Herein, expanded graphite is successfully combined with waterborne polyurethane to develop porous foams with underwater oleophobic properties for the separation of surfactant-free, oil-in-water mixtures and emulsions. To obtain foams with different pore sizes and therefore with different performances in the oil-water filtration process, two solvent-free fabrication processes are adopted. In the first one, the expanded graphite granules are mixed with the waterborne polyurethane (PUEGr), and in the second method, calcium carbonate is introduced to the two-component mixture (PUEGr_t). In both cases, the obtained foams exhibit hydrophilicity and oleophilicity in air and oleophobicity underwater, and they have porous interconnected networks, while their pore size distribution differs significantly. The foams can be used as 3D filters, able to separate, through gravity, surfactant-free, oil-in-water mixtures (10% w/w oil in water) with high oil rejection efficiencies and flow rates that depend on the type of foam. In particular, in the gravity-driven filtration process using 100 mL of the feed liquid, the PUEGr foams have an oil rejection efficiency of 96.85% and flow rate of 9988 L m-2 h-1, while for the PUEGr_t foams the efficiency is higher (99.99%) and the flow rate is lower (8547 L m-2 h-1) due to their smaller pore size. Although the PUEGr_t foams have slower separation performance, they are more efficient for the separation of surfactant-free emulsions (1% w/w oil in water) reaching an oil rejection efficiency of 98.28%, higher than the 95.66% of the PUEGr foams of the same thickness. The foams can be used for several filtration cycles, as well as in harsh conditions without deteriorating their performance. The nature of raw materials, the simple solvent-free preparation method, the effective gravity-driven filtration even in harsh conditions, and their reusability suggest that the herein engineered foams have great potential for practical applications in oil-water separation through highly energy-efficient filtration.
Keywords: oil rejection efficiency; porous materials; underwater oleophobicity; water remediation; waterborne polyurethane.