Design of a super-hydrophilic/super-oleophobic g-C3N4/Ti(OH)4/PFOA nanocomposite coated mesh as a smart nanofilter with robust anti-fouling properties for separation of oil and water emulsions

The design and development of efficient approaches for water–oil separation have had widespread interest. This study aimed to synthesize nanocomposites based on Ti(OH)₄ and g-C₃N₄ nanosheets (CN-NS) to show experimentally that the inclusion of Ti(OH)₄ nanoparticles of 9.2 nm size into CN-NS leads to an improved oil-water separation efficiency and anti-fouling performance. So, a novel, reusable, and recyclable super-hydrophilic/underwater super-oleophobic CN-NS/Ti(OH)₄ nanocomposite-coated stainless steel mesh was developed to separate oil-in-water emulsions. Super-wettability was obtained in the CN-NS/Ti(OH)₄ nanocomposite with WCA = 0° and UOCA = 154°, respectively, showing significant super-hydrophilicity and underwater super-oleophobicity. Surface hydrophilicity increased after anchoring Ti(OH)₄ on the CN-NS surface, resulting from oxygen-containing functional groups and consequently making defects on the mesh surface. Enhanced underwater oleophobicity of nanocomposite coated mesh is attributed to its higher surface roughness, which is a result of its micro-nano meter and mesoporous hierarchical structure. Moreover, the self-cleaning property of the as-prepared mesh was demonstrated by visible light irradiation on the contaminated mesh. In addition, perfluorooctanoic acid (PFOA) reduced energy in CN-NS/Ti(OH)₄/PFOA mesh, resulting in a super-hydrophilic/super-oleophobic mesh. The CN-NS/Ti(OH)₄/PFOA nanocomposite-coated filter was observed to separate water from a 1 wt% water-in-oil emulsion at 0.2 bar pressure with a filtration flux of 317.2 L m⁻² h⁻¹ and 95% separation efficiency.     

High-flux whisker layer ceramic membrane prepared by gel spin-coating method for low-pressure oil/water emulsion filtration

Insufficient permeability and membrane fouling significantly influence the efficiency of ceramic microfiltration (MF) membranes in oil/water emulsion treatment. In this study, a high-flux whisker layer ceramic MF membrane with super-hydrophilicity was successfully fabricated through gel-spin coating method and a low-temperature oxidation method, which was used to separate oil/water emulsion. The effects of the whisker layer and surface wettability were systematically investigated, and the mechanism of in-situ gelling and pore size distribution was proposed. The super-hydrophilic ceramic MF membrane with an average pore size of 250 nm exhibited a high gas flux of 934 m³/(m²·h·bar) and excellent pure water flux of 9754 L/(m² h bar). Even after a long-term circulating filtration process, the super-hydrophilic ceramic MF membrane still maintained a high water flux of over 50 L/(m²·h) at a transmembrane pressure of 5 KPa during the treatment of oil-in-water emulsion with a concentration of 1000 mg/L. Overall, the developed ceramic MF membrane demonstrated high permeability and excellent anti-fouling performance, making it a promising candidate for oil/water emulsion wastewater treatment.     

Preparing ceramic membranes for oil-in-water emulsions separation with oil-based drilling cutting pyrolysis residues (ODPRs) as raw material

Oil-based drilling cutting pyrolysis residues (ODPRs) are one of the solid wastes from pyrolysis of the oil-based drilling cuttings (OBDCs) that need to be recycled as raw materials to avoid the possible pollution. In this study, a facile low-cost ceramic membrane for oil-in-water emulsions separation was prepared with ODPRs incorporating with fly ash as raw material. CaCO₃ in ODPRs would decompose acting as pore-forming agent, and anorthite was formed in resultant membranes. The obtained membrane with 30 wt% ODPRs and 70 wt% fly ash fired at 1050 °C possessed apparent porosity of 38.2%, mean pore size of 0.4 μm, flexural strength of 13.1 MPa, and Darcy permeability of 1.06 × 10⁻¹³ m². Consequently, commendable filtration performance for oil-in-water emulsions was presented. In addition, the ceramic membrane showed favorable recyclability and corrosion resistance. Leaching test indicated that the membrane is safe for oil-in-water emulsion separation. Hereby, this paper confirmed the availability of ODPRs for preparing ceramic filtration membranes, and provided a new environmental conservation way to treat oil-in-water emulsions that was consistent with the sustainable development goals.     

One-step preparation of asymmetric ceramic membranes based on sea urchin-like mullite whisker skeletons and their oil-water separation properties

In this work, novel sandwich-type asymmetric ceramic microfiltration membranes with a sea urchin-like mullite whisker skeleton were prepared one step. Their structural properties and oil-water separation performance were investigated. The results show that after sintering at 1400 °C, the prepared membrane possesses good hydrophilic, underwater oleophobic, and anti-fouling properties. During the continuous separation of a 300 mg/L oil-in-water emulsion, a maximum stable flux of 267 L·m⁻²·h⁻¹ was achieved without membrane cleaning. After chemical cleaning and simple physical cleaning, the membranes recovered to a steady flux of 397 L·m⁻²·h⁻¹ and 305 L·m⁻²·h⁻¹, respectively, and maintained a 95% oil rejection. The good underwater oleophobicity and selective permeability brought about by the flat-lying whiskers on the top surface, coupled with the efficient water channels between the sea urchin-like structures inside the membrane, are considered to be the main reasons for its improved separation characteristics over conventional low-cost ceramic membranes.     

Microstructure–performance relationships of hollow-fiber membranes with highly efficient separation of oil-in-water emulsions

The critical breakthrough pressure related to the membrane surface wettability and pore size is a key parameter determining membrane performance in particular applications, such as oil–water mixture separations. A series of hydrophilic polysulfone hollow-fiber membranes with different pore sizes were prepared and characterized to evaluate the separation performance of oil-in-water emulsions and to develop an optimum membrane for such emulsions. For the optimum membrane, the absolute value for the cosine of the surface oil droplet contact angle (0.72) was close to the ratio of the outer surface pore size to the oil droplet size (0.71); it was also similar to the absolute value of the cosine of the underwater oil contact angle on the polysulfone material (0.65). From the point of view of the surface wettability, theoretical calculations were performed to select a suitable membrane with the aim of reaching the maximum efficiency in practical oil–water mixture separation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47615.     

Porous Al2O3 ceramics with directional gradient pore structure modified by cobweb-bridged WO3 nanowires for oil/water emulsions separation

A novel Al₂O₃ ceramic membrane modified by cobweb-bridged WO₃ nanowires was successfully fabricated for oil/water emulsions separation. Freeze-casting was employed to obtain directional gradient Al₂O₃ porous ceramics at first. Then, the cobweb-bridged WO₃ nanowires were successfully introduced into the separation layer by in-situ hydrothermal synthesis to construct the WO₃ nanowires/Al₂O₃ membrane. Results showed that WO₃ nanowires increased the surface roughness from 45.9 nm to 54.8 nm, the instantaneous water contact angle (WCA) and underwater oil contact angle (UOCA) reached the optimum values of 8.5° and 157.8°, respectively. Construction of cobweb-bridged WO₃ nanowires not only achieved a high separating efficiency of oil/water emulsions up to 92.35%, but also maintained high permeation fluxes at around 1600 L/m²·h·bar. After 10 cycles, the separation efficiency of the membrane remained above 90%. Moreover, the WO₃ nanowires/Al₂O₃ membrane still maintained underwater superoleophobicity after being immersed in strongly acidic, alkaline, and saline solutions, showing a high UOCA above 150° for all tested oil. The WO₃ nanowires/Al₂O₃ membrane is promising in oil/water emulsions separation application for its high separation efficiency, durability, and excellent chemical stability.     

CO2 capture based on Al2O3 ceramic membrane with hydrophobic modification

In this paper, Al₂O₃ ceramic membrane is modified to hydrophobicity by grafting 1 H,1 H,2 H,2 H-perfluorodecyltriethoxysilane. And its properties are characterized in detail. CO₂ capture performance of ceramic membrane is investigated by experiments. Results show that wetting resistance after modification is significantly improved, and contact angle increases from the initial 49.8–130.9°. However, hydrophobic modification has no significant effect on the crystalline phase, surface morphology and pore size distribution of the ceramic membrane. With ethanolamine (MEA) as absorbent, CO₂ mass transfer rate and capture efficiency using modified hydrophobic ceramic membrane are 46.6 × 10⁻³ mol/(m²·s) and 98.0%, showing significantly increase compared to the original membrane. After 72 h immersion in MEA solution, quality of ceramic membrane does not change significantly. And there is almost no change in average pore size. We believe this study will provide a reference for the industrial application for CO₂ capture by gas-liquid membrane contactor with ceramic membrane.     

Using a simple method to prepare UiO-66-NH2/chitosan composite membranes for oil–water separation

Chitosan (CS) was used as a cross-linking agent to modify UiO-66-NH₂, and the modified UiO-66-NH₂ was fixed on the mixed cellulose membrane (MCE) through vacuum filtration technology to prepare a new type of membrane. The membrane exhibited excellent hydrophilicity in the air and excellent super-oleophobic performance underwater, and effectively separated various oil–water emulsions. When separating petroleum ether-water emulsion, the filtration flux of the modified membrane was 2000 L m⁻² h⁻¹ higher than that of MCE, and the separation efficiency can reach more than 95%. After 10 cycles, the flux of the modified membrane was about four times of that MCE, which was 500 L m⁻² h⁻¹. Most importantly, the membrane still maintained underwater superoleophobicity in the environment of strong acid, strong base, and salt solution.     

Self-cleaning ceramic tiles coated with Nb2O5-doped-TiO2 nanoparticles

In this work, 5 mol% Nb₂O₅-doped TiO₂ synthesized sol was sprayed on glazed ceramic tiles. The crystallization of TiO₂ nanoparticles occurs on the surface of the tiles after annealing at 600–900 °C, this innovative approach leads to a drastic decrease in the titania grain size as detected by SEM and XRD. The superhydrophilic and self-cleaning performance was evaluated by measuring the water contact angle under UV irradiation and by degradation of methylene blue according to ISO 10678 and JIS R1703-2. The results showed a high performance of doped samples at all temperatures tested, with a marked dependence on the anatase-to-rutile ratio and crystallite size. At 800 °C, the doped samples achieved water contact angle near to zero in just 15 min of UV irradiation, which confirms the high performance of the self-cleaning ceramic tiles.     

A TiO2 modified whisker mullite hollow fiber ceramic membrane for high-efficiency oil/water emulsions separation

Design and preparation of membranes with ultrahigh separation performance and antifouling property for oil-in-water (O/W) emulsions remains challenging. In this study, a high flux mullite/TiO₂ ceramic composite membrane was prepared via multi-precipitation of TiO₂ on a whisker mullite hollow fiber support synthesized by combining phase inversion and high-temperature sintering techniques. The results showed that the generated whisker mullite structure improved the permeation flux, and the micro-nano structured TiO₂ functional layer endowed the membrane surface with superhydrophility and stability. The retention of the optimal composite membrane (M20T13) that was soaked in the titanium solution 20 times for 13 min each time for the O/W emulsions like n-hexane, toluene and engine oil maintained over 98 %, and the flux after 6 h filtration was 668.34 L·m⁻²·h⁻¹, 487.25 L·m⁻²·h⁻¹ and 258.66 L·m⁻²·h⁻¹, respectively, much higher than that of the optimal substrate (F3A1, mass ratio of fly ash: Al₂O₃ = 3:1). Moreover, the flux recovery rate of M20T13 was much higher than that of F3A1 after chemical backwashing. This work manifests great potential in O/W treatment fields.     

Impact of TiO2 nanoparticles and nanowires on corrosion protection performance of chemically bonded phosphate ceramic coatings

The impact of the addition of TiO₂ nanoparticles and nanowires on the morphology, phase characteristics, contact angle, and electrochemical performance of chemically bonded phosphate ceramic coatings (CBPCs) was investigated. The chemical composition and surface morphology of the TiO₂ nanoparticle and nanowire modified with and without (heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysilane were characterized. Results indicated that the hydrophobic –CF₂– and –CF₃ groups were successfully introduced into the TiO₂ nanoparticles and nanowires after modification. Corrosion resistance of CBPCs with TiO₂ was evidently improved compared with that without TiO₂. Such improvement was mainly due to the combined effects of low surface energy materials and micro/nano structures. In addition, CBPCs with TiO₂ nanowires exhibited higher hydrophobicity and corrosion resistance than those with TiO₂ nanoparticles because of the special columnar structure of the nanowires.     

Preparation of super-hydrophilic amorphous titanium dioxide thin film via PECVD process and its application to dehumidifying heat exchangers

The super-hydrophilic amorphous titanium dioxide (TiO₂) thin film was prepared by plasma-enhanced chemical vapor deposition (PECVD) process for an application to dehumidifying finned-tube heat exchangers. The chemical components and surface structure were characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscope (SEM). The wettability and long-term durability were investigated by measuring the water contact angle and by performing wet/dry cycles. The samples were subjected to 1000 times of wet/dry cycles to establish long-term durability. The water contact angle of the amorphous TiO₂ thin film was about 8° at as-deposited film with O₂ plasma treatment and was about 15° after 1000 wet/dry cycles. The amorphous TiO₂ thin film had excellent wettability and long-term durability under full wetting conditions.     

Application of piezoelectric quartz for self-cleaning membrane preparation

Separation membranes that are prepared from piezoelectric ceramics can generate ultrasound on-line to maintain surface cleanliness. Here, a lead-free piezoelectric support is presented consisting of quartz. The Na₂O and Al₂O₃ were employed as sintering aids to improve the mechanical performance of piezoelectric quartz support while avoid the formation of no-piezoelectric cristobalite. A ZrO₂-based thin microfiltration membrane layer was applied on the optimized support. The membrane structure, thus obtained had an average pore size and ultrasonic emission of 270 nm and 5.1 mV, respectively. The stationary permeance of the membrane in the treatment of oil-in-water emulsion was 163 L m^?2?h^?1?bar^?1 (LMH/bar). With the application of alternating voltages of 60 V and 100 V, the permeance increased to 198 and 225 LMH/bar, respectively, and the oil rejection was maintained above 97%. The in-situ ultrasound directly acted on membrane surface, so it removed more fouling resistance at lower power than the external one.     

Recycling of waste attapulgite to prepare ceramic membranes for efficient oil-in-water emulsion separation

Large-scale application of ceramic membranes is restricted by high cost resulting from raw materials and sintering process. In this study, low-cost ceramic membranes were prepared with waste attapulgite (WAT) and α-Al₂O₃ as starting materials and used for oily wastewater treatment. The optimal membrane sintered at 1100 °C possessed excellent properties, with open porosity of 41.6%, flexural strength of 37.2 MPa and average pore size of 0.40 μm. The membrane also displayed outstanding permeability and chemical stability. The hydrophilicity and underwater oleophobicity were enhanced after surface modification. When used for oil-in-water emulsion filtration, the permeate flux reached 236.8 L m^?2 h^?2 bar^-1 under a low transmembrane pressure of 0.2 bar and the oil rejection exceeded 99%. Membrane cleaning with a simple ultrasonic treatment could easily achieve flux recovery. This study proposed a feasible strategy for both solid waste utilization and oily wastewater treatment.     

Super-insulating,ultralight and high-strength mullite-based nanofiber composite aerogels

Ceramic nanofiber aerogel is one of the most attractive insulation materials in recent years. However, its practical application ability is limited at high temperature due to high radiation heat transfer. Herein, we constructed a novel closed-cell/nanowire structured mullite-based nanofiber composite aerogel via electrospinning technology and solvothermal synthesis method. Hollow TiO₂ spheres were used as pore-making material and infrared opacifier to reduce fiber solid heat conduction and high temperature radiation heat transfer simultaneously. In addition, TiO₂ nanowires grown in-situ on the fiber surface further decrease the radiation heat transfer of aerogel and improve the mechanical properties. The unique structure endows the aerogel with high mechanical robustness (0.32–0.35 MPa, 10% strain), low density (39.2–47.5 mg/cm³) and ultralow thermal conductivity (~0.017 W m^?1 K^?1 at 25 ℃ and ~0.056 W m^?1 K^?1 at 1000 ℃). This work offers a novel strategy for the development of ceramic nanofiber aerogel at high temperature.     

Preparation and capacitance performance of nitrided lithium titanate nanoarrays

Nitrided lithium titanate (N-Li₄Ti₅O₁₂) nanoarrays with nanowire and nanotube structures were designed as the electrode materials of lithium-ion supercapacitor for electrochemical energy storage. Two types of TiO₂ nanoarrays were used as the precursor which involved TiO₂ nanowire array prepared by hydrothermal process and TiO₂ nanotube array prepared by anodization process. Li₄Ti₅O₁₂ nanoarrays were formed through hydrothermal reaction or sonochemical reaction of TiO₂ nanoarrays with lithium hydroxide and then calcination treatment process. Finally, N-Li₄Ti₅O₁₂ nanoarrays were formed through nitriding treatment of Li₄Ti₅O₁₂ using ammonia as nitrogen source. The electroactive N-Li₄Ti₅O₁₂ nanowire array and nanotube array exhibited the specific capacitance of 607.2 F g⁻¹ and 814.4 F g⁻¹ at a current density of 1 A g⁻¹, respectively. The corresponding capacitance retention was determined to be 92.1% and 94.2% after 1000 cycles at high current density of 5 A g⁻¹. The corresponding capacitance still kept 182.9 and 352.1 F g⁻¹ at much higher current density of 20 A g⁻¹, presenting reasonable rate capability for N-Li₄Ti₅O₁₂ nanoarrays. The improved capacitance performance of N-Li₄Ti₅O₁₂ nanotube array was ascribed to the more amount of TiN and more accessible nanotube surface area, which contributed to the improved conductivity and fast diffusion of electrolyte ions on the surface of electrode. Both N-Li₄Ti₅O₁₂ nanowire array and nanotube array with well-aligned integrative structure exhibited an excellent cycling stability during continuous charge/discharge process. Well-designed N-Li₄Ti₅O₁₂ nanoarrays with high capacitance, good cycling stability and rate capability presented the promising application as feasible electrode materials of lithium-ion supercapacitors for the energy storage.     

Synthesis and characterization of PVA/PES thin film composite nanofiltration membrane modified with TiO2 nanoparticles for better performance and surface properties

Novel polyethersulfone (PES)/poly (vinyl alcohol) (PVA)/titanium dioxide (TiO₂) composite nanofiltration membranes were prepared by dip-coating of PES membrane in PVA and TiO₂ nanoparticles aqueous solution. Glutaraldehyde (GA) was used as a cross-linker for the composite polymer membrane in order to enhance the chemical, thermal as well as mechanical stabilities. TiO₂ nanoparticles with different concentrations (0, 0.05, 0.1, 0.5 wt.%) were coated on the surface of PVA/PES composite membrane. The morphological study was investigated by atomic force microscopy (AFM), scanning surface microscopy (SEM) and along with X-ray diffraction (XRD). In addition, the membranes performances, in terms of permeate flux, ion rejection and swelling factor were also investigated. It was found that the increase in TiO₂ solution concentration can highly affect the surface morphology and filtration performance of coated membranes. The contact angle measurement and XRD studies indicated that the TiO₂ nanoparticles successfully were coated on the surface of PVA/PES composite membranes. However, rougher surface was obtained for membranes by TiO₂ coating. The filtration performance data showed that the 0.1 wt.% TiO₂-modified membrane presents higher performance in terms of flux and NaCl salt rejection. Finally, TiO₂ modified membranes demonstrated the lower degree of swelling.     

Synthesis and characterization of bionanocomposites of poly(lactic acid) and TiO2 nanowires by in situ polymerization

Bionanocomposites from biopolymers and inorganic nanoparticles are of great interest for packaging materials due to their enhanced physical, thermal, mechanical, and processing characteristics. In this study, poly(lactic acid) (PLA) nanocomposites with covalent bonding between TiO₂ nanowire surface and PLA chains were synthesized through in situ melt polycondensation. Molecular weight, structure, morphology, and thermal properties were characterized. Fourier transform infrared spectroscopy confirmed that PLA chains were covalently grafted onto TiO₂ nanowire surface. Transmission electron microscopy images also revealed clearly a third phase presence on the nanowires after the grafting process. Those grafted PLA chains exhibited significantly increased glass transition temperature and thermal stability, compared with pure PLA. The weight-average molecular weight of PLA/2% TiO₂ nanowire bulk nanocomposites increased by 66% compared with that of pure PLA. The electron microscopy results showed that strong interfacial interaction and homogeneous distribution were achieved between inorganic nanowires and organic PLA matrix in the bulk nanocomposites. The PLA matrix in bulk nanocomposites exhibited elevated glass transition temperature and decreased crystallization ability as the TiO₂ nanowire concentrations were increased from 0 to 2%.     

Fibrous ceramic membrane constructed by mullite whiskers for the treatment of oil-in-water emulsions

Ceramic membranes with high porosity and excellent separation efficiency are necessary for the efficient treatment of large-scale wastewaters. However, the conventional ceramic membranes are usually prepared by particles-packing, which inhibits the advances of separation efficiency because of the low porosity and connectivity. Here, a fibrous ceramic membrane with mullite whiskers-interlocked structure was prepared by gas-solid reaction. The effects of aluminum fluoride (AlF₃) on the formation and growth of mullite whiskers, and then the permeability and selectivity of the ceramic membranes were investigated. With the increase of AlF₃ contents, the mullite phase evolved from needle-like, rod-like to flake-like structure, thus the catalyst accelerated the growth of mullite whiskers in the diameter direction. For the ceramic membrane sintered at 1400°C, the porosity increased from 58% to 76% while the average pore sizes increased from 0.65 to 3.93 μm because of the whisker-constructed structures. For the ceramic membrane sintered at 1450°C, the emulsion flux increased stably from 295 L/(m²·h) to 992 L/(m²·h) with the increase of trans-membrane pressure, and the oil rejection exceeded 98%. Thus, this study provides a feasible strategy for the preparation of ceramic membranes with high porosity and excellent separation performances.     

Structural,dielectric and mechanical behaviors of (La,Nb) Co-doped TiO2/Silicone rubber composites

Ceramic/polymer composites have great potential to achieve the concomitant enhancement of both dielectric constant and breakdown field while maintaining other superior properties of the polymer matrix, ideal for elastomer sensors, actuators, capacitive energy storage, and many other applications. However, material incompatibility between the ceramic filler and the polymer matrix often leads to void formation, particle aggregation and phase separation, with significantly degraded performance. Herein, through surface modification, co-doped TiO₂ particles were uniformly dispersed and bridged onto the silicone rubber matrix via a silane coupling agent for fabricating composites via mechanical mixing and hot-pressing. The synthesized composites exhibit enhanced dielectric constant, increased from 2.78 to 5.06 when 50 wt% co-doped TiO₂ particles are incorporated. Their dielectric loss is less than 0.001 in a broad frequency range. Theoretical modelling and experimental results reveal that the morphology and dispersion state of co-doped TiO₂ particles were crucial to the dielectric properties of the silicone rubber-based composites. Besides, the composites are thermally stable up to 400 °C. Significantly increased tensile strength (612 kPa) and elongation at break (330%) were obtained for the composite incorporated with 30 wt% co-doped TiO₂ particles, accompanied by a moderate increased elastic module (540 kPa). Such composites have the potential for different applications.