranes were modified by surface initiated atom transfer radical polymerization (SI-ATRP) to graft poly(sulfobetaine methacrylate) (PSBMA) brushes to the membrane surface. Protein adsorption tests and chemical force microscopy show that a large brush layer thickness (greater than 100 nm) is necessary in order to impart effective fouling resistance. In dynamic fouling experiments with bovine serum albumin (BSA) as a model foulant, however, the modified membranes exhibited only a slight increase of flux recovery after fouling compared to pristine PVDF membranes. Despite the thick PSBMA brush layer, this low water flux recovery indicates that internal fouling takes place within the membrane pores. To prevent internal fouling, we grafted PSBMA brushes to both the surface and internal structure of the membranes. Nevertheless, dynamic fouling experiments again showed only a minute improvement in water flux recovery. While a thick brush layer is required for effective fouling resistance, we note that the small pore size of UF membranes imposes a fundamental limit on the brush layer thickness inside the pores. Finally, we discuss the challenges of polymer brush grafting for antifouling UF membrane modification and suggest possible alternative methods to create fouling resistant UF membranes.

Amine enrichment and poly(ethylene glycol) (PEG) surface modification of thin-film composite forward osmosis membranes for organic fouling control

Despite significant advances in forward osmosis (FO) membrane development, organic fouling, due to adsorption of organic molecules prevalent in natural waters and wastewater effluents, remains a major technical problem, decreasing process performance and membrane life. We report the fabrication, characterization, and testing of thin film composite (TFC) FO membranes functionalized with poly(ethylene glycol) (PEG) for improved fouling resistance. The membranes comprise a microporous polysulfone support over which a polyamide selective layer is synthesized by interfacial polymerization. To facilitate PEG grafting, a second interfacial reaction is carried out between ethylenediamine and acyl chloride groups on the nascent polyamide layer, yielding a selective layer rich in primary amine groups. The resulting amine-rich active layer is functionalized with PEG diglycidyl ether, whose epoxide groups readily react with primary amines. Surface characterization by ATR-FTIR spectroscopy and zeta-potential measurements shows the presence of PEG and amine groups on the membrane surface, and contact angle measurements demonstrate that the PEG-functionalized active layer is more hydrophilic than that of control polyamide membrane surfaces (whose active layer does not contain a grafted PEG layer). We report the results of dynamic fouling experiments using alginate as model organic foulant, showing that membrane fouling is significantly reduced in the case of PEGylated membranes, due to the presence of a PEG barrier that hinders foulant adsorption. Finally, we use AFM adhesion force measurements to demonstrate that the interaction energy between a carboxylated colloidal probe and the PEGylated membrane is significantly weakened as compared to the control polyamide surface. The approach of amine enrichment of the membrane active layer that is reported in this work holds promise as a versatile platform on which to study different anti-fouling modifications.