CN112341211B - Ceramic-based bionic material and preparation method and application thereof - Google Patents

Ceramic-based bionic material and preparation method and application thereof Download PDF

Info

Publication number
CN112341211B
CN112341211B CN202011117330.0A CN202011117330A CN112341211B CN 112341211 B CN112341211 B CN 112341211B CN 202011117330 A CN202011117330 A CN 202011117330A CN 112341211 B CN112341211 B CN 112341211B
Authority
CN
China
Prior art keywords
ceramic
sintering
temperature
resin
drying
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011117330.0A
Other languages
Chinese (zh)
Other versions
CN112341211A (en
Inventor
吕静
李明
管晴雯
祁碧菽
爱德华多·塞兹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China University of Petroleum Beijing
Original Assignee
China University of Petroleum Beijing
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China University of Petroleum Beijing filed Critical China University of Petroleum Beijing
Priority to CN202011117330.0A priority Critical patent/CN112341211B/en
Publication of CN112341211A publication Critical patent/CN112341211A/en
Application granted granted Critical
Publication of CN112341211B publication Critical patent/CN112341211B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/6346—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6565—Cooling rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density

Abstract

The invention provides a ceramic-based bionic material and a preparation method and application thereof. The preparation method comprises casting the surface of the biomaterial with liquid resin, and solidifying the resinSeparating the resin template from the biological material to obtain a resin template; pouring the ceramic slurry into the resin template, and drying and forming at 80-90% RH to obtain a green body; subjecting the green body to a temperature of from 1 to 1.5 K.min‑1Heating at a certain rate to perform pre-sintering, and performing pre-sintering at a temperature of 10-15 K.min‑1And heating at the speed of the temperature rise to sinter to obtain the ceramic-based bionic material. The invention also provides the ceramic-based bionic material prepared by the method and application of the ceramic-based bionic material as an underwater oleophobic material. The ceramic-based bionic material provided by the invention has excellent super-oleophobic property for different oil products, and has good stability, corrosion resistance, impact resistance and longer service life.

Description

Ceramic-based bionic material and preparation method and application thereof
Technical Field
The invention relates to the technical field of bionic engineering and surface engineering, in particular to a ceramic-based bionic material and a preparation method and application thereof.
Background
In the marine ecosystem, the problem of oil pollution caused by industrial accidental oil leakage, social production activities and scientific exploration and research is becoming more serious. Meanwhile, there is an increasing activity in such oil-contaminated water, and the development of materials having low adhesion, super-oleophobic property and toughness under water has attracted much attention from scientists.
In recent years, a layered micro/nano protruding structure surface with high surface energy, which is simulated according to the oleophobic property of biological structures such as sharkskin, nacreous layer of shell, seaweed and the like, is considered to be one of the most outstanding underwater super oleophobic surfaces, and the preparation of the underwater super oleophobic surface material by adopting metal oxide, polyelectrolyte, polymer hydrogel and the like is researched and developed at present. The structure of the surfaces of aquatic oil-resistant organisms such as fish scales, shrimp shells, lotus leaf lower surfaces and the like has the common point that the surfaces have micro-nano structures and show hydrophilic wettability in air.
Although these bionic materials have excellent underwater oleophobic performance, the material of the materials can limit the application of the oleophobic materials, for example, metal oxides are easy to corrode in seawater, so that the effective oleophobic structure is lost; in addition, although the surface structure of the biomaterial can be repeatedly etched by the fluid organic matters such as polyelectrolyte and polymer hydrogel, the excellent underwater oleophobic property of the biomaterial is easy to lose efficacy due to the poor mechanical strength and the easy damage of the effective structure by external mechanical force.
Ceramic materials have excellent mechanical properties and the microstructure of the ceramic surface has been explored for the past few decades, for example by laser ablation, micro powder injection moulding and the like. However, the ceramic surfaces produced based on these methods have the following problems or limitations in the geometry and dimensions of the microscopic features: 1. complex micro-curved structures are difficult to construct, 2. the micro-structures are limited in size, typically less than 3 x 3cm, and tend to be expensive.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a super-oleophobic ceramic-based bionic material and a preparation method and application thereof. The preparation method of the ceramic-based bionic material can avoid cracks of the ceramic material in the drying process, and the prepared bionic material is repeatedly etched with the micro-nano structure on the surface of the biological material and has related properties caused by repeated etching of the micro-nano structure.
In order to achieve the aim, the invention provides a preparation method of a ceramic-based bionic material, which comprises the following steps:
step one, casting the surface of a biological material by using liquid resin, and separating the resin from the biological material after curing to obtain a resin template;
pouring the ceramic slurry into the resin template, and drying and forming at 80-90% RH (relative humidity) to obtain a green body;
step three, the green body is processed at 1-1.5 K.min-1Heating at a certain rate to perform pre-sintering, and performing pre-sintering at a temperature of 10-15 K.min-1Heating at a certain rate to sinter to obtain the final productCeramic-based biomimetic materials.
In a specific embodiment of the invention, the preparation method comprises the steps of firstly re-etching the micro-nano structure on the surface of the biological material into resin, then spreading ceramic slurry with certain fluidity and adhesiveness onto the surface of the resin template, and fully filling the microstructure of the resin template with the ceramic slurry to obtain the ceramic-based bionic material with the micro-nano structure on the surface of the biological material completely re-etched. Because the cured resin has lower surface tension, the resin is used as an intermediate template, and the problems that the ceramic material directly uses the biological material as the template for repeated etching and cracks are generated in the drying process can be avoided.
In a specific embodiment of the invention, the resin is liquid at normal temperature, can keep certain fluidity and low viscosity for a long time, and can completely repeatedly etch the nano-scale structure on the surface of the biological material; after the curing agent or the heating treatment, the resin can be cured and completely retain the surface characteristics of the repeatedly engraved biological material. The resin preferably comprises one of PDMS (polydimethylsiloxane), PMMA (polymethyl methacrylate) or polycraft K4 translucent silicone rubber (the manufacturer may be MB Fibreglass). The resin is more preferably PDMS, which can maintain a viscosity of less than 50cPs for more than 12 hours at room temperature, with a low viscosity sufficient for completely replicating the nanostructures of biological surfaces.
In a specific embodiment of the present invention, the biomaterial is typically a biomaterial having a micro-nanostructured surface. The embodiment of the invention can adopt biological materials with underwater oleophobic surfaces and also can adopt biological materials with micro-nano structure in air hydrophobic surfaces, such as rose petals, lotus leaves and the like with air hydrophobic surfaces.
In an embodiment of the present invention, step one may include an operation of casting the liquid resin and the curing agent of the resin on the surface of the biomaterial. The mass ratio of the liquid resin to the curing agent can be controlled to be (1-10):1, for example, the mass ratio of the PDMS to the curing agent of the PDMS is generally controlled to be 10:1, and the mass ratio of the Polycraft K4 translucent silicone rubber to the curing agent thereof is generally controlled to be 1: 1.
In the embodiment of the invention, the first step may further comprise degassing and drying the liquid resin cast on the surface of the biomaterial, wherein the liquid resin is generally cured during the drying process, and the drying time can be controlled to be 24h-48 h. The degassing is generally a vacuum degassing to prevent the presence of air bubbles remaining in the resin from affecting the replica effect on the surface of the biomaterial. The degassing time can be controlled to be 30min-60min, and the degassing can be carried out in a vacuum device at the pressure of-5 MPa.
In the second embodiment of the present invention, the volume fraction of the solid particles in the ceramic slurry is generally controlled to be 25-30% so as to make the ceramic slurry have certain fluidity. Too small volume fraction of the solid particles can result in too long time for drying the ceramic slurry, and too large volume fraction of the solid particles is not beneficial to completely spreading the ceramic slurry, thereby affecting the complete coverage and repeated engraving effect of the ceramic slurry on the micro-nano structure on the surface of the resin.
In the second embodiment of the present invention, the ceramic slurry is generally formed by dispersing ceramic powder in a dispersant. The ceramic powder is generally a powder that is hydrophilic in air, and specifically may include one or a combination of two or more of alumina powder, beryllia powder, and titania powder, and the dispersant may include polyacrylic acid (PAA) solution or Dolapix ET 85 (the manufacturer may be ZSCHIMMER & SCHWARZ). The particle size of the ceramic powder is generally controlled to be 200nm to 300 nm.
In a specific embodiment of the present invention, in step two, the method for preparing the ceramic slurry generally comprises: mixing ceramic powder (such as alumina powder) with dispersant (such as 2-2.5 wt% polyacrylic acid alkaline aqueous solution), ultrasonic treating, and adding octanol dropwise to obtain ceramic slurry with volume of 40-60cm3. The pH of the basic aqueous solution of polyacrylic acid is generally 10 to 11. The ultrasonic process generally leads to the primary depolymerization of the ceramic slurry, the power of the ultrasonic can be controlled to be 50W, the frequency of the ultrasonic can be controlled to be 26kHz, and the amplification rate of the ultrasonic can be controlled60-65%, and the ultrasonic treatment time can be controlled to 15-20 min.
In a specific embodiment of the present invention, a small amount of octanol may be added to degas the ceramic slurry during the preparation of the ceramic slurry, avoiding the occurrence of bubble voids. The addition amount of the octanol is generally controlled to 3 to 5 drops, namely 5 to 10 mu L.
In a specific embodiment of the present invention, the method for preparing the ceramic slurry may further include rolling the ceramic slurry after the ultrasonic treatment for 24h to 36h to further depolymerize the ceramic slurry.
In the second step of the embodiment of the invention, the drying conditions (such as humidity and the like) in the drying process of the ceramic slurry are controlled, so that the generation of cracks in the preparation process of the material can be further avoided, the related performance of the ceramic bionic material is enhanced, and the service life of the ceramic bionic material is prolonged. The drying and forming time can be adjusted according to the thickness of the resin template and the height of the ceramic slurry, generally, the ceramic slurry is firstly dried under a high humidity condition to avoid the generation of cracks, and then dried under a low humidity condition to shorten the drying time. For example, the dry forming process may include continuing to dry at 40-50% RH after drying at 80-90% RH to the top anhydrous layer of the ceramic slurry; the drying time at 80-90% RH can be controlled to 24-36 h, and the drying time at 40-50% RH can be controlled to 3d-4 d. Both drying stages can be carried out at temperatures of 20-30 ℃.
In a particular embodiment of the invention, the green body obtained in step two generally has a compactness of around 60%.
In a specific embodiment of the present invention, in step three, the pre-sintering process is used to remove the dispersant (e.g., polyacrylic acid) and octanol in the ceramic slurry. The temperature of the pre-sintering can be controlled to be 500-600 ℃, and the time of the pre-sintering can be controlled to be 1-1.5 h.
In the specific embodiment of the present invention, in the third step, the sintering temperature may be controlled to 1150-1600 ℃, and the sintering time may be controlled to 15min-1.5 h.
In a specific embodiment of the present invention, in step three, the sintering processThe formula may include: after pre-sintering, at 10-15 K.min-1The temperature is raised to 1150-1250 ℃ and sintered for 15min-1.5h (preferably 1h-1.5h), or after pre-sintering, sintered for 10-15 K.min-1The temperature is raised to 1250-1600 ℃ (for example 1450-1600 ℃) and the sintering time is 15min-1.5h (preferably 15min-30 min).
In the specific embodiment of the invention, the compactness of the prepared ceramic-based bionic material can be controlled by controlling the sintering temperature. Generally, the ceramic-based bionic material with the compactness of less than 90 percent can be obtained by sintering at the temperature of less than 1250 ℃, and the ceramic-based bionic material with the compactness of more than 90 percent can be obtained by sintering at the temperature of more than 1250 ℃. For example, the ceramic-based bionic material with the compactness of 70 plus or minus 3%, 80 plus or minus 3% and 90 plus or minus 3% can be obtained by respectively controlling the sintering temperature to 1150 ℃, 1205 ℃ and 1250 ℃; the ceramic-based bionic material with the compactness of 70 +/-3-80 +/-3% can be obtained by controlling the sintering temperature to 1150-. Accordingly, the time for sintering may be adjusted according to the temperature of sintering.
In the third step, the sintering process may further include the operation of reducing the temperature to 980--1。
In a specific embodiment of the present invention, in step three, the sintering process may include: after pre-sintering, at 10-15 K.min-1The temperature is raised to 1250-1600 ℃ (preferably 1450-1600 ℃) and sintering is carried out for 15-30 min, the temperature is lowered to 980-1020 ℃, and the temperature is kept for 24-36 h.
In a specific embodiment of the present invention, in step three, the sintering process may include: after pre-sintering, at 10-15 K.min-1The temperature is raised to 1150-1250 ℃ for sintering for 1-1.5 h, the temperature is lowered to 980-1020 ℃ and the temperature is kept for 24-36 h.
In a specific embodiment of the present invention, in the above preparation method, by controlling the temperature increase rate of the sintering process in the third step, the conversion of the ceramic slurry can be suppressedThe enlargement of the formed ceramic particles and the retention of ultra-fine grains and a certain porosity in the sintered product. For example, for the ceramic-based bionic material with the compactness of more than 90%, a two-step high-temperature sintering mode (namely, the temperature rise rate in the sintering process is higher than that in the pre-sintering process) can be adopted to avoid the excessive growth of crystal grains in the sintering process, so that ultrafine crystal grains and certain porosity generated by the accumulation of the ultrafine crystal grains are retained in the ceramic-based bionic material with the high compactness. For example, step three may include: the green body obtained in the step two is heated for 1 to 1.5 K.min-1The temperature is raised to 500-600 ℃ for pre-sintering for 1-1.5 h, and then 10-15 K.min-1The temperature is raised to 1450-1600 ℃, the mixture is sintered for 15-30 min, the temperature is rapidly lowered to 980-1020 ℃, the temperature is kept for 24-36 h, the compactness of the ceramic-based bionic material obtained in the sintering process can reach 97 +/-2.5 percent, and the ultrafine grains and a certain porosity are kept.
In a specific embodiment of the present invention, the above preparation method may comprise:
1. mixing liquid resin and a curing agent, casting the mixture on the surface of a biological material, degassing for 30-60 min under the pressure of-5 MPa, drying and curing for 24-48 h at room temperature, and separating the cured resin from the biological material to obtain a resin template;
2. mixing ceramic powder with dispersant to form ceramic slurry with solid volume fraction of 25-30% (volume is controlled to 40-60cm3) Ultrasonically treating the ceramic slurry at 50W power, 26kHz frequency and 60-65% magnification for 15min-20min, dropwise adding a small amount (generally 3-5 drops) of octanol, degassing, rolling the degassed ceramic slurry for 24h-36h by using an alumina ball with the diameter of about 1mm, forming the ceramic slurry on a resin template, drying the ceramic slurry at 80-90% RH (preferably at 80-90% RH for 24h-36h, and then drying the ceramic slurry at 40-50% RH for 3d-4d) to form a green body;
3. mixing the green body at 1-1.5 K.min-1The temperature is raised to 500-600 ℃ (preferably 600 ℃), and the presintering is carried out for 1-1.5 h to remove the dispersant (such as polyacrylic acid) and octanol serving as a surfactant; pre-sintered sample is processed at 10-15 K.min-1Heating to 1150-1600 deg.C, sintering for 15-1.5 h, and sintering at 40-50 K.min-1Is reduced in rateAnd (4) heating to 980 and 1020 ℃, and preserving the heat for 24-36 h to obtain the ceramic-based bionic material.
The invention also provides the ceramic-based bionic material prepared by the preparation method. In some embodiments, the ceramic-based biomimetic material is generally conical protrusions which are formed by ceramic particles and distributed on the surface and arranged continuously.
In the ceramic-based bionic material, the diameter of the bottom of the conical protrusions is generally 16-20 μm, the height of the conical protrusions is generally 10-14 μm, and the distance between the protrusions is generally 4-6 μm.
In the embodiment of the present invention, the particle size of the ceramic particle is generally 0.2-0.3 μm, and considering that the particle size of the ceramic powder used in the preparation process is generally 200-300nm, it can be seen that the sintering process does not cause significant increase of the ceramic particle in the preparation process of the biomimetic material. In some embodiments, the surface of the conical protrusions is generally distributed with ultrafine grains (with a grain size of 0.2-0.3 μm), and the ceramic-based biomimetic material generally has a certain porosity (10-30%).
In the specific embodiment of the invention, the ceramic-based bionic material prepared by taking rose petals, lotus leaves and the like as biological materials can show excellent underwater super-oleophobic property for different oil products, and has good stability, corrosion resistance and longer service life of impact resistance. The ceramic-based bionic material is subjected to modified coating, the super-oleophobic property of the bionic material after the modified coating can show the cyclic responsiveness to pH, and the application range is wide.
In a specific embodiment, on the basis that the ceramic-based bionic material has super oleophobic performance, the reduction of the grain size and the increase of the pore structure in the ceramic-based bionic material can further improve the oleophobic performance of the material in water.
In a specific embodiment of the present invention, the compactness of the ceramic biomimetic material is generally 70 ± 3% to 97 ± 2.5%.
The invention further provides application of the ceramic-based bionic material as an underwater super oleophobic material. The ceramic-based bionic material can show good super-oleophobic property, low adhesion, resistance to external force damage, acid and alkali corrosion resistance, seawater corrosion resistance, impact resistance and the like when being used as a super-oleophobic material. When the ceramic-based bionic material is subjected to modified coating, the super-oleophobic property of the ceramic-based bionic material after the modified coating also shows the capability of circularly responding to pH.
The invention has the beneficial effects that:
1. the preparation method provided by the invention can avoid the problem that the ceramic material cracks in the drying process, and the surface of the prepared bionic material can retain the micro-nano structure of the surface of the biological material and retain related properties caused by the micro-nano structure, such as super-oleophobic property and the like.
2. When the biological material with the hydrophobic surface, such as rose petals, is used as a template, the ceramic-based bionic material provided by the invention has excellent underwater super-oleophobic property for different oil products, and has good stability, corrosion resistance, impact resistance and longer service life. The ceramic-based bionic material is subjected to modified coating, so that the bionic material can show the response to pH cycle, and the application range is wide.
Drawings
FIG. 1 is a schematic flow chart of the preparation of the ceramic-based biomimetic material in example 1.
FIG. 2 is an SEM image of the ceramic-based biomimetic material prepared in example 1.
FIG. 3 is an SEM photograph of rose petals used in example 1.
Fig. 4 is a morphology characterization result of the lotus leaves adopted in example 2 and the ceramic-based biomimetic material prepared in example 2.
FIG. 5 is an SEM image of a ceramic-based biomimetic material prepared by using three different resin materials as templates in example 3.
Fig. 6 is a schematic diagram of the adhesion testing process.
FIG. 7 is a photograph of the ceramic-based biomimetic material in test example 1 showing the contact angle measurement of chloroform in water.
FIG. 8 is a graph showing the results of measuring the adhesion between the ceramic-based biomimetic material and chloroform in water in test example 1.
FIG. 9 is a graph showing the measurement results of the contact angle and the adhesion force of the ceramic-based biomimetic material in test example 4 with chloroform at different pH values in water.
Fig. 10 is a graph showing the measurement results of the contact angle and the adhesion force between the ceramic-based biomimetic material and chloroform in water after being soaked in seawater in test example 5.
FIG. 11 is a photograph of the apparatus used in the sand blast test of test example 6.
FIG. 12 is a graph showing the measurement results of the contact angle and the adhesion force between the ceramic-based biomimetic material and chloroform in water after sand impact in test example 6.
Fig. 13 is a graph showing the measurement results of the contact angle and the adhesion force of the ceramic-based biomimetic material after spraying gold and chloroform in water in test example 7.
Fig. 14 is a contact angle cycle test result diagram of the ceramic-based biomimetic material subjected to gold spraying in test example 8 in different pH environments.
Fig. 15 is an SEM image of the experimental group samples in test example 9.
FIG. 16 is an SEM photograph of a control sample of test example 9.
Fig. 17 is a photograph of the biomimetic material prepared in comparative example 1 after a dye drop is dropped on the upper surface.
FIG. 18 is a photograph of the biomimetic material prepared in example 1 after a dye drop is dripped on the upper surface.
Fig. 19 is a photograph of the biomimetic material prepared in comparative example 2 after dropping dyeing liquid drops on the upper surface.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a preparation method of a ceramic-based biomimetic material, the flow of which is shown in fig. 1, and the preparation method specifically comprises the following steps:
1. mixing 10g of liquid PDMS and 1g of PDMS curing agent to obtain PDMS mixed solution, fully stirring at 20 ℃, then casting on the surface of rose petals, vacuum degassing for 30min, drying and curing at room temperature for 24h, and separating the cured PDMS from the surface of the rose petals to obtain a PDMS template;
2. preparing a polyacrylic acid aqueous solution with the mass fraction of 2 wt%, and adjusting the pH of the solution to 10 by using ammonia water to obtain an alkaline solution of polyacrylic acid. The alumina powder was dispersed in an alkaline solution of polyacrylic acid to obtain a ceramic slurry with a solid volume fraction of 25%. Take 50cm3The ceramic slurry is subjected to ultrasound in an UP200Ht ultrasonic amplitude transformer, the ultrasonic power is controlled to be 50W, the frequency is 26kHz, the amplification rate is controlled to be 65%, the ultrasonic time is 15min, then 4 drops (7 mu L) of octanol are dripped for degassing, and then the degassed ceramic slurry is rolled for 36h by using an alumina ball;
3. pouring the ceramic slurry into the structured silicone resin PDMS template in the step 1 to obtain a PDMS template loaded with the ceramic slurry; drying at 90% RH for 24h, then drying at 45% RH for 3d and forming to form a green body (i.e. dehydrated ceramic slurry-PMDS) with a compactness of about 60%;
4. the green body is heated at 1 K.min-1Raising the temperature to 600 ℃, and preserving the temperature for 1h for pre-sintering to remove polyacrylic acid and octanol; the presintered sample was then placed in a tube furnace at 10 K.min-1And heating to 1150 ℃, and sintering for 1h to obtain the ceramic-based bionic material.
Fig. 2 is an SEM photograph of the ceramic-based biomimetic material prepared in this example, and fig. 3 is an SEM photograph of the surface of rose petals used in this example. As can be seen from FIG. 3, the surface of the rose petals used as the biological template has continuous protrusions, FIG. 2 shows that the surface protrusions are perfectly copied into the bionic material prepared in the embodiment, and the bottom diameter of the protrusions in the bionic material prepared in the embodiment is 16-20 μm, the height is 10-14 μm, the distance between the protrusions is 4-6 μm, and the size is similar to the corresponding characteristic size of the protrusions in the rose petals. As can be seen from FIG. 2, a large number of ultrafine grains are deposited in the protrusions of the ceramic-based biomimetic material.
The porosity of the material was calculated according to the following formula:
P＝(m2-m1)/(m2-m3) X 100%, where P is the porosity of the sample, m1The mass of the sample after drying is in kg; m is2To saturate the sample in the airMass in gas, unit is kg; m is3The mass of the saturated sample in kg is the mass of the saturated sample in water.
The test process is as follows: weigh the dried sample to mass m1(ii) a Pouring water into the beaker, weighing the total mass M of water and beaker0The sample was completely submerged below the water level in the beaker, which was set at 1.0X 103Keeping the sample in Pa vacuum for 5min, taking out, standing for 30min, and weighing the total mass M of the sample, the beaker and the water1To obtain m3＝M1-M0(ii) a Finally, taking out the sample from the beaker, wiping off the adhesive water on the surface of the sample, and recording the mass of the sample as m2。
The porosity of the sample of example 1 was measured as 10% as described above.
The ceramic-based biomimetic material prepared in example 1 was subjected to mechanical testing, which included: when the 4-point bending device on the Zwick iLine general testing machine is used for measuring the bending strength, the displacement rate is 0.2mm/min, and the displacement rate of the unilateral notched beam test is 0.01 mm/min. Each data point was tested for 3 to 5 samples. The total length, width and height of the sample were 10X 4X 3 mm. The same instrument was used with plates to test the compressive strength of 5mm x 5mm cubes at a rate of 1.3 mm/min. The bionic material sample prepared by the embodiment has the compressive strength of 432MPa and the bending strength of 212MPa, and shows excellent mechanical properties.
Example 2
According to the method and experimental parameters provided in the embodiment 1, the ceramic-based bionic material is prepared by replacing rose petals with lotus leaves. Fig. 4 shows the morphology characterization results of the lotus leaves and the ceramic-based biomimetic material prepared in this example. In fig. 4, the pictures a to c are photographs, SEM pictures and AFM pictures of lotus leaves, respectively, and the pictures d to f in fig. 4 are photographs, SEM pictures and AFM pictures of the ceramic-based biomimetic material, respectively. As can be seen from FIG. 4, the ceramic-based biomimetic material prepared by the preparation method provided by the invention can completely reconstruct the micro-nano structure on the surface of the carved lotus.
Example 3
According to the method and parameters provided in example 1, PMMA and polycraft K4 semi-transparent silicone rubber are respectively used to replace PDMS to prepare the ceramic-based bionic material as resin templates, specifically, a mixed solution of polycraft K4 semi-transparent silicone rubber and a curing agent thereof with a mass ratio of 1:1 is used to prepare the ceramic-based bionic material, or PMMA solution is used to replace PDMS in step 1 of example 1. The process of curing the PMMA solution into the resin template comprises the following steps: dissolving the dissolved PMMA in toluene to obtain a PMMA solution with the mass fraction of 15%, and spin-coating the PMMA solution on a clean silicon wafer. The biomaterial is then placed on the PMMA surface under a slight pressure of about 0.2 to 0.3MPa to keep the biomaterial in contact with the PMMA. A thin PDMS block may be placed on top of the biological surface as a buffer before applying pressure to evenly distribute the pressure. The samples were annealed at a temperature of 110 ℃ and 120 ℃ which was higher than the glass transition temperature of PMMA (Tg 100 ℃), annealed on a hot stage for 30 minutes, and then the biological surface was removed.
FIG. 5 is an SEM image of a ceramic-based biomimetic material prepared by using the above three resin materials as templates. The resin templates of the bionic material corresponding to the graphs a, b and c in fig. 5 are PDMS (i.e. example 1), PMMA and polycraft K4 semi-transparent silicone rubber, respectively. As can be seen from FIG. 5, the micro-nano structure on the surface of the biological material can be better replicated by using the three materials as the resin templates.
In the following tests, the contact angle test was conducted using a static contact angle measurement mode in a contact angle measuring instrument; the adhesion test was performed using the test procedure shown in fig. 6. The specific process of the adhesion test is as follows: the adhesion measurement between the oil droplets (2-3 μ L) and the sample was performed by a high sensitivity micro-electromechanical balancing system (μ N resolution). A typical operation is to first attach a copper cap attached to the balance to the test oil droplet and then control the test solid surface to move towards the droplet at a constant rate until it contacts the droplet. Subsequently, the sample is moved down and away from the droplet and the adhesion curve is analyzed throughout the process to obtain the adhesion between the droplet and the surface.
Test example 1
The test example provides the water contact angle and adhesion test of the ceramic-based biomimetic material prepared in example 1.
The ceramic-based biomimetic material as a sample was placed in water, and a contact angle between chloroform (i.e., chloroform) as a simulated oil and the surface of the sample was measured using a contact angle measuring instrument, and fig. 7 is a measurement photograph. From fig. 7, the contact angle between chloroform and the sample in water can be measured to be 161 degrees, which proves that the ceramic-based biomimetic material in example 1 has super-oleophobic property in water.
The ceramic-based biomimetic material is placed in water as a sample, and the adhesion between chloroform as simulated oil and the sample in water is measured by an underwater oil drop adhesion tester, and fig. 8 is a test result. As can be seen from FIG. 8, the adhesion of the sample to chloroform in water is 2.8 μ N, indicating that the ceramic-based biomimetic material of example 1 has low oil adhesion in water.
Test example 2
The test example provides the contact angle and adhesion test of the ceramic-based biomimetic material of example 1 and different simulated oil products in water.
Chloroform, 1, 2-dichloroethane, petroleum ether and n-hexane were selected as simulated oil products, and the contact angle and adhesion of the biomimetic material and the oil products in water were tested according to the method of test example 1, and the results are summarized in table 1.
TABLE 1
Simulated oil product Contact angle (°) Adhesion (μ N)
Chloroform 161.3±1.4 2.8±1.2
1, 2-dichloroethane 164.6±2.1 3.2±1.4
Petroleum ether 160.4±1.8 3.1±0.8
N-hexane 157.8±2.6 2.6±1.3
As can be seen from the table 1, the contact angles of the bionic material and various oil products in water are all larger than 150 degrees, the adhesion force is less than 5 mu N, and the bionic material on the surface and different oil products show better super-oleophobic property and low adhesion property in water.
Test example 3
The test example tests the contact angle and the adhesion force of the ceramic-based biomimetic material in example 1 and chloroform in water after being treated by different physical methods.
Taking 4 parts of the ceramic-based biomimetic material of example 1, respectively carrying out finger friction, tape adhesion and tearing, cold water soaking and hot water soaking, testing the contact angle and the adhesion force of the biomimetic material after the treatment to chloroform in water according to the method of test example 1, and the test results are summarized in table 2.
TABLE 2
Physical processing mode Contact angle (°) Adhesion (μ N)
Finger rubbing 160.6±1.2 2.6±0.6
Attaching and tearing tape 161.5±1.6 2.2±1.5
Soaking in cold water 159.8±0.8 2.6±1.2
Soaking in hot water 162.2±2.4 1.8±1.4
The test results of table 2 and test example 1 show that the contact angle and the adhesion force of the ceramic-based biomimetic material and chloroform in water do not change significantly after physical treatment in different ways, which proves that the ceramic-based biomimetic material of example 1 has the capability of resisting external force damage and retaining the surface effective structure.
Test example 4
The test example tested the contact angle and adhesion of the ceramic-based biomimetic material of example 1 with chloroform in water at different pH's (1-14). Fig. 9 summarizes the contact angle and adhesion test results. As can be seen from FIG. 9, the adhesion force of the ceramic-based biomimetic material of example 1 and chloroform in water with different pH values is about 2 μ N, and the contact angle is about 160 °, i.e. different pH values have little influence on the oleophobic property of the biomimetic material, which indicates that the ceramic-based biomimetic material of example 1 has excellent acid-base corrosion resistance.
Test example 5
The test example tests the contact angle and adhesion of the ceramic-based biomimetic material of example 1 to chloroform after being soaked in seawater for different times (1-30 days).
Fig. 10 summarizes the results of the contact angle and adhesion tests described above. As can be seen from fig. 10, after the ceramic-based biomimetic material in example 1 is soaked in seawater for different times, the adhesion with chloroform is about 2 μ N, and the contact angle is about 160 °, i.e., different soaking times have little influence on the oleophobic property of the ceramic-based biomimetic material, which indicates that the ceramic-based biomimetic material in example 1 has excellent seawater corrosion resistance and long service life in seawater.
Test example 6
The test example tests the contact angle and the adhesion force of the ceramic-based bionic material in example 1 and chloroform in seawater after the ceramic-based bionic material is impacted by sand grains of different degrees.
FIG. 11 is a photograph of the apparatus used in the sand impact test. As shown in FIG. 11, the ceramic based biomimetic material sample was placed on the right side of the glass cup and the sand particles impacted the upper surface of the biomimetic material sample at an inclination angle of 45 ° from the upper funnel. The impact height of the sand particles on the sample can be realized by adjusting the height of the iron support.
The grain size of the sand particles used in this test example is 200-600 μm, the ceramic-based biomimetic material of example 1 is impacted by different impact heights, and the measured contact angle and adhesion force are summarized in fig. 12. As can be seen from fig. 12, after the ceramic-based biomimetic material in example 1 is subjected to impact of sand grains with different strengths, the adhesion force of the ceramic-based biomimetic material to chloroform in water is about 2 μ N, and the contact angle of the ceramic-based biomimetic material is about 160 °, i.e., the impact strengths have little influence on the oleophobic property of the ceramic-based biomimetic material, which indicates that the ceramic-based biomimetic material in example 1 has excellent impact resistance and long service life in an impact environment.
Test example 7
The test example provides a test for the hydrophobic performance of the ceramic-based bionic material after gold spraying.
The gold spraying treatment process comprises the following steps: firstly, the ceramic-based biomimetic material of example 1 was subjected to gold spraying by a sputter coater (Leica, SCD500), and then the ceramic-based biomimetic material after gold spraying was immersed in a mixed thiol solution for 12 hours, taken out, rinsed with ethanol, and dried in a nitrogen atmosphere, thereby realizing HS (CH) in which2)9CH3And HS (CH)2)10Grafting a COOH molecular layer on the surface of the ceramic-based bionic material. Wherein the mixed mercaptan solution is HS (CH) with the mass ratio of 2:32)9CH3And HS (CH)2)10Dissolving COOH in ethanol to obtain solution, and mixing HS (CH) in thiol solution2)9CH3And HS (CH)2)10The total molar concentration of COOH was 1 mmol/L.
Testing of gold-sprayed and grafted mixed molecular layer HS (CH)2)9CH3，HS(CH2)10And the COOH treated ceramic-based bionic material has a contact angle with chloroform in deionized water with different pH values. Fig. 13 shows the contact angle test results. As can be seen from FIG. 13, as the pH increased, the layer of gold-sprayed grafted mixed molecule HS (CH)2)9CH3，HS(CH2)10The contact angle between the bionic material after COOH and chloroform is gradually increased. In the solution with the pH value less than or equal to 10, the modified ceramic-based bionic material shows lipophilicity; in the solution with the pH value being more than 10, the modified ceramic-based bionic material shows oleophobic property. The test results prove that the ceramic-based bionic material provided by the invention is sprayed with gold and grafted with a mixed molecular layer HS (CH)2)9CH3，HS(CH2)10After COOH; its oleophilic and oleophobic properties exhibit the ability to respond to pH conditions.
Test example 8
The test example provides the spraying and grafting of a mixed molecular layer HS (CH) under different pH conditions2)9CH3，HS(CH2)10And (4) performing cycle test on the hydrophilic and hydrophobic performances of the ceramic-based bionic material of the example 1 after COOH. The gold spraying and grafting methods were the same as in test example 7.
The cycle test method comprises the following steps: spraying gold and grafting mixed molecular layer HS (CH)2)9CH3，HS(CH2)10The ceramic-based biomimetic material after COOH was placed in deionized water at pH 2 and pH 12 cyclically, and the contact angle of the ceramic-based biomimetic material with chloroform during this procedure was measured, and the results of the contact angle test are summarized in fig. 14.
As can be seen from FIG. 14, when the pH of the solution was 2, the contact angle between the ceramic-based biomimetic material and chloroform was 0 °, when the pH was 12, the contact angle between the ceramic-based biomimetic material and chloroform was 160 °, and when the pH was changed from 12 to 2, the contact angle between the ceramic-based biomimetic material and chloroform was also changed from 160 ° to 0 °, and the results after multiple cycles were the same. The test results show that the oleophilic and oleophobic performance of the ceramic-based bionic material subjected to the gold spraying treatment has good stability on the response capability of the ceramic-based bionic material under the pH condition.
Test example 9
The test example uses the sintering conditions of the ceramic slurry as variables, and compares the influence of two sintering modes of two-step high-temperature sintering and one-step high-temperature sintering on the surface structure of the ceramic-based bionic material.
The two-step high-temperature sintering method is the same as the method provided by the invention, namely the heating rate in the pre-sintering process is different from the heating rate in the sintering process, and specifically comprises the following steps:
a green compact was prepared according to steps 1-3 of the preparation method provided in example 1, and then the green compact was heated at 1 K.min-1Raising the temperature to 600 ℃, and preserving the temperature for 1h for pre-sintering to remove polyacrylic acid and octanol; the presintered sample was then placed in a tube furnace at 10 K.min-1And respectively heating to 1200 ℃, sintering for 15min, then rapidly cooling to 1000 +/-20 ℃, and preserving heat for 24h to obtain the ceramic bionic sample, and recording as a sample A.
A green compact was prepared according to steps 1-3 of the preparation method provided in example 1, and then the green compact was heated at 1 K.min-1Raising the temperature to 600 ℃, and preserving the temperature for 1h for pre-sintering to remove polyacrylic acid and octanol; the presintered sample was then placed in a tube furnace at 10 K.min-1And respectively heating to 1600 ℃, sintering for 15min, then rapidly cooling to 1000 +/-20 ℃, and preserving heat for 24h to obtain the ceramic-based bionic material, and recording as a sample B.
The solidity of sample a was 80% and the solidity of sample B was 97%. Samples a and B were designated as experimental group samples.
The heating rate of the sintering process in the one-step high-temperature sintering is the same as that of the pre-sintering process and is lower than that of the sintering process in the two-step high-temperature sintering, and the method specifically comprises the following steps:
a green compact was prepared according to steps 1-3 of the preparation method provided in example 1, and then the green compact was heated at 1 K.min-1Raising the temperature to 600 ℃, and preserving the temperature for 1h for pre-sintering to remove polyacrylic acid and octanol; the presintered sample was then placed in a tube furnace at 1 K.min-1And heating to 1200 ℃, sintering for 15min, then quickly cooling to 1000 +/-20 ℃, and preserving heat for 24h to obtain the ceramic-based bionic material, and recording as a sample C.
A green compact was prepared according to steps 1-3 of the preparation method provided in example 1, and then the green compact was heated at 1 K.min-1Raising the temperature to 600 ℃, and preserving the temperature for 1h for pre-sintering to remove polyacrylic acid and octanol; the presintered sample was then placed in a tube furnace at 1 K.min-1And heating to 1400 ℃, sintering for 15min, then rapidly cooling to 1000 +/-20 ℃, and preserving heat for 24h to obtain the ceramic-based bionic material, and recording as a sample D.
A green compact was prepared according to steps 1-3 of the preparation method provided in example 1, and then the green compact was heated at 1 K.min-1Raising the temperature to 600 ℃, and preserving the temperature for 1h for pre-sintering to remove polyacrylic acid and octanol; the presintered sample was then placed in a tube furnace at 1 K.min-1And heating to 1600 ℃, sintering for 15min, then rapidly cooling to 1000 +/-20 ℃, and preserving heat for 24h to obtain the ceramic-based bionic material, and recording as a sample E.
The solidity of sample C was 83%, the solidity of sample D was 91%, and the solidity of sample E was 99%. Sample C-sample E were designated as control samples.
Fig. 15 is an SEM photograph of a sample prepared by two-step high temperature sintering, wherein a is an SEM image of sample a, and B is an SEM image of sample B. Fig. 16 is an SEM photograph of a sample prepared by one-step high-temperature sintering, in which a is an SEM image of sample C, b is an SEM image of sample D, and C is an SEM image of sample E. As can be seen from a comparison of fig. 15 and 16, the grain size of the sample prepared by the one-step high temperature sintering is significantly larger than that of the sample prepared by the two-step high temperature sintering at the same sintering temperature.
The contact angle test was performed on the above 5 samples according to the method of test example 1, and the results were: the contact angle for sample a was 164 °, the contact angle for sample B was 158 °, the contact angle for sample C was 160 °, the contact angle for sample D was 154 °, and the contact angle for sample E was 152 °. The results show that although the contact angles between the sample prepared by the two-step high-temperature sintering and the sample prepared by the one-step high-temperature sintering in water and chloroform are both larger than 90 degrees, the contact angle between the sample prepared by the two-step high-temperature sintering and chloroform in water is larger than the contact angle between the sample prepared by the one-step high-temperature sintering and chloroform in water at the same sintering temperature, because the two-step high-temperature sintering improves the heating rate in the sintering process, inhibits the increase of the ceramic particle size, and enables the prepared sample to retain the ultra-fine crystal grains with smaller size and higher degree of porosity, so that the microstructure of the obtained bionic material is closer to the micro-nano structure of the biological material.
The above results show that the preparation method provided by the invention can better retain the size characteristics of the micro-nano structure on the surface of the biological material, and further can obtain more excellent properties caused by the surface structure characteristics of the biological material, such as water oleophobic properties and the like.
Comparative example 1
This comparative example provides a method for preparing a biomimetic material, which is similar to the method provided in example 1, except that this comparative example does not perform drying under 90% RH in step 3, but directly dries the PDMS resin template loaded with ceramic slurry at 40% RH for 14 days to form a green body. Fig. 17 is a photograph of the biomimetic material obtained by this method. And (3) dropping the dyed liquid on the upper surface of the bionic material, and observing the dyed liquid at the bottom of the material, wherein the dyed liquid shows that a crack exists in the middle of the material, and the liquid spreads to the bottom of the material along the crack in the middle of the material. This result illustrates that: direct drying of ceramic slurries at low humidity can lead to cracking in the middle of the material. Fig. 18 is a photograph of the bionic material prepared in example 1, on which a dye drop is dropped, and it can be seen from fig. 18 that cracks are prevented from being generated by using the drying conditions provided by the present invention.
Comparative example 2
The comparative example provides a preparation method of a biomimetic material, which is similar to the operation and experimental parameters of the method provided in example 1, and is different in that the comparative example directly uses the lotus leaf surface to replace PDMS as a template for preparation (i.e. directly casts ceramic slurry on the lotus leaf surface). Fig. 19 is a photograph of the bionic material prepared in the present comparative example, on which a drop of dye was dropped, and it can be seen from fig. 19 that the biological surface template directly used in the present comparative example generates cracks during the drying process. In contrast, as can be seen from fig. 18, when the PDMS template is used for the double etching, the ceramic-based biomimetic material does not crack during the drying process. The result shows that the specific resin can avoid the generation of cracks in the preparation process, is beneficial to the completion of the micro-nano structure of the biological material and prolongs the service life of the material.

Claims (24)

1. A preparation method of a ceramic-based biomimetic material comprises the following steps:
step one, casting the surface of a biological material by using liquid resin, and separating the resin from the biological material after curing to obtain a resin template; the biological material is a biological material with a micro-nano structure, and the biological material is provided with an underwater oleophobic surface or an air hydrophobic surface;
pouring the ceramic slurry into the resin template, and drying and forming at 80-90% RH to obtain a green body;
step three, the green body is processed at 1-1.5 K.min-1Heating at a certain rate to perform pre-sintering, and performing pre-sintering at a temperature of 10-15 K.min-1And heating at the speed of the temperature rise to sinter to obtain the ceramic-based bionic material.
2. The method of claim 1, wherein the resin comprises one of PDMS, PMMA, or polycraft K4 translucent silicone rubber.
3. The production method according to claim 2, wherein the resin is PDMS.
4. The method of claim 1, wherein the biological material comprises rose petals or lotus leaves.
5. The production method according to claim 1, wherein in the second step, the volume fraction of the solid particles in the ceramic slurry is 25 to 30%.
6. The production method according to claim 5, wherein the ceramic slurry is formed by dispersing ceramic powder in a dispersant.
7. The production method according to claim 6, wherein the ceramic powder comprises one or a combination of two or more of alumina powder, beryllium oxide powder, and titanium dioxide powder, and the dispersant comprises a polyacrylic acid solution or Dolapix ET 85.
8. The production method according to claim 7, wherein the ceramic powder has a particle size of 200nm to 300 nm.
9. The production method according to claim 6, wherein the production method of the ceramic slurry comprises: and mixing ceramic powder with the dispersing agent, performing ultrasonic treatment, and dropwise adding octanol to obtain the ceramic slurry.
10. The method according to claim 1 or 5, wherein the step two, the drying and shaping process further comprises drying at 40-50% RH after drying at 80-90% RH.
11. The method of claim 10, wherein the drying time at 80-90% RH is 24-36 h, and the drying time at 40-50% RH is 3d-4 d.
12. The method according to claim 10, wherein the temperature of drying in the second step is 20 to 30 ℃.
13. The preparation method according to claim 1, wherein in the third step, the temperature of the pre-sintering is 500-600 ℃, and the time of the pre-sintering is 1-1.5 h;
in the third step, the sintering temperature is 1150-1600 ℃, and the sintering time is 15min-1.5 h.
14. The method of claim 13, wherein in step three, the sintering process comprises: after pre-sintering, at 10-15 K.min-1The temperature is raised to 1150-1250 ℃ at a rate of 1-1.5 h; or pre-sintering at 10-15 K.min-1The temperature is raised to 1250-1600 ℃ at the speed of 15-30 min.
15. The preparation method as claimed in claim 14, wherein in the third step, the sintering process further comprises cooling to 980-.
16. The method of claim 15, wherein the cooling rate is 40-50K-min-1。
17. The method of claim 1 or 13, wherein in step three, the sintering process comprises: at 10-15 K.min-1The temperature is raised to 1250-1600 ℃, the sintering is carried out for 15-30 min, the temperature is lowered to 980-1020 ℃, and the heat preservation is carried out for 24-36 h.
18. The method of claim 17, wherein in step three, the sintering process comprises: at 10-15 K.min-1The temperature is raised to 1450-1600 ℃, the sintering is carried out for 15-30 min, the temperature is lowered to 980-1020 ℃, and the temperature is kept for 24-36 h.
19. A ceramic-based biomimetic material prepared by the preparation method of any of claims 1-18.
20. The ceramic-based biomimetic material according to claim 19, wherein the ceramic-based biomimetic material is comprised of ceramic particles with a surface distribution of continuously arranged pyramidal protrusions.
21. The ceramic-based biomimetic material according to claim 20, wherein said pyramidal protrusions have a base diameter of 16-20 μm, a height of 10-14 μm, and a pitch between protrusions of 4-6 μm.
22. The ceramic-based biomimetic material according to claim 20, wherein the ceramic particles have a particle size in the range of 0.2-0.3 μm.
23. The ceramic-based biomimetic material according to claim 19 or 20, wherein the ceramic-based biomimetic material has a solidity of 70 ± 3% to 97 ± 2.5%.
24. Use of the ceramic based biomimetic material according to any of claims 19-23 as an underwater superoleophobic material.
CN202011117330.0A 2020-10-19 2020-10-19 Ceramic-based bionic material and preparation method and application thereof Active CN112341211B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011117330.0A CN112341211B (en) 2020-10-19 2020-10-19 Ceramic-based bionic material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011117330.0A CN112341211B (en) 2020-10-19 2020-10-19 Ceramic-based bionic material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112341211A CN112341211A (en) 2021-02-09
CN112341211B true CN112341211B (en) 2021-08-10

Family

ID=74362141

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011117330.0A Active CN112341211B (en) 2020-10-19 2020-10-19 Ceramic-based bionic material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112341211B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115403357B (en) * 2022-08-23 2023-01-31 南京水凝科技有限公司 Underwater super-oleophobic bionic ceramic substrate and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101487130B (en) * 2009-01-06 2010-09-22 北京航空航天大学 Duplicating method for making scaliness biological epidermis morphology duplicating template by pulse electroforming method
CN101942638B (en) * 2010-09-30 2012-03-21 中国科学院宁波材料技术与工程研究所 Preparation method of bionic controllable adhesive hydrophobic gold surface
CN105504324B (en) * 2015-12-23 2018-07-03 中国航空工业集团公司北京航空制造工程研究所 A kind of polymer matrix composites with super-hydrophobic bionic surface and preparation method thereof
CN107522475B (en) * 2017-09-08 2019-12-27 大连理工大学 Shell-like ceramic matrix composite and preparation method thereof
CN108752821B (en) * 2018-06-14 2020-10-16 中国科学院金属研究所 Silicon carbide/resin bionic composite material with micro-oriented structure and preparation method thereof
WO2020022998A1 (en) * 2018-07-25 2020-01-30 Yildiz Tekni̇k Üni̇versi̇tesi̇ Biomimetic biomaterial and production method thereof

Also Published As

Publication number Publication date
CN112341211A (en) 2021-02-09

Similar Documents

Publication Publication Date Title
Chen et al. Creating robust superamphiphobic coatings for both hard and soft materials
CN110240830A (en) The conductive ink of sintering certainly, preparation method and application based on liquid metal particle
CN112341211B (en) Ceramic-based bionic material and preparation method and application thereof
CN102140218B (en) Ultra-oleophobic underwater self-cleaning polymer composite film with biomimic structure and manufacturing method thereof
WO2006021038A1 (en) Ceramic and metallic components and methods for their production from flexible gelled materials
Li et al. Superhydrophobicity of bionic alumina surfaces fabricated by hard anodizing
Jin et al. Development of ethylene glycol-based gelcasting for the preparation of highly porous SiC ceramics
Li et al. Mechanical properties of polydopamine (PDA) thin films
CN113000845A (en) Bionic drag reduction surface and manufacturing method thereof
Zhu et al. A soft moulding process for manufacture of net-shape ceramic microcomponents
Liu et al. 4D printing of lead zirconate titanate piezoelectric composites transducer based on direct ink writing
Lin et al. Nonswellable hydrogels with robust micro/nano-structures and durable superoleophobic surfaces under seawater
CN113773547A (en) Elastic piezoelectric film with good biocompatibility and flexibility and preparation method and application thereof
Stastny et al. Gel-tape casting as a novel method for the production of flexible fine-grained alumina sheets
Ji et al. Super-floatable multidimensional porous metal foam integrated with a bionic superhydrophobic surface
Mouazer et al. Silicon carbide foams by polyurethane replica technique
JP4514847B2 (en) Method for producing ceramic porous body
CN112773945A (en) Method for preparing ceramic-magnetofluid composite bracket
Xie et al. Gelation behavior and mechanical properties of gelcast lead zirconate titanate ceramics
Swinerd et al. Silk inverse opals from template-directed β-sheet transformation of regenerated silk fibroin
Guo et al. A novel method for preparation of interconnected pore-gradient ceramic foams by gelcasting
Wang et al. Gelcasting of sol–gel derived mullite based on gelation of modified poly (isobutylene-alt-maleic anhydride)
CN115403357B (en) Underwater super-oleophobic bionic ceramic substrate and preparation method thereof
CN114000138A (en) Method for preparing super-hydrophobic surface by utilizing nano metal hot pressing
Chen et al. 3D Printing of Ceramics with Controllable Green‐Body Configuration Assisted by the Polyvinyl Alcohol‐Based Physical Gels

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant