CN113080683A - Hydrophobic layer and application thereof, pot and preparation method thereof and cooking equipment - Google Patents
Hydrophobic layer and application thereof, pot and preparation method thereof and cooking equipment Download PDFInfo
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- CN113080683A CN113080683A CN201911339649.5A CN201911339649A CN113080683A CN 113080683 A CN113080683 A CN 113080683A CN 201911339649 A CN201911339649 A CN 201911339649A CN 113080683 A CN113080683 A CN 113080683A
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
- A47J27/00—Cooking-vessels
- A47J27/002—Construction of cooking-vessels; Methods or processes of manufacturing specially adapted for cooking-vessels
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Abstract
The invention relates to the field of household appliances, and discloses a hydrophobic layer, application thereof, a pot, a preparation method thereof and cooking equipment. The hydrophobic layer is provided with a plurality of concave parts and convex parts which are distributed on the surface and are arranged at intervals in micron sizes, and a plurality of micro-nano-sized pores are distributed on the surfaces of the concave parts and the convex parts. The present invention provides hydrophobic, non-stick properties by providing a hydrophobic layer with a relief structure and surface pores.
Description
Technical Field
The invention relates to the field of household appliances, in particular to a hydrophobic layer, application thereof, a pot, a preparation method thereof and cooking equipment.
Background
Many non-hydrophobic articles require hydrophobic properties on their surfaces to accommodate their use. For example, containers for holding food, such as inner pots or inner containers of cooking devices, such as electric cookers or pressure cookers, are frequently used in consumer electronics. Most of the base materials of these containers are metals that can contact food, but these metals are not very hydrophobic, and tend to cause sticking during cooking and steaming of rice, resulting in difficulty in cleaning. In addition, these containers sometimes have an antibacterial layer, such as a titanium dioxide layer or a silver layer, provided on the surface of the base material in order to achieve an antibacterial effect. When the hydrophobicity of the antibacterial layers is poor, the phenomenon of sticking to the pot during cooking and rice steaming is easily caused, the pot is not easy to clean, and the antibacterial effect is influenced because the food materials are completely stuck to the surfaces of the antibacterial layers.
The prior art provides the surface of an object without hydrophobicity to achieve the hydrophobic effect through Teflon coating, hydrophobic inorganic ceramic layers and other modes, and provides the non-stick effect on food materials when used for containing a container of food. However, the above techniques are all provided by an additional layer structure, which utilizes the hydrophobicity of the layer structure itself to provide the hydrophobic property of the surface of the article. However, such additional structures also require a solution to the problem of bonding to the body of the article, and in addition, some articles have surfaces that are not suitable for the additional layer structure. Furthermore, none of the above techniques can achieve a simultaneous antibacterial effect.
Therefore, there is a need to develop new techniques for improving the hydrophobic property of the surface of an article to meet the demands of use.
Disclosure of Invention
The invention aims to solve the problem that the surface of an article does not have hydrophobicity, and provides a hydrophobic layer, application, a pot, a preparation method thereof and cooking equipment, wherein the hydrophobic layer has a special surface structure, so that the surface of a base material can be improved and directly has hydrophobic performance; it is further possible to provide both antimicrobial and non-stick properties to the antimicrobial hydrophobic layer.
In order to achieve the above object, a first aspect of the present invention provides a hydrophobic layer, which has a plurality of concave portions and convex portions distributed on a surface, the concave portions and the convex portions being arranged at intervals of micron size, and a plurality of micro-nano-sized micro-pores being distributed on the surfaces of the concave portions and the convex portions.
In a second aspect, the invention provides the use of a hydrophobic layer according to the invention as an anti-adhesive layer on a surface of an object.
The invention provides a cooker, which comprises a body and a non-stick layer arranged on at least part of the inner surface of the body, wherein the non-stick layer is a hydrophobic layer in the invention.
The fourth aspect of the invention provides a method for manufacturing a pot, comprising the following steps: forming a hydrophobic layer having concave portions and convex portions on at least a part of the inner surface of the body by micro-arc oxidation; performing micro-corrosion on the surface of the hydrophobic layer for 1-2min by using acid liquor to obtain a non-sticky hydrophobic layer with micro-nano holes formed on the surfaces of the concave parts and the convex parts; wherein the acid liquor contains the following components in a weight ratio of 5-7: 1 hydrochloric acid and hydrofluoric acid; the body is made of titanium or titanium alloy.
A fifth aspect of the invention provides a cooking apparatus comprising the pot of the invention.
Through the technical scheme, the hydrophobic layer with the concave-convex structure and the surface micro-nano pore structure can be provided. The surface of the hydrophobic layer has a hydrophobic angle of over 100 deg. The hydrophobic layer can be used as an inner surface hydrophobic layer of the pot, can be directly formed on the inner surface of the pot through micro-arc oxidation and surface acid corrosion, and can enable the inner surface of the pot to have non-stick performance to food materials. Furthermore, the hydrophobic layer can be a metal oxide layer and can be a nano titanium dioxide layer, so that the inner surface of the pot can have antibacterial performance and non-stick performance to food materials. The hydrophobic layer provided by the invention can improve the hydrophobic property of the surface of an article without an additional layer structure or considering the problem of the bonding property with a base material.
Drawings
FIG. 1 is a front view of a cookware provided by the present invention;
FIG. 2 is a top view of the pot provided by the present invention;
FIG. 3 is an enlarged schematic view of the non-stick layer of the bottom of the cookware provided by the present invention;
FIG. 4 is a schematic view of a partial enlarged structure of the non-stick layer provided by the present invention.
Description of the reference numerals
1. Body 2, pot bottom 3, non-stick layer
4. Void 5, recess 6, protrusion
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a hydrophobic layer, which is provided with a plurality of concave parts and convex parts which are distributed on the surface and are arranged at intervals in micron size, and a plurality of micro-nano-sized micropores are distributed on the surfaces of the concave parts and the convex parts.
The hydrophobic layer provided by the invention has the concave-convex structure with concave parts and convex parts on the surface, and the micro-nano holes distributed on the surface of the concave-convex structure, so that the hydrophobic layer has better hydrophobicity. Through tests, the hydrophobic angle of the surface of the hydrophobic layer provided by the invention can reach more than 100 degrees. For a hydrophobic layer using a titanium dioxide material, the surface hydrophobic angle itself is 20 °. The hydrophobic layer provided by the invention has the structure, so that the improved hydrophobicity can be effectively realized, and the non-sticky performance is provided. The hydrophobic angle of the surface can be measured by a shape measuring laser microscopy system of the kirschner VK-X100 series. When further using on the pan, above-mentioned hydrophobic layer structure can improve the heat conductivility of pan when improving the pan and not be stained with the performance to improve the homogeneity of heat conduction.
In some embodiments of the present invention, the hydrophobic layer is provided with a relief structure on the surface, preferably the depth of the recesses or the height of the protrusions is greater than 5 μm, preferably 5-10 μm; further, the interval between adjacent ones of the projections or recesses is not more than 100. mu.m, preferably 2 to 100. mu.m. The hydrophobic layer may be provided on top of any component, the recesses and protrusions having the above-mentioned dimensional definition may better enable the relief structure to reduce contact of water droplets or other objects with the component, and may withstand water droplets, which are easily slid by the pressure of air, providing non-tackiness between the other objects and the hydrophobic layer. In the present invention, preferably, the concave portion is disposed adjacent to the convex portion, and the depth of the concave portion or the height of the convex portion is a vertical distance from the top of the convex portion to the bottom of the adjacent concave portion. When the depth of the concave part or the height of the convex part is larger than 5 micrometers, the surface area of a concave-convex structure forming micro-nano pores can be increased on the surface of the hydrophobic layer, so that the number of the micro-nano pores is increased, and the hydrophobic performance is improved; when the depth of the concave portion or the height of the convex portion is less than 10 μm, the roughness of the hydrophobic layer can be prevented from being too large, which may result in lowering of the non-stick property; when further using on the pan, unsmooth structure's above-mentioned size scope can improve the homogeneity of pan heat conduction to improve heat transfer efficiency, and then improve the efficiency of being heated of taking care of the thing in the pan, can also improve the resistant scraping performance of pan in addition.
In some embodiments of the present invention, preferably, the convex portion and the concave portion are adjacently disposed. A concave part is arranged between two adjacent convex parts, and a convex part is arranged between two adjacent concave parts. The interval between two adjacent convex parts is the width of the concave part, and the interval between two adjacent concave parts is the width of the convex part. More preferably, the protrusions or recesses are uniformly spaced. The interval between the adjacent convex parts or concave parts is within the range, so that the contact area between the micro-nano pores and water drops can be increased, and the hydrophobic property is improved; the interval is too large, so that the contact area between the water drops and the micro-nano pores is reduced, the supporting effect of air in the micro-nano pores on the water drops at multiple angles is reduced, and the hydrophobic property is reduced; when the hydrophobic layer is applied to the pot, the limitation of the range can ensure better hydrophobic performance, and can improve the heat transfer performance and the uniformity of heat conduction, so that the condiments and the like can be fully heated. When the size of the uneven structure is not limited to the above range, an effective supporting effect on water droplets cannot be obtained, and a good hydrophobic effect cannot be achieved. The hydrophobic layer, for example titanium dioxide, has a surface hydrophobic angle of 20 ° per se, whereas the hydrophobic angle can only be increased to more than 100 ° if the relief structure of the surface structure is within the above-defined range.
In some embodiments of the present invention, the concave-convex structure is provided to be regularly arranged, and the hydrophobic layer is provided to have better non-stickiness. Preferably, a plurality of the concave and convex portions are distributed in an array structure. Each of the plurality of concave and convex portions may be independent and then sequentially arranged at substantially equal intervals with respect to each other to form the array structure distribution. When the concave-convex structure of the hydrophobic layer is distributed in the array structure, the scratch resistance of the hydrophobic layer can be improved; when further using on the pan, can improve the homogeneity of pan heat conduction, avoid the heat in the too concentrated phenomenon in a certain region, and can increase the homogeneity of the distribution in micro-nano hole, improve hydrophobic effect.
In some embodiments of the present invention, the bottom of the concave portion and the top of the convex portion may be provided with a spherical shape, which is more favorable for the water drop to slide on the surface of the hydrophobic layer. Preferably, the top of the convex part presents an upward convex spherical shape with a radius of curvature of not more than 1 μm, preferably with a radius of curvature of 0.5-1 μm; the bottom of the concave portion takes the shape of a concave spherical surface having a radius of curvature of not more than 1 μm, preferably 0.5 to 1 μm. The curvature radius cannot be too small, otherwise, the water drops are punctured by sharp points, and the supporting effect cannot be provided; the curvature radius can not be too large, and if the curvature radius is too large, the concave-convex structure is too gentle, and the function of supporting the water drops is not obvious.
In some embodiments of the present invention, the provided surface of the concave-convex structure has micro-nano pores, so that the surface of the hydrophobic layer can be improved to promote a sliding effect on a water droplet by improving a dragging effect of air on the water droplet, and further, the non-adhesiveness of the surface of the hydrophobic layer to the water droplet is improved. Preferably, the pores have a pore opening diameter of 0.1 to 3 μm and a depth of 0.1 to 1 μm. The porosity can be determined by the shape measurement laser microscopy system method of the kirnshi VK-X100 series. When the diameter of the orifice and the depth of the pore are in the above ranges, the capillary adsorption effect can be prevented, the supporting effect of air on water drops can be improved, the diffusion effect on heat can be improved, and the heating of a conditioned matter can be improved; in addition, air in the pores can form certain thermal resistance, so that the heat dispersion of the layer is improved, and the uniformity of heat conduction is improved. The diameter of the orifice is less than 3 mu m, the distribution quantity of pores on the surface of the concave-convex structure can be increased, the water drop can be supported at multiple angles, and the hydrophobic property is improved. The depth of the pores is less than 1 μm, which can prevent the occurrence of a hair-sucking phenomenon and can reduce the influence on the internal layer structure.
In some embodiments of the invention, the hydrophobic layer may be a metal oxide layer. Further, the material may be selected to provide the hydrophobic layer with antimicrobial properties. As for the metal oxide layer, the hydrophobic property of the metal oxide layer is poor, the existing hydrophobic solution is that a fluororesin coating with non-stick property is covered on the surface of the metal oxide layer, so that the hydrophobic property of the metal oxide layer is solved, and although the good hydrophobic property can be achieved, other effects of the metal oxide, such as corrosion resistance, photocatalysis antibacterial effect and the like, are completely destroyed. By arranging the metal oxide layer with the hydrophobic layer structure, the non-stick performance can be improved while the performance of the metal oxide is ensured. Preferably, the hydrophobic layer has antibacterial properties, and further preferably, the metal oxide layer is a titanium dioxide layer or a zinc oxide layer or a silver oxide layer. The hydrophobic layer can be ensured to have antibacterial performance at the same time. More preferably, the metal oxide layer is a nano titanium dioxide layer, a nano silver oxide layer or a nano zinc oxide layer. For example, the nano titanium dioxide layer, the nano silver oxide layer or the nano zinc oxide layer has hydrophobic property while providing antibacterial property. Furthermore, the preferable nanometer titanium dioxide layer is provided with a plurality of micron-sized concave parts and convex parts which are arranged at intervals and distributed on the surface, a plurality of micro-nano-sized pores are distributed on the surfaces of the concave parts and the convex parts, the area of titanium dioxide photocatalysis can be increased, and the antibacterial effect is improved.
In some embodiments of the present invention, the hydrophobic layer is prepared by micro-arc oxidation treatment and surface acid etching of the surface of the metal substrate. The metal oxide layer formed has the above-described structure. Preferably, a metal oxide hydrophobic layer with the concave-convex structure is formed on the surface of the metal substrate by a micro-arc oxidation method, and then the surface of the metal oxide hydrophobic layer is corroded by an etching solution, such as an acid solution, to form the micro-nano pore structure. The hydrophobic layer is formed, for example, on the surface of the metal substrate which is titanium or a titanium alloy. Or the hydrophobic layer is prepared by arranging a metal oxide layer on the surface of the metal substrate and performing surface acid corrosion on the metal oxide layer. For example, a silver oxide layer or a zinc oxide layer is arranged on the surface of the metal substrate, and then the silver oxide layer or the zinc oxide layer is subjected to etching solution to form the micro-nano pore structure.
In some embodiments of the present invention, the structure of the hydrophobic layer can be illustrated by the schematic illustrations of the non-stick layer formed on the surface of the cookware shown in fig. 1-4. As shown in fig. 3 and 4, the non-stick layer 3 has a concave portion 5 and a convex portion 6 on the surface of the body 1, and micro-nano pores 4 are formed on the surfaces of the concave portion and the convex portion.
In a second aspect, the invention provides the use of a hydrophobic layer according to the invention as an anti-adhesive layer on a surface of an object.
In a third aspect, the present invention provides a cookware, as shown in fig. 1-4, comprising a body 1, and a non-stick layer 3 disposed on at least a portion of the surface of the body, wherein the non-stick layer is a hydrophobic layer in the present invention.
In some embodiments of the present invention, preferably, the body is a pure metal matrix or a composite layer matrix; the pure metal matrix is a pure titanium matrix or a titanium alloy matrix, and the inner surface of the composite layer matrix is pure titanium or a titanium alloy.
In some embodiments of the present invention, by providing the non-stick layer on the surface of the body, as shown in fig. 3, the non-stick layer 3 has the concave-convex structure (including the concave part 5 and the convex part 6) and the surface aperture 4 (the surfaces of the concave part and the convex part) as described above, so that the cookware can provide non-stick property with food. Through testing, in the cookware provided by some embodiments of the invention, the hydrophobic angle of the surface of the non-stick layer can reach over 100 degrees.
In some embodiments of the present invention, by changing the physical microstructure arranged on the surface of the non-stick layer, the effect that the inner surface of the inner pan is non-stick and hydrophobic to food can be achieved without adding a special non-stick layer, and the original design function of the inner surface of the inner pan, such as the antibacterial performance of the arranged antibacterial layer, can not be affected.
In some embodiments of the present invention, further, the non-stick layer may be a layer formed of a material capable of providing an antibacterial effect, provided on a surface of the body. Antibacterial materials such as titanium dioxide, silver oxide or zinc oxide may be used. Preferably, the non-stick layer is a metal oxide layer, preferably a titanium dioxide layer, more preferably a nano titanium dioxide layer. The surface hydrophobic angle of the titanium dioxide layer is 20 degrees, but the hydrophobic angle of the surface of the non-stick layer can reach more than 100 degrees. The non-stick layer may be a non-stick layer when the material of the body is capable of forming a surface by in situ processing. Preferably, the pot provided by some embodiments of the present invention can effectively realize that the surface of the antibacterial layer has hydrophobicity, and the antibacterial layer is not covered, and still can provide antibacterial effect.
In some embodiments of the present invention, the non-stick layer protects the body, provides an antibacterial effect, and has the above-mentioned concave-convex structure and pore structure of the surface, so as to improve the non-stick property of the surface of the non-stick layer.
In some embodiments of the present invention, the body is made of a titanium-containing metal material, and a nano titanium dioxide layer can be directly formed on the surface of the body by a method such as micro-arc oxidation. Preferably, the body is made of titanium or a titanium alloy. Further, the nano titanium dioxide layer is subjected to surface acid corrosion to obtain the non-stick layer.
In some embodiments of the present invention, the non-stick layer may cover the whole outer surface of the body, or only a part of the surface of the body, for example, the surface contacting with food material on the inner surface of the body, such as the inner surface of the bottom of the body.
The fourth aspect of the invention provides a method for manufacturing a pot, comprising the following steps: forming a surface layer with a concave part and a convex part on at least part of the inner surface of the body through micro-arc oxidation; performing micro-etching on the surface of the surface layer by using acid liquor for 1-2min to obtain a non-stick layer with micro-nano holes formed on the surfaces of the concave parts and the convex parts; wherein the acid liquor contains the following components in a weight ratio of 5-7: 1 hydrochloric acid and hydrofluoric acid; the body is made of titanium or titanium alloy.
In some embodiments of the present invention, preferably, the non-stick layer is a nano titanium dioxide layer prepared by micro arc oxidation of a part of the surface of the body. The nano titanium dioxide layer can provide an antibacterial effect and has a thickness of not less than 10 μm. The obtained nano titanium dioxide layer has a concave-convex structure, and the concave-convex structure is described above and is not described in detail.
In some embodiments of the present invention, the micro etching is to form a micro-nano pore structure on the surface of the nano titanium dioxide layer, which may be beneficial to the surface of the nano titanium dioxide layer to have improved hydrophobicity and non-stick property with food. Preferably, the acid solution may be formed by mixing dilute hydrochloric acid and dilute hydrofluoric acid, as long as the final acid solution contains hydrochloric acid and hydrofluoric acid in amounts satisfying the above conditions. The concentration of the dilute hydrochloric acid may be 3 to 20 wt%, and the concentration of the dilute hydrofluoric acid may be 3 to 20 wt%.
In some embodiments of the present invention, by controlling the composition of the acid solution and the time for performing the micro-etching, a structure and distribution with appropriate pore forming aperture diameter and depth can be realized, which is beneficial for the nano titanium dioxide layer to provide non-stick property with food. The corrosion time is more than 2min or less than 1min, proper pore structure and distribution on the surface can not be obtained, and the non-stick effect on the surface of the nano titanium dioxide layer can not be achieved. Also, when the composition of the acid liquid is selected outside the above-defined range, it is not possible to achieve the desired pore structure and distribution on the surface.
In some embodiments of the present invention, after the microetching is performed, it is washed with clean water, and then the microporous structure of the surface of the antibacterial layer may be observed in a magnified manner and the hydrophobic angle of the surface may be measured.
The invention also provides a pot manufactured by the manufacturing method.
Preferably, at least part of the inner surface of the pot is provided with a concave part and a convex part which are distributed on the surface and are arranged at intervals of a plurality of micron sizes, and a hydrophobic layer which is distributed on the surfaces of the concave part and the convex part and is provided with a plurality of micro-nano-sized pores.
In some embodiments of the present invention, an antibacterial layer having an antibacterial function is provided by forming a nano titanium dioxide layer on at least a part of the surface of a body made of titanium or a titanium alloy through micro-arc oxidation of the body; and then, modifying the surface of the antibacterial layer through controlled micro-corrosion, forming a distributed concave-convex structure and surface pores on the surface of the antibacterial layer, realizing that the surface has hydrophobicity, obtaining a pot with a hydrophobic layer which is antibacterial and non-sticky to food, and having antibacterial and non-sticky effects at the same time.
Preferably, the depth of the recesses or the height of the protrusions is greater than 5 μm, preferably 5-10 μm.
Preferably, the spacing between adjacent said projections or recesses is no more than 100 μm, preferably 2-100 μm. Preferably, the top of the convex portion exhibits a convex spherical shape with a radius of curvature of not more than 1 μm, preferably 0.5 to 1 μm, and the bottom of the concave portion exhibits a concave spherical shape with a radius of curvature of not more than 1 μm, preferably 0.5 to 1 μm.
Preferably, a plurality of the concave and convex portions are distributed in an array structure.
Preferably, the pores have a pore opening diameter of 0.1 to 3 μm and a depth of 0.1 to 1 μm.
Preferably, the hydrophobic layer has a thickness of at least 10 μm.
Preferably, the hydrophobic angle of the surface of the hydrophobic layer is 100 ° or more.
A fifth aspect of the invention provides a cooking apparatus comprising the pot of the invention.
Preferably, the cooking device is an electric cooker, an electric pressure cooker or a soybean milk maker.
The present invention will be described in detail below by way of examples.
Example 1
Carrying out micro-arc oxidation treatment on the inner surface of the bottom of the titanium metal body to form a nano titanium dioxide layer with the thickness of about 12 microns; the arrangement depth of the surface distribution array structure is about 8 μm concave parts, convex parts with the height of about 8 μm are distributed between two adjacent concave parts, and the interval between the adjacent convex parts or concave parts is about 80 μm; the top of the convex portion and the bottom of the concave portion respectively assume convex spherical shapes and concave spherical shapes having a radius of curvature of about 0.9 μm.
Coating acid liquor (the weight ratio of hydrochloric acid to hydrofluoric acid is 5: 1) on the nano titanium dioxide layer for micro-corrosion for 1min, and then cleaning the nano titanium dioxide layer with clear water to obtain a hydrophobic layer. The hydrophobic layer was subjected to surface magnification observation and measurement. The structure having pores has a pore opening diameter of about 0.32 μm and a pore depth of about 0.54 μm. The microstructure is schematically shown in FIG. 4.
The hydrophobic angle of the surface of the hydrophobic layer was measured to be 100 °.
Example 2
Micro-arc oxidation treatment is carried out on the inner surface of the bottom of the titanium alloy (with the mark of TC4) body to form a nano titanium dioxide layer with the thickness of about 10 mu m; the arrangement depth of the surface distribution array structure is about 6 μm concave parts, convex parts with the height of about 6 μm are distributed between two adjacent concave parts, and the interval between the adjacent convex parts or concave parts is about 90 μm; the top of the convex portion and the bottom of the concave portion assume convex and concave spherical shapes having a radius of curvature of about 1 μm, respectively.
Coating acid liquor (the weight ratio of hydrochloric acid to hydrofluoric acid is 6: 1) on the nano titanium dioxide layer for micro-corrosion for 2min, and then cleaning the nano titanium dioxide layer with clear water to obtain a hydrophobic layer. The hydrophobic layer was subjected to surface magnification observation and measurement. The structure having pores has a pore opening diameter of about 0.79 μm and a pore depth of about 0.91. mu.m. The microstructure is schematically shown in FIG. 4.
The hydrophobic angle of the surface of the hydrophobic layer was measured to be 110 °.
Example 3
Carrying out micro-arc oxidation treatment on the inner surface of the bottom of the titanium metal body to form a nano titanium dioxide layer with the thickness of about 15 mu m; the arrangement depth of the surface distribution array structure is about 9 μm concave parts, convex parts with the height of about 9 μm are distributed between two adjacent concave parts, and the interval between the adjacent convex parts or concave parts is about 100 μm; the top of the convex portion and the bottom of the concave portion respectively assume convex spherical shapes and concave spherical shapes having a radius of curvature of about 0.8 μm.
Coating acid liquor (the weight ratio of hydrochloric acid to hydrofluoric acid is 7: 1) on the nano titanium dioxide layer for micro-corrosion for 1min, and then cleaning the nano titanium dioxide layer with clear water to obtain a hydrophobic layer. The hydrophobic layer was subjected to surface magnification observation and measurement. The structure having pores has a pore opening diameter of about 0.62 μm and a pore depth of about 0.73. mu.m. The microstructure is schematically shown in FIG. 4.
The hydrophobic angle of the surface of the hydrophobic layer was measured to be 120 °.
Example 4
Carrying out micro-arc oxidation treatment on the inner surface of the bottom of the titanium metal body to form a nano titanium dioxide layer with the thickness of about 12 microns; the arrangement depth of the surface distribution array structure is about 7 μm, convex parts with the height of about 7 μm are distributed between two adjacent concave parts, and the interval between the adjacent convex parts or concave parts is about 5 μm; the top of the convex portion and the bottom of the concave portion respectively assume convex spherical shapes and concave spherical shapes having a radius of curvature of about 0.9 μm.
Coating acid liquor (the weight ratio of hydrochloric acid to hydrofluoric acid is 5: 1) on the nano titanium dioxide layer for micro-corrosion for 1min, and then cleaning the nano titanium dioxide layer with clear water to obtain a hydrophobic layer. The hydrophobic layer was subjected to surface magnification observation and measurement. The structure having pores has a pore opening diameter of about 0.33 μm and a pore depth of about 0.40. mu.m. The microstructure is schematically shown in FIG. 4.
The surface of the hydrophobic layer was measured to have a hydrophobic angle of 105 °.
Comparative example 1
Carrying out micro-arc oxidation treatment on the inner surface of the bottom of the titanium metal body to form a titanium dioxide layer with the thickness of about 12 microns;
coating acid liquor (the weight ratio of hydrochloric acid to hydrofluoric acid is 8: 1) on the titanium dioxide layer for micro-corrosion for 3min, and then cleaning the titanium dioxide layer with clear water to obtain the antibacterial hydrophobic layer. And carrying out surface amplification observation and measurement on the antibacterial hydrophobic layer.
The surface distribution array structure of the antibacterial hydrophobic layer is provided with micropores with the width of about 110 μm and the depth of about 5 μm. Convex parts with the width of about 110 mu m are distributed between two adjacent micropores, and the tops of the convex parts and the bottoms of the micropores respectively present convex spherical shapes and concave spherical shapes with the curvature radius of about 1 mu m.
The hydrophobic angle of the surface of the antimicrobial hydrophobic layer was measured to be 50 °.
Comparative example 2
Carrying out micro-arc oxidation treatment on the inner surface of the bottom of the titanium metal body to form a titanium dioxide layer with the thickness of about 12 microns;
the surface distribution array structure of the antibacterial hydrophobic layer is provided with micropores with the width of about 110 μm and the depth of about 5 μm. Convex parts with the width of about 110 mu m are distributed between two adjacent micropores, and the tops of the convex parts and the bottoms of the micropores respectively present convex spherical shapes and concave spherical shapes with the curvature radius of about 1 mu m.
The hydrophobic angle of the surface of the antimicrobial hydrophobic layer was measured to be 50 °.
It can be seen from the examples and comparative examples that by adopting the method provided by the invention, a hydrophobic layer with hydrophobic performance, a concave-convex array structure with proper surface distribution size and a surface pore structure can be formed, and the hydrophobic angle is more than 100 degrees. Can be used on the surface of cookware. The cookware made of titanium or titanium alloy can form the surface of a nano titanium dioxide layer, and has antibacterial and non-adhesive properties.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. The hydrophobic layer is provided with a plurality of concave parts and convex parts which are distributed on the surface and are arranged at intervals of a plurality of micron sizes, and a plurality of micro-nano-sized pores are distributed on the surfaces of the concave parts and the convex parts.
2. A hydrophobic layer according to claim 1, wherein the depth of the recesses or the height of the protrusions is larger than 5 μ ι η, preferably 5-10 μ ι η;
preferably, the spacing between adjacent said projections or recesses is no more than 100 μm, preferably 2-100 μm.
3. A hydrophobic layer according to claim 1 or 2, wherein a plurality of said recesses and protrusions are distributed in an array structure.
4. A hydrophobic layer according to any one of claims 1-3, wherein the tops of said protrusions exhibit a convex spherical shape with a radius of curvature of not more than 1 μm, preferably with a radius of curvature of 0.5-1 μm; the bottom of the concave portion takes the shape of a concave spherical surface having a radius of curvature of not more than 1 μm, preferably 0.5 to 1 μm.
5. Hydrophobic layer according to any one of claims 1-4, wherein the pores have an orifice diameter of 0.1-3 μm and a depth of 0.1-1 μm.
6. Hydrophobic layer according to any one of claims 1-5, wherein the hydrophobic layer surface has a hydrophobic angle of 100 ° or more.
7. Hydrophobic layer according to any one of claims 1-6, wherein the hydrophobic layer is a metal oxide layer, preferably the metal oxide layer is a titanium dioxide layer or a zinc oxide layer or a silver oxide layer, more preferably the metal oxide layer is a nano titanium dioxide layer, a nano silver oxide layer or a nano zinc oxide layer.
8. The hydrophobic layer of any one of claims 1 to 7, wherein the hydrophobic layer is prepared by subjecting the surface of the metal substrate to micro-arc oxidation and surface acid etching, or is prepared by providing a metal oxide layer on the surface of the metal substrate and subjecting the metal oxide layer to surface acid etching.
9. Use of a hydrophobic layer according to any one of claims 1-8 as a non-stick layer on a surface of an object.
10. A cookware, comprising: a body, and a non-stick layer disposed on at least a portion of an inner surface of the body, the non-stick layer being the hydrophobic layer of any of claims 1-8.
11. The cookware of claim 10, wherein said body is a pure metal or composite layered substrate; the pure metal matrix is a pure titanium matrix or a titanium alloy matrix, and the inner surface of the composite layer matrix is pure titanium or a titanium alloy.
12. A preparation method of a pot comprises the following steps:
forming a surface layer with a concave part and a convex part on at least part of the inner surface of the body through micro-arc oxidation;
performing micro-etching on the surface of the surface layer by using acid liquor for 1-2min to obtain a non-stick layer with micro-nano holes formed on the surfaces of the concave parts and the convex parts;
wherein the acid liquor contains the following components in a weight ratio of 5-7: 1 hydrochloric acid and hydrofluoric acid; the body is made of titanium or titanium alloy.
13. A cooking apparatus comprising the pot of claim 10 or 11 or the pot made by the manufacturing method of claim 12; preferably, the cooking device is an electric cooker, an electric pressure cooker or a soybean milk maker.
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