Atmospheric Pressure Plasma-Treated Polyurethane Foam as Reusable Absorbent for Removal of Oils and Organic Solvents from Water.

This paper reports the optimization of a two-step atmospheric pressure plasma process to modify the surface properties of a polyurethane (PU) foam and, specifically, to prepare a superhydrophobic/superoleophilic absorbent for the removal of oils and nonpolar organic solvents from water. In particular, in the first step, an oxygen-containing dielectric barrier discharge (DBD) is used to induce the etching/nanotexturing of the foam surfaces; in the second step, an ethylene-containing DBD enables uniform overcoating with a low-surface-energy hydrocarbon polymer film. The combination of surface nanostructuring and low surface energy ultimately leads to simultaneous superhydrophobic and superoleophilic wetting properties. X-ray photoelectron spectroscopy, scanning electron microscopy and water contact angle measurements are used for the characterization of the samples. The plasma-treated PU foam selectively absorbs various kinds of hydrocarbon-based liquids (i.e., hydrocarbon solvents, mineral oils, motor oil, diesel and gasoline) up to 23 times its own weight, while it completely repels water. These absorption performances are maintained even after 50 absorption/desorption cycles and after immersion in hot water as well as acidic, basic and salt aqueous solutions. The plasma-treated foam can remove mineral oil while floating on the surface of mineral oil/water mixtures with a separation efficiency greater than 99%, which remains unaltered after 20 separation cycles.

Preparation and characterization of cellulose nanofiber cryogels as oil absorbents and enzymatic lipolysis scaffolds.

Cellulose nanofiber (CNF) materials have received much attention as sustainable "green" materials with high mechanical properties. Their application in oil absorption and enzymatic lipolysis makes them further attractive from the perspective of environmental issues including marine pollution preservation. Herein, we prepared CNF cryogels with various surface properties, evaluated their capacities as oil absorbents and applied them as lipase-lipolysis scaffolds. Their obtained cryogels consisted of various modified CNFs and their structure and properties were investigated. Moreover, lipase-supported CNF cryogels were prepared for enzymatic lipolysis. The cryogels of protonated TEMPO-oxidized CNF showed the highest absorption capacity for olive oil, while all the CNF cryogels possessed similar absorption abilities towards water. In enzymatic lipolysis with lipase, the TEMPO-oxidized CNF (TOCN-Na+) cryogel showed the highest specific activity. The specific activities of lipase in TOCN-Na+ cryogels remained unchanged after being stored at 40 °C for 3 days.

White Graphene-Cobalt Oxide Hybrid Filler Reinforced Polystyrene Nanofibers for Selective Oil Absorption.

In this work, stable hydrophobic nanocomposites are made from electrospun fibers of polystyrene (PS) containing a hybrid filler combination of (i) hexagonal boron nitride (hBN) and (ii) cobalt oxide (Co3O4) nanomaterials. Good synergistic interaction is observed between the nanomaterials, since the growth of Co3O4 was carried out in presence of white graphene nanosheets. Filler synergy modifies the PS surfaces, by enhancing the filler-polymer interfacial interactions and provides good tensile strength. The hydrophobic films are gamma irradiated to improve crosslinking within the polymer nanocomposites. Since gamma irradiation enhances the surface roughness, its hydrophobicity/oleophilicity increases much and the final nanofibers show good oil-water separation efficiency. The nanofibers act as sponge clothing to skim the oil from a mixture of oil and water. Durability of the fibers in hot water and in presence of ultrasonic waves is also tested and good response is achieved. Contact angle studies are performed to investigate the surface properties and to check the influence of gamma irradiation on the surface wettability. The gamma-irradiated PS nanocomposite fiber shows a contact angle of 152° ± 2° compared to the 140° ± 1° of the neat PS fiber, evidencing the superhydrophobicity. Both the effects of crosslink density enhancement and hybrid filler distribution make the composite fibers stronger in oil absorption application even at higher operation temperatures. The fibers are reported to be robust and durable, in addition.

Micron-Size White Bamboo Fibril-Based Silane Cellulose Aerogel: Fabrication and Oil Absorbent Characteristics.

Micron-size white bamboo fibrils were fabricated from white bamboo and used as a source for the production of highly porous and very lightweight cellulose aerogels for use as a potential oil absorbent. The aerogels were fabricated through gelation from an aqueous alkali hydroxide/urea solution, followed by a conventional freeze-drying process. The morphology and physical properties of the aerogels were characterized by field emission scanning electron microscopy and Brunauer-Emmett-Teller surface area analysis, respectively. Successful silanization of the cellulose aerogel was confirmed by energy-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, and water contact angle measurements. The fabricated silane cellulose aerogel exhibited excellent absorption performance for various oil and organic solvents with typical weight gains ranging from 400% to 1200% of their own dry weight, making them promising versatile absorbents for a range of applications, including water purification.

Mitigation of Lost Circulation in Oil-Based Drilling Fluids Using Oil Absorbent Polymers.

In order to mitigate the loss circulation of oil-based drilling fluids (OBDFs), an oil-absorbent polymer (OAP) composed by methylmethacrylate (MMA), butyl acrylate (BA), and hexadecyl methacrylate (HMA) was synthesized by suspension polymerization and characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and scanning electronic microscopy (SEM). The oil-absorptive capacity of OAP under different solvents was measured as the function of temperature and time. The effect of the OAP on the rheological and filtration properties of OBDFs was initially evaluated, and then the sealing property of OAP particles as lost circulation materials (LCMs) was examined by a high-temperature and high-pressure (HTHP) filtration test, a sand bed filtration test, a permeable plugging test, and a fracture sealing testing. The test results indicated that the addition of OAP had relatively little influence on the rheological properties of OBDF at content lower than 1.5 w/v % but increased the fluid viscosity remarkably at content higher than 3 w/v %. It could reduce the HTHP filtration and improve the sealing capacity of OBDF significantly. In the sealing treatment, after addition into the OBDF, the OAP particles could absorb oil accompanied with volume enlargement, which led to the increase of the fluid viscosity and slowing down of the fluid loss speed. The swelled and deformable OAP particles could be squeezed into the micro-fractures with self-adoption and seal the loss channel. More important, fluid loss was dramatically reduced when OAP particles were combined with other conventional LCMs by a synergistic effect.

Fabrication and evaluation of nanocellulose sponge for oil/water separation.

Nanocellulose sponge was fabricated by a facile method: freeze-drying of nanocellulose aqueous suspension to sponge state, following by hydrophobic treatment with stearoyl chloride at 50 °C for 1 h. The obtained nanocellulose sponge showed superhydrophobicity (160° of water contact angle) and superoleophilicity with high protection from water but selective absorption of oil. Its absorption capacities for various kinds of oil and non-polar liquids were 25-55 times higher than its dry weight and exhibited excellent selectivity for absorbing of oil which spilled on the surface of water or underwater with high separation efficiency. This superhydrophobic nanocellulose sponge can be easily recovered by simple squeezing and reused at least 10 cycles with remained high separation efficiency. It is expected that such a biodegradable nanocellulose sponge can be applied to solve the oil spill accident and treat the oily wastewater from households and industries.

One-Step Preparation of Highly Hydrophobic and Oleophilic Melamine Sponges via Metal-Ion-Induced Wettability Transition.

Hydrophobic and oleophilic absorbent materials have received wide attention in recent years for potential applications in pollutant removal from accidental spills of oil or organic chemicals. In this work, we report a metal-ion-induced hydrophobic melamine sponge (MII-HMS) prepared by a one-step solution immersion process. The commercial melamine sponge (intrinsically superhydrophilic with a water contact angle of ∼0°) is immersed in an aqueous solution of transition metal ions (e.g., FeCl3, Fe(NO3)3, Zn(NO3)2, Ni(NO3)2, and Co(NO3)2) for a short period, followed by drying. This simple process renders the transition of the superhydrophilic melamine sponge to become highly hydrophobic (a water contact angle of ∼130°). Results from X-ray photoelectron spectroscopy and infrared spectroscopy suggest that the unprecedented transition is likely due to the formation of metal complexes during immersion. The MII-HMS is also oleophilic, exhibiting excellent oil absorption capabilities, ∼71-157 times of its weight, for a wide range of oils and organic solvents. Our work offers a simple, scalable, and economical approach to fabricate highly efficient absorbent materials for potential applications in oil spill recovery and environmental remediation.

Selective Cooperation with Liquids for Environmentally Friendly and Comprehensive Oil-Water Separation.

A hydrophobic 3 D material having smart relationship with oil under water (having both water affinity and water repellency in absence and presence of oil), is developed here using a scalable and facile 1,4-conjugate addition reaction between acrylate and amine groups at ambient conditions without using any catalyst. The material that was soaked with water in air is capable of absorbing both heavy and light oils with an efficiency above 1000 wt %, and the impregnated metastable aqueous phase was spontaneously and selectively ejected out from the material. This unprecedented super-oil-absorbance property remained intact in diverse scenarios, including extremes of temperature (100 and 10 °C), pressure (184.7 mbar), and prolonged (7 days) exposures to extremes of pH (1 and 12), surfactants-contaminated (dodecyltrimethylammonium bromide/sodium dodecyl sulfate, DTAB/SDS, 1 mm) water, artificial sea water, etc. Furthermore, this super-oil-absorbent having outstanding durability was exploited also in demonstrations of comprehensive and facile clean-up of oil from various forms of oil-water mixtures (i.e., floating light-oil, sediment heavy-oil, oil-in-water emulsions, etc.) in extremes and complex settings that are relevant to practical scenarios including marine oil spills, following ecofriendly and energy-efficient selective-absorption/active-filtration principles.

The electrospinning of the copolymer of styrene and butyl acrylate for its application as oil absorbent.

Electrospun polystyrene materials have been employed as oil absorbents, but they have visible drawbacks such as poor strength at low temperature and unreliable integrity because of brittleness and insufficient cohesive force among fibers. Butyl acrylate can polymerize into flexible chains, and its polymer can be used as elastomer and adhesive material. Thereby it is possible to obtain the material that has better performance in comparison with electrospun polystyrene material through the electrospinning of the copolymer of styrene and butyl acrylate. In this work, a polymer was synthesized through suspension polymerization by using styrene and butyl acrylate as comonomers. The synthesis of the copolymer of styrene and butyl acrylate was verified through dissolution and hydrolysis experimental data; as well through nuclear magnetic resonance spectrometry. The viscous flow activation energy of the solution consisting of copolymer and N, N-dimethylformamide was determined via viscosity method and then adopted to establish the entanglement characteristics of butyl acrylate's chain segments. Finally, in order to electrospin the copolymer solution into fibrous membrane, the effects of monomer feed ratio and spinning parameters were investigated. The prepared fibrous membrane was found to have a potential use as oil absorbent.

Fabrication of Porous Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Monoliths via Thermally Induced Phase Separation.

This study deals with the fabrication of biodegradable porous materials from bacterial polyester, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB3HHx), via thermally induced phase separation. P3HB3HHx monoliths with topological porous structure were prepared by dissolution of P3HB3HHx in dimethyl sulfoxide (DMSO) at 85 °C and subsequent quenching. The microstructure of the resulting P3HB3HHx monoliths was changed by the P3HB3HHx concentration of the polymer solution. Differential scanning calorimetry and polarized optical microscope analysis revealed that the P3HB3HHx monoliths crystallized during phase separation and the subsequent aging. The mechanical properties, such as compression modulus and stress, of the monoliths depended on the 3-hydroxyhexanoate content of P3HB3HHx. Furthermore, the P3HB3HHx monolith absorbed linseed oil in preference to water in a plant oil⁻water mixture. In combination with the biodegradable character of P3HB3HHx, the present study is expected to contribute to the development of bio-based materials.