Composite non-stick layer and its preparation method, cookware and cooking utensils

Abstract

This invention provides a composite non-stick layer, its preparation method, cookware, and cooking utensils. The composite non-stick layer comprises: a substrate layer having a first surface; and a non-stick coating layer disposed on the first surface. The non-stick coating layer includes a first coating layer, which comprises a first rigid skeleton and a non-stick filler. The first rigid skeleton has through-pores, and the non-stick filler fills the pores. The porosity of the first rigid skeleton is 5%-30%. The first rigid skeleton in the first coating layer provides good wear resistance to the non-stick coating, and the non-stick filler filling the pores provides good non-stick properties. Therefore, the composite non-stick layer of this invention simultaneously possesses good wear resistance and non-stick properties. The porosity of the first rigid skeleton is 5%-30%, which provides an appropriate pore ratio, effectively satisfying the filling requirements of the non-stick filler, resulting in a composite non-stick layer with both good non-stick properties and good wear resistance.

Description

Technical Field

[0001] This invention relates to the field of household appliance technology, specifically to composite non-stick layers and their preparation methods, cookware, and cooking utensils. Background Technology

[0002] As people's demand for easy-to-clean cooking utensils continues to increase, non-stick coatings are becoming increasingly common in woks. However, traditional non-stick coatings suffer from low hardness and poor wear resistance, making them susceptible to damage from metal spatulas and steel wool. While traditional metal cookware, such as stainless steel and iron pans, can be cooked with metal spatulas and cleaned with steel wool, their lack of non-stick properties results in a less than ideal cooking experience. To address the issues of short lifespan, poor wear resistance, and easy peeling of non-stick coatings, the industry has begun researching the lotus leaf effect, engraving micro-nano structures on the surface of the pan to achieve a wear-resistant and non-stick effect. However, this physical non-stick layer relies more on the uneven structure to lock in oil, requiring users to actively add oil during cooking. The oil film forms on the heated surface to achieve a certain degree of non-stickness, but this is not true non-stick; the actual non-stick effect varies with usage time and the amount of oil added, failing to meet market expectations. Summary of the Invention

[0003] The present invention aims to at least partially solve one of the technical problems in the related art. Therefore, one object of the present invention is to provide a composite non-stick layer that has superior wear resistance and non-stick properties.

[0004] In one aspect of the invention, a composite non-stick layer is provided. According to an embodiment of the invention, the composite non-stick layer comprises: a substrate layer having a first surface; and a non-stick coating layer disposed on the first surface, the non-stick coating layer comprising a first coating layer, the first coating layer comprising a first rigid skeleton and a non-stick filler, the first rigid skeleton having through pores, the non-stick filler filling the pores, wherein the porosity of the first rigid skeleton is 5%-30%. Thus, the first rigid skeleton in the first coating layer can provide better wear resistance to the non-stick coating layer, and the non-stick filler filling the pores can provide good non-stick properties to the non-stick coating layer; that is, the composite non-stick layer of the present invention simultaneously possesses good wear resistance and non-stick properties. The porosity of the first rigid skeleton is 5%-30%. This appropriate porosity can effectively meet the filling requirements of the non-stick filler, giving the composite non-stick layer good non-stick properties and good wear resistance. If the porosity is less than 5%, the proportion of the non-stick surface area of ​​the non-stick coating will be too low, and the non-stick effect will be limited. If the porosity is greater than 30%, the first rigid skeleton will be relatively loose, affecting the wear resistance and structural stability of the first rigid skeleton.

[0005] According to an embodiment of the present invention, the non-stick filler is contained in any cross-section where the distance between the first coating and the first surface is greater than or equal to X, where X is 20 to 100 micrometers and X is less than the thickness of the first coating.

[0006] According to an embodiment of the present invention, any of the cross-sections and / or longitudinal sections of the first coating contains the first rigid skeleton and the non-stick filler.

[0007] According to an embodiment of the present invention, on any cross-section where the distance between the first coating and the first surface is greater than or equal to 1 mm... 2 The area contains both the first rigid skeleton and the non-stick filler.

[0008] According to an embodiment of the present invention, 1 mm of any cross-section or longitudinal section of the first coating 2 The area contains both the first rigid skeleton and the non-stick filler.

[0009] According to an embodiment of the present invention, in any of the cross-sectional or longitudinal sections of the first coating, 1 mm 2 Within the region, the area ratio of the first rigid skeleton to the non-stick filler is 2 to 19.

[0010] According to an embodiment of the present invention, the width of the pore is 5 to 150 micrometers.

[0011] According to an embodiment of the present invention, the particle size of the non-stick filler is less than or equal to the minimum value of the pore width.

[0012] According to an embodiment of the present invention, the first rigid skeleton is formed by stacking particles, and the gaps between the particles constitute the pores.

[0013] According to an embodiment of the present invention, the thickness of the first coating is 50 to 300 micrometers.

[0014] According to an embodiment of the present invention, the non-stick coating and the substrate layer are bonded in at least one of the following ways: the surface of the non-stick coating near the substrate layer has a first uneven structure, the surface of the substrate layer near the non-stick coating has a second uneven structure, and the non-stick coating and the substrate layer are bonded by interlocking the first uneven structure and the second uneven structure; or the non-stick coating and the substrate layer are bonded by a metallurgical method in which a portion of the material of the non-stick coating near the substrate layer diffuses into the substrate layer.

[0015] According to an embodiment of the present invention, the non-stick coating further includes a second coating disposed on the surface of the first coating near the substrate layer, the second coating including a second rigid skeleton.

[0016] According to an embodiment of the present invention, the second rigid skeleton and the first rigid skeleton are an integral structure, and optionally, the hardness of the first rigid skeleton and / or the second rigid skeleton is greater than or equal to 200 HV.

[0017] According to an embodiment of the present invention, the porosity of the first rigid skeleton is greater than or equal to the porosity of the second rigid skeleton.

[0018] According to an embodiment of the present invention, the non-stick filler extends from the first coating to the second coating.

[0019] According to an embodiment of the present invention, the porosity of the second rigid skeleton gradually increases in the direction close to the first rigid skeleton, and the porosity of the surface of the second rigid skeleton close to the first rigid skeleton is less than or equal to the porosity of the first rigid skeleton.

[0020] According to an embodiment of the present invention, the thickness of the second coating is 1 / 10 to 1 / 3 of the thickness of the non-stick coating.

[0021] According to an embodiment of the present invention, the thickness of the second coating is 20 to 100 micrometers.

[0022] In another aspect of the present invention, a method for preparing the aforementioned composite non-stick layer is provided. According to an embodiment of the present invention, the method for preparing the composite non-stick layer includes: forming a non-stick coating on a first surface of a substrate layer, wherein the step of forming the non-stick coating includes the step of forming a first coating, wherein the step of forming the first coating includes: forming a first rigid skeleton by thermal spraying of hard particles, the first rigid skeleton having through pores, the porosity of the first rigid skeleton being 5%-30%; and filling the pores with non-stick filler to obtain the first coating. Thus, the first rigid skeleton formed by thermal spraying can provide better wear resistance for the non-stick coating, and the non-stick filler filling the pores can provide good non-stick properties for the non-stick coating; that is, the composite non-stick layer prepared by the above method has both good wear resistance and non-stick properties. Furthermore, the preparation of the first rigid skeleton by thermal spraying can ensure a strong bond between the first rigid skeleton and the substrate layer, improving the stability between the layer structures, and the preparation process is mature and easy for industrial production. The porosity of the first rigid skeleton is 5%-30%. This appropriate porosity can effectively meet the filling requirements of the non-stick filler, giving the composite non-stick layer good non-stick properties and good wear resistance. If the porosity is less than 5%, the proportion of the non-stick surface area of ​​the non-stick coating will be too low, and the non-stick effect will be limited. If the porosity is greater than 30%, the first rigid skeleton will be relatively loose, affecting the wear resistance and structural stability of the first rigid skeleton.

[0023] According to an embodiment of the present invention, the step of forming the first rigid skeleton includes: melting the rigid particles to obtain semi-molten particles with molten surface and unmelted interior; thermally spraying the semi-molten particles onto a first surface and stacking them to form the first rigid skeleton.

[0024] According to an embodiment of the present invention, a method for filling the pores with the non-stick filler includes: coating a non-stick filler emulsion onto the surface of the first rigid skeleton away from the substrate layer; impregnating the non-stick filler emulsion into the pores by at least one of ultrasonication, negative pressure, and vortexing; and curing the non-stick filler emulsion impregnated into the pores to obtain the first coating.

[0025] According to an embodiment of the present invention, the non-stick filler is a silicon-based non-stick filler, and the curing temperature is 250-320℃; the non-stick filler is a fluorine-based non-stick filler, and the curing temperature is 350-420℃.

[0026] According to an embodiment of the present invention, the step of forming the non-stick coating further includes: forming a second rigid skeleton on the first surface by thermal spraying before forming the first rigid skeleton.

[0027] In another aspect, the present invention provides a cookware according to an embodiment of the invention, which includes the aforementioned composite non-stick layer, wherein the substrate layer of the composite non-stick layer constitutes the cookware body, and the non-stick coating layer of the composite non-stick layer is located on one side of the cooking space of the cookware. Thus, the cookware simultaneously possesses good wear resistance and non-stick properties, thereby improving the performance and service life of the cookware. Those skilled in the art will understand that the cookware possesses all the features and advantages of the aforementioned composite non-stick layer, which will not be elaborated further here.

[0028] In another aspect, the present invention provides a cooking utensil, which, according to an embodiment of the invention, includes the pot described above. Thus, the pot of this cooking utensil possesses both good wear resistance and non-stick properties, thereby improving the performance and lifespan of the cooking utensil. Those skilled in the art will understand that this cooking utensil possesses all the features and advantages of the composite non-stick layer described above, which will not be elaborated further here. Attached Figure Description

[0029] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0030] Figure 1 This is a schematic diagram of the composite non-stick layer in one embodiment of the present invention;

[0031] Figure 2This is a schematic diagram of the non-stick coating structure in another embodiment of the present invention;

[0032] Figure 3 This is a scanning electron microscope image of the non-stick coating in another embodiment of the present invention;

[0033] Figure 4 This is a schematic diagram of the composite non-stick layer in another embodiment of the present invention;

[0034] Figure 5 This is a schematic diagram of the composite non-stick layer in another embodiment of the present invention.

[0035] The reference numerals in the attached drawings are as follows: substrate layer 10, first surface 11, non-stick coating 20, first coating 21, first rigid skeleton 211, non-stick filler 212, pores 213, first uneven structure 201, second uneven structure 101, and second coating 22. Detailed Implementation

[0036] The present invention will be explained below with reference to embodiments. Those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in the field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0037] The present invention will now be described with reference to specific embodiments. It should be noted that these embodiments are merely descriptive and do not limit the present invention in any way.

[0038] In one aspect of the invention, a composite non-stick layer is provided. According to an embodiment of the invention, referring to... Figure 1 , Figure 2 and Figure 3 The composite non-stick layer includes: a substrate layer 10 having a first surface 11; and a non-stick coating layer 20 disposed on the first surface 11, comprising a first coating layer 21, the first coating layer 21 comprising a first rigid skeleton 211 and a non-stick filler 212, the first rigid skeleton having through pores 213, and the non-stick filler 212 filling the pores 213. Figure 2(The pores 213 are filled with non-stick filler 212), wherein the porosity of the first rigid skeleton 211 is 5%-30%. Therefore, the first rigid skeleton 211 in the first coating 21 can provide better wear resistance to the non-stick coating 21, and the non-stick filler 212 filling the pores 213 can provide good non-stick properties to the non-stick coating 21. That is, the composite non-stick layer of the present invention has both good wear resistance and non-stick properties. Furthermore, the permeability of the pores 213 ensures the connectivity of the non-stick filler 212 distribution in the first coating 21, thus better ensuring that the composite non-stick layer maintains good non-stick properties during long-term use. The porosity of the first rigid skeleton is 5%-30%. This appropriate porosity can effectively meet the filling requirements of the non-stick filler, giving the composite non-stick layer good non-stick properties and good wear resistance. If the porosity is less than 5%, the proportion of the non-stick surface area of ​​the non-stick coating will be too low, and the non-stick effect will be limited. If the porosity is greater than 30%, the first rigid skeleton will be relatively loose, affecting the wear resistance and structural stability of the first rigid skeleton.

[0039] In some embodiments, the hardness of the first rigid skeleton is greater than or equal to 200 HV. In some specific embodiments, the hardness of the first rigid skeleton can be higher than that of a stainless steel spatula (the hardness of stainless steel is less than or equal to 210 HV). Therefore, the high hardness of the first rigid skeleton provides good hardness and mechanical properties for the non-stick coating, ensuring that the non-stick coating will not be damaged by external forces during long-term use. The hardness of the first rigid skeleton can be tested using a Vickers hardness tester, taking three test points at the middle of the first rigid skeleton or the first coating and averaging their hardness values; this average value is the average hardness of the first rigid skeleton.

[0040] According to an embodiment of the present invention, the thickness of the first coating 21 is 50 to 300 micrometers, for example, 50 micrometers, 80 micrometers, 100 micrometers, 120 micrometers, 150 micrometers, 180 micrometers, 200 micrometers, 230 micrometers, 250 micrometers, 270 micrometers, or 300 micrometers. That is, the thickness of the first rigid skeleton is 50 to 300 micrometers. This provides good strength for the composite non-stick layer. When the first coating 21 is directly attached to the substrate layer 10, the above-mentioned thickness allows the first coating to adhere well to the substrate layer, improving the interlayer bonding force between the two. If the thickness of the composite non-stick coating is less than 50 μm, there is a risk of wear through after long-term use, which cannot fully meet the user's long-term use requirements. If the thickness of the composite non-stick coating exceeds 300 micrometers, it does not substantially help the product's service life. On the contrary, the excessive thickness of the composite non-stick coating will reduce the interfacial bonding strength between the composite non-stick coating and the substrate layer.

[0041] According to an embodiment of the present invention, non-stick filler 212 is contained in any cross-section of the first coating 21 at a distance greater than or equal to X from the first surface 11, where X is 20 to 100 micrometers and X is less than the thickness of the first coating. For example, X can specifically be 20 micrometers, 30 micrometers, 40 micrometers, 50 micrometers, 60 micrometers, 70 micrometers, 80 micrometers, 90 micrometers, or 100 micrometers. Thus, in any cross-section of the first coating 21 of a certain thickness away from the substrate layer 10, both a first rigid skeleton and non-stick filler are simultaneously present, demonstrating the connectivity of the pores, i.e., the connectivity of the distribution of the non-stick filler 212. Therefore, during long-term use, the first coating 21 will experience a certain degree of wear, causing its thickness to gradually decrease. Thus, the above requirements can effectively ensure that the non-stick properties of the composite non-stick layer do not deteriorate or fail as the thickness of the first coating 21 decreases during long-term use. In other words, the composite non-stick layer can effectively maintain good wear resistance and non-stick properties away from the substrate layer surface during long-term use. Here, the cross section refers to the cross section of the composite non-stick layer in the direction perpendicular to the thickness direction of the composite non-stick layer, while the cross section of the composite non-stick layer in the thickness direction of the composite non-stick layer is the longitudinal section.

[0042] In some specific embodiments, the distance between the first coating 21 and the first surface 11 is greater than or equal to 1 mm on any cross-section of X. 2 The region contains a first rigid skeleton 211 and a non-stick filler 212. Thus, in any cross-section of the first coating 21 of a certain thickness on the side away from the substrate layer 10, a 1mm diameter is formed. 2 The presence of both a first rigid skeleton and non-stick filler within the defined area further demonstrates the connectivity of the pores, i.e., the connectivity of the distribution of the non-stick filler 212. Furthermore, the high density of the non-stick filler ensures better non-stick properties and uniformity of the non-stick coating. Thus, during prolonged use, the first coating 21 will experience some wear, gradually thinning its thickness. Therefore, the above requirements effectively ensure that the non-stick properties of the composite non-stick layer do not deteriorate or fail as the thickness of the first coating 21 decreases over time. In other words, the composite non-stick layer maintains good wear resistance and non-stick properties away from the substrate surface throughout prolonged use. Here, "cross-section" refers to the section taken perpendicular to the thickness direction of the composite non-stick layer; a section taken along the thickness direction is called a longitudinal section.

[0043] Furthermore, as mentioned above, the thickness of the first coating 21 is 50-300 micrometers. If the thickness of the first coating 21 is relatively thin, such as 50-100 micrometers, then in the above requirement that "any cross-section of the first coating 21 at a distance greater than or equal to X (X is 20-100 micrometers) from the first surface 11 simultaneously contains the first rigid skeleton and the non-stick filler", X can be a lower spacing, such as X being 20-30 micrometers or X being 20-50 micrometers. "Any cross-section of the first coating 21 at a distance greater than or equal to 20-30 micrometers (or 20-50 micrometers) from the first surface 11 simultaneously contains the first rigid skeleton and the non-stick filler", that is to say, the spacing between any cross-section and the first surface in the above requirement that "any cross-section simultaneously contains the first rigid skeleton and the non-stick filler" is 20-30 micrometers or 20-50 micrometers. In some specific embodiments, the thickness of the first coating 21 is 50 micrometers, and in any cross-section of the first coating 21 at a distance of 20 micrometers or more from the first surface 11, both a first rigid skeleton and a non-stick filler are present simultaneously. In other specific embodiments, the thickness of the first coating 21 is 70 micrometers, and in any cross-section of the first coating 21 at a distance of 30 micrometers or more from the first surface 11, both a first rigid skeleton and a non-stick filler are present simultaneously. In still other specific embodiments, the thickness of the first coating 21 is 100 micrometers, and in any cross-section of the first coating 21 at a distance of 50 micrometers or more from the first surface 11, both a first rigid skeleton and a non-stick filler are present simultaneously.

[0044] According to embodiments of the present invention, any cross-section or longitudinal section of the first coating contains a first rigid skeleton and the non-stick filler. This further ensures that the pores are interconnected from the upper surface to the lower surface of the first coating (i.e., the first rigid skeleton has interconnected pores 213, and the non-stick filler 212 fills the pores 213), effectively ensuring the connectivity of the non-stick filler in the first coating. Simultaneously, it further ensures the uniformity of the first rigid skeleton. Therefore, on the one hand, it ensures good non-stick properties of the composite non-stick layer, and on the other hand, it ensures good wear resistance of the composite non-stick layer. In some specific embodiments, 1 mm of any cross-section or longitudinal section of the first coating... 2 The area contains both a first rigid skeleton and a non-stick filler. This further ensures the permeability of the pores, the connectivity of the non-stick filler, and the uniformity of the first rigid skeleton. Therefore, it guarantees both good non-stick properties and excellent wear resistance of the composite non-stick layer. Furthermore, in some embodiments, within 1 mm of any cross-section or longitudinal section of the first coating... 2Within the defined area, the area ratio of the first rigid skeleton to the non-stick filler ranges from 2 to 19, for example, the area ratios of the first rigid skeleton to the non-stick filler are 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, and 19. Within any cross-section or longitudinal section of the first coating, a 1mm... 2 Within the specified area, the area ratio of the first rigid skeleton to the non-stick filler affects the non-stick properties and wear resistance of the composite non-stick layer. The ratio range of 2 to 19 mentioned above can well meet the requirements for non-stick properties and wear resistance when the composite non-stick layer is used in cookware. When 1 mm of any cross-section or longitudinal section of the first coating... 2 Within the specified area, when the area ratio of the first rigid skeleton to the non-stick filler is less than 2, the area proportion of the first rigid skeleton is too small, resulting in relatively poor wear resistance of the composite non-stick layer, making it prone to wear during cooking and cleaning. When the wear ratio of the first rigid skeleton to the non-stick filler is less than 2, the wear resistance of the composite non-stick layer is relatively poor, making it easily worn during cooking and cleaning. 2 Within the area, when the area ratio of the first rigid skeleton to the non-stick filler is greater than 19, the area ratio of the non-stick filler is too small, the non-stick properties of the composite non-stick layer are relatively poor, and it is relatively difficult to clean.

[0045] It should be noted that in products with the same composite non-stick layer, the composite non-stick layer may vary by 1 mm in different cross-sections or longitudinal sections. 2 Within the area, the area ratio of the first rigid skeleton and the non-stick filler can be the same or different. If different, it is acceptable as long as it is between 2 and 19.

[0046] According to an embodiment of the present invention, the difference in porosity at any cross-section or longitudinal section of the first rigid skeleton is less than or equal to 2.0%. For example, the difference in porosity at any cross-section or longitudinal section of the first rigid skeleton is 2.0%, 1.8%, 1.6%, 1.4%, 1.2%, 1.0%, 0.8%, 0.6%, 0.5%, 0.4%, 0.2%, 0.1%, 0.05%, or 0. Thus, the porosity of the first coating does not change significantly at different locations, meaning the porosity stability is good. This results in better uniformity of the first coating's wear resistance and non-stick properties, avoiding localized poor non-stickness or wear resistance. Moreover, even with prolonged use, the first coating will maintain good non-stickness and wear resistance despite wear to a certain thickness. This meets the requirements for cookware use. It should be noted that in products with the same composite non-stick layer, the difference in porosity at any two cross-sections or longitudinal sections of the first rigid skeleton can be equal or not completely equal, as long as it is less than or equal to 2.0%. This ensures both the wear resistance and the uniformity of the non-stick properties of the first coating.

[0047] According to embodiments of the present invention, the width of the pores is 5 to 150 micrometers, for example, 5 micrometers, 10 micrometers, 20 micrometers, 40 micrometers, 50 micrometers, 80 micrometers, 100 micrometers, 110 micrometers, 120 micrometers, 130 micrometers, 140 micrometers, and 150 micrometers. This effectively ensures that the non-stick filler can be smoothly filled into the pores while maintaining the good hardness of the rigid skeleton. If the width of the pores is less than 5 micrometers, not only will the narrow emulsion penetration channels of the non-stick filler affect the filling effect, but the emulsion of the non-stick filler will also need to overcome the additional pressure caused by surface tension when penetrating into the pores, affecting the penetration effect. If the width of the pores is greater than 150 micrometers, the porous first rigid skeleton will be relatively loose. Although the emulsion penetration of the non-stick filler becomes easier, the overall structural strength of the porous first rigid skeleton will decrease, and the porous first rigid skeleton will be easily damaged. It should be noted that in products with the same composite non-stick layer, the width of the pores at different locations may vary, as long as the width of the pores is between 5μm and 150μm.

[0048] According to an embodiment of the present invention, the first rigid skeleton is formed by stacking particles, with the gaps between the particles forming pores. This results in better bonding between the particles, giving the first rigid skeleton good stability. Simultaneously, the particle stacking method creates interconnected pores between the particles, further improving the connectivity of the pores. In some embodiments, the particle size is 50 to 100 micrometers. This helps to obtain the aforementioned first rigid skeleton with a width of 5 to 150 micrometers, pores, and a porosity of 5% to 30%. If the particle size is too small, the gaps between the particles are smaller during the particle stacking process, thus reducing the porosity of the first rigid skeleton and potentially affecting the connectivity of the pores. Conversely, if the particle stack is large, the gaps between the particles are larger, significantly increasing the porosity of the first rigid skeleton, resulting in an overall larger porosity and affecting the wear resistance of the first coating. The first rigid skeleton is formed by hard particles. During the preparation process, the hard particles are gradually sprayed onto the substrate in a semi-molten state and the first rigid skeleton is formed by the stacking of particles (i.e., particle stacking).

[0049] According to embodiments of the present invention, the non-stick coating and the substrate layer can be bonded by interlocking or / and by metallurgical means, as follows:

[0050] In some embodiments, refer to Figure 4The non-stick coating 20 has a first uneven structure 201 on the surface near the substrate layer 10, and the substrate layer 10 has a second uneven structure 101 on the surface near the non-stick coating 20. The non-stick coating 20 and the substrate layer 10 are bonded together by the interlocking of the first uneven structure 201 and the second uneven structure 101. In this way, the non-stick coating and the substrate layer are embedded in each other, which greatly improves the bonding force between the non-stick coating and the substrate layer, thereby improving the structural stability of the composite non-stick layer. In particular, during the manufacturing process, hard particles are sprayed onto the surface of the substrate layer, so that the hard particles are partially embedded in the substrate layer, which in turn creates the second uneven structure 101 on the surface of the substrate layer near the non-stick coating. Since the first hard skeleton is formed by the stacking of particles, the surface of the non-stick coating near the substrate layer is also formed with hard particles, thus forming the first uneven structure 201 on the surface of the non-stick coating near the substrate layer. The first uneven structure and the second uneven structure formed by the above reasons can interlock tightly, thereby effectively improving the bonding force between the non-stick coating and the substrate layer.

[0051] In other embodiments, the non-stick coating 20 and the substrate layer 10 are bonded through a metallurgical method where material from the non-stick coating 20 near the surface of the substrate layer 10 diffuses into the substrate layer 10. Specifically, during the preparation of the non-stick coating, some material used to prepare the first rigid skeleton diffuses into the substrate layer, causing the material of the first rigid skeleton in the substrate layer to become integrated with the first rigid skeleton. This effectively enhances the bonding force between the non-stick coating 20 and the substrate layer 10, thereby improving the structural stability of the composite non-stick layer. In still other embodiments, the bonding between the non-stick coating 20 and the substrate layer 10 combines both interlocking and metallurgical bonding methods, significantly improving the bonding force between the non-stick coating and the substrate layer, and further enhancing the structural stability of the composite non-stick layer.

[0052] According to an embodiment of the present invention, referring to Figure 5 The non-stick coating 20 also includes a second coating 22, which is disposed on the surface of the first coating 21 near the substrate layer 10. The second coating 22 includes a second rigid skeleton. Thus, the second coating 22, as a transition layer, can further improve the bonding strength between the non-stick coating 20 and the substrate layer 10, thereby further improving the overall structural stability of the composite non-stick layer and extending the service life of cookware using the composite non-stick layer.

[0053] In some embodiments, the hardness of the first rigid skeleton is greater than or equal to 200 HV. In some specific embodiments, the hardness of the first rigid skeleton can be higher than that of a stainless steel spatula (the hardness of stainless steel is less than or equal to 210 HV). Therefore, the high hardness of the first rigid skeleton provides good hardness and mechanical properties for the non-stick coating, ensuring that the non-stick coating will not be damaged by external forces during prolonged use. The testing method for the hardness of the second rigid skeleton is the same as that for the first rigid skeleton.

[0054] Those skilled in the art will understand that if the non-stick coating 20 only includes the first coating 21, the first coating 21 is in direct contact with the substrate layer 10, and the first coating 21 and the substrate layer 10 are bonded by interlocking or / and by metallurgical means; if the non-stick coating 20 includes the first coating 21 and the second coating 22, the second coating 22 is in direct contact with the substrate layer 10, and the second coating 22 and the substrate layer 10 are bonded by interlocking or / and by metallurgical means.

[0055] According to embodiments of the present invention, the second rigid skeleton and the first rigid skeleton are an integral structure. This better ensures the integrity of the non-stick coating, thereby improving its structural stability. In some embodiments, the first and second rigid skeletons can be prepared by the same method, such as thermal spraying. Thus, the first and second rigid skeletons can be prepared using the same process, requiring only adjustment of certain process parameters. This results in stronger connectivity between the first and second rigid skeletons, further improving the bonding strength between them and between the non-stick coating and the substrate layer.

[0056] According to an embodiment of the present invention, the second coating 22 serves as a transition layer. The second rigid skeleton has a porous structure with a porosity of 1% to 20%, and the porosity of the first rigid skeleton is greater than or equal to that of the second rigid skeleton. Specifically, the porosity of the second rigid skeleton can be 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, etc. Thus, the structure of the second rigid skeleton in the second coating 22 is more compact than the structure of the first rigid skeleton 211 in the first coating 21, allowing the second coating 22 to bond firmly with the substrate layer 10. This improves the bonding strength between the non-stick coating 20 and the substrate layer 10, thereby further extending the service life of the cookware. Furthermore, the relatively dense structure of the transition layer prevents corrosive media from easily penetrating the substrate even if the non-stick material filling the pores of the rigid skeleton is damaged, further improving the corrosion resistance of the cookware.

[0057] According to embodiments of the present invention, the porosity of the second rigid skeleton gradually increases in the direction near the first rigid skeleton 211, and the porosity of the surface of the second rigid skeleton near the first rigid skeleton 211 is less than or equal to the porosity of the first rigid skeleton 211. Therefore, the structure of the side of the second rigid skeleton near the substrate layer is more compact, which can further improve the bonding strength between the non-stick coating and the substrate layer, and also further improve the corrosion resistance of the composite non-stick layer. In some specific embodiments, the porosity of the second rigid skeleton gradually increases from 1% in the direction near the first rigid skeleton 211 to or close to the porosity of the first rigid skeleton.

[0058] Furthermore, the non-stick filler extends from the first coating to the second coating, meaning that the pores of the second rigid skeleton can also be further filled with non-stick filler. When filling the pores of the first rigid skeleton with non-stick filler, some of the non-stick filler seeps from the pores of the first rigid skeleton into the pores of the second rigid skeleton, providing an "anchoring" effect and further increasing the bonding force between the first and second coatings without affecting its non-stick properties. The non-stick filler can completely or partially fill the pores of the second rigid skeleton; those skilled in the art can choose flexibly according to actual needs, and no restrictions are imposed here.

[0059] According to an embodiment of the present invention, the thickness of the second coating is 1 / 10 to 1 / 3 of the thickness of the non-stick coating (the sum of the thicknesses of the first and second coatings). For example, the thickness of the second coating is 1 / 10, 1 / 9, 1 / 8, 1 / 7, 1 / 6, 1 / 5, 1 / 4, or 1 / 3 of the thickness of the non-stick coating. Therefore, the aforementioned thickness percentage of the second coating serves both as a transition, further improving the bonding strength between the non-stick coating 20 and the substrate layer 10, and ensuring that the thickness percentage of the first coating is relatively large, so that the first coating will not be completely worn through during long-term use of the composite non-stick layer, thus affecting the non-stick properties of the composite non-stick layer.

[0060] In some embodiments of the present invention, the thickness of the second coating is 20 to 100 micrometers, for example, the thickness of the second coating is 20 micrometers, 30 micrometers, 40 micrometers, 50 micrometers, 60 micrometers, 70 micrometers, 80 micrometers, or 100 micrometers. The aforementioned thickness of the second coating can effectively serve as a transition, further improving the bonding strength between the non-stick coating 20 and the substrate layer 10.

[0061] In embodiments of the present invention, the material of the substrate layer includes, but is not limited to, stainless steel, aluminum alloy, iron, titanium alloy, etc., so that the substrate layer has good thermal conductivity and strength, meeting the requirements for use of cookware.

[0062] In embodiments of the present invention, the rigid skeleton is a metal-based skeleton, a ceramic-based skeleton, or a metal / ceramic-based skeleton. The rigid skeletons of the above materials possess excellent wear resistance and thermal conductivity, meeting the requirements for cookware use. Furthermore, the metal-based skeleton is at least one of stainless steel and a boron-iron hybrid material, a titanium-based alloy, and an iron-based amorphous system material. In some embodiments, the metal-based skeleton includes iron and auxiliary materials, the auxiliary materials including at least one of chromium (Cr), boron (B), silicon (Si), carbon (C), nickel (Ni), and oxygen (O). Therefore, Fe was chosen as the main element. Fe has a low cost and good thermal conductivity and wear resistance, which can well meet the requirements of cookware. In addition, Fe has been used for cookware since ancient times, and users have good acceptance of it. Adding Cr and Ni can help improve the corrosion resistance of the composite non-stick coating, thus solving the problem of iron pots being prone to rusting. C, B, and Si are the forming elements of iron-based amorphous materials. Amorphous materials have no grain boundaries, which can avoid grain boundary corrosion and further improve corrosion resistance. At the same time, amorphous materials have higher hardness. O can form a Cr2O3 protective film with Cr, which also helps to improve the corrosion resistance of the composite non-stick coating.

[0063] According to embodiments of the present invention, the non-stick filler is an organic or inorganic non-stick material containing fluorine or silicon, such as PTFE, PFA, fluorosilanes, siloxanes, etc. Therefore, the aforementioned non-stick filler is a low surface energy wetting material, a nano- or ultrafine nanometer-scale superhydrophobic medium, and can ensure unimpeded passage through the smallest pore size within the rigid framework. In some embodiments, the particle size of the non-stick filler is less than or equal to the minimum width of the pores, thus better ensuring that the non-stick filler can more smoothly penetrate into the pores of the first rigid framework.

[0064] In another aspect of the present invention, a method for preparing the aforementioned composite non-stick layer is provided. According to an embodiment of the present invention, the method for preparing the composite non-stick layer includes: forming a non-stick coating 20 on a first surface 11 of a substrate layer 10, wherein the step of forming the non-stick coating 20 includes the step of forming a first coating 21, and the step of forming the first coating 21 includes:

[0065] S100: A first rigid skeleton 211 is formed by thermal spraying. The first rigid skeleton 211 has through pores 213 and the porosity of the first rigid skeleton 211 is 5%-30%.

[0066] In embodiments of the present invention, the thermal spraying process conditions satisfy at least one of the following: the particle size of the hard particles is 5–100 micrometers (e.g., 5 micrometers, 10 micrometers, 20 micrometers, 30 micrometers, 40 micrometers, 50 micrometers, 60 micrometers, 70 micrometers, 80 micrometers, 90 micrometers, 100 micrometers); the powder feeding rate is 0.5–3 r / min (e.g., 0.5 r / min, 1.0 r / min, 1.5 r / min, 2.0 r / min, 2.5 r / min, 3.0 r / min); and the acetylene flow rate is 3–10 L / min (e.g., 3 L / min, 4 L / min, 5 L / min). The oxygen flow rate is 3–10 L / min (e.g., 3 L / min, 4 L / min, 5 L / min, 6 L / min, 7 L / min, 8 L / min, 9 L / min, 10 L / min); the spraying distance is 20–150 mm (e.g., 20 mm, 30 mm, 40 mm, 50 mm, 60 mm, 70 mm, 80 mm, 90 mm, 100 mm, 110 mm, 120 mm, 130 mm, 140 mm, 150 mm). Therefore, under the above thermal spraying process conditions, a first rigid skeleton with suitable pore width, suitable thickness, and good porosity can be effectively obtained, ensuring that the pore width, thickness, porosity, and other parameters of the first rigid skeleton meet the aforementioned range requirements.

[0067] In an embodiment of the present invention, the step of forming the first rigid skeleton includes: melting the rigid particles to obtain semi-molten particles with a molten surface and an unmelted interior; then thermally spraying the semi-molten particles onto a first surface and stacking them to form the first rigid skeleton. In the above process, the rigid particles are pre-melted into semi-molten particles before thermal spraying, and the molten surfaces of two adjacent rigid particles can be fused together, which can greatly improve the bonding strength between the particles, thereby improving the structural stability of the first rigid skeleton.

[0068] Furthermore, the thickness of the semi-molten particles during melting can be 1 / 10 to 1 / 3 of the diameter of the hard particles. For example, the thickness of the semi-molten particles during melting can be 1 / 10, 1 / 9, 1 / 8, 1 / 7, 1 / 6, 1 / 5, 1 / 4, or 1 / 3 of the diameter of the hard particles. In this way, the molten surfaces of two adjacent hard particles can be well fused together, greatly improving the bonding strength between particles, while preventing the molten portion of the semi-molten particles from filling the gaps between particles, thus affecting the width and connectivity of the pores.

[0069] S200: Fill the pores 213 with non-stick filler 212 to obtain the first coating 21. A structural schematic diagram can be found below. Figure 2 and Figure 3 .

[0070] In an embodiment of the present invention, a method for filling the pores 213 with non-stick filler 212 includes:

[0071] S210: Apply a non-stick filler emulsion to the surface of the first rigid skeleton 211 away from the substrate layer 10. The specific coating method is not particularly required, and those skilled in the art can choose flexibly according to the actual situation.

[0072] The non-stick filler is an organic or inorganic non-stick material containing fluorine or silicon, such as PTFE, PFA, fluorosilanes, siloxanes, etc. Therefore, the aforementioned non-stick filler is a low surface energy wettable material, a nano- or ultrafine nanometer-scale superhydrophobic medium, and can ensure unimpeded passage through the smallest pores within the rigid framework.

[0073] S220: The non-stick filler emulsion is impregnated into the pores by at least one of ultrasonic, negative pressure, and vortex methods. Thus, the above method is simple and easy to implement, and can effectively impregnate the non-stick filler emulsion into the pores, improving the utilization rate of the non-stick filler.

[0074] In some embodiments, a specific method for impregnating the non-stick filler emulsion into the pores by ultrasound can be as follows: coating the surface of a first rigid skeleton with a non-stick filler emulsion, and then placing it in an ultrasonic environment for ultrasound treatment. The ultrasonic process conditions are: frequency ≥ 20 kHz, power density ≥ 0.3 W / cm³. 2 The ultrasonic temperature is 20-40℃, and the ultrasonic time is 5-30 minutes. Under these conditions, the non-stick filler emulsion can quickly and uniformly penetrate into the pores and fill the pores of the first rigid skeleton; moreover, the above conditions are relatively mild and will not affect the bonding force between the first rigid skeleton and the substrate layer due to ultrasonication.

[0075] In some embodiments, a specific method for impregnating the non-stick filler emulsion into the pores using negative pressure can be as follows: the surface of the first rigid skeleton is coated with the non-stick filler emulsion, and then it is placed in a negative pressure environment. The negative pressure process conditions are: during the impregnation of the non-stick filler emulsion into the pores, the negative pressure is 0.15–0.4 bar at room temperature, and the negative pressure impregnation time is 5–30 min. Therefore, under these conditions, the non-stick filler emulsion can quickly and uniformly impregnate into the pores, filling the pores of the first rigid skeleton; moreover, the negative pressure will not adversely affect the bonding force between the first rigid skeleton and the substrate layer.

[0076] In some embodiments, the specific method for vortexing to allow the non-stick filler emulsion to penetrate into the pores can be as follows: placing the first rigid skeleton into the non-stick filler emulsion and stirring the non-stick filler emulsion at a certain stirring rate. The vortexing process conditions are: at room temperature, a stirring speed of 100-500 rpm, a stirring time of 5-30 min, and a stirring volume of 20-100 ml / stirring element (i.e., the stirring volume is the volume that each stirring element is responsible for stirring; the number of stirring elements can be determined based on the total amount of non-stick filler emulsion). Therefore, under the above conditions, the non-stick filler emulsion can quickly and uniformly penetrate into the pores, filling the pores of the first rigid skeleton; moreover, the vortexing effect will not adversely affect the bonding force between the first rigid skeleton and the substrate layer.

[0077] S230: Curing the non-stick filler emulsion immersed in the pores to obtain the first coating 21.

[0078] In some embodiments, the non-stick filler is a silicon-based non-stick filler, and the curing temperature is 250-320°C, for example, curing temperatures of 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, and 320°C. Therefore, at these temperatures, the non-stick filler emulsion can be cured quickly without adversely affecting the first rigid skeleton and the non-stick filler.

[0079] In some embodiments, the non-stick filler is a fluoropolymer-based non-stick filler, and the curing temperature is 350-420°C, for example, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, or 420°C. Therefore, at these temperatures, the non-stick filler emulsion can be cured rapidly without adversely affecting the first rigid skeleton and the non-stick filler.

[0080] In an embodiment of the present invention, after curing the non-stick filler, the surface of the first coating is further subjected to sandblasting or grinding to remove the surface heterogeneous layer, and finally a non-stick coating in which a porous skeleton and low surface energy substances in the pores are interlocked is obtained.

[0081] According to embodiments of the present invention, the first rigid skeleton formed by thermal spraying can provide better wear resistance to the non-stick coating, and the non-stick filler filling the pores can provide good non-stick properties to the non-stick coating. That is, the composite non-stick layer prepared by the above method has both good wear resistance and non-stick properties. In addition, the preparation of the first rigid skeleton by thermal spraying can make the first rigid skeleton and the substrate layer have strong bonding strength, improve the stability between the layer structures, and the preparation process is mature and easy to industrialize. The porosity of the first rigid skeleton is 5%-30%. In this way, the pore ratio is appropriate, which can effectively meet the filling of the non-stick filler, so that the composite non-stick layer has good non-stick properties and good wear resistance at the same time. If the porosity is less than 5%, the proportion of the non-stick surface area of ​​the non-stick coating is too low, and the non-stick effect will be limited. If the porosity is greater than 30%, the first rigid skeleton will be relatively loose, affecting the wear resistance and structural stability of the first rigid skeleton.

[0082] According to an embodiment of the present invention, the step of forming the non-stick coating 20 further includes: before forming the first rigid skeleton 211, forming a second rigid skeleton on the first surface 11 by thermal spraying for forming the second coating 22, such as... Figure 5 As shown. The second rigid skeleton, as a transition layer, can further improve the bonding strength between the non-stick coating 20 and the substrate layer 10, thereby further improving the overall structural stability of the composite non-stick layer and extending the service life of cookware using the composite non-stick layer.

[0083] According to an embodiment of the present invention, the second rigid skeleton and the first rigid skeleton are an integral structure. Both the first rigid skeleton and the second rigid skeleton are prepared by thermal spraying. Thus, the first rigid skeleton and the second rigid skeleton can be prepared in one process. During the preparation, only some process parameters need to be adjusted.

[0084] According to an embodiment of the present invention, the porosity of the second rigid skeleton gradually increases in the direction approaching the first rigid skeleton 211, and the porosity of the surface of the second rigid skeleton near the first rigid skeleton 211 is less than or equal to the porosity of the first rigid skeleton 211. Therefore, the structure of the side of the second rigid skeleton near the substrate layer is more compact, which can further improve the bonding strength between the non-stick coating and the substrate layer, and also further improve the corrosion resistance of the composite non-stick layer.

[0085] Furthermore, the pores of the second rigid skeleton can also be filled with non-stick filler. That is, when filling the pores of the first rigid skeleton with non-stick filler, some of the non-stick filler seeps from the pores of the first rigid skeleton into the pores of the second rigid skeleton. The non-stick filler can fill the pores of the second rigid skeleton completely or partially. Those skilled in the art can choose flexibly according to actual needs, and no restrictions are imposed here.

[0086] In another aspect, the present invention provides a cookware according to an embodiment of the invention, which includes the aforementioned composite non-stick layer, wherein the substrate layer of the composite non-stick layer constitutes the cookware body, and the non-stick coating layer of the composite non-stick layer is located on one side of the cooking space of the cookware. Thus, the cookware simultaneously possesses good wear resistance and non-stick properties, thereby improving the performance and service life of the cookware. Those skilled in the art will understand that the cookware possesses all the features and advantages of the aforementioned composite non-stick layer, which will not be elaborated further here.

[0087] In another aspect, the present invention provides a cooking utensil, which, according to an embodiment of the invention, includes the pot described above. Thus, the pot of this cooking utensil possesses both good wear resistance and non-stick properties, thereby improving the performance and lifespan of the cooking utensil. Those skilled in the art will understand that this cooking utensil possesses all the features and advantages of the composite non-stick layer described above, which will not be elaborated further here.

[0088] In the embodiments of the present invention, there are no special requirements on the specific types of cooking utensils described above, and those skilled in the art can choose flexibly according to the actual situation. In some embodiments, the cooking utensils described above can be woks, stew pots, rice cookers, pressure cookers, saucepans, frying pans, steamers, etc.

[0089] Example

[0090] Examples 1-15 and Comparative Examples 1-2 are shown in Table 1, wherein the steps for preparing the composite non-stick layer include:

[0091] A first rigid skeleton is formed on the first surface of the substrate layer by thermal spraying. The material forming the first rigid skeleton is a mixture of stainless steel 304 and boron-containing iron-based material, wherein the boron content is 3% by mass.

[0092] A silicon-based non-stick filler emulsion is coated onto the surface of the first rigid skeleton away from the substrate layer;

[0093] Ultrasonic waves are used to allow the non-stick filler emulsion to penetrate into the pores.

[0094] The non-stick filler emulsion immersed in the pores was cured at 300°C to obtain the first coating.

[0095] The surface of the first coating is sandblasted and polished to remove the surface heterogeneous layer, resulting in a non-stick coating.

[0096] Example 16

[0097] The difference between Example 16 and Examples 1-15 above in preparing the composite non-stick layer is that the material forming the first rigid skeleton is stainless steel 430.

[0098] The porosity, pore size, and thickness of the non-stick coating (which is the same as the thickness of the first coating in this embodiment) of the first rigid skeleton in Examples 1-16 and Comparative Examples 1-2, as well as the test results, can be found in Table 1 below. The test methods are as follows:

[0099] 1. Salt spray test: According to GB / T 10125 "Artificial atmosphere corrosion test - salt spray test", the finished product sample is placed in a neutral salt spray test chamber at 35℃±2℃ and continuously sprayed with a 5% sodium chloride solution. After every 12 hours, it is taken out, rinsed with water and air-dried, and the surface quality is visually inspected.

[0100] 2. Hardness Test: The coating hardness was tested using a microhardness tester. Five locations on the sample surface were randomly selected for testing. A diamond square pyramid with a 0.2 kgf load and a 136° apex angle was pressed into the material surface and held for 30 seconds. The Vickers hardness value was obtained by dividing the load value by the surface area of ​​the indentation.

[0101] 3. Abrasion Resistance Test: Fix the sample on a flat abrasion testing machine with the porous skeleton layer of the sample facing upwards and place a scouring pad flat on it. Apply a load of 2.5 kg on the scouring pad, set the frequency to 33 times / min, and apply a pushing and pulling force. One back-and-forth motion constitutes one cycle, with a unidirectional movement distance of 10 cm. Start the flat abrasion testing machine. Replace the scouring pad friction surface every 500 cycles and observe the surface condition of the coating.

[0102] 4. Non-stickiness test: The SINDIN SDC-350 contact angle meter was used to test the hydrophobic angle of the initial wear-resistant non-stick layer surface and the surface after 100,000 wear cycles in the flat plate wear tester. The contact angle between the water droplet and the sample surface was observed. The larger the hydrophobic angle, the better the non-stickiness.

[0103] 5. Porosity test: The test shall be conducted according to the national standard GB / T 17721-1999; or, in an embodiment of the present invention, the porosity shall be measured at 1 mm of any cross-section or longitudinal section of the first coating. 2 The porosity is calculated within the specified region using the following formula: S 凹 / (S 凸 +S 凹 ), S 凸 S represents the area value corresponding to the convex portion. 凹 The area value corresponding to the recessed portion is represented by the convex portion, which is a rigid skeleton, while the recessed portion is a pore where non-stick filler has penetrated. Therefore, the porosity is related to S. 凸 and S 凹 It is related to the value.

[0104] Table 1

[0105]

[0106]

[0107]

[0108] The test results of Comparative Example 1 show that the porosity of the first hard skeleton is too small (<5%, measured 3%), so the proportion of low surface energy wettables is low, which does not significantly improve the surface non-stickiness and the hydrophobic angle value is low. Comparative Example 2 shows that when the skeleton porosity is too high (>30%, measured 50%), the skeleton will be relatively loose. Even if the intrinsic hardness of the skeleton material is very high, the indenter will crush the loose skeleton on the surface during hardness testing. That is, the skeleton's support is insufficient, resulting in a lower actual hardness value. After 100,000 wear tests on the plate, some parts of the hard skeleton layer have been worn through, which is reflected in the significant decrease in the sample's non-stickiness. In contrast, in Comparative Example 1, due to the very low porosity, the measured hardness of the skeleton is relatively high (550 HV). Furthermore, the excessively high porosity makes the porous, first-stage hard skeleton structure unstable. Although the initial surface of the non-stick coating before wear has a high proportion of low surface energy wettants due to the large porosity, resulting in a high initial hydrophobic angle (135°), the loose skeleton's protective effect on low surface energy wettants is limited. After the flat plate abrasion test, the skeleton is significantly damaged, and the non-stick properties decrease drastically. Example 7 illustrates that when the pore size is too small (<5 micrometers), the emulsion penetration channels are too narrow, affecting the penetration effect. The further into the non-stick coating, the worse the emulsion penetration. After 100,000 abrasion cycles on the flat plate, since the wear has reached the interior of the non-stick coating, the low surface energy emulsion at that location has not formed a good filling in the pores, resulting in a poor surface finish. The adhesion will be lower; Example 10 shows that when the pore size is too large (>160 micrometers), the porous skeleton will be relatively loose, the overall structural strength of the porous skeleton will decrease, the support and protection effect of the skeleton for superhydrophobic wetters will decrease, and although the wear-resistant non-stick layer is not worn through after 100,000 wear cycles on a flat plate, due to the damage of the skeleton, a certain proportion of the low surface energy wetters in the pores will be destroyed, and the surface non-stickiness will decrease to a certain extent; Example 11 shows that when the non-stick coating is too thin (<50 micrometers, measured 30 micrometers), the durable protection of the porous first hard skeleton is insufficient. After 100,000 wear cycles on a flat plate, the wear-resistant non-stick layer is worn through, and the non-stickiness is greatly reduced; Example 16 shows that the material of the first hard skeleton must be selected as corrosion-resistant metal or ceramic material, otherwise it cannot pass the corrosion resistance test, and the non-stick coating is at risk of corrosion and rust in actual use.

[0109] The terms "first" and "second" used in this document are for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature marked "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this application, "multiple" means two or more, unless otherwise explicitly specified.

[0110] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0111] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A composite non-stick layer, characterized in that, include: A substrate layer having a first surface; A non-stick coating is disposed on the first surface. The non-stick coating includes a first coating layer, which includes a first rigid skeleton and a non-stick filler. The first rigid skeleton has through-pores, and the non-stick filler fills the pores. The porosity of the first rigid skeleton is 5%-30%. The non-stick filler is contained in any cross-section where the distance from the first coating to the first surface is greater than or equal to X, where X is 20 to 100 micrometers and X is less than or equal to the thickness of the first coating. The first coating contains the first rigid skeleton and the non-stick filler in any of its cross-sections and / or longitudinal sections.

2. The composite non-stick layer according to claim 1, characterized in that, On any cross section where the distance between the first coating and the first surface is greater than or equal to X, 1 mm 2 The region contains the first rigid skeleton and the non-stick filler.

3. The composite non-stick layer according to claim 1, characterized in that, 1 mm of any of the cross-sections and / or longitudinal sections of the first coating 2 The region contains the first rigid skeleton and the non-stick filler.

4. The composite non-stick layer according to claim 3, characterized in that, 1 mm of any of the cross-sections and / or longitudinal sections of the first coating 2 Within the region, the area ratio of the first rigid skeleton to the non-stick filler is 2 to 19.

5. The composite non-stick layer according to claim 1, characterized in that, The width of the pores is 5 to 150 micrometers.

6. The composite non-stick layer according to claim 5, characterized in that, The particle size of the non-stick filler is less than or equal to the minimum width of the pores.

7. The composite non-stick layer according to claim 1, characterized in that, The first rigid skeleton is formed by stacking particles, and the gaps between the particles constitute the pores.

8. The composite non-stick layer according to any one of claims 1 to 7, characterized in that, The thickness of the first coating is 50~300 micrometers.

9. The composite non-stick layer according to any one of claims 1 to 7, characterized in that, The non-stick coating and the substrate layer are combined in at least one of the following ways: The non-stick coating has a first uneven structure on the surface near the substrate layer, and the substrate layer has a second uneven structure on the surface near the non-stick coating. The non-stick coating and the substrate layer are bonded together by interlocking the first uneven structure and the second uneven structure. The non-stick coating and the substrate layer are bonded by a metallurgical method through material diffusion from the surface portion of the non-stick coating near the substrate layer to the substrate layer.

10. The composite non-stick layer according to any one of claims 1 to 7, characterized in that, The non-stick coating further includes a second coating disposed on the surface of the first coating near the substrate layer, the second coating including a second rigid skeleton.

11. The composite non-stick layer according to claim 10, characterized in that, The second rigid skeleton and the first rigid skeleton are an integral structure.

12. The composite non-stick layer according to claim 10, characterized in that, The porosity of the first rigid skeleton is greater than or equal to the porosity of the second rigid skeleton, and / or the hardness of the first rigid skeleton and the second rigid skeleton is greater than or equal to 200 HV.

13. The composite non-stick layer according to claim 12, characterized in that, The non-stick filler extends from the first coating to the second coating.

14. The composite non-stick layer according to claim 12, characterized in that, In the direction close to the first rigid skeleton, the porosity of the second rigid skeleton gradually increases, and the porosity of the surface of the second rigid skeleton close to the first rigid skeleton is less than or equal to the porosity of the first rigid skeleton.

15. The composite non-stick layer according to claim 10, characterized in that, The ratio of the thickness of the second coating to the thickness of the non-stick coating is in the range of 1 / 10 to 1 / 3.

16. The composite non-stick layer according to claim 15, characterized in that, The thickness of the second coating is 20 to 100 micrometers.

17. A method for preparing the composite non-stick layer according to any one of claims 1 to 16, characterized in that, include: Forming a non-stick coating on a first surface of a substrate layer, the step of forming the non-stick coating includes the step of forming a first coating, the step of forming the first coating including: Hard particles are thermally sprayed to form a first hard skeleton, the first hard skeleton having through pores and a porosity of 5%-30%; The pores are filled with non-stick filler to obtain the first coating.

18. The method according to claim 17, characterized in that, The steps for forming the first rigid framework include: The hard particles are melted to obtain semi-molten particles with a melted surface and an unmelted interior; The semi-molten particles are thermally sprayed onto the first surface and stacked to form the first rigid skeleton.

19. The method according to claim 17, characterized in that, The method of filling the pores with the non-stick filler includes: A non-stick filler emulsion is coated onto the surface of the first rigid skeleton away from the substrate layer; The non-stick filler emulsion is impregnated into the pores by at least one of ultrasound, negative pressure, and vortex. The non-stick filler emulsion immersed in the pores is cured to obtain the first coating.

20. The method according to claim 19, characterized in that, The non-stick filler is a silicon-based non-stick filler, and the curing temperature is 250-320℃; the non-stick filler is a fluorine-based non-stick filler, and the curing temperature is 350-420℃.

21. The method according to claim 17, characterized in that, The step of forming the non-stick coating further includes: Before the first rigid skeleton is formed, a second rigid skeleton is formed on the first surface by the thermal spraying.

22. A cookware, characterized in that, Includes the composite non-stick layer according to any one of claims 1 to 16, wherein the substrate layer in the composite non-stick layer constitutes the cookware body of the cookware, and the non-stick coating layer in the composite non-stick layer is located on one side of the cooking space of the cookware.

23. A cooking utensil, characterized in that, Includes the cookware described in claim 22.

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