CN115572184B - Method for constructing multi-level micron coarse structure on ceramic glaze - Google Patents
Method for constructing multi-level micron coarse structure on ceramic glaze Download PDFInfo
- Publication number
- CN115572184B CN115572184B CN202211234220.1A CN202211234220A CN115572184B CN 115572184 B CN115572184 B CN 115572184B CN 202211234220 A CN202211234220 A CN 202211234220A CN 115572184 B CN115572184 B CN 115572184B
- Authority
- CN
- China
- Prior art keywords
- ceramic
- powder
- glaze
- hydrophobic
- 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
Links
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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Abstract
The invention relates to the technical field of superhydrophobic technology, in particular to a method for constructing a multilevel micron coarse structure on a ceramic glaze.
Description
Technical Field
The invention relates to the technical field of preparation of hydrophobic materials, in particular to a method for constructing a multi-level micron coarse structure on a ceramic glaze.
Background
At present, micro-nano multi-scale particles with high wear-resistant coarse structures are widely applied to the field of construction of super-hydrophobic material surfaces, and super-hydrophobic surfaces constructed by the micro-nano multi-scale particles have excellent performance in basic research and practical application, so that the focus of attention is focused on the aspect of the regulation and control mechanism of the morphology and chemical composition of the micro-nano multi-scale particles, and in general, the micro-nano multi-scale particle coarse structures for constructing the super-hydrophobic surfaces are mostly realized through physical adsorption or chemical bonding between micro-scale and nano-scale structures with different shape and scale, wherein the bonding modes comprise adhesion, electrostatic mutual attraction, ionic bonding, coordination bonding, hydrogen bonding, conjugate delocalization and the like.
However, the mutual combination action among micro-nano multi-scale particle structures constructed based on the mode is generally weak, and the problem that the morphology of a coarse structure is damaged easily occurs when extreme conditions are encountered, so that the constructed functional surface has the defects of reduced superhydrophobicity, poor physicochemical stability, poor durability and the like.
The existing micro-nano multi-scale particles for constructing the super-hydrophobic surface are mainly prepared by the following two methods: (1) Firstly, constructing a rough structure, and then, modifying the low surface energy; (2) The micro-nano multi-scale hydrophobic layer has low intrinsic mechanical strength, so that the application of the micro-nano multi-scale hydrophobic layer in the ceramic field with certain wear resistance requirement is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for constructing a multi-level micron coarse structure on a ceramic glaze, which solves the technical problems of low wear resistance and poor long-term stability of the hydrophobic performance of the existing hydrophobic coating constructed on the ceramic glaze.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for constructing a multi-level micron coarse structure on a ceramic glaze comprises the following steps:
(1) Adding ceramic powder into an organic polymer water solution, and uniformly dispersing by ultrasonic to obtain ceramic suspension;
(2) Spraying the ceramic suspension obtained in the step (1) onto the ceramic glaze, drying and roasting, namely forming a multi-stage micron coarse structure on the ceramic glaze;
the particle size of the ceramic powder is 1-50 mu m, and the structure of the ceramic powder is at least one selected from a spherical structure, an octahedral structure, a flower-like structure and a columnar structure;
the organic polymer in the organic polymer aqueous solution is at least one selected from ethylenediamine tetraacetic acid (EDTA), polyvinylpyrrolidone (PVP), polysilicate aluminum sulfate (PASS), polyvinyl alcohol (PVA) and carboxymethyl cellulose (CMC).
Preferably, the ceramic powder is at least one selected from the group consisting of spinel powder with an octahedral structure, alumina powder with a spherical structure, mullite powder with a columnar structure, and alumina powder with a flower-like structure, wherein the grain size of the spinel powder with an octahedral structure is 1-20 μm, the grain size of the alumina powder with a spherical structure is 1-10 μm, the grain size of the mullite powder with a columnar structure is 0.5-10 μm, and the grain size of the alumina powder with a flower-like structure is 10-50 μm.
Preferably, the preparation method of the spinel powder with the octahedral structure comprises the following steps: alumina, magnesia and aluminum fluoride are mixed according to the mass ratio of 20-35:60-75: ball-milling and mixing 1-6, and calcining at 1400-1550 ℃ for 1-6h to obtain the spinel powder with the octahedral structure.
Preferably, the preparation method of the alumina powder with the spherical structure comprises the following steps: urea and aluminum sulfate are mixed according to the mole ratio of 0.1-0.2:0.01, and placing in 100-150mL of water solution with the temperature of 180-200 ℃ for reaction for 12-18h, grinding, and calcining for 2-4h at 1150-1250 ℃ to obtain the alumina powder with the spherical structure.
Preferably, the preparation method of the mullite powder with the columnar structure comprises the following steps: alumina, silicon oxide and aluminum fluoride are mixed according to the mass ratio of 60-75:25-35: ball-milling and mixing 1-5, and calcining at 1400-1550 ℃ for 2-7h to prepare the mullite powder with columnar structure.
Preferably, the preparation method of the alumina powder with the flower-like structure comprises the following steps: mixing aluminum oxide sheet with PVP solution with mass concentration of 3-8% at a mass ratio of 5:95, and thermally spraying to the surface of the carrier at 70-90 ℃ to prepare the aluminum oxide aggregate with flower-like structure.
Preferably, the multi-stage micro roughness structure has a bipolar pore structure in which the primary pore size is 6-105 μm and the secondary pore size is 0.8-5 μm.
Preferably, in the step (1), the mass ratio of the ceramic powder to the organic polymer aqueous solution is 1-10:90-99, and the mass fraction of the organic polymer aqueous solution is 1-10%.
Preferably, in the step (1), the ultrasonic power is 300-600W, and the ultrasonic time is 10-300s.
Preferably, in the step (2), the spraying temperature is 55-70 ℃, the spraying time is 15-25s, the drying temperature is 50-60 ℃, the drying time is 15-30min, the roasting temperature is 900-1300 ℃, and the roasting time is 20-40min.
Preferably, in the step (2), the step of cleaning and drying the ceramic glaze is further included before spraying the ceramic suspension on the ceramic glaze; further preferably, the cleaning is performed by water, and the drying can be performed in an oven or natural air drying.
Preferably, the ceramic glaze surface comprises feldspar glaze, lime glaze, lead glaze, zinc glaze, magnesium glaze or lithium glaze.
The invention also provides a ceramic, the glaze of which has a multi-stage micron coarse structure, and the multi-stage micron coarse structure is prepared by the method.
Preferably, the method further comprises immersing the ceramic in a hydrophobic coating, taking out, and air-drying and curing to obtain the ceramic with the hydrophobic layer structure.
Preferably, the hydrophobic coating is selected from any one of fluorine/silicon hydrophobic materials, hydrophobic high molecular melt polymers and organic-inorganic hybrid hydrophobic materials.
Preferably, the impregnation temperature is 5-40 ℃ and the impregnation time is 20-35s.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts micron-sized ceramic powder with specific shape, and obtains ceramic suspension by mixing with organic macromolecule water solution, then sprays the ceramic suspension onto ceramic glaze, and then dries and bakes the ceramic suspension to make a series of physical and chemical changes between the multilevel micron ceramic particles and the ceramic glaze, sinters the multilevel micron ceramic particles on the enamel surface layer, so that the ceramic surface forms a ceramic-based multilevel micron coarse structure with height difference and two or more micron-sized pore distribution, and the obtained hydrophobic coating has excellent wear resistance and long-term stability of hydrophobic property after the ceramic with multilevel micron coarse structure is loaded, and the hydrophobic property and wear resistance of the hydrophobic coating are not obviously reduced after a plurality of wear-resisting tests.
(2) The ceramic with the multilevel micron coarse structure provided by the invention can obviously improve the self-cleaning performance of the glazed hydrophobic coating and also can improve the service life of the hydrophobic coating under the wearing working condition.
(3) The ceramic powder with a specific structure is adopted, and the ceramic-based multilevel micron coarse structure is obtained, so that after the ceramic with the coarse structure is loaded with the hydrophobic coating, the excellent wear resistance and the long-term stability of the hydrophobic performance of the hydrophobic coating can be further ensured.
(4) The multi-stage micron coarse structure obtained by the invention has a bipolar pore structure, wherein the primary pore diameter is 6-105 mu m, the secondary pore diameter is 0.8-5 mu m, and the excellent wear resistance and the long-term stability of the hydrophobic performance of the hydrophobic coating can be further ensured.
(5) Compared with the traditional single-scale structure, the secondary coarse structure of the multi-scale coarse structure plays a certain role in protecting the hydrophobic coating, enriches the pore structure, leads to more reduction of the actual contact area fraction of the solid and the liquid drop, and reduces the area fraction of the hydrophobic material, so that the multi-scale coarse structure is more beneficial to maintaining the stability of the hydrophobic performance.
(6) The invention has low cost of raw materials, simple preparation process and equipment, convenient operation, high production efficiency and no pollution, and can be widely used for modifying the hydrophobic coating on the ceramic surface; the invention does not affect the molding, glazing and firing process system of the original ceramic, can obviously improve the wear resistance of the ceramic glaze hydrophobic coating, has long service life, high ageing resistance and excellent hydrophobic property after the hydrophobic coating is loaded on the ceramic glaze hydrophobic coating, and has practical application value without further modification after the multistage micron coarse structure is constructed by the method.
Drawings
FIG. 1 is a scanning electron microscope image of a multi-stage micro-roughness structure prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a multi-stage micro-roughness structure prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of a multi-stage micro-roughness structure prepared in example 3 of the present invention;
FIG. 4 is a scanning electron microscope image of a multi-stage micro-roughness structure prepared in example 4 of the present invention;
FIG. 5 is a schematic view of a multi-stage micro-roughness structure prepared in examples 1-4 of the present invention;
FIG. 6 is a scanning electron microscope image of the ceramic glaze in comparative example 1;
FIG. 7 is a scanning electron microscope image of the micro roughness structure obtained in the step (4) of the comparative example 2;
FIG. 8 is a graph showing contact angle test of a hydrophobic layer having a ceramic with a hydrophobic layer structure prepared in example 1 and comparative examples 1-2 according to the present invention;
FIG. 9 is a rolling angle test of the hydrophobic layer having the ceramic of the hydrophobic layer structure prepared in example 1 and comparative examples 1-2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following preferred examples, but the present invention is not limited to the following examples.
Unless otherwise specified, the chemical reagents involved in the present invention are all commercially available.
The ceramics used in the following examples and comparative examples were selected from the group consisting of Jingdezhen white glaze, belonging to the group of feldspar glazes, available from Jingdezhen porcelain industries, inc.; perfluorodecyl trichlorosilane is available from Hubei Kohle materials science, inc., CAS:78560-44-8; alumina ceramic powder of lamellar structure was purchased from the company of the chemical industry, the company of the chemical industry of the ridge; ethylenediamine tetraacetic acid (EDTA) was purchased from national pharmaceutical chemicals limited, analytically pure; polyvinylpyrrolidone (PVP) was purchased from the company, asiatai joint chemical limited, tin-free, analytically pure; polysilicate aluminum sulfate (PASS) was purchased from Chongqing American chemical Co., ltd; polyvinyl alcohol (PVA) was purchased from national pharmaceutical group chemical company, 99%; carboxymethyl cellulose (CMC) was purchased from alatin, ds=0.7, 200-500mpa.s; hydrophobic coating A, hydrophobic coating B and hydrophobic coating C were all purchased from Shenzhen View high Material technologies Co.
Example 1
A preparation method of ceramic with a hydrophobic layer structure comprises the following steps:
(1) Cleaning the ceramic with water, and naturally air-drying to obtain a clean ceramic glaze for later use;
(2) Adding 3g of EDTA into 100g of deionized water, heating, stirring and dissolving to obtain an organic polymer aqueous solution;
(3) Mixing and ball milling 2.83g of alumina, 6.87g of magnesia and 0.3g of aluminum fluoride, putting the mixture into a muffle furnace after ball milling is finished, calcining the mixture for 5 hours at 1450 ℃, and grinding the mixture to prepare spinel ceramic powder with the particle size of 10-20 mu m and an octahedral structure; mixing and ball milling 2.83g of aluminum oxide, 6.87g of magnesium oxide and 0.3g of aluminum fluoride, putting the mixture into a muffle furnace after ball milling is finished, calcining the mixture for 1h at 1500 ℃, and grinding the mixture to prepare spinel ceramic powder with the particle size of 1-10 mu m and an octahedral structure; the spinel powder with two particle size distributions can improve the high and low levels of the distribution of particles on the glaze;
(4) Respectively weighing 3.5g of spinel ceramic powder with two particle size distributions, adding the spinel ceramic powder into 93g of the organic polymer aqueous solution prepared in the step (2), and carrying out ultrasonic treatment for 300 seconds under the condition that ultrasonic power is 300W to obtain ceramic suspension;
(5) Spraying the ceramic suspension obtained in the step (4) onto the ceramic glaze, wherein the spraying temperature is 60 ℃, the spraying time is 20s, the ceramic suspension is uniformly attached to the ceramic glaze, then drying the ceramic glaze at 50 ℃ for 20min, then placing the ceramic glaze into a high-temperature furnace, heating the ceramic glaze to 900 ℃, roasting the ceramic glaze for 20min, and naturally cooling the ceramic glaze to obtain the ceramic with a multistage micron coarse structure;
(6) And (3) cleaning the ceramic with the glaze having the multilevel micron coarse structure obtained in the step (5) by deionized water, drying, then dipping the ceramic in the hydrophobic coating A (20 wt% of fluorine modified silicon dioxide, 3wt% of liquid silicone rubber and 77wt% of butyl acetate) at the dipping temperature of 30 ℃ for 20 seconds, taking out the ceramic, and performing air drying and curing for 36 hours to obtain the ceramic with the hydrophobic layer structure.
In the embodiment, a jade dew-shaped multilevel micro-rough structure with a two-stage pore structure is formed on the ceramic glaze in the step (5), wherein the primary pore diameter is 6-18 μm, the secondary pore diameter is 2-4 μm, the microstructure of the multilevel micro-rough structure is shown in fig. 1, and the structural schematic diagram is shown in fig. 5 (a).
Example 2
A preparation method of ceramic with a hydrophobic layer structure comprises the following steps:
(1) Cleaning the ceramic with water, and naturally air-drying to obtain a clean ceramic glaze for later use;
(2) Adding 5.5g of PASS and 2.5g of CMC into 100g of deionized water, heating, stirring and dissolving to obtain an organic polymer aqueous solution, wherein the high-concentration mixed polymer solution plays a role of steric hindrance;
(3) Placing 0.2mol of urea and 0.01mol of aluminum sulfate into a hydrothermal reaction kettle, reacting for 12 hours at 180 ℃, drying, grinding, placing into a muffle furnace, and calcining for 2 hours at 1200 ℃ to prepare alumina ceramic powder with a particle size of 1-10 mu m and a spherical structure;
(4) Adding 5g of alumina ceramic powder into 95g of the organic polymer aqueous solution prepared in the step (2), and performing ultrasonic treatment for 10s under the condition that the ultrasonic power is 600W to obtain ceramic suspension;
(5) Spraying the ceramic suspension obtained in the step (4) onto the ceramic glaze, wherein the spraying temperature is 70 ℃, the spraying time is 25 seconds, so that the ceramic suspension is uniformly attached to the ceramic glaze, then drying the ceramic glaze at 60 ℃ for 30 minutes, then placing the ceramic glaze into a high-temperature furnace, heating the ceramic glaze to 1300 ℃, roasting the ceramic glaze for 40 minutes, and naturally cooling the ceramic glaze to obtain the ceramic with a multistage micron coarse structure;
(6) And (3) cleaning the ceramic with the glaze having the multilevel micron coarse structure obtained in the step (5) by deionized water, drying, then dipping the ceramic in a hydrophobic coating B (the main components are 20wt% of semi-fluorine modified silicon dioxide, 3wt% of organic silicon resin and 77wt% of ethanol) at a dipping temperature of 40 ℃ for 15 seconds, taking out the ceramic, and performing air drying and curing for 36 hours to obtain the ceramic with the hydrophobic layer structure.
In the embodiment, a fish-roe-shaped multi-stage micro-coarse structure with a two-stage pore structure is formed on the ceramic glaze in the step (5), wherein the primary pore diameter is 8-15 μm, the secondary pore diameter is 1-5 μm, the microstructure of the multi-stage micro-coarse structure is shown in fig. 2, and the schematic structural diagram is shown in fig. 5 (b).
Example 3
A preparation method of ceramic with a hydrophobic layer structure comprises the following steps:
(1) Cleaning the ceramic with water, and naturally air-drying to obtain a clean ceramic glaze for later use;
(2) Adding 3g of PVA into 100g of deionized water, heating, stirring and dissolving to obtain an organic polymer aqueous solution;
(3) Mixing and ball milling 6.7g of alumina, 3g of silica and 0.3g of aluminum fluoride, and then placing the mixture in a muffle furnace to calcine for 5 hours at 1450 ℃ to prepare mullite ceramic powder with the grain diameter of 0.5-10 mu m and a columnar structure;
(4) Adding 10g of mullite ceramic powder into 90g of the organic polymer aqueous solution prepared in the step (2), and performing ultrasonic treatment for 300 seconds under the condition that the ultrasonic power is 300W to obtain ceramic suspension;
(5) Spraying the ceramic suspension obtained in the step (4) onto the ceramic glaze, wherein the spraying temperature is 55 ℃, the spraying time is 15s, the ceramic suspension is uniformly attached to the ceramic glaze, then drying the ceramic glaze at 60 ℃ for 15min, then placing the ceramic glaze into a high-temperature furnace, heating the ceramic glaze to 1250 ℃, roasting the ceramic glaze for 20min, and naturally cooling the ceramic glaze to obtain the ceramic with a multistage micron coarse structure;
(6) And (3) cleaning the ceramic with the glaze having the multilevel micron coarse structure obtained in the step (5) by deionized water, drying, then soaking the ceramic in the hydrophobic coating perfluorodecyl trichlorosilane at 20 ℃ for 20 seconds, taking out, and then air-drying and curing for 36 hours to obtain the ceramic with the hydrophobic layer structure.
In the embodiment, a weed-shaped multi-stage micro-coarse structure with a two-stage pore structure is formed on the ceramic glaze in the step (5), wherein the primary pore diameter is 6-14 μm, the secondary pore diameter is 0.8-3.2 μm, the microstructure of the multi-stage micro-coarse structure is shown in fig. 3, and the structural schematic diagram is shown in fig. 5 (c).
Example 4
A preparation method of ceramic with a hydrophobic layer structure comprises the following steps:
(1) Cleaning the ceramic with water, and naturally air-drying to obtain a clean ceramic glaze for later use;
(2) Adding 5g PVP into 100g deionized water, heating, stirring and dissolving to obtain an organic polymer aqueous solution, wherein the solution has the characteristic of bonding aluminum oxide sheets into microspheres;
(3) Adding 10g of alumina ceramic powder with a sheet structure into 91g of the organic polymer water solution prepared in the step (2), and performing ultrasonic treatment for 100s under the condition that the ultrasonic power is 400W to obtain ceramic suspension;
(4) Spraying the ceramic suspension obtained in the step (3) onto the ceramic glaze, wherein the spraying temperature is 65 ℃, the spraying time is 25 seconds, so that the ceramic suspension is uniformly attached to the ceramic glaze, then drying the ceramic glaze at 50 ℃ for 30 minutes, then placing the ceramic glaze into a high-temperature furnace, heating the ceramic glaze to 1250 ℃, roasting the ceramic glaze for 30 minutes, and naturally cooling the ceramic glaze to obtain the ceramic with a multistage micron coarse structure;
(5) And (3) cleaning the ceramic with the glaze having the multilevel micron coarse structure obtained in the step (4) by deionized water, drying, then dipping the ceramic in a hydrophobic coating C (main components of fluorine modified silicon dioxide 15wt%, polyurethane 5wt% and ethanol 80 wt%) at a dipping temperature of 30 ℃ for 30 seconds, taking out, and then air-drying and curing for 36 hours to obtain the ceramic with the hydrophobic layer structure.
In the embodiment, a rosette-shaped multi-stage micro-coarse structure with a two-stage pore structure is formed on the ceramic glaze in the step (4), wherein the primary pore diameter is 50-105 μm, the secondary pore diameter is 1-5 μm, the microstructure of the multi-stage micro-coarse structure is shown in fig. 4, and the schematic structural diagram is shown in fig. 5 (d).
Comparative example 1
The comparative example provides a ceramic having a hydrophobic layer structure, which is prepared by a method different from example 1 in that a ceramic suspension is not sprayed on a ceramic glaze, and specifically comprises the following steps:
(1) Cleaning the ceramic with water, and naturally air-drying to obtain a clean ceramic glaze for later use;
(2) And (3) dipping the ceramic obtained in the step (1) in a hydrophobic coating A (main components: 20wt% of fluorine modified silicon dioxide, 3wt% of silicon rubber SYCGARD and 77wt% of butyl acetate) at a dipping temperature of 30 ℃ for 20 seconds, taking out, and then air-drying and curing for 36 hours to obtain the ceramic with a hydrophobic layer structure.
Comparative example 2
The present comparative example provides a ceramic having a hydrophobic layer structure, which is prepared by a method different from example 1 in that an organic polymer is not added to a ceramic suspension, and specifically includes the steps of:
(1) Cleaning the ceramic with water, and naturally air-drying to obtain a clean ceramic glaze for later use;
(2) Selecting industrial waste porcelain powder (from Jiangxi Baixin electric porcelain Co., ltd.), sieving with a 250 mesh sieve, and taking out the part under the sieve;
(3) Adding 9g of waste porcelain powder into 91g of deionized water, and performing ultrasonic treatment for 300s under the condition that the ultrasonic power is 300W to obtain ceramic suspension;
(4) Spraying the ceramic suspension obtained in the step (3) onto the ceramic glaze, wherein the spraying temperature is 60 ℃, the spraying time is 20s, the ceramic suspension is uniformly attached to the ceramic glaze, then drying the ceramic glaze at 50 ℃ for 20min, then placing the ceramic glaze into a high-temperature furnace, heating the ceramic glaze to 900 ℃, roasting the ceramic glaze for 20min, and naturally cooling the ceramic glaze to obtain ceramic with a micron coarse structure;
(5) And (3) cleaning the ceramic with the micro-coarse structure on the glaze surface obtained in the step (4) by deionized water, drying, then dipping the ceramic in a hydrophobic coating A (20 wt% of fluorine modified silicon dioxide, 3wt% of silicon rubber SYCGARD and 77wt% of butyl acetate) at a dipping temperature of 30 ℃ for 20 seconds, taking out the ceramic, and performing air drying and curing for 36 hours to obtain the ceramic with the hydrophobic layer structure.
The ceramics having the hydrophobic layer structures obtained in examples 1 to 4 and comparative examples 1 to 2 were subjected to contact angle and rolling angle tests, and then the hydrophobic layer of the ceramics was subjected to abrasion resistance tests 100 times, and then the contact angle, rolling angle and abrasion rate of the hydrophobic layer were tested;
the abrasion resistance test comprises the following specific steps: the method comprises the steps of taking polyurethane sponge as a wearing medium, testing the wearing resistance of a hydrophobic coating by adopting a linear wearing instrument (Taber-5750), wherein the load is 100g in the sample wearing process, the wearing speed is 5cm/s, the wearing path is 50cm each time, the mass of a sample is weighed 1 time each time, the contact angle and the rolling angle are tested, the total wearing is 100 times, and the ratio of the coating mass loss to the coating amount after 100 times is the wearing rate;
the contact angle and rolling angle of each sample after being coated with a hydrophobic coating and after abrasion were characterized using a contact angle tester (HARKE-SPCA) from beijing hake, according to the GB/T30047-2013 standard, the test results being shown in table 1 and fig. 8-9:
TABLE 1
As can be seen from fig. 8 and 9, the roughness structure can effectively improve the abrasion resistance of the hydrophobic layer relative to the smooth glaze, and the multi-stage roughness structure can more effectively improve the abrasion resistance of the hydrophobic layer relative to the conventional single-stage roughness structure, which is attributed to the fact that: 1. the multi-stage coarse structure has a richer pore structure than the single-stage coarse structure, so that more composite space can be reserved for the hydrophobic coating; 2. in the abrasion process, ceramic particles in the single-stage coarse structure are easy to be exposed in a large area, so that the surface energy of a hydrophobic layer is improved, the protection of the multi-stage coarse structure on the hydrophobic coating is divided into two dimensions, wherein the I-stage structure can be used for manufacturing a pore structure so as to improve the hydrophobicity, and the II-stage structure prevents the ceramic particles from being exposed in a large area and plays a role in keeping the surface energy of the hydrophobic layer low. The patent provides four typical multistage coarse structure construction methods: the method comprises a jade dew-shaped multilevel coarse structure formed by spinels with two grain distributions in the first example; in the second example, a sterically hindered alumina fish roe-shaped multilevel micron coarse structure is formed by mixing high-concentration polymer solution; in the third example, the weed-like multilevel micro-coarse structure is generated by powder agglomeration and random direction dumping of the mullite column; and in the fourth example, the alumina rosette-shaped multilevel micron coarse structure is constructed by the agglomeration of the PVP solution on the flaky alumina powder.
Finally, it should be noted that: the above examples are not intended to limit the present invention in any way. Modifications and improvements will readily occur to those skilled in the art upon the basis of the present invention. Accordingly, any modification or improvement made without departing from the spirit of the invention is within the scope of the invention as claimed.
Claims (8)
1. The method for constructing the multi-level micron coarse structure on the ceramic glaze is characterized by comprising the following steps:
(1) Adding ceramic powder into an organic polymer water solution, and uniformly dispersing by ultrasonic to obtain ceramic suspension;
(2) Spraying the ceramic suspension obtained in the step (1) onto the ceramic glaze, drying and roasting, namely forming a multi-stage micron coarse structure on the ceramic glaze;
the particle size of the ceramic powder is 1-50 mu m, the ceramic powder is at least one selected from spinel powder with an octahedral structure, alumina powder with a spherical structure, mullite powder with a columnar structure and alumina powder with a flower-like structure, wherein the particle size of the spinel powder with the octahedral structure is 1-20 mu m, the particle size of the alumina powder with the spherical structure is 1-10 mu m, the particle size of the mullite powder with the columnar structure is 0.5-10 mu m and the particle size of the alumina powder with the flower-like structure is 10-50 mu m;
the organic polymer in the organic polymer aqueous solution is at least one selected from ethylenediamine tetraacetic acid, polyvinylpyrrolidone, polysilicate aluminum sulfate, polyvinyl alcohol and carboxymethyl cellulose;
the multi-stage micron coarse structure has a bipolar pore structure, wherein the primary pore diameter is 6-105 mu m, and the secondary pore diameter is 0.8-5 mu m.
2. The method according to claim 1, wherein in the step (1), the mass ratio of the ceramic powder to the organic polymer aqueous solution is 1-10:90-99, and the mass fraction of the organic polymer aqueous solution is 1-10%.
3. The method of claim 1, wherein in step (1), the ultrasonic power is 300 to 600W and the ultrasonic time is 10 to 300s.
4. The method according to claim 1, wherein in the step (2), the spraying temperature is 55-70 ℃, the spraying time is 15-25s, the drying temperature is 50-60 ℃, the drying time is 15-30min, the baking temperature is 900-1300 ℃, and the baking time is 20-40min.
5. A ceramic, characterized in that the glazed surface of the ceramic has a multi-stage micro-roughness structure, which is produced by the method according to any one of claims 1 to 4.
6. The ceramic of claim 5, further comprising immersing the ceramic in a hydrophobic coating, removing the ceramic, and air-drying and curing the ceramic to obtain the ceramic with the hydrophobic layer structure.
7. The ceramic of claim 6, wherein the hydrophobic coating is selected from any one of a fluorine/silicon hydrophobic material, a hydrophobic high molecular melt polymer, an organic-inorganic hybrid hydrophobic material.
8. The ceramic according to claim 7, wherein the impregnation temperature is 5-40 ℃ and the impregnation time is 20-35s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211234220.1A CN115572184B (en) | 2022-10-10 | 2022-10-10 | Method for constructing multi-level micron coarse structure on ceramic glaze |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211234220.1A CN115572184B (en) | 2022-10-10 | 2022-10-10 | Method for constructing multi-level micron coarse structure on ceramic glaze |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115572184A CN115572184A (en) | 2023-01-06 |
| CN115572184B true CN115572184B (en) | 2023-07-21 |
Family
ID=84584720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211234220.1A Active CN115572184B (en) | 2022-10-10 | 2022-10-10 | Method for constructing multi-level micron coarse structure on ceramic glaze |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115572184B (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU613982B2 (en) * | 1987-11-27 | 1991-08-15 | Ecc International Limited | Porous inorganic material |
| CN105521934B (en) * | 2016-02-02 | 2018-05-15 | 浙江大学 | A kind of preparation method of aluminum surface super hydrophobic coating |
| CN105689236A (en) * | 2016-02-02 | 2016-06-22 | 浙江大学 | Preparing method for aluminum surface super-hydrophobic coating with micro-nano composite structure |
| CN107555963A (en) * | 2016-06-30 | 2018-01-09 | 南京理工大学 | A kind of super-hydrophobic ceramic preparation method |
| GB201814353D0 (en) * | 2018-09-04 | 2018-10-17 | Cambridge Nanoceramix Ltd | Implant with ceramic coating and method of applying a ceramic coating |
| CN113173805A (en) * | 2021-04-30 | 2021-07-27 | 萍乡学院 | Method for constructing ceramic-based lotus leaf bionic hydrophobic micro-nano mastoid structure on glaze |
| CN113429867B (en) * | 2021-06-23 | 2022-06-10 | 南方科技大学 | Micro-nano composite super-hydrophobic wear-resistant coating and preparation method thereof |
| CN114029217A (en) * | 2021-10-25 | 2022-02-11 | 杭州老板电器股份有限公司 | Enamel coating with micro-nano surface structure and processing method thereof |
-
2022
- 2022-10-10 CN CN202211234220.1A patent/CN115572184B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN115572184A (en) | 2023-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110845224B (en) | High-strength anti-aging porcelain insulator and preparation method thereof | |
| CN112441824B (en) | Low-temperature-resistant high-voltage power transmission porcelain insulator and preparation method thereof | |
| CN102914165B (en) | High-stability long-service-life sagger for roasting lithium battery anode material and manufacturing method | |
| CN1901989B (en) | Ceramic structures having hydrophobic coatings | |
| CN105715003B (en) | Porcelain aluminum plate and preparation method thereof | |
| CN110922203A (en) | Porcelain insulator for high-voltage transmission line and manufacturing method thereof | |
| CN111018485A (en) | High-cold-resistance porcelain insulator and preparation method thereof | |
| CN109400214B (en) | A kind of high intensity domestic ceramics prestressing force coating material and preparation method thereof and ceramic | |
| CN113443892B (en) | High-toughness conical suspension type porcelain insulator and preparation method thereof | |
| CN112898003B (en) | High-strength siliceous brown glaze electric porcelain and preparation method thereof | |
| CN112573909B (en) | Ceramic wear-resistant material based on nano silica sol and preparation method thereof | |
| CN113354437A (en) | Toughening column type porcelain insulator and preparation method thereof | |
| CN115572184B (en) | Method for constructing multi-level micron coarse structure on ceramic glaze | |
| JP2013056809A (en) | Alumina ceramic toughened with black zirconia and method for manufacturing the same | |
| CN111363421A (en) | Fluorine-silicon nano waterproof heat-insulation composite material and preparation method thereof | |
| CN113248946A (en) | Coating composition for manufacturing ceramic-like coating and preparation method and application thereof | |
| JP5080736B2 (en) | Refractory manufacturing method and refractory obtained thereby | |
| CN114804634B (en) | Colored glaze for porcelain insulator and preparation method thereof | |
| CN115340409B (en) | Sagger coating for lithium battery positive electrode material and preparation method of sagger coating | |
| CN115678331A (en) | Temperature-resistant fireproof coating | |
| CN115612400A (en) | Wear-resistant and anti-scouring coating and preparation method thereof | |
| CN112680049A (en) | High-weather-resistance anti-contamination siliceous real stone paint and preparation method thereof | |
| CN113354425B (en) | Acid-resistant spray paint suitable for spherical roof of hot blast stove | |
| CN113213963B (en) | Light refractory material prepared from construction waste and preparation method thereof | |
| CN115433017B (en) | Refractory brick material and preparation method and application thereof |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230627 Address after: 337099 Anyuan New District, Pingxiang City, Jiangxi Province Applicant after: PINGXIANG University Applicant after: JINGDEZHEN University Applicant after: PINGXIANG BEST ELECTRIC CO.,LTD. Address before: No. 211, Ping'an North Avenue, Pingxiang City, Jiangxi Province Applicant before: PINGXIANG University |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |