ABSTRACT
Biobased membranes made with green solvents have numerous advantages in the water purification industry; however, their long-term use is impeded by severe membrane fouling and low structural stability. Herein, we proposed a facile and green approach to fabricate an eco-friendly and biodegradable electrospun membrane by simply blending polycaprolactone (PCL) with sulfonated kraft lignin (SKL) in a green solvent (i.e., acetic acid) without needing any additional post-treatment. We investigated the influence of SKL content on the surface morphology, chemical composition, and mechanical properties of the electrospun membrane. The SKL-modified membranes (L-5 and L-10) showed superhydrophilicity and underwater superoleophobicity with a water contact angle (WCA) of 0° (<3 s) and an underwater-oil contact angle (UWOCA) over 150° due to the combined effect of surface roughness and hydrophilic chemical functionality. Furthermore, the as-prepared membranes demonstrated excellent pure water flux of 800-900 LMH and an emulsion flux of 170-480 LMH during the gravity-driven filtration of three surfactant-stabilized oil-in-water emulsions, namely, mineral oil/water, gasoline/water, and n-hexadecane/water emulsions. In addition, these membranes exhibited superior antioil-fouling performance with excellent separation efficiency (97-99%) and a high flux recovery ratio (>98%). The 10 wt % SKL-incorporated membrane (L-10) also showed consistent separation performance after 10 cyclic tests, indicating its excellent reusability and recyclability. Furthermore, the stability of the membrane under harsh pH conditions was also evaluated and proved to be robust enough to maintain its wettability in a wide pH range (pH 1-10).
ABSTRACT
A worldwide steady increase in oily wastewater, due to oil spillage and various industrial discharges, requires immediate efforts toward development of an effective strategy and materials to preserve the natural water bodies. Designing a superwettable fibrous membrane of robust structure and anti-fouling property for efficient separation of oil-water mixtures and emulsions is therefore highly demanding. The electrospun fibrous membrane, which possesses porosity and flexibility and properties including superwettability and tunable functionality, can be considered as apposite materials for this cause. In this approach, we combined two strategies, viz., Pickering emulsion and near gel resin (nGR) emulsion electrospinning together to produce a fibrous nanocomposite membrane for efficient oil-water separation and demulsification. nGR Pickering emulsions were stabilized using hydrophilic SiO2 nanoparticles and successfully optimized for fabricating the crosslinked core sheath-structured fibrous membrane. The prepared membrane provided twofold functionality due to the core sheath structure of the fibers. The crosslinked polystyrene core offered high oil adsorption capacity, whereas SiO2-functionalized crosslinked polyvinyl alcohol sheath provided a rough, superhydrophilic surface with underwater oleophobic behavior to the membrane. The optimized SiO2-Pickering emulsion-templated nanocomposite membrane demonstrated excellent underwater anti-oil adhesion behavior (UWOCA â¼148°) with efficient oil-water separation capacity of more than 99% and separation flux up to 3346 ± 91 L m-2 h-1. The membrane was evaluated against various oil-water emulsions and found to have a superior separation efficiency. Moreover, excellent anti-oil adhesion property provided the intact membrane, where consistent separation performance was achieved up to 10 separation cycles without any loss. The membrane was used for separation of hot oil-water emulsions and showed no structural disintegration or loss in separation performance when exposed to elevated temperatures. The developed nanocomposite membranes could efficiently be used for separation and demulsification, and their applications can be explored in various other fields including selective sorption, catalysis, and storage in future.
ABSTRACT
Electrospun fibers and matrices have been researched for their utility in various fields; however, because of poor mechanical strength and loss of structural integrity, their commercial viability is limited. A near gel resin (nGR) of polystyrene (PS) was used in the present approach to fabricate cross-linked fibrous matrices of better mechanical strength and oil adsorption while retaining the structural integrity. Electrospinnability of nGR was assessed in bulk (i.e., in styrene monomer) and solution (i.e., in dimethyl formamide) forms with variations in formulation and electrospinning conditions. Ultimately, a uniform cross-linked fibrous matrix of PS was prepared using an oil-in-water emulsion, where the oil phase composed of a monomer (styrene), an initiator (benzoyl peroxide), and a cross-linker (divinylbenzene) was dispersed in a continuous phase of aqueous poly(vinyl alcohol) (PVA). The monomer conversion in the oil phase was carried out below the gel point, and the nGR of PS formed in dispersed droplets was electrospun to fabricate uniform fibrous matrices with the help of a template polymer, that is, PVA. The effect of various material and process parameters on the gelation behavior, electrospinnability, and fiber uniformity was studied and optimized to produce uniform core-sheath fibrous matrices of cross-linked PS. Postelectrospinning heat treatment of matrices was carried out to achieve complete monomer conversion and cross-linking. Fiber formation behavior of the emulsion was assessed using ionic and nonionic surfactants. The cross-link density of the matrices was optimized to achieve the desired structural morphology and dimensional stability. The process of fabrication of emulsion electrospun cross-linked fibers can be further extended to a variety of other monomers in order to enhance the suitability of fibrous matrices for many applications.
