Micro-nano Binary Structure Research Articles

Surface engineering of cellulose film with myristic acid for high strength, self-cleaning and biodegradable packaging materials

Developing sustainable, renewable, hydrophobic, and biodegradable packaging material to replace petroleum-based plastic products remains a challenge. Herein, original cellulose/myristic acid composite films were fabricated by solvent-vaporized controllable crystallization of natural myristic acid on anisotropic cellulose films. The myristic acid crystals that evenly distributed on the surface of cellulose film generated micronano binary structure and the interstitial space between microplates, resulting in high hydrophobicity (water contact angle = 132°) and excellent self-cleaning property of the composite film. The resultant film exhibited good tensile strength and toughness under both dry (188.7 MPa, 34.4 MJ m−3) and humid conditions (119.9 MPa, 28.7 MJ m−3). Moreover, these composite films could be degraded completely after approximately 102 days in soil with an average environment temperature of 32 °C. This work provided a low-cost and sustainable pathway for the fabrication of high-strength, self-cleaning, and waterproof packaging materials instead of plastics.

Construct a stable super-hydrophobic surface through acetonitrile extracted lignin and nano-silica and its application in oil-water separation

It remains a great challenge for the simple, environmentally friendly and low-cost production of oil/water separation membrane. Under this backdrop, a highly efficient membrane based on filter paper, acetonitrile extracting lignin and silica is reported. Two impregnation steps are involved for the membrane preparation, firstly, a thin layer of lignin is coated on the surface of the filter paper and then, silica nanoparticles are adhered to the pre-coated filter paper, leading to the formation of a micro-nano binary structure, which turns the hydrophilicity nature of the filter paper into lipophilicity and strong hydrophobicity. The modified filter paper has a contact angle of 168°, which is 118° higher than that of a reference membrane prepared by technical lignin and silica nanoparticles. The modified filter paper exhibits an excellent separation efficiency as high as 98.6% in the process of oil/water separation. Notably, considering the applied low-cost substrates and the simple dipping operation, this modification route is expected to be easily extended to a versatile of other substrates that need to be hydrophobized.

Micro/Nanoscale Structured Superhydrophilic and Underwater Superoleophobic Hybrid-Coated Mesh for High-Efficiency Oil/Water Separation.

A novel micro/nanoscale rough structured superhydrophilic hybrid-coated mesh that shows underwater superoleophobic behavior is fabricated by spray casting or dipping nanoparticle–polymer suspensions on stainless steel mesh substrates. Water droplets can spread over the mesh completely; meanwhile, oil droplets can roll off the mesh at low tilt angles without any penetration. Besides overcoming the oil-fouling problem of many superhydrophilic coatings, this superhydrophilic and underwater superoleophobic mesh can be used to separate oil and water. The simple method used here to prepare the organic–inorganic hybrid coatings successfully produced controllable micro-nano binary roughness and also achieved a rough topography of micro-nano binary structure by controlling the content of inorganic particles. The mechanism of oil–water separation by the superhydrophilic and superoleophobic membrane is rationalized by considering capillary mechanics. Tetraethyl orathosilicate (TEOS) as a base was used to prepare the nano-SiO2 solution as a nano-dopant through a sol-gel process, while polyvinyl alcohol (PVA) was used as the film binder and glutaraldehyde as the cross-linking agent; the mixture was dip-coated on the surface of 300-mesh stainless steel mesh to form superhydrophilic and underwater superoleophobic film. Properties of nano-SiO2 represented by infrared spectroscopy and surface topography of the film observed under scanning electron microscope (SEM) indicated that the film surface had a coarse micro–nano binary structure; the effect of nano-SiO2 doping amount on the film’s surface topography and the effect of such surface topography on hydrophilicity of the film were studied; contact angle of water on such surface was tested as 0° by the surface contact angle tester and spread quickly; the underwater contact angle to oil was 158°, showing superhydrophilic and underwater superoleophobic properties. The effect of the dosing amount of cross-linking agent to the waterproof swelling property and the permeate flux of the film were studied; the oil–water separation effect of the film to oil–water suspension and oil–water emulsion was studied too, and in both cases the separation efficiency reached 99%, which finally reduced the oil content to be lower than 50 mg/L. The effect of filtration times to permeate flux was studied, and it was found that the more hydrophilic the film was, the stronger the stain resistance would be, and the permeate flux would gradually decrease along with the increase of filtration times.

A new approach for preparation of semi-transparent superhydrophobic coatings by ultrasonic spray hydrolysis of methyltrimethoxysilane

A novel nebulizing spray hydrolysis approach was used for preparation of semi-transparent superhydrophobic coatings. Methyltrimethoxysilane was dissolved in water:ethanol mixture and ultrasonically sprayed on different substrates. Superhydrophobic coatings with a contact angle (CA) as high as 164° and a sliding angle below 5° were obtained. FESEM and AFM revealed a hierarchical micro-nano binary structure with nanometric roughness of the coatings. The coated glass substrate exhibited transmittance close to 80%. The prepared coating showed great self-cleaning and water jet repellency behaviors. The superhydrophobicity of the samples was remained after subjecting to ambient conditions for 50 days. The coating was also durable under water flushing test.

Preparation of Ni/graphene hydrophobic composite coating with micro-nano binary structure by poly-dopamine modification

In this study, poly-dopamine (pDA) was used to prepare a nickel-graphene (GR) composite coating on 45# steel by utilizing the electrodeposition techniques. The pDA has two advantages for the Ni/GR@pDA composite coatings: (1) improving the dispersion of graphene in the aqueous solution; (2) enhancing the bonding force between GR and the substrate. The high resolution transmission electronic microscope (HRTEM) and the energy dispersive spectroscope (EDS) confirmed that GR was coated with a layer of pDA, which is the product of the situ spontaneous oxidative polymerization reaction of dopamine (DA). Dispersion test result showed that the modified GR could disperse in the aqueous solution stably for more than 4 h. The dispersion of GR was improved obviously. The friction-wear and corrosion experiments indicated that the performance of composite coating was raised significantly than the pure Ni coating. Because the grains of the composite coating were refined, the micro-nano binary structure was formed on the coating surface. Hence the hydrophobicity of the coating was greatly improved.

Silicone/Ag@SiO2 core-shell nanocomposite as a self-cleaning antifouling coating material.

The effects of Ag@SiO2 core–shell nanofiller dispersion and micro-nano binary structure on the self-cleaning and fouling release (FR) in the modelled silicone nano-paints were studied. An ultrahydrophobic polydimethylsiloxane/Ag@SiO2 core–shell nanocomposite was prepared as an antifouling coating material. Ag@SiO2 core–shell nanospheres with 60 nm average size and a preferential {111} growth direction were prepared via a facile solvothermal and a modified Stöber methods with a controlled shell thickness. Ag@SiO2 core–shell nanofillers were inserted in the silicone composite surface via solution casting technique. A simple hydrosilation curing mechanism was used to cure the surface coating. Different concentrations of nanofillers were incorporated in the PDMS matrix for studying the structure–property relationship. Water contact angle (WCA) and surface free energy determinations as well as atomic force microscopy and scanning electron microscope were used to investigate the surface self-cleaning properties of the nanocomposites. Mechanical and physical properties were assessed as durability parameters. A comparable study was carried out between silicone/spherical Ag@SiO2 core–shell nanocomposites and other commercial FR coatings. Selected micro-foulants were used for biological and antifouling assessments up to 28 days. Well-distributed Ag@SiO2 core–shell (0.5 wt%) exhibited the preferable self-cleaning with WCA of 156° and surface free energy of 11.15 mN m−1.

Drag reduction in reservoir rock surface: Hydrophobic modification by SiO2 nanofluids

Based on the adsorption behavior of modified silica nanoparticles in the sandstone core surface, the hydrophobic surface was constructed, which consists of micro-nanoscale hierarchical structure. This modified core surface presents a property of drag reduction and meets the challenge of high injection pressure and low injection rate in low or ultra-low permeability reservoir. The modification effects on the surface of silica nanoparticles and reservoir cores, mainly concerning hydrophobicity and fine structure, were determined by measurements of contact angle and scanning electron microscopy. Experimental results indicate that after successful modification, the contact angle of silica nanoparticles varies from 19.5° to 141.7°, exhibiting remarkable hydrophobic properties. These modified hydrophobic silica nanoparticles display a good adsorption behavior at the core surface to form micro-nanobinary structure. As for the wettability of these modified core surfaces, a reversal has happened from hydrophilic into hydrophobic and its contact angle increases from 59.1° to 105.9°. The core displacement experiments show that the relative permeability for water has significantly increased by an average of 40.3% via core surface modification, with the effects of reducing injection pressure and improving injection performance of water flooding. Meanwhile, the mechanisms of drag reduction and improving water injection operation induced from the modified core surface were uncovered. The present study will establish a fundamental understanding on the drag reduction at the core surface modified by nanofluids and its applications in more industries.

Formation of Super-Hydrophobic Surface by Accumulating Pollution on RTV Silicone Rubber Coating Surface

The Super-hydrophobic surface can be obtained easily by pollution accumulation on room temperature vulcanized (RTV) silicone rubber coating surface. The photos taken by digital camera show that the amount of pollution on the RTV coating surface was increased with time, and after one year, the RTV coating surface nearly could hardly be seen. The water state contact angle (CA) measurement, which was investigated by the static contact angle instrument, reveals that the CA value of RTV coating surface is increased with increasing the pollution accumulation, and in suitable amount of pollution accumulation, the super-hydrophobic surface (water contact angle of 152o and roll-off angle smaller than 5 o) was obtained. The scanning electric microscope (SEM) of RTV coating with different pollution accumulation was investigated. It shows that the continuous micro-nanobinary structure can be formed with enough dust particles on the RTV surface. The mechanism of the effect of pollution accumulation on the wetting property was analyzed, the migration of hydrophobic molecular in RTV coating onto the pollution surface and the formation of micro-nanobinary structure on the RTV coating surface have synergistic effect on the super-hydrophobic surface formation caused by the pollution accumulation.

Preparation of stable superhydrophobic film on stainless steel substrate by a combined approach using electrodeposition and fluorinated modification

A combined electrodeposition and fluorinated modification approach for preparation of stable superhydrophobic film on SS316L substrate is presented. Nickel film with micro-nano binary structure was coated on the substrate using electrodeposition techniques and then followed by a fluorinated modification process to obtain superhydrophobic surface. The surface morphology of the nickel film at micro/nano scale was characterized at different electrodeposition current densities. Results show that when the current density fall in the range from 5 to 9A/dm2, the contact angle with 5μL water droplets on the nickel film after fluorinated modification is higher than 160°, and the sliding angle with 10μL water droplets is as low as 1°. Moreover, the superhydrophobic film has a very low contact angle hysteresis of 2.2°. Results also show that the superhydrophobic nickel film on SS316L has satisfied stability both in strong acid and alkaline solutions, and the superhydrophobic property can still keep fairly well after a durability testing last for more than 400 days under ambient conditions.

Biomimetic Superhydrophobic Surface of High Adhesion Fabricated with Micronano Binary Structure on Aluminum Alloy

Triggered by the microstructure characteristics of the surfaces of typical plant leaves such as the petals of red roses, a biomimetic superhydrophobic surface with high adhesion is successfully fabricated on aluminum alloy. The essential procedure is that samples were processed by a laser, then immersed and etched in nitric acid and copper nitrate, and finally modified by DTS (CH3(CH2)11Si(OCH3)3). The obtained surfaces exhibit a binary structure consisting of microscale crater-like pits and nanoscale reticula. The superhydrophobicity can be simultaneously affected by the micronano binary structure and chemical composition of the surface. The contact angle of the superhydrophobic surface reaches up to 158.8 ± 2°. Especially, the surface with micronano binary structure is revealed to be an excellent adhesive property with petal-effect. Moreover, the superhydrophobic surfaces show excellent stability in aqueous solution with a large pH range and after being exposed long-term in air. In this way, the multifunctional biomimetic structural surface of the aluminum alloy is fabricated. Furthermore, the preparation technology in this article provides a new route for other metal materials.

Controllable Stearic Acid Crystal Induced High Hydrophobicity on Cellulose Film Surface

A novel, highly hydrophobic cellulose composite film (RCS) with biodegradability was fabricated via solvent-vaporized controllable crystallization of stearic acid in the porous structure of cellulose films (RC). The interface structure and properties of the composite films were investigated with wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), FT-IR, solid-state (13)C NMR, water uptake, tensile testing, water contact angle, and biodegradation tests. The results indicated that the RCS films exhibited high hydrophobicity (water contact angle achieved to 145°), better mechanical properties in the humid state and lower water uptake ratio than RC. Interestingly, the stearic acid crystallization was induced by the pore wall of the cellulose matrix to form a micronano binary structure, resulting in a rough surface. The rough surface with a hierarchical structure containing micronanospace on the RCS film surface could trap abundant air, leading to the high hydrophobicity. Moreover, the RCS films were flexible, biodegradable, and low-cost, showing potential applications in biodegradable water-proof packaging.

Superhydrophobicity determines the buoyancy performance of kapok fiber aggregates

Superhydrophobicity is commonly regarded as a surface property that has important consequences for self-cleaning applications. Here we show interestingly that the superhydrophobicity is closely connected to the bulk buoyancy performance of kapok fiber aggregates, a natural material endowed with superhydrophobicity and extraordinary high porosity. First of all, we have determined the superhydrophobicity of a single kapok fiber, which can be ascribed to its micro-nano-binary structure (MNBS) and the thin hydrophobic paraffinic wax layer covered on the surface. Second, based on classic capillary and wicking theory, the buoyancy performance of the kapok fiber aggregates can be modeled and we demonstrate that their buoyancy performance is actually determined by the superhydrophobicity of individual kapok fibers. Our results also suggest an optimized density ∼0.015gcm−3 for using kapok fiber aggregates as the lightest natural buoyancy.

Surface studies on superhydrophobic and oleophobic polydimethylsiloxane–silica nanocomposite coating system

Superhydrophobic and oleophobic polydimethylsiloxane (PDMS)–silica nanocomposite double layer coating was fabricated by applying a thin layer of low surface energy fluoroalkyl silane (FAS) as topcoat. The coatings exhibited WCA of 158–160° and stable oleophobic property with oil CA of 79°. The surface morphology was characterized by field emission scanning electron microscopy (FESEM) and surface chemical composition was determined by energy dispersive X-ray spectrometery (EDX) and X-ray photoelectron spectroscopy (XPS). FESEM images of the coatings showed micro-nano binary structure. The improved oleophobicity was attributed to the combined effect of low surface energy of FAS and roughness created by the random distribution of silica aggregates. This is a facile, cost-effective method to obtain superhydrophobic and oleophobic surfaces on larger area of various substrates.

Fabrication of stable superhydrophilic surfaces on titanium substrates

We report a method of producing superhydrophilic surfaces on titanium substrates via sandblasting and dip-coating with colloidal silica nanoparticles. The surface exhibits a high level of hydrophilic stability, as it stays superhydrophilic for an excess of 40 days and through multiple wetting–dewetting cycles. The combination of microscale roughness from the sandblasting and nanoscale roughness from the silica particles results in a micro-nano binary structure, which greatly enhances the hydrophilicity of the titanium samples. Due to the simplicity and ease of implementation of this method, such a surface is suitable for potential use in a variety of applications, such as prosthetic dentistry and other biomedical fields.

Effect of microstructure and surface roughness on the wettability of superhydrophobic sol–gel nanocomposite coatings

Sol–gel nanocomposite coatings were fabricated by spraying precursor mixtures containing hydrophobically modified silica (HMS) nanoparticles dispersed in sol–gel matrices prepared with acid-catalyzed tetraethoxysilane (TEOS), and methyltriethoxysilane (MTEOS). The hydrophobicity of the coatings increased with increase in the concentration of HMS nanoparticles. Superhydrophobic coatings with water contact angle (WCA) of 166° and roll-off angle <2° were obtained by optimizing the sol–gel processing parameters and the concentration of silica nanoparticles in the coating. FESEM studies have shown that surface has a micro-nano binary structure composed of microscale bumps and craters with protrusions of nanospheres. The properties of composite coatings fabricated by spin coating and spray coating methods were compared. It was found that the microstructure and the wettability were also dependent on the method of application of the coating.

Wettability of Zinc Oxide Surfaces with Controllable Structures

Zinc oxide (ZnO) surfaces with controllable structures (i.e, microstructure, nanostructure, and micronanobinary structure) have been created by controlling pH at < 4 or > 10.5 in the Zn(gray) + H2O2 reaction. The resulting surface shows superhydrophobicity. It is found that the water contact angle (CA) of the surface with micronanobinary structure is greater than that of nanostructure and that of nanostructure is greater than that of the microstructure. Theoretical analysis is completely in agreement with the experimental results.

Fabrication of Biomimetic Superhydrophobic Coating with a Micro‐Nano‐Binary Structure

AbstractSummary: A superhydrophobic coating was facilely fabricated in one step by casting bisphenol A polycarbonate (PC) solution under moisture. Vapor‐induced phase separation occurred during the solidifying process and a rough surface with a micro‐nano‐binary structure (MNBS) similar to the microstructure shown on lotus leaf was formed.SEM image of a single micro‐flower.magnified imageSEM image of a single micro‐flower.

Specifying lubricants for a new 80 inch hot strip mill : P. D. Metzger, Lubrication Eng., 22 (9) (1966) 358–367; 4 figs., 5 tables, 2 refs.

Superhydrophobicity is commonly regarded as a surface property that has important consequences for self-cleaning applications. Here we show interestingly that the superhydrophobicity is closely connected to the bulk buoyancy performance of kapok fiber aggregates, a natural material endowed with superhydrophobicity and extraordinary high porosity. First of all, we have determined the superhydrophobicity of a single kapok fiber, which can be ascribed to its micro-nano-binary structure (MNBS) and the thin hydrophobic paraffinic wax layer covered on the surface. Second, based on classic capillary and wicking theory, the buoyancy performance of the kapok fiber aggregates can be modeled and we demonstrate that their buoyancy performance is actually determined by the superhydrophobicity of individual kapok fibers. Our results also suggest an optimized density ∼0.015 g cm−3 for using kapok fiber aggregates as the lightest natural buoyancy.