Non-stick coating and its preparation method, as well as non-stick cookware

Abstract

This application provides a non-stick layer, a method for preparing the same, and a non-stick cookware. The non-stick layer comprises an inorganic non-metallic compound layer with a polycrystalline structure. The metallic elements in the inorganic non-metallic compound layer include a first metallic element and a second metallic element. The first metallic element includes rare earth metals and / or alkaline earth metals, and the second metallic element includes transition metals. The non-stick layer of this application, using an inorganic non-metallic compound layer with a polycrystalline structure, has low surface energy and good impact toughness, thereby enabling the product's non-stick layer to possess both good initial non-stick properties and long-lasting non-stick properties.

Description

Technical Field

[0001] This application relates to the technical field of non-stick cookware, and more specifically, to a non-stick layer for cookware or cups, a method for preparing the same, and non-stick cookware. Background Technology

[0002] Fluoropolymer coatings are common non-stick coatings in this field. However, while non-stick coatings made with fluoropolymer coatings have excellent initial non-stick properties, they are easily damaged by spatulas and prone to aging or decomposition due to high temperatures during use. These problems have seriously affected the service life of coatings formed with fluoropolymer coatings, resulting in generally poor long-term non-stick properties.

[0003] Therefore, developing a non-stick layer that combines initial non-stick properties with long-term non-stick properties remains a problem that needs to be solved. Summary of the Invention

[0004] Therefore, the purpose of this application is to provide a non-stick layer and its preparation method, as well as non-stick cookware, to solve the problem that the layers formed by existing non-stick materials cannot simultaneously possess both initial non-stick and long-lasting non-stick properties.

[0005] According to a first aspect of this application, a non-stick layer is provided, wherein the non-stick layer comprises an inorganic non-metallic compound layer having a polycrystalline structure, wherein the metal element in the inorganic non-metallic compound layer comprises a first metal element and a second metal element, wherein the first metal element comprises a rare earth metal element and / or an alkaline earth metal element, and the second metal element comprises a transition metal element.

[0006] The non-stick layer according to this application includes an inorganic non-metallic compound layer with a polycrystalline structure. Compared with the same material layer having an amorphous structure (completely disordered atomic arrangement, lacking long-range periodic structure), the inorganic non-metallic compound layer with a polycrystalline structure is composed of multiple randomly oriented grains. The atomic arrangement inside each grain is long-range ordered. The inconsistent arrangement direction between grains causes the interior of the inorganic non-metallic compound layer to exhibit disorder, thereby reducing surface energy and achieving initial non-stickiness. In addition, compared with the same material layer having an amorphous structure, the polycrystalline structure can improve the impact toughness of the inorganic non-metallic compound layer, making the non-stick layer less prone to partial or overall peeling when subjected to external forces (such as scraping with a spatula or dropping), thus greatly improving the long-term non-stickiness of the non-stick layer.

[0007] In some embodiments, the inorganic nonmetallic compound layer is an oxide layer, and its general formula is A. x B y C zWherein, A is the alkaline earth metal element, B is titanium among the transition metal elements, and C is oxygen, wherein 2x+2y=2z, 2x+3y=2z, or 2x+4y=2z; or, the inorganic non-metallic compound layer is an oxide layer, and the general formula is A x B y C z Wherein, A is the alkaline earth metal element, B is iron or cobalt among the transition metal elements, and C is oxygen, wherein 2x + 3y = 2z or 2x + 2y = 2z; or, the inorganic non-metallic compound layer is an oxide layer, and the general formula is A x B y C z Wherein, A is the alkaline earth metal element, B is manganese among the transition metal elements, and C is oxygen, wherein 2x+2y=2z, 2x+4y=2z, 2x+6y=2z, or 2x+7y=2z; or, the inorganic non-metallic compound layer is an oxide layer, and the general formula is A x B y C z Wherein, A is the rare earth metal element, B is titanium among the transition metal elements, and C is oxygen, wherein 3x+2y=2z, 3x+3y=2z, or 3x+4y=2z; or, the inorganic non-metallic compound layer is an oxide layer, and the general formula is A x B y C z Wherein, A is the rare earth metal element, B is iron or cobalt among the transition metal elements, and C is oxygen, wherein 3x + 3y = 2z or 3x + 2y = 2z; or, the inorganic non-metallic compound layer is an oxide layer, and the general formula is A x B y C z Wherein, A is the rare earth metal element, B is manganese among the transition metal elements, and C is oxygen, wherein 3x+2y=2z, 3x+4y=2z, 3x+6y=2z, or 3x+7y=2z; or, the inorganic non-metallic compound layer is a halide layer, and the general formula is A x B y C z Wherein, A is the alkaline earth metal element, B is titanium among the transition metal elements, and C is a halogen element, wherein 2x+2y=z, 2x+3y=z, or 2x+4y=z; or, the inorganic non-metallic compound layer is a halide layer, and the general formula is A x B y C zWherein, A is the alkaline earth metal element, B is iron or cobalt among the transition metal elements, and C is a halogen element, wherein 2x + 3y = z or 2x + 2y = z; or, the inorganic non-metallic compound layer is a halide layer, and the general formula is A x B y C z Wherein, A is the alkaline earth metal element, B is manganese among the transition metal elements, and C is a halogen element, wherein 2x+2y=z, 2x+4y=z, 2x+6y=z, or 2x+7y=z; or, the inorganic non-metallic compound layer is a halide layer, and the general formula is A x B y C z Wherein, A is the rare earth metal element, B is titanium among the transition metal elements, and C is a halogen element, wherein 3x+2y=z, 3x+3y=z, or 3x+4y=z; or, the inorganic non-metallic compound layer is a halide layer, and the general formula is A x B y C z Wherein, A is the rare earth metal element, B is iron or cobalt among the transition metal elements, and C is a halogen element, wherein 3x + 3y = z or 3x + 2y = z; or, the inorganic non-metallic compound layer is a halide layer, and the general formula is A x B y C z Wherein, A is the rare earth metal element, B is manganese among the transition metal elements, and C is a halogen element, wherein 3x+2y=z, 3x+4y=z, 3x+6y=z, or 3x+7y=z; or, the inorganic non-metallic compound layer is an oxide layer with the general formula Al. x1 A2 x2 B y C z Wherein, A1 is an alkaline earth metal element, A2 is a rare earth metal element, B is a transition metal element, and C is oxygen element, wherein 2x1+3x2+3y=2z or 2x1+3x2+4y=2z; or, the inorganic non-metallic compound layer is an oxide layer, and the general formula is A1 x1 A2 x2 B y C zIn this embodiment, A1 is an alkaline earth metal element, A2 is a rare earth metal element, B is a transition metal element, and C is a halogen, where 2x1+3x2+3y=z or 2x1+3x2+4y=z. In these embodiments, the inorganic non-metallic compound layer composed of the above elements possesses an oxide perovskite structure or a halide perovskite structure, thus giving the inorganic non-metallic compound layer good thermal stability, high hardness, and wear resistance. Furthermore, the numerous grain boundaries in the polycrystalline structure effectively passivate cracks and disperse stress, providing good toughness. Its synergistic effect with the perovskite structure compensates for the brittleness of the inorganic non-metallic compound layer due to increased hardness, resulting in improved wear resistance, crack resistance, and thermal stability of the non-stick layer.

[0008] In some embodiments, the alkaline earth metal element includes at least one selected from calcium, strontium, and barium; the transition metal element includes at least one selected from titanium, manganese, iron, and cobalt; the halogen includes iodine or chlorine; and the rare earth metal element includes at least one selected from lanthanum, neodymium, and yttrium. In these embodiments, the inorganic non-metallic compound layer composed of the above elements can combine the advantages of food safety, process feasibility, and chemical stability.

[0009] In some embodiments, the inorganic non-metallic compound layer having a polycrystalline structure accounts for no less than 80% of the total mass of the non-stick layer. In these embodiments, using the inorganic non-metallic compound layer having a polycrystalline structure as the main component can meet the cookware's requirements for both initial and long-term non-stick properties.

[0010] In some embodiments, the polycrystalline structure of the inorganic non-metallic compound layer includes micron- and / or nano-sized grains. The grain size is refined to the micron or nano-level. The small grain size (fine grains) can directly and significantly increase the number of grain boundaries. Grain boundaries are regions with disordered atomic arrangement and dense defects. Their energy state is higher than that of the grain interior, and the grain boundary region will dominate in the inorganic non-metallic compound layer, thereby leading to a significant reduction in the overall surface energy of the inorganic non-metallic compound layer. This can improve the non-stickiness of the non-stick layer with the inorganic non-metallic compound layer as the main body.

[0011] In some embodiments, the grains of the inorganic non-metallic compound layer contain subgrains. The presence of subgrains results in a certain number of subgrain boundaries within the grains. Subgrain boundaries are also high-energy regions with irregular atomic arrangements, which can further increase the interface density within the inorganic non-metallic compound layer and further reduce the overall surface energy of the inorganic non-metallic compound layer, thereby further improving the non-stick properties. In addition, subgrain boundaries can also work synergistically with grain boundaries to greatly enhance the crack propagation resistance (fracture toughness) of the non-stick layer, thereby further preventing the non-stick layer from cracking or peeling off due to brittleness.

[0012] In some embodiments, at least a portion of the grains of the inorganic non-metallic compound layer possess a layered structure. This layered structure leads to high-density stacking faults and lattice distortion within the inorganic non-metallic compound layer, increasing the energy state within the grains and promoting the formation of a polycrystalline structure. Furthermore, the layered structure can also synergize with grain boundaries and subgrain boundaries to further prevent the non-adhesive layer from cracking or peeling due to brittleness.

[0013] In some embodiments, the inorganic non-metallic compound layer also contains carbonized products of a binder. These carbonized products are derived from the carbonization of the binder in the mixed slurry. Before carbonization, these carbonized products are used to connect the first and second metal compounds, ensuring the bonding force within each particle of the raw material, thereby guaranteeing the bonding stability of the inorganic non-metallic compound particles after sintering. As a specific example, the mass ratio of the carbonized products of the binder to the inorganic non-metallic compound layer is (0.4-3.5):(96.5-99.6). Having a suitable mass ratio of carbonized products of the binder to the inorganic non-metallic compound layer avoids excessive carbonized products of the binder from affecting the overall strength of the inorganic non-metallic compound layer.

[0014] According to a second aspect of this application, a method for preparing a non-stick layer is provided, wherein the method comprises: forming a mixed slurry comprising an adhesive, a first metal compound having a crystalline structure, and a second metal compound having a crystalline structure, wherein the first metal compound comprises a rare earth metal compound and / or an alkaline earth metal compound, and the second metal compound comprises a transition metal compound; performing spray drying on the mixed slurry to form non-stick particles; sintering the non-stick particles to allow the first metal compound and the second metal compound in the non-stick particles to react with each other, thereby obtaining a non-stick material mainly composed of an inorganic non-metallic compound having a polycrystalline structure; and spraying the non-stick material onto a substrate to manufacture the non-stick layer.

[0015] According to the non-stick layer preparation method of this application embodiment, the formed non-stick particles have a mixed form of a first metal compound and a second metal compound. During the sintering of the non-stick particles, the first metal compound and the second metal compound, which have crystalline structures, can form an inorganic non-metallic compound with a polycrystalline structure after sintering due to the material properties. Compared with the same material with a crystalline structure, during the sintering process, the atoms of the first metal compound and the second metal compound can migrate from high-energy positions (such as the surface and defects) to low-energy positions (grain boundaries and grain interiors), thereby reducing surface energy and achieving non-stick properties. In addition, compared with the same material with an amorphous structure or a crystalline structure, having a polycrystalline structure can ensure the impact toughness of the inorganic non-metallic compound, making the non-stick layer formed by the non-stick material less prone to partial or overall peeling off when subjected to external forces (such as scraping with a spatula or dropping), thereby greatly improving the long-lasting non-stick properties of cookware with a non-stick layer.

[0016] In some embodiments, the step of sintering the non-stick particles includes sintering the non-stick particles at a temperature of 75%-85% of their melting point. In these embodiments, heating the non-stick particles at 75%-85% of their melting point allows the metal compounds in the particles to soften but not melt. After softening, the high-temperature energy of sintering accelerates diffusion, promotes homogenization of the composition, and facilitates solid-phase reactions. This allows for the formation of inorganic non-metallic compounds through sintering without excessively affecting the granular structure of the non-stick particles, thereby obtaining a non-stick material with non-stick properties.

[0017] In some embodiments, the step of sintering the non-stick particles includes: heating the non-stick particles to 300℃-450℃ and holding for 2h-4h; then, continuing to heat to 700℃-900℃ and holding for 1h-3h; and then heating to 1000℃-1100℃ at a heating rate of 1℃ / min-5℃ / min and holding for 2h-4h. In these embodiments, through staged heat preservation sintering, the first metal compound and the second metal compound, which have crystalline structures, can interact during the sintering process, such as through diffusion and reaction, thereby changing the original crystal structure and forming a polycrystalline inorganic non-metallic compound.

[0018] In some embodiments, the mass of the binder in the mixed slurry is 0.2%-0.25% of the total mass of the first and second metal compounds. During the spray drying stage, the binder encapsulates the metal compound particles to form non-stick particles with a particle agglomeration structure. During sintering, the binder in the non-stick particles volatilizes or carbonizes, thereby generating micro-nano-scale pores in situ within the non-stick material formed by the non-stick particles. These pores constitute a three-dimensional interconnected oil-retaining structure. When the non-stick material is applied to the non-stick layer, grease and other substances can permeate and be stored in the pores, forming an grease lubrication layer, thereby improving the non-stickiness of the non-stick layer formed by the non-stick material.

[0019] In some embodiments, the binder is used to connect a first metal compound and a second metal compound, enabling individual particles of the first and second metal compounds to connect and form non-stick particles with an aggregated structure. As an example, the binder includes alcohol-based binders and / or cellulose-based binders. In some embodiments, the cellulose-based binder includes at least one of hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose binders, and the alcohol-based binder includes at least one of polyvinyl alcohol, polyacryl alcohol, and higher alcohols containing six or more carbon atoms. These binders can ensure adhesive performance while also considering the food safety performance of the non-stick material and controlling material costs.

[0020] According to this application, the first metal compound and the second metal compound have the same anion type during the reaction. This avoids interference from anions in the reaction process, thereby enabling the formation of a relatively pure inorganic non-metallic compound through the coordination and recombination of metal elements at high temperature, and avoiding interference from byproducts.

[0021] In some embodiments, the first metal compound is selected from at least one of oxides, hydroxides, and carbonates, and the second metal compound is selected from oxides; or, the first metal compound is selected from chlorides, and the second metal compound is selected from chlorides; or, the first metal compound is selected from iodides, and the second metal compound is selected from iodides.

[0022] In these embodiments, the first metal compound is selected from at least one of oxides, hydroxides, and carbonates. These first metal compounds are thermally decomposed before sintering to form corresponding metal oxides, and have the same anion type as the second metal compound. Based on this, the first metal compound and the second metal compound under the above-defined conditions can have the same anion type during sintering, and these compounds can react to form structurally stable inorganic non-metallic compounds. At the same time, it can balance the overall food safety and manufacturing convenience of the non-stick material.

[0023] In some embodiments, the transition metal compound includes at least one selected from titanium oxide, manganese oxide, iron oxide, cobalt oxide, titanium chloride, manganese chloride, iron chloride, cobalt chloride, titanium iodide, manganese iodide, iron iodide, and cobalt iodide; and / or, the alkaline earth metal compound includes at least one selected from calcium oxide, calcium hydroxide, calcium carbonate, strontium oxide, strontium hydroxide, strontium carbonate, barium oxide, barium hydroxide, barium carbonate, calcium chloride, strontium chloride, barium chloride, calcium iodide, strontium iodide, and barium iodide; and / or, the rare earth metal compound includes at least one selected from lanthanum oxide, neodymium oxide, yttrium oxide, lanthanum chloride, neodymium chloride, yttrium chloride, lanthanum iodide, neodymium iodide, and yttrium iodide. In the above embodiments, the specific combination of metal compounds (pairwise combinations of transition metals, alkaline earth metals, and rare earth metal compounds) can form inorganic non-metallic compounds with polycrystalline structures and stable structures, while balancing the overall food safety and manufacturing convenience of the non-stick material.

[0024] According to this application, when the first metal compound is an alkaline earth metal compound, the atomic ratio of the alkaline earth metal element in the first metal compound to the transition metal element in the second metal compound is 2:3-3:2; when the first metal compound is a rare earth metal compound, the atomic ratio of the rare earth metal element in the first metal compound to the transition metal element in the second metal compound is 2:3-3:2; when the first metal compound is both a rare earth metal compound and an alkaline earth metal compound, the ratio of the total number of rare earth metal elements and alkaline earth elements in the first metal compound to the number of transition metal elements in the second metal compound is 2:3-3:2. In these embodiments, the atomic ratio of the metal elements in the first metal compound and the second metal compound can control the grain size and distribution of the final product, suppress side reactions, and thus affect the purity of the polycrystalline inorganic non-metallic compound in the non-stick material.

[0025] In some embodiments, the median particle size of the first metal compound and the second metal compound in the mixed slurry is 1.5 μm-2.5 μm, respectively. Such a fine particle size allows each metal compound particle in the mixed slurry to have a large specific surface area, exposing more active sites, thereby greatly increasing the contact area between the two metal compounds. This shortens the diffusion path of each ion in the subsequent reaction process, increases the contact probability, and thus accelerates the chemical reaction rate and shortens the time for forming non-metallic compounds, thereby accelerating the formation of inorganic non-metallic compounds with polycrystalline structures.

[0026] In some embodiments, the porosity of the particles of the non-stick material is 25%-55%, and the pore size is 500 nanometers-4 micrometers. In these embodiments, the non-stick material having the above pore distribution can form a non-stick layer with a three-dimensional porous structure through particle stacking, thus effectively adsorbing and storing edible oil, thereby further enhancing the non-stick properties of products with this non-stick layer.

[0027] In some embodiments, the median particle size of the non-stick material is 30μm-45μm. This allows for the formation of a non-stick layer with a suitable pore structure using this particle size, thus facilitating oil storage and improving non-stick properties. Furthermore, the granulated powder particles themselves possess a large specific surface area, ensuring the bonding force between the non-stick layer and the matrix.

[0028] According to a third aspect of this application, another method for preparing a non-stick layer is provided, wherein the method comprises the following steps: mixing a first metal compound and a second metal compound to obtain a mixture, wherein the first metal compound includes a rare earth metal compound and / or an alkaline earth metal compound, and the second metal compound includes a transition metal compound; heating the mixture to melt it, causing the first metal compound and the second metal compound to react with each other; performing a cooling process to obtain a non-stick material mainly composed of an inorganic non-metallic compound with a polycrystalline structure; and spraying the non-stick material onto a substrate to manufacture the non-stick layer. This non-stick layer possesses good impact resistance and is not easily peeled off locally or entirely when subjected to external forces (such as scraping with a spatula or dropping), thereby significantly improving the long-lasting non-stick properties of cookware with a non-stick layer.

[0029] In some embodiments, the step of heating the mixture for melting includes: heating the mixture to a temperature 30°C-100°C higher than the melting point of the metal compound with the highest melting point in the mixture, and melting at that temperature for 3-6 hours. In these embodiments, heating the mixture to the melting point of the metal compound with the highest melting point allows the mixture to fully melt to form a mixed molten liquid. After melting, the high-temperature energy of melting accelerates the diffusion of ions in the mixed molten liquid, promotes homogenization of the composition and ionic reactions, forming a liquid inorganic non-metallic compound. This also reduces the possibility of impurity phases forming due to component segregation, thereby avoiding the influence of impurity phases on the surface energy of the non-stick material and ensuring the non-stick properties of the non-stick layer formed by the non-stick material and the non-stick uniformity of each region.

[0030] In some embodiments, the cooling rate of the cooling process is controlled between 10°C / min and 20°C / min. By controlling the cooling rate, the size of the grains can be effectively controlled to obtain a polycrystalline structure with micron- and nano-sized grains.

[0031] In some embodiments, the step of spraying the non-stick material onto a substrate to produce the non-stick layer includes: crushing the inorganic non-metallic compound having a polycrystalline structure; pressing the crushed inorganic non-metallic compound into an initial target; pressing and sintering the initial target under a protective atmosphere to obtain a non-stick material used as a target; and physically vapor-depositing the non-stick material to produce a dense non-stick layer.

[0032] According to a fourth aspect of this application, a non-stick cookware is provided, wherein the non-stick cookware includes a cookware substrate and a non-stick layer formed on the cookware substrate, wherein the non-stick layer is formed of a non-stick material, the non-stick material being either the non-stick material described above or a non-stick material prepared according to the preparation method of the non-stick material described above.

[0033] In some embodiments, the non-stick layer has a porous structure filled with grease and / or silicone oil, thereby further optimizing the non-stick properties of the non-stick layer. Attached Figure Description

[0034] The above and / or other features and aspects of the inventive concept will become clear and readily understood through the description of the embodiments in conjunction with the accompanying drawings.

[0035] Figure 1 and Figure 2 These are SEM images of non-stick materials provided according to embodiments of this application; Figure 3 and Figure 4 These are SEM images of the cross-section of the non-stick material provided in the embodiments of this application; Figure 5 The XRD pattern of the non-stick material provided in the embodiments of this application is shown. Figures 6 to 8 These are SIM photographs taken at different magnifications of the same location of the non-stick layer formed by the non-stick material according to the embodiments of this application; Figure 9 This is a SIM photograph of another location of the non-stick layer formed by the non-stick material according to the embodiments of this application; Figure 10 This is a schematic diagram of the cross-sectional structure of the cookware provided in the embodiment of this application after being cut along the thickness direction; Figure 11 yes Figure 10 A magnified structural diagram at point I in the middle.

[0036] Symbol explanation: 100. Cookware; 110. Substrate; 111. Raised area; 112. Groove; 120. Non-stick layer. Detailed Implementation

[0037] Example embodiments of the present invention will now be described in more detail.

[0038] Fluoropolymer coatings are common organic non-stick coatings. Non-stick layers made with fluorine-based coatings have excellent initial non-stick properties, but they are easily damaged by spatulas and prone to aging or decomposition at high temperatures during use. These problems have seriously affected the lifespan of non-stick coatings formed with fluorine-based coatings, resulting in generally poor long-term non-stick performance. Furthermore, perfluoroalkyl and polyfluoroalkyl compounds (PFAS) are indispensable raw materials for the synthesis of fluorine-based coatings. With increasingly stringent industry regulations on PFAS, the withdrawal of fluorine-based coatings from cookware is inevitable. This also means that the materials available for non-stick coatings on cookware are gradually decreasing, thus creating a pressing need for developing new non-stick materials in the cookware manufacturing industry.

[0039] Currently, no organic material with a lower surface energy than fluoropolymer coatings has been found, but the cookware industry's demand for non-stick coatings remains constant. Ceramic coatings are now considered a potential replacement for fluoropolymer coatings. Ceramic coatings are liquid organic coatings with silicone oil as the main non-stick component. The resulting polysiloxane non-stick coating, while initially possessing non-stick properties close to fluoropolymer coatings, quickly loses its non-stick effect as the silicone oil is continuously consumed by the high temperatures during cooking. Therefore, the long-lasting non-stick properties of ceramic coatings cannot meet the non-stick requirements of cookware.

[0040] With the development of the non-stick industry, in response to the environmental and durability shortcomings of organic coatings, the industry has turned to the development of inorganic amorphous solid spraying materials (such as composite oxides with amorphous structures and polymetallic cationic metal salts with amorphous structures). These inorganic amorphous solid spraying materials can form a non-stick layer that meets the requirements of cookware non-sticking, and because they use inorganic ceramic materials to replace organic polymer materials, they can achieve a "no organic layer" non-stick effect, and therefore have been favored by most users for a long time.

[0041] Although coatings formed by existing inorganic amorphous solid spraying materials have good non-stick properties, they are also brittle. When subjected to external forces (such as scraping with a spatula or dropping), cracks are easily generated and rapidly propagated, causing the coating to peel off locally or entirely, which will significantly affect the long-lasting non-stick properties of the non-stick layer.

[0042] The inventors discovered that by forming an inorganic non-metallic compound with a polycrystalline structure and using it as a non-stick material, the impact resistance and non-stick properties of the non-stick layer formed by the non-stick material can be achieved, thereby achieving the purpose of long-lasting non-stickness.

[0043] According to a first aspect of this application, a method for preparing a non-stick material is provided. The method includes: forming a mixed slurry comprising a binder, a first metal compound having a crystalline structure, and a second metal compound having a crystalline structure, wherein the first metal compound comprises a rare earth metal compound and / or an alkaline earth metal compound, and the second metal compound comprises a transition metal compound; spray drying the mixed slurry to form non-stick particles; and sintering the non-stick particles to allow the first and second metal compounds in the non-stick particles to react with each other, thereby obtaining a non-stick material primarily composed of an inorganic non-metallic compound having a polycrystalline structure. The metal elements in the inorganic non-metallic compound layer include a first metal element and a second metal element, wherein the first metal element includes a rare earth metal element and / or an alkaline earth metal element, and the second metal element includes a transition metal element.

[0044] In these embodiments, the inorganic non-metallic compound is a product obtained by the reaction of the first and second metallic compounds in the aforementioned non-stick particles. The term "non-stick material primarily composed of inorganic non-metallic compounds" means that, in addition to containing inorganic non-metallic compounds, the non-stick material also contains metallic materials and may contain trace amounts of impurities (e.g., carbonization products of the adhesive).

[0045] According to the non-stick material preparation method of this application embodiment, the formed non-stick particles have a mixed form of a first metal compound and a second metal compound. During the sintering of the non-stick particles, the first metal compound and the second metal compound, which have crystalline structures, can react synergistically after sintering due to material properties (e.g., internal atomic radius) to form an inorganic non-metallic compound with a polycrystalline structure. Compared with the same material having a crystalline structure, during the sintering process, the atoms of the first metal compound and the second metal compound can migrate from high-energy positions (e.g., surface, defects) to low-energy positions (grain boundaries, intragranularity), thereby reducing surface energy and achieving non-stick properties. In addition, compared with the same material having an amorphous structure or a crystalline structure, having a polycrystalline structure can ensure the impact toughness of the inorganic non-metallic compound, making the non-stick layer formed by the non-stick material with a polycrystalline inorganic non-metallic compound as the main body less prone to partial or overall peeling off when subjected to external forces (e.g., scraping with a spatula, dropping), thereby greatly improving the long-lasting non-stick properties of cookware with a non-stick layer.

[0046] In addition, in this application, the polycrystalline structure of the inorganic non-metallic compound has high chemical activity at the grain boundaries, which can adsorb oil molecules (such as grease) and form a stable oil film, thereby reducing the possibility of material adhesion and further improving the non-stick performance of the non-stick layer formed by the non-stick material.

[0047] Furthermore, compared to equivalent materials with single-crystal structures, polycrystalline structures with fine grains can improve the hardness and wear resistance of non-stick materials through grain boundary strengthening effects, thereby further optimizing the long-lasting non-stick properties of non-stick layers formed from non-stick materials.

[0048] In the embodiments of this application, the non-stick material has low surface energy, quantified by contact angle, which is 90°-105°. The non-stick material has a melting point of 1500-2500℃, which is relatively high, thus enabling it to possess good high-temperature resistance.

[0049] The following will describe in detail, with reference to specific embodiments, the preparation method of the non-stick material according to this application.

[0050] Provide adhesive According to this application, the binder is used to improve the rheological properties of the mixed slurry, promote the development of the spray drying process, and ensure the formability of the non-stick particles. In the non-stick particles, the binder is used to connect the first metal compound and the second metal compound, so that the individual particles of the first metal compound and the second metal compound can be connected to each other to construct non-stick particles with an aggregated structure. As an example, the binder is an aqueous binder, specifically an aqueous binder solution with a mass concentration of 0.4wt%-0.5wt%. As some embodiments, the binder includes alcohol-based binders and / or cellulose-based binders.

[0051] Specifically, cellulose-based adhesives include at least one of hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose adhesives, and alcohol-based adhesives include at least one of polyvinyl alcohol, polyacryl alcohol, and other higher alcohols containing six or more carbon atoms. However, this application is not limited to these, and suitable adhesives can be selected according to actual needs, as long as these adhesives can ensure bonding performance while also taking into account the food safety performance of the non-stick material and controlling the cost of the material.

[0052] It should be noted that the binder according to this application may volatilize or carbonize during the subsequent sintering process. Whether the binder volatilizes or carbonizes depends largely on the heating rate, sintering temperature, and time of the subsequent sintering stage. Here, carbonization is the process by which organic matter undergoes thermal decomposition at high temperatures, removing hydrogen, oxygen, and other low-molecular-weight compounds as residual carbon. Volatilization is the process by which organic matter changes from a liquid to a gaseous state after reaching its boiling point. That is, in this process, the binder in the non-stick particles will change to a gaseous state, leaving pores on the non-stick particles.

[0053] Forming a mixture According to this application, the first metal compound includes rare earth metal compounds and / or alkaline earth metal compounds. These rare earth / alkaline earth metal compounds typically have a cubic or hexagonal crystal system, and their regular lattice arrangement provides an ordered template for subsequent reactions, guiding the growth of polycrystalline structures. The second metal compound includes transition metal compounds. These transition metal compounds possess diverse crystal structures (such as tetragonal, cubic, and hexagonal) and can form heterogeneous interfaces with the first metal compound, promoting grain boundary pinning and inhibiting grain coarsening. The rare earth / alkaline earth metal compounds and transition metal compounds can react to form inorganic non-metallic compounds with low surface energy and high chemical stability, serving as non-stick materials.

[0054] In the embodiments of this application, the first metal compound and the second metal compound have the same anion type during the reaction, which can reduce the occurrence of side reactions in the non-stick particles during high-temperature sintering and ensure the purity of the reaction. Specifically, when reacting in the sintered state, metal compounds of the same type generally have similar diffusion behaviors and reaction pathways in the non-stick particles, and have a synergistic effect. For example, oxide-oxide systems easily form oxygen bridge bonds (O2-O3 ... 2- It can tightly connect different metal compounds together, making the bond stronger and preventing brittle fracture of materials. Thus, it can construct the final inorganic non-metallic compound with a polycrystalline structure through element diffusion.

[0055] According to embodiments of this application, when the first metal compound is an alkaline earth metal compound, and the alkaline earth metal compound is selected from at least one of oxides, hydroxides, and carbonates, the second metal compound is selected from oxides. It should be noted that hydroxides and carbonates decompose at high temperatures before the metal compound softens, forming oxides, thus creating metal compounds with the same anion type as the second metal compound. When the alkaline earth metal compound is selected from chlorides, the second metal compound is selected from chlorides; when the alkaline earth metal compound is selected from iodides, the second metal compound is selected from iodides. When the first metal compound is a rare earth metal compound, the rare earth metal compound is selected from oxides, chlorides, or iodides, and the second metal compound has the same anion as the rare earth metal compound, or it can be understood that the second metal compound is selected from compounds with the same anion type as the rare earth metal compound.

[0056] In some embodiments, the first metal compound and the second metal compound are both in particulate form with a size on the micrometer scale. Such a small size can promote effective contact between the first metal compound and the second metal compound, increase the contact area between the first metal compound and the second metal compound during the reaction, reduce the diffusion energy barrier, and thus promote the formation of a polycrystalline structure.

[0057] In some embodiments, the transition metal compound includes at least one of the oxides corresponding to the transition metal and the halides corresponding to the transition metal. The oxides corresponding to the transition metal include at least one of titanium oxides (TiO2, Ti2O3), manganese oxides (MnO, MnO2, Mn3O4), iron oxides (FeO, Fe2O3, Fe3O4), and cobalt oxides (CoO, Co2O3, Co3O4); the halides corresponding to the transition metal include at least one of titanium chlorides (TiCl3, TiCl4), manganese chlorides (MnCl2, MnCl3), iron chlorides (FeCl2, FeCl3), cobalt chlorides (CoCl2, CoCl3), titanium iodides (TiI3, TiI4), manganese iodides (MnI2, MnI3), iron iodides (FeI2, FeI3), and cobalt iodides (CoI2, CoI3).

[0058] In some embodiments, the alkaline earth metal compound includes at least one of the oxides and halides corresponding to alkaline earth metals. The oxides corresponding to alkaline earth metals include at least one of calcium oxide (CaO), calcium hydroxide (Ca(OH)2), calcium carbonate (CaCO3); strontium oxide (SrO), strontium hydroxide (Sr(OH)2), strontium carbonate (SrCO3); barium oxide (BaO), barium hydroxide (Ba(OH)2), and barium carbonate (BaCO3); the halides corresponding to alkaline earth metals include at least one of calcium chloride (CaCl2), strontium chloride (SrCl2), barium chloride (BaCl2), calcium iodide (CaI2), strontium iodide (SrI2), and barium iodide (BaI2).

[0059] In some embodiments, the rare earth metal compound includes at least one of rare earth metal oxides and rare earth metal halides. The rare earth metal oxides include at least one of lanthanum oxide (La₂O₃), neodymium oxide (Nd₂O₃), and yttrium oxide (Y₂O₃); the rare earth metal halides include at least one of lanthanum chloride (LaCl₃), neodymium chloride (NdCl₃), yttrium chloride (YCl₃), lanthanum iodide (LaI₃), neodymium iodide (NdI₃), and yttrium iodide (YI₃).

[0060] In the above embodiments, the specific combination of metal compounds (two-way combinations between transition metals, alkaline earth metals and rare earth metal compounds) can form inorganic non-metallic compounds with polycrystalline structures and stable structures. At the same time, it can balance the overall food safety and manufacturing convenience of the non-stick material.

[0061] According to this application, the first metal compound and the second metal compound are particulate and have a crystalline structure. Mixing the first and second metal compounds to obtain a mixture ensures effective contact between them. This improves the contact reliability between the corresponding metal elements in the non-stick particles during sintering, guarantees the contact area, reduces the diffusion barrier, and promotes the reaction of the metal elements in the non-stick particles to form a liquid inorganic non-metallic compound. A cooling process then promotes uniform nucleation of the polycrystalline structure, resulting in a polycrystalline inorganic non-metallic compound used as a non-stick material.

[0062] In an exemplary embodiment, the first metal compound and the second metal compound can be mechanically mixed using a ball mill. Specific process parameters include: ball milling speed of 150-200 r / min, time of 6-10 h, and ball-to-material ratio of 1:1-2:1. Under these conditions, the median particle size of the mixture can be refined to 1.5 μm-2.5 μm. Furthermore, through mixing, the particles of the first and second metal compounds can be uniformly distributed, thus effectively avoiding local segregation and facilitating the increase of the first metal element (such as Ca) in subsequent reactions. 2+ ) and the second metallic element (such as Ti) 4+ The increased contact probability and diffusion efficiency of inorganic non-metallic compounds can shorten the sintering time and ensure the purity and consistency of the compounds.

[0063] According to this application, when the first metal compound in the mixture is an alkaline earth metal compound, the atomic ratio of the alkaline earth metal element in the first metal compound to the transition metal element in the second metal compound is 2:3-3:2; when the first metal compound in the mixture is a rare earth metal compound, the atomic ratio of the rare earth metal element in the first metal compound to the transition metal element in the second metal compound is 2:3-3:2; when the first metal compound is both a rare earth metal compound and an alkaline earth metal compound, the ratio of the total number of rare earth metal elements and alkaline earth elements in the first metal compound to the number of transition metal elements in the second metal compound is 2:3-3:2.

[0064] In these embodiments, the atomic ratio of the metal elements in the first metal compound and the second metal compound can control the grain size and distribution of the final product, and can suppress side reactions and prevent excessive unreacted raw materials from remaining in the final product, thereby affecting the purity of the polycrystalline inorganic non-metallic compound in the non-stick material.

[0065] According to this application, the fineness and uniformity of the raw materials forming the mixture directly affect the solid-phase reaction rate of the non-stick particles at high temperatures and the uniformity of each part, avoiding local component deviation and inhibiting the formation of impurity phases or abnormally grown grains. As a specific example, the median particle size of the first and second metal compounds in the mixture is 1.5 μm-2.5 μm, respectively. Such a fine particle size allows each metal compound particle in the mixture to have a large specific surface area, exposing more active sites, thereby greatly increasing the contact area between the two metal compounds. This shortens the diffusion path of each element in the subsequent non-stick particles, increases the contact probability, and thus accelerates the chemical reaction rate, shortens the time for forming non-metallic compounds, and accelerates the formation of inorganic non-metallic compounds with polycrystalline structures.

[0066] Forming a mixed slurry According to this application, the mixed slurry has fluidity and includes a first metal compound, a second metal compound, and a binder. It should be noted that, in addition to the aforementioned core components (the first metal compound, the second metal compound, and the binder), the mixed slurry may also include trace amounts of a dispersant for dispersion and a defoamer for defoaming. This allows for more uniform dispersion of the particles of the first and second metal compounds in the mixed slurry, ensuring the uniformity of the components in the non-stick particles obtained after spray drying; and it can promptly destroy air bubbles introduced during the preparation of the mixed slurry, thereby preventing porosity defects in the spray-dried non-stick particles without affecting construction efficiency.

[0067] As an example, the dispersant includes at least one of water, polyacrylate and citrate, and the defoamer includes at least one of silicone defoamer and polyether defoamer.

[0068] In some embodiments, stirring can form a mixed slurry comprising a first metal compound, a second metal compound, and a binder. Before spray drying, the first metal compound, the second metal compound, and the binder are thoroughly mixed to form the mixed slurry, ensuring uniform distribution of the first / second metal compound within the particles and avoiding localized component segregation. It should be noted that this application does not impose excessive restrictions on the order in which the three raw materials—the first metal compound, the second metal compound, and the binder—are added. For example, all three raw materials can be added simultaneously to the mixing device, and uniform mixing can be achieved through mechanical stirring or ultrasonic dispersion; alternatively, two raw materials can be mixed first (e.g., obtaining the mixture described above), and then the third raw material (the binder) can be added for secondary mixing.

[0069] In some exemplary embodiments, the step of forming the mixed slurry includes mixing the mixture and the binder. In other embodiments, the step of forming the mixed slurry may also be a step of directly mixing the first metal compound, the second metal compound, and the binder.

[0070] In the above embodiments, a first metal compound and a second metal compound are mixed with an adhesive to form a mixed slurry. The adhesive in the mixed slurry acts as a connecting bridge, which can enhance the structural stability of the non-stick particles formed after spray drying, so that the obtained non-stick material has a certain mechanical strength, thereby ensuring the stability of the non-stick layer formed by the non-stick material in the future, and thus avoiding breakage that would affect the formation of the three-dimensional pore structure of the non-stick layer.

[0071] According to this application, the mass of the binder in the mixed slurry is 0.2%-0.25% of the total mass of the first and second metal compounds. During the spray drying stage, the binder encapsulates the metal compound particles to form non-stick particles with a particle agglomeration structure. During sintering, the binder in the non-stick particles volatilizes or carbonizes, thereby generating micro-nano-level pores in situ within the non-stick material formed by the non-stick particles. These pores constitute a three-dimensional interconnected oil-retaining structure. When the non-stick material is applied to a non-stick layer, grease and other substances can permeate and be stored in the pores, forming an grease lubrication layer, thereby improving the non-stickiness of the non-stick layer formed by the non-stick material.

[0072] It should be noted that the respective proportions of the first metal compound and the second metal compound can be referenced to the atomic proportions in the mixture mentioned above. Under this ratio, the first metal compound and the second metal compound can react as fully as possible under the influence of high-temperature energy to form inorganic non-metallic compounds.

[0073] According to some embodiments of this application, a nucleating agent comprising 0.1%-0.5% of the total mass of the mixed slurry is added to the mixed slurry. The nucleating agent is an oxide powder having a mismatch of less than 15% with the theoretical lattice constant calculated based on the theoretical chemical formulas of the first and second metal compounds.

[0074] In these embodiments, by adding a nucleating agent to the mixed slurry, the nucleating agent can induce the simultaneous formation of a large number of fine grains, avoiding grain coarsening or porosity caused by insufficient local nucleation, thereby further ensuring the formation of polycrystalline structures and ensuring the uniform distribution and close arrangement of polycrystalline grains.

[0075] In some embodiments, the nucleating agent is selected from at least one of aluminum oxide, magnesium oxide, yttrium oxide, and ABC3 type perovskite oxide. These nucleating agents can serve as the core for heterogeneous nucleation, effectively reducing the nucleation barrier and promoting the uniform and dense growth of polycrystalline structures, thereby refining the grains and improving the density and mechanical strength of the final non-stick material.

[0076] Spray drying to form non-sticky granules According to this application, after pulping, the mixed slurry is spray-dried, which enables the mixed slurry to be rapidly formed into non-sticky particles. In some embodiments, spray drying equipment (such as a pressure spray dryer, centrifugal spray dryer, etc.) can be used to atomize the mixed slurry into fine droplets. The atomized droplets come into contact with hot air, the solvent (water) evaporates rapidly, and the first metal compound, the second metal compound, and the binder form the basic structure of the non-sticky particles. As an example, the mixed slurry can be conveyed to a high-speed atomizing disc to form droplets, and then hot air is used to blow the droplets into a drying tower. The droplets have a brief residence time during their descent, and finally form wet non-sticky particles.

[0077] As a specific example, the spray disc frequency of the centrifugal spray dryer is 40Hz-50Hz, corresponding to a spray disc rotation speed of approximately 1200r / min-1500r / min (assuming a 4-pole motor and no reducer). The inlet temperature of the centrifugal spray dryer is 270℃-290℃ to ensure instantaneous drying of the mixed slurry and prevent sticking to the wall. The outlet temperature is 140℃ to ensure the degree of drying of non-stick particles.

[0078] Perform post-granulation processing According to this application, the method for preparing the non-stick material may further include a step of dispersing the granulated non-stick particles. Specifically, the non-stick particles are dispersed at 800 r / min-1200 r / min for 1 h-2 h using a high-speed disperser, and then sieved through a 200-400 mesh sieve to remove agglomerated particles from the non-stick particles.

[0079] Sintering of the spray-dried non-stick particles According to the preparation method of the non-stick material of this application, the non-stick particles obtained by spray drying are sintered. During the high-temperature sintering process, the first and second metal compounds slightly melt, and their physical state gradually changes from solid to semi-solid or viscous. Thus, the first and second metal compounds undergo a solid-phase reaction through grain boundary diffusion or volume diffusion to generate a new phase (such as rare earth titanates or perovskite compounds), i.e., forming the inorganic non-metallic compound according to this application. During the reaction, rare earth / alkaline earth metal ions are adsorbed at the grain boundaries, reducing the grain boundary migration rate and inhibiting grain coarsening; simultaneously, the polycrystalline structure of the transition metal compound provides heterogeneous nucleation sites, promoting the formation of fine grains, thereby causing the inorganic non-metallic compound to exhibit a polycrystalline structure.

[0080] Specifically, in this application, when the lattice constants of rare earth metal compounds (such as La2O3 and CeO2) and transition metal compounds (such as Fe2O3 and Co3O4) are relatively similar, solid solutions or eutectic structures are easily formed during sintering, promoting grain growth. As an example, La2O3 (lattice constant a = 1.06 nm) and Fe2O3 (a = 0.50 nm) have a high degree of lattice mismatch, but by adding alkaline earth metal compounds (such as MgO, a = 0.42 nm), the local lattice can be adjusted, reducing the mismatch and promoting polycrystalline formation.

[0081] In this application, the first metal compound and the second metal compound are oxides. Oxides have high activity (e.g., nano-sized CeO2, Fe2O3) and are prone to diffusion and reaction during sintering to form grains with clear grain boundaries.

[0082] In some embodiments, sintering includes a first stage and a second stage, the first stage being for degreasing (e.g., removing binders, defoamers, and dispersants), and the second stage being for reacting a first metal compound and a second metal compound to form an inorganic nonmetallic compound according to the present application.

[0083] As an example, the non-stick particles are placed in a sintering furnace under an inert atmosphere such as nitrogen or argon. The initial sintering temperature is room temperature, and the heating rate is 15℃ / min-20℃ / min. The higher heating rate allows the binder to volatilize at this stage. The temperature is then raised to 300℃-450℃ at a heating rate of 15℃ / min-20℃ / min and held for 2-4 hours to decompose or carbonize the binder in the spray-dried non-stick particles as much as possible. Then, the temperature is raised to 700℃-900℃ at a heating rate of 55℃ / min-100℃ / min and held for 1-3 hours. The debinding process is monitored in real time using the weight loss method, and debinding is considered complete when the weight remains stable. After debinding, the temperature is slowly raised to 1000℃-1100℃ at a heating rate of 1℃ / min-5℃ / min for high-temperature sintering and held for 2-4 hours to allow the first and second metal compounds to form an inorganic non-metallic compound through metallurgical bonding. After the entire sintering process is completed, the temperature is controlled to be cooled to below 150℃ before the particles are removed from the furnace. It should be noted that the temperature is slowly increased to 1000℃-1100℃ at a heating rate of 1℃ / min-5℃ / min for high-temperature sintering. This relatively low heating rate helps to prevent the non-stick particles from bubbling due to the rapid evaporation of gases inside them.

[0084] In these embodiments, the first and second metal compounds, possessing crystalline structures, can interact during sintering through processes such as diffusion and reaction, thereby altering their original crystalline structures and forming a polycrystalline inorganic non-metallic compound. Furthermore, the particles of adjacent first and second metal compounds interact to interlock at their contact points, resulting in volume shrinkage and the creation of pores between the particles. The final material, a carbonized product containing an inorganic non-metallic compound and a binder, with a certain three-dimensional porous structure, serves as a non-stick material. Additionally, during sintering, the contacting first and second metal compounds interlock at their contact points after sintering to form non-stick particles, ensuring sufficient inter-particle bonding to guarantee the stability of the non-stick particles in subsequent processes.

[0085] In some embodiments, the step of sintering the non-stick particles includes sintering the non-stick particles at a temperature of 75%-85% of the melting point of the non-stick particles, and sintering the non-stick particles at this temperature for 2-4 hours.

[0086] In these embodiments, heating the non-stick particles at a temperature of 75%-85% of their melting point allows the metal compounds in the particles to soften without melting. After softening, the high-temperature energy of sintering accelerates diffusion and promotes homogenization of the composition. This allows the formation of inorganic non-metallic compounds through sintering without excessively affecting the granular structure of the non-stick particles, thereby obtaining a non-stick material with non-stick properties.

[0087] In some embodiments, 90% of the adhesive evaporates, while 10% of the adhesive carbonizes. Specifically, this is defined by the mass ratio of the carbonized product of the adhesive to the inorganic non-metallic compound in the non-stick material. For example, in the non-stick material, the mass ratio of the carbonized product of the adhesive to the inorganic non-metallic compound is (1-3):(97-99). Therefore, the resulting non-stick layer contains both inorganic non-metallic compounds and carbonized products of the adhesive, with the carbonized product of the adhesive adhering to a portion of the surface of the inorganic non-metallic compound particles. Continuing with the example above, in the non-stick layer, the mass ratio of the carbonized product of the adhesive to the inorganic non-metallic compound is (1-3):(97-99).

[0088] In these embodiments, the non-stick material also contains a small amount of carbonized binder products. Since the carbonized binder products are mainly composed of non-polar carbon elements and have a certain degree of oleophilicity, they can further enhance the overall oleophilicity of the non-stick particles, making the non-stick layer formed therefrom easier to fill with oil molecules.

[0089] In this application, when at least one of CaO, Ca(OH)2, and CaCO3, and TiO2 are selected as raw materials, and the atomic ratio of calcium to titanium is set to 2:3-3:2 to manufacture inorganic non-metallic compounds, the resulting inorganic non-metallic compound comprises CaTiO3 with a polycrystalline structure, with CaTiO3 having a polycrystalline structure as the main component. When barium carbonate (BaCO3) and iron(III) oxide (Fe3O4) are selected as raw materials, and the atomic ratio of barium to iron is set to 2:3-3:2, the resulting inorganic non-metallic compound comprises BaFeO3 or BaFe with a polycrystalline structure. 12 O 19 And with BaFeO3 having a polycrystalline structure or BaFe having a polycrystalline structure 12 O 19 The polycrystalline inorganic non-metallic compound obtained by using cesium oxide (Cs₂O) and manganese dioxide (MnO₂) as raw materials, with the atomic ratio of cesium to manganese set to 2:3-3:2, comprises polycrystalline Cs₂MnO₄ or CsMnO₄ as the main phase. Similarly, when lanthanum trioxide (La₂O₃) and manganese dioxide (MnO₂) are selected as raw materials, and the atomic ratio of lanthanum to manganese is set to 2:3-3:2, the polycrystalline inorganic non-metallic compound obtained by using lanthanum trioxide (La₂O₃) and manganese dioxide (MnO₂) as raw materials, comprises polycrystalline La₂(MnO₄)₃ or LaMnO₃ as the main phase. When lanthanum trioxide (La₂O₃) and titanium dioxide (TiO₂) are selected as raw materials, and the atomic ratio of lanthanum to titanium is set to 2:3-3:2, the resulting inorganic non-metallic compound with a polycrystalline structure includes either LaTiO₃ or La₂Ti₂O₇, with LaTiO₃ or La₂Ti₂O₇ as the main component. Similarly, when yttrium trioxide (Y₂O₃) and titanium dioxide (TiO₂) are selected as raw materials, and the atomic ratio of yttrium to titanium is set to 2:3-3:2, the resulting inorganic non-metallic compound with a polycrystalline structure includes either YTiO₃ or Y₂Ti₂O₇, with YTiO₃ or Y₂Ti₂O₇ as the main component. It should be noted that when the atomic ratio of the two raw materials is not 1:1, it means that one of the two raw materials is in excess. Although it may be in excess, it will not excessively affect the non-stickiness of inorganic non-metallic compounds, which are mainly composed of polycrystalline structures.

[0090] Figure 1 and Figure 2 These are SEM images of non-stick materials provided according to embodiments of this application; Figure 3 and Figure 4 This is an SEM image of a cross-section of a non-stick material provided according to an embodiment of this application. (Refer to...) Figures 1 to 4 It can be seen that inorganic non-metallic compounds have obvious porous structures, and the pores in the three-dimensional porous structure are generally uniformly distributed.

[0091] According to this application, the non-stick particles after spray drying have pores inside or between the particles, allowing gas or liquid to pass through. Furthermore, the pores in the three-dimensional pore structure of the non-stick particles formed by spray drying in this application are mostly open or interconnected pores (i.e., through-cells), with a few being closed pores. This ensures the oil storage capacity of the formed non-stick layer. For example, the volume ratio of through-cells is approximately 80%-90%, with the remainder being closed pores. When using this non-stick material to form a non-stick layer through spraying, the three-dimensional pore structure of the non-stick particles can be preserved as much as possible in the non-stick layer, thus forming a non-stick layer with a three-dimensional pore structure. The pores of the three-dimensional pore structure of the non-stick layer match oil molecules, easily adsorbing oil molecules and locking them with a certain adhesion force, allowing the oil molecules to be released slowly. Therefore, it can exhibit excellent non-stick performance due to the oil film non-stick principle.

[0092] According to this application, during the sintering stage, the metal elements in the non-stick particles can diffuse and recombine at high temperatures to form a polycrystalline inorganic non-metallic compound with a perovskite structure (ABO3 type).

[0093] Continuing with the example above, the first metal compound is at least one of strontium oxide, strontium carbonate, and cesium hydroxide, and the second metal compound is titanium oxide. Both strontium carbonate and cesium hydroxide will decompose upon heating to form strontium oxide. Then, as the temperature rises, the mixture of strontium oxide and titanium oxide will completely soften and, through diffusion and coordination recombination, form an inorganic non-metallic compound with an ABO3 perovskite structure.

[0094] In a preferred embodiment, the alkaline earth metal compound is calcium oxide, and the transition metal compound is titanium dioxide. Titanium and calcium are non-toxic and harmless metals and can form stable, insoluble compounds. Calcium atoms have a relatively large radius of 0.197 nanometers, which is just enough to occupy a cubic cavity formed by eight oxygen octahedrons (six oxygen atoms forming one oxygen octahedron). Titanium atoms have a relatively smaller radius of 0.147 nanometers, which is just enough to occupy the center of an oxygen octahedron formed by six oxygen atoms. Oxygen atoms have an even smaller radius of 0.074 nanometers; six oxygen atoms forming one oxygen octahedron can accommodate one titanium atom, thus forming an inorganic non-metallic compound with a perovskite structure.

[0095] In some embodiments, the step of sintering non-stick particles can be carried out under an inert atmosphere (such as argon) to avoid the oxidation of metal elements interfering with the reaction.

[0096] cool down According to this application, the method for manufacturing cookware further includes performing a cooling process on an inorganic non-metallic compound obtained by coordination and recombination of internal metal elements, thereby obtaining an inorganic non-metallic compound having a perovskite-type structure and a polycrystalline structure as a non-stick material.

[0097] In some embodiments, the cooling rate of the cooling process is controlled between 10°C / min and 20°C / min. By controlling the cooling rate, the size of the grains can be effectively controlled to obtain a polycrystalline structure with micron- and nano-sized grains.

[0098] In other embodiments, the cooling process is annealing. Annealing prevents abnormal grain growth, resulting in a fine, uniform grain structure, which helps improve the hardness, toughness, and wear resistance of the non-stick material, while eliminating internal stress. Furthermore, annealing eliminates high-temperature atomic diffusion component segregation, making the material composition more uniform, thereby improving the consistency and stability of the bulk non-stick material.

[0099] As a specific example, the annealing process is a multi-stage annealing process, including a first stage and a second stage. In the first stage, the temperature is lowered to 1100℃-1300℃ and held for 0.5h-2h. In the second stage, the temperature is further lowered to 700℃-900℃ and held for 5h-15h, and then cooled to room temperature.

[0100] In these embodiments, the first-stage high-temperature holding process provides energy for grain nucleation and prevents abnormally rapid grain growth and excessive grain coarsening, thus laying the foundation for the formation of fine and uniform grain (fine-grained) structures. The second-stage low-temperature holding process promotes the formation and stabilization of fine grains. In this embodiment, the synergistic effect of high-temperature nucleation and low-temperature inhibition overcomes the grain coarsening limit of a single annealing process, thereby improving the grain refinement of the polycrystalline structure of the non-stick material.

[0101] Particulate inorganic nonmetallic compounds were prepared. According to this application, the cooling process yields a particulate non-stick material. In some embodiments of this application, the method for preparing the non-stick material further includes sieving the non-stick material to obtain a non-stick material with a desired particle size. This allows for the preparation of a non-stick layer with a three-dimensional porous structure capable of storing oil by adjusting the particle size of the non-stick material.

[0102] In other embodiments, the non-stick material has multiple particle size ranges. For example, a D10 value greater than 10 μm is selected (to limit the content of fine powder), a D50 value controlled within the range of 30 μm-45 μm (the main control range), and a D90 value less than 70 μm (to control the upper limit of coarse powder). Such a particle size distribution can further optimize the three-dimensional pore structure of the non-stick layer.

[0103] According to a second aspect of this application, another method for preparing a non-stick material for cookware or cups is provided, wherein the method for preparing the non-stick material includes mixing a first metal compound having a crystalline structure and a second metal compound having a crystalline structure to obtain a mixture, wherein the first metal compound includes a rare earth metal compound and / or an alkaline earth metal compound, and the second metal compound includes a transition metal compound; heating the mixture to melt it, causing the first metal compound and the second metal compound to react with each other; and performing a cooling process to obtain a non-stick material mainly composed of an inorganic non-metallic compound having a polycrystalline structure.

[0104] According to the method for preparing non-stick materials in this application, by pre-mixing various metal compounds, effective contact between the various metal compounds in the mixture can be ensured, thereby improving the contact reliability of each atom of the first metal compound and the second metal compound during the melting process. This allows the first metal compound and the second metal compound, which have crystalline structures, to react synergistically after melting due to material properties (e.g., internal atomic radius) to form an inorganic non-metallic compound with a polycrystalline structure. Subsequently, a cooling process promotes the uniform nucleation of the polycrystalline structure, thereby forming an inorganic non-metallic compound with a polycrystalline structure as a non-stick material. Compared with the same material having a crystalline structure, during the melting process, the ions of the first metal compound and the second metal compound can migrate from high-energy positions (e.g., surface, defects) to low-energy positions (grain boundaries, intragranular areas), thereby reducing surface energy and achieving non-stick properties. In addition, compared with the same material having an amorphous structure (completely disordered atomic arrangement, lacking long-range periodic structure) or a crystalline structure, having a polycrystalline structure can ensure the impact resistance and toughness of inorganic non-metallic compounds, making the non-stick layer formed by the non-stick material less likely to peel off locally or entirely when subjected to external forces (such as scraping with a spatula or dropping), thereby greatly improving the long-lasting non-stick properties of cookware with a non-stick layer.

[0105] The following will describe in detail, with reference to specific embodiments, a method for manufacturing the non-stick material according to this application.

[0106] Forming a mixture According to this application, a mixture is obtained by mixing a first metal compound having a crystal structure and a second metal compound having a crystal structure using a mixing method such as mechanical mixing.

[0107] Forming a mixed molten liquid and melting According to this application, a mixture is heated to form a mixed melt, and then smelted to allow the ions in the mixed melt to react, resulting in a liquid inorganic non-metallic compound. A cooling process is then performed on the liquid inorganic non-metallic compound to crystallize it into a polycrystalline structure, thereby obtaining a non-stick material. By forming a mixed melt from the mixture and then smelting it, compared to a solid-solid reaction, the individual metal ions exhibit good contact, eliminating the diffusion limitations of solid-phase reactions and allowing the ions in the mixed melt to fully react, resulting in a liquid inorganic non-metallic compound. In an exemplary embodiment, the specific steps include: heating the mixture to form a mixed melt containing corresponding metal cations and anions; providing reaction energy through high-temperature smelting to allow the ions in the mixed melt to react, thereby forming a liquid inorganic non-metallic compound. After smelting, a cooling process is performed on the liquid inorganic non-metallic compound to crystallize it into a polycrystalline inorganic non-metallic compound including a perovskite-type structure, which serves as the non-stick material.

[0108] In some embodiments, the step of forming a mixed melt and melting the mixture includes bringing the mixture to a molten state at a temperature not lower than the melting point of the mixture and performing high-temperature melting. In a preferred embodiment, the step of forming a mixed melt and melting the mixed melt includes: heating the mixture to a temperature 30°C-100°C higher than the melting point of the highest melting point metal compound in the mixture, and melting the mixed melt at that temperature for 3-6 hours.

[0109] In these embodiments, heating the mixture with the melting point of the metal compound with the highest melting point in the mixture allows the mixture to melt fully. After melting, the high-temperature energy of smelting accelerates the diffusion of various ions in the molten mixture, promotes homogenization of the composition, and forms a liquid inorganic non-metallic compound. This also reduces the possibility of impurity phases forming due to component segregation, thereby avoiding the influence of impurity phases on the surface energy of the non-stick material and ensuring the non-stick properties of the non-stick layer formed by the non-stick material and the non-stick uniformity of each region.

[0110] According to this application, during the smelting stage, ions in the mixed molten liquid diffuse and recombine at high temperatures to form a polycrystalline inorganic non-metallic compound with a perovskite structure (ABO3 type). Continuing the example above, the first metal compound is at least one of strontium oxide, strontium carbonate, and cesium hydroxide, and the second metal compound is titanium oxide. Both strontium carbonate and cesium hydroxide decompose upon heating to form strontium oxide. Then, with increasing temperature, the mixture of strontium oxide and titanium oxide completely melts to form a mixed molten liquid. At this point, the chemical bonds in the raw materials break, and metal cations (such as A-site: Sr) move freely in the mixed molten liquid.2+ B position: Ti 4+ ) and anions (such as O) 2- It exists in the form of ) In the mixed molten liquid (molten state), ions diffuse and coordinate recombine to form new chemical structures. Specifically, ions migrate rapidly through Brownian motion, and A-site cations (such as Sr) exist in this form. 2+ ) and B-site cations (such as Ti) 4+ Competition and O 2- Coordination forms a BO6 octahedron (with the B-site ion at its center and six O atoms). 2- It forms a three-dimensional network structure with vertices and a transitional structure in which A-site ions fill the interstices of the octahedrons, and finally stabilizes after cooling to form an inorganic non-metallic compound with an ABO3 perovskite structure.

[0111] In a preferred embodiment, the alkaline earth metal compound is calcium oxide, and the transition metal compound is titanium dioxide. Titanium and calcium are non-toxic and harmless metals and can form stable, insoluble compounds. Calcium atoms have a relatively large radius of 0.197 nanometers, which is just enough to occupy a cubic cavity formed by eight oxygen octahedrons (six oxygen atoms forming one oxygen octahedron). Titanium atoms have a relatively smaller radius of 0.147 nanometers, which is just enough to occupy the center of an oxygen octahedron formed by six oxygen atoms. Oxygen atoms have an even smaller radius of 0.074 nanometers; six oxygen atoms forming one oxygen octahedron can accommodate one titanium atom, thus forming an inorganic non-metallic compound with a perovskite structure.

[0112] In some embodiments, stirring or other methods can be used to accelerate the uniform distribution of cations and anions in the mixed molten liquid, eliminate local concentration gradients, and provide a homogeneous environment for subsequent reactions. Furthermore, the melting and smelting steps of the mixed molten liquid can be carried out under an inert atmosphere (such as argon) to avoid interference from metal ion oxidation.

[0113] cool down According to this application, the method for preparing non-stick materials further includes performing a cooling process on an inorganic non-metallic compound that is in a liquid state after coordination and recombination of internal metal ions, thereby obtaining an inorganic non-metallic compound with a perovskite-type structure and a polycrystalline structure as a non-stick material.

[0114] In some embodiments, the cooling rate of the cooling process is controlled between 10°C / min and 20°C / min. By controlling the cooling rate, the size of the grains can be effectively controlled to obtain a polycrystalline structure with micron- and nano-sized grains.

[0115] In other embodiments, the cooling process is annealing. Annealing prevents abnormal grain growth, resulting in a fine, uniform grain structure, which helps improve the hardness, toughness, and wear resistance of the non-stick material, while eliminating internal stress. Furthermore, annealing eliminates high-temperature atomic diffusion component segregation, making the material composition more uniform, thereby improving the consistency and stability of the bulk non-stick material.

[0116] As a specific example, the annealing process is a multi-stage annealing process, including a first stage and a second stage. In the first stage, the temperature is lowered to 1100℃-1300℃ and held for 0.5h-2h. In the second stage, the temperature is further lowered to 700℃-900℃ and held for 5h-15h, and then cooled to room temperature.

[0117] In these embodiments, the first-stage high-temperature holding process provides energy for grain nucleation and prevents abnormally rapid grain growth and excessive grain coarsening, thus laying the foundation for the formation of fine and uniform grain (fine-grained) structures. The second-stage low-temperature holding process promotes the formation and stabilization of fine grains. In this embodiment, the synergistic effect of high-temperature nucleation and low-temperature inhibition overcomes the grain coarsening limit of a single annealing process, thereby improving the grain refinement of the polycrystalline structure of the non-stick material.

[0118] To obtain a non-stick material in bulk According to this application, the cooling process yields a non-stick material in block form, such as a columnar or square block. This application does not specifically limit the shape of this material. It should be noted that the non-stick material has a large size that is macroscopic and unsuitable for coating. For example, the block-shaped non-stick material may be columnar, with a diameter of 1-2 meters and a height of 1-2 meters.

[0119] Non-stick materials for crushed blocks According to this application, non-stick materials in block form can be crushed to obtain non-stick materials suitable for coating or for manufacturing target materials. Specifically, a jaw crusher is used to crush the material into small pieces, which are then ground to a suitable particle size using a Raymond mill, ball mill, or similar equipment.

[0120] In some embodiments, the non-stick material exhibits an irregular structure, where an irregular structure refers to a structure lacking uniformity in shape and size. As a specific example, an irregular structure can be obtained by breaking up a block-shaped non-stick material; in this case, it can be called an "irregularly broken structure."

[0121] In these embodiments, the non-stick material exhibits an irregular morphology. This irregular structure facilitates the formation of a micron- to nanometer-scale composite surface texture on the non-stick layer, thereby further optimizing the long-lasting non-stick performance through the lotus leaf effect. Furthermore, the fractured structure corresponds to the splitting at grain boundaries in the polycrystalline material. The disordered atomic arrangement at these grain boundaries results in a higher energy state, making it easier for them to adsorb or react with fatty acids in cooking oils, forming a low-surface-energy fatty acid salt layer. This further enhances the non-stick performance of the non-stick layer formed from the non-stick material. Moreover, the irregular structure of the non-stick material facilitates anchoring and bonding with the substrate surface during non-stick layer formation, thereby further improving the adhesion between the substrate and the non-stick layer and preventing delamination due to corrosion, impact, or other factors.

[0122] In this application, the non-stick material obtained after pulverization can be used as the material for forming the non-stick layer of cookware or cups. Alternatively, the pulverized non-stick material can be processed to a certain extent. For example, the pulverized particles can be made into a target material so that the non-stick material can be suitable for the physical vapor deposition process to form a layer.

[0123] In some embodiments of this application, the method for manufacturing non-stick materials further includes sieving the crushed non-stick materials to obtain non-stick materials with a D50 value controlled in the range of 30μm~45μm, which can, to a certain extent, ensure that the non-stick layer formed by the non-stick materials has a three-dimensional porous structure for oil storage.

[0124] In a preferred embodiment, a D10 value greater than 10 μm is selected (to limit the content of fine powder), a D50 value controlled within the range of 30 μm to 45 μm (the main control range), and a D90 value less than 70 μm (to control the upper limit of coarse powder). Such a particle size distribution can further optimize the three-dimensional pore structure of the non-stick layer.

[0125] Target material According to this application, the method for preparing non-stick materials further includes: crushing block-shaped non-stick materials and pressing them into initial targets; sintering and pressing the initial targets under a protective atmosphere to obtain non-stick materials used as targets.

[0126] In these embodiments, the initial target material can shrink under the successive effects of pressing pressure and sintering temperature, reducing the porosity of the non-stick material used as the target material, achieving high densification of the non-stick material used as the target material, and improving the bonding strength of the non-stick material used as the target material. This can prevent the non-stick material used as the target material from cracking during sputtering, thus meeting the actual requirements of physical vapor deposition processes.

[0127] In an exemplary embodiment, the sintering temperature is 0.7 to 0.9 times the melting point of the initial target material. This temperature ensures that the grains of the initial target material do not grow excessively while achieving densification of the initial target material to obtain a non-stick material for use as a target material.

[0128] In an exemplary embodiment, the pressure applied during pressing is 3-4 MPa, thereby enabling the initial target material to be formed into the desired shape, such as a cylinder or a plate.

[0129] In some embodiments, the initial target material melting step can be carried out under a protective atmosphere to ensure the chemical purity of the final target material.

[0130] According to a third aspect of this application, a non-stick material is provided, wherein the non-stick material is used in cookware.

[0131] In the embodiments, the non-stick material comprises an inorganic non-metallic compound having a polycrystalline structure, wherein the metal element in the inorganic non-metallic compound comprises a first metal element and a second metal element, wherein the first metal element comprises rare earth metal elements and / or alkaline earth metal elements, and the second metal element comprises transition metal elements.

[0132] In these embodiments, compared to the same material with an amorphous structure (completely disordered atomic arrangement, lacking long-range periodic structure), inorganic non-metallic compounds with a polycrystalline structure are composed of multiple randomly oriented grains. The atomic arrangement inside each grain is long-range ordered. The inconsistent arrangement directions between grains cause the interior of the inorganic non-metallic compound to exhibit disorder, thereby reducing surface energy and achieving initial non-stickiness. In addition, compared to the same material with an amorphous structure, the polycrystalline structure can ensure the impact toughness of the inorganic non-metallic compound, making the non-stick layer of the non-stick material less prone to partial or overall peeling when subjected to external forces (such as scraping with a spatula or dropping), thus greatly improving the long-lasting non-stickiness of the non-stick layer.

[0133] In the embodiments, some inorganic non-metallic compounds (e.g., oxide-containing types) possess a calcium titanate-type structure, which can synergistically enhance the hardness, wear resistance, and thermal stability of the material through polycrystalline structures, thereby further improving the long-lasting non-stick performance of the non-stick layer formed by the non-stick material. Here, the inorganic non-metallic compound possesses a polycrystalline structure, which emphasizes the characteristics of the grain dimension, i.e., the material is composed of a large number of randomly oriented small grains (single crystals) at the microscopic level, with grain boundaries existing between the grains. The emphasis on the grain dimension of the polycrystalline structure is relative to the single crystal (perfect lattice) at the microscopic level, and is independent of chemical composition or crystal type. The perovskite-type structure refers to the atomic arrangement structure within a single unit cell, emphasizing the arrangement of atoms / ions, such as cubic, orthorhombic, or tetragonal crystal systems. Its core feature is that B-site ions are surrounded by octahedrons formed by C-site ions, and A-site ions fill the interstices of the octahedrons. Because inorganic non-metallic compounds possess both polycrystalline and calcium titanate-type structures, these two structures can work synergistically to further enhance the material's hardness, wear resistance, and thermal stability. This improved material performance, in turn, strengthens the long-lasting non-stick properties of the non-stick layer formed from the non-stick material.

[0134] In existing technologies, high-hardness materials are usually accompanied by high brittleness, and the layers they form are relatively brittle, making them prone to cracking during use.

[0135] In some embodiments of this application, the inorganic non-metallic compound layer has high hardness. As an example, the inorganic non-metallic compound layer is an oxide-containing layer with the general formula A. x B y C z Where A is an alkaline earth metal element, B is titanium, a transition metal element, and C is oxygen, and 2x+2y=2z, 2x+3y=2z, or 2x+4y=2z; or, the inorganic non-metallic compound layer is an oxide layer, and the general formula is A x B y C z Where A is an alkaline earth metal element, B is iron or cobalt from the transition metal elements, and C is oxygen, and 2x + 3y = 2z or 2x + 2y = 2z; or, the inorganic non-metallic compound layer is an oxide layer, and the general formula is A x B y C z Where A is an alkaline earth metal element, B is manganese (a transition metal element), and C is oxygen, and 2x+2y=2z, 2x+4y=2z, 2x+6y=2z, or 2x+7y=2z; or, the inorganic nonmetallic compound layer is an oxide layer, and the general formula is A x B y C zWhere A is a rare earth metal element, B is titanium (a transition metal element), and C is oxygen, and 3x+2y=2z, 3x+3y=2z, or 3x+4y=2z; or, the inorganic non-metallic compound layer is an oxide layer, and the general formula is A x B y C z Where A is a rare earth metal element, B is iron or cobalt from the transition metal elements, and C is oxygen, and 3x + 3y = 2z or 3x + 2y = 2z; or, the inorganic non-metallic compound layer is an oxide layer, and the general formula is A x B y C z Where A is a rare earth metal element, B is manganese (a transition metal element), and C is oxygen, and 3x+2y=2z, 3x+4y=2z, 3x+6y=2z, or 3x+7y=2z; or, the inorganic non-metallic compound layer is a halide layer, and the general formula is A x B y C z Where A is an alkaline earth metal element, B is titanium, a transition metal element, and C is a halogen element, wherein 2x+2y=z, 2x+3y=z, or 2x+4y=z; or, the inorganic non-metallic compound layer is a halide layer, and the general formula is A x B y C z Where A is an alkaline earth metal element, B is iron or cobalt from the transition metal elements, and C is a halogen element, where 2x + 3y = z or 2x + 2y = z; or, the inorganic nonmetallic compound layer is a halide layer, and the general formula is A x B y C z Where A is an alkaline earth metal element, B is manganese (a transition metal element), and C is a halogen element, wherein 2x+2y=z, 2x+4y=z, 2x+6y=z, or 2x+7y=z; or, the inorganic nonmetallic compound layer is a halide layer, and the general formula is A x B y C z Where A is a rare earth metal element, B is titanium, a transition metal element, and C is a halogen element, and 3x+2y=z, 3x+3y=z, or 3x+4y=z; or, the inorganic non-metallic compound layer is a halide layer, and the general formula is A x B y C z Where A is a rare earth metal element, B is iron or cobalt from the transition metal elements, and C is a halogen element, where 3x + 3y = z or 3x + 2y = z; or, the inorganic non-metallic compound layer is a halide layer, and the general formula is A x B y C zWhere A is a rare earth metal element, B is manganese (a transition metal element), and C is a halogen element, and 3x+2y=z, 3x+4y=z, 3x+6y=z, or 3x+7y=z; or, the inorganic non-metallic compound layer is an oxide layer with the general formula Al. x1 A2 x2 B y C z Where A1 includes alkaline earth metals, A2 includes rare earth metals, B includes transition metals, and C is oxygen. x1 +3 x2 +3y=2z or 2 x1 +3 x2 +4y=2z; or, the inorganic non-metallic compound layer is an oxide-containing layer with the general formula A1. x1 A2 x2 B y C z Where A1 includes alkaline earth metals, A2 includes rare earth metals, B includes transition metals, and C is a halogen. x1 +3 x2 +3y=z or 2 x1 +3 x2 +4y=z.

[0136] In these embodiments, the inorganic non-metallic compounds composed of the above elements have an oxygen / halide perovskite structure, which gives the non-stick material good thermal stability, high hardness and wear resistance. The numerous grain boundaries in the polycrystalline structure can effectively passivate cracks and disperse stress, and have good toughness. Its synergistic effect with the perovskite structure can make up for the defect of non-stick materials being prone to brittleness due to increased hardness, so that the non-stick layer formed by the non-stick material has improved wear resistance, crack resistance and thermal stability.

[0137] As an example, inorganic non-metallic compounds have a hardness close to that of ceramics, making them scratch-resistant and wear-resistant. For example, the Vickers hardness of inorganic non-metallic compounds is 400HV-600HV. Such hardness can improve the wear resistance of the non-stick layer formed by the non-stick material, making it less prone to damage, thereby indirectly improving the long-lasting non-stick performance of the non-stick layer.

[0138] In some embodiments, the alkaline earth metal element includes at least one of calcium, strontium, and barium; the transition metal element includes at least one of titanium, manganese, iron, and cobalt; the halogen includes iodine or chlorine; and the rare earth metal element includes at least one of lanthanum, neodymium, and yttrium.

[0139] In these embodiments, the non-stick material composed of the above-mentioned elements can combine the advantages of food safety, process feasibility, and chemical stability.

[0140] The non-stick material according to this application is mainly composed of an inorganic non-metallic compound with a polycrystalline structure. In addition to the aforementioned components, the non-stick material may inevitably contain impurities or other phases. It should be noted that, following the preparation method of the non-stick material, the inorganic non-metallic compound with a polycrystalline structure may include not only the polycrystalline portion but also unreacted first or second metal compounds with a crystalline structure and a small amount of glass phase. Thus, the inorganic non-metallic compound constituting a multi-component synergistic system with a polycrystalline structure serves as the main body of the non-stick material of this application, possessing low surface energy and good toughness, thereby exhibiting durable non-stick properties.

[0141] In these embodiments, the main component is an inorganic non-metallic compound with a polycrystalline structure. This polycrystalline structure consists of numerous micron- and / or nano-sized grains with clear grain boundaries and random grain orientation, forming an isotropic structure that meets the cookware's requirements for both initial and long-lasting non-stick properties. Furthermore, in the polycrystalline structure, the irregular atomic arrangement on the grain surface creates a micro- to nano-rough surface in the non-stick layer, further enhancing non-stick properties through a "lotus leaf effect."

[0142] According to some embodiments of this application, the non-stick material is granular, and the granular non-stick material is suitable for a process of forming a granular layer, wherein the process of forming the granular layer can be a spraying process. In these processes, the granules of the non-stick material are heated to a state where only the surface is molten (the surface is slightly melted and the interior is not melted) and then sprayed onto the cookware substrate, retaining the polycrystalline structure in the inorganic non-metallic compound to form a non-stick layer. Alternatively, a plasma arc or similar high-energy heat source is used to simultaneously melt the granules of the non-stick material and a thin layer on the substrate surface. After rapid solidification, a metallurgical bonding layer is formed on the substrate as a non-stick layer. It should be noted that in the process of forming a non-stick layer using a non-stick material, even if the surface of the inorganic non-metallic compound in the non-stick material is completely melted, it will be cooled after melting and recrystallized to form a polycrystalline structure, similar to how plastic can be repeatedly melted and melted. Since the main influencing factor of the polycrystalline structure is the difference in the radii of the atoms in the raw material, even if the surface of the inorganic non-metallic compound is completely melted and recrystallized, the polycrystalline structure in the area will not be excessively damaged. According to other embodiments of this application, the non-stick material is formed as a target or used as a target, and the non-stick material used as a target is suitable for deposition processes, such as physical vapor deposition.

[0143] In some embodiments, the polycrystalline structure of the inorganic nonmetallic compound includes micron- and / or nano-sized grains. The grain size is refined to the micron or nanometer level. Smaller grain sizes (fine grains) can directly and significantly increase the number of grain boundaries. Grain boundaries are regions with disordered atomic arrangement and dense defects, and their energy state is higher than that of the grain interior. When the non-stick material has micron- and nano-sized grains, grain boundary regions dominate the formation of the non-stick material. From a thermodynamic perspective, this leads to a significant reduction in the overall surface energy of the non-stick material, thereby achieving the goal of improving the non-stick properties of the non-stick layer.

[0144] In addition, during the process of forming a non-stick layer using non-stick materials mainly composed of inorganic non-metallic compounds with polycrystalline structures, the micro- and nano-scale grains of the inorganic non-metallic compounds randomly accumulate to form a micro- and nano-scale uneven structure on the surface of the non-stick layer. This greatly reduces the actual contact area between the food and the surface of the non-stick layer, increases the contact angle, and generates a superhydrophobic / oleophobic "lotus leaf effect" to further enhance the physical non-stick effect.

[0145] Furthermore, the numerous grain boundaries in the micro- and nano-scale grain structures of inorganic non-metallic compounds serve as an effective barrier to inhibit crack propagation in the non-stick layer. Specifically, when the non-stick layer is subjected to external impact, cracks will deflect, branch, or be pinned when they encounter grain boundaries during propagation, requiring more energy to continue propagating. This enhances the toughness of the non-stick layer and effectively prevents it from fracturing or peeling off due to brittleness.

[0146] In some embodiments, the inorganic non-metallic compound grains contain subgrains. The presence of subgrains results in a certain number of subgrain boundaries within the grains. Subgrain boundaries are also high-energy regions with irregular atomic arrangements, which can further increase the interface density within the inorganic non-metallic compound and further reduce the overall surface energy of the inorganic non-metallic compound, thereby further improving the non-stick properties. In addition, subgrain boundaries can also work synergistically with grain boundaries to greatly enhance the crack propagation resistance (fracture toughness) of the non-stick layer, thereby further preventing the non-stick layer from cracking or peeling off due to brittleness.

[0147] In some embodiments, at least a portion of the grains of the inorganic nonmetallic compound possesses a layered structure. This layered structure leads to high-density stacking faults and lattice distortion within the inorganic nonmetallic compound, increasing the energy state within the grains and promoting the formation of polycrystalline structures. Furthermore, the layered structure can also synergize with grain boundaries and subgrain boundaries to further prevent the non-adhesive layer from cracking or peeling due to brittleness.

[0148] Figure 5 Based on the XRD pattern of the non-stick material provided in the embodiments of this application, combined with Figure 5It can be seen that its peak is a discrete broadened peak with sharp and broadened diffraction peaks, which is completely different from the (bun peak, no sharp peak and continuous broadening) of amorphous materials, indicating that the non-stick material has a crystalline structure and is not an amorphous structure.

[0149] In addition, in the embodiments of this application, the peak half-width (HWHM) is greater than 0.2°, which shows that the non-stick material of this application is not a single crystal structure, but has polycrystalline (subcrystalline or fine-grained) characteristics.

[0150] It can be seen that its peak has a broadening phenomenon, and the peak half-width (half-peak width) is greater than 0.2°. Therefore, it can be seen that the non-stick material of this application has polycrystalline (subcrystalline or fine-grained) characteristics.

[0151] In some embodiments, the inorganic non-metallic compound also contains carbonized products of a binder, which are derived from the carbonization of the binder in the mixed slurry. These carbonized products of the binder are used to connect the first metal compound and the second metal compound before carbonization, ensuring the bonding force within each particle of the raw material, so as to ensure the bonding stability of the particles of the sintered inorganic non-metallic compound.

[0152] Specifically, the carbonization products of the adhesive are oleophilic carbonization products. This ensures the oleophilicity of the non-stick layer formed by the non-stick material during subsequent use, which is beneficial for locking in oil molecules. As a result, the non-stick performance of the non-stick layer can be further improved due to the principle of oil film non-stick.

[0153] In some embodiments, the mass ratio of the carbonized product of the binder to the inorganic non-metallic compound in the non-stick material is (1-3):(97-99). Having a suitable mass ratio of carbonized product of the binder to the inorganic non-metallic compound avoids excessive carbonized product of the binder from affecting the overall strength of the non-stick material.

[0154] In some embodiments, the non-stick material is granular with a three-dimensional porous structure. The porosity of individual particles of the non-stick material is 25%-55%, and the pore size is 500 nanometers-4 micrometers. The pores are interconnected and naturally packed together in an irregular arrangement to form a three-dimensional porous structure, which facilitates the formation of a non-stick layer with three-dimensional pores.

[0155] In these embodiments, an inorganic non-metallic compound with a three-dimensional porous structure is used as a non-stick material. It can form a non-stick layer with a three-dimensional porous structure through particle stacking. In this way, it can effectively adsorb and store edible oil, thereby further enhancing the non-stick performance of products with this non-stick layer.

[0156] In some embodiments, the median particle size D50 of the non-stick material is 30μm-45μm, the D10 value is greater than 10μm (limiting the lower limit of fine powder), and the D90 value is less than 70μm (controlling the upper limit of coarse powder). In this way, on the one hand, a non-stick layer with a suitable pore structure can be formed by the non-stick material with this particle size, which is conducive to oil storage and improves non-stickiness; on the other hand, the granulated powder particles themselves have a large specific surface area, which can ensure the bonding force between the non-stick layer and the matrix.

[0157] According to a fourth aspect of this application, a method for manufacturing a non-stick layer is provided. The method includes the preparation method of the aforementioned non-stick material, and the step of spraying the non-stick material onto a substrate to form an inorganic non-metallic compound layer with a polycrystalline structure, which serves as the non-stick layer. The non-stick material is either the non-stick material prepared using the aforementioned non-stick material method or the non-stick material described above. In embodiments, the non-stick material can retain its polycrystalline structure or further crystallize into a polycrystalline structure during the layer formation process, thereby obtaining an inorganic non-metallic compound with a polycrystalline structure as the main body or all of the non-stick layer. It should be noted that during the process of forming a non-stick layer using the non-stick material, even if the surface of the non-stick material is completely melted, it will cool and crystallize to form a polycrystalline structure, similar to how plastic can be repeatedly melted and remelted. Since the main influencing factor of the polycrystalline structure is the difference in the radii of the atoms in the raw material, even if the surface of the non-stick material is completely melted and recrystallized, the polycrystalline structure in the affected area will not be excessively damaged.

[0158] In some embodiments, the process for forming the layer includes a process for forming a particle layer, and the various aspects will be described in detail below.

[0159] According to this application, the process for forming a particulate layer specifically includes the steps of using a particulate non-stick material and forming a non-stick layer by plasma spraying. In an exemplary embodiment, the plasma spraying current is 350A-500A, the voltage is 50V-70V, the main gas flow rate is 1000L / h-2000L / h, the hydrogen flow rate is 200L / h-300L / h, the gun distance is 150mm-200mm, and the workpiece linear speed is 25m / min-35m / min.

[0160] In some embodiments, the thickness of the non-stick layer formed by the particulate non-stick material is 40 micrometers to 100 micrometers. Such a thickness enables the non-stick layer to have multiple performance advantages, such as good durable non-stick properties, bonding performance, and internal stress of the non-stick layer.

[0161] In some embodiments, the non-stick layer formed by plasma spraying is relatively loose and porous, possessing high porosity and large pore size. For example, the non-stick layer has a porosity of 3-5% and a pore size of 1-3 micrometers. Such a large pore size and porosity allow the non-stick layer to function as an oil-retaining structure for cookware, creating an oil film layer on the product's surface, thereby further enhancing the durable non-stick performance of the cookware's non-stick layer.

[0162] According to a fifth aspect of this application, a non-stick layer is provided, wherein the non-stick layer is used in cookware or cups, is formed of a non-stick material, and retains or reforms properties similar to those of the non-stick material, such as elemental composition, polycrystalline structure, perovskite structure, etc.

[0163] Figures 6 to 8 These are SIM photographs taken at different magnifications of the same location of the non-stick layer formed by the non-stick material according to the embodiments of this application. Figure 9 This is a SIM photograph of another location of the non-stick layer formed by the non-stick material according to an embodiment of this application. (Combined with...) Figures 6 to 9 It can be seen that the non-stick layer has a polycrystalline structure, from Figure 9 It can also be seen that the non-stick layer has subgrain boundaries.

[0164] In some embodiments, the non-stick layer comprises an inorganic non-metallic compound layer having a polycrystalline structure, wherein carbonized products of the binder are dispersed in the inorganic non-metallic compound layer.

[0165] In these embodiments, carbonized products of the binder are dispersed in the inorganic non-metallic compound. On the one hand, the presence of carbonized products of the binder facilitates the connection of each particle of the inorganic non-metallic compound, ensuring the bonding force within each particle of the non-stick material. On the other hand, using the carbonized products of the binder as a connecting bridge between each particle of the matrix enables the non-stick material to exhibit high overall hardness and stability.

[0166] In some embodiments, in the non-adhesive layer, the mass ratio of the carbonization product of the adhesive to the inorganic non-metallic compound is (1-3):(97-99).

[0167] According to this application, the non-stick material is a porous granulated powder, and the non-stick layer formed by this non-stick material has a three-dimensional porous structure because it retains the pores. As an example, the porosity of the non-stick layer is 3%-5%, and the pore size is 100 nanometers-3 micrometers, preferably 800 nanometers-2 micrometers. This porous structure ensures the non-stick performance of cookware with the non-stick layer due to the stable release of the oil film.

[0168] According to a sixth aspect of this application, a method for manufacturing a non-stick cookware is provided. The method includes providing a non-stick material and a cookware substrate, and spraying an inorganic non-metallic compound with a polycrystalline structure onto the cookware substrate as a non-stick material to form a non-stick layer with a polycrystalline structure, thereby manufacturing the cookware.

[0169] The following describes a method for manufacturing a cooker according to an embodiment of this application, with reference to specific embodiments.

[0170] Provide matrix According to this application, the substrate 110 can be made of commonly used materials. Exemplarily, the material can be stainless steel, titanium, aluminum, their corresponding alloys, and composite materials. As an example, stainless steel or multilayer stainless steel composite sheets can be used, which are deep-drawn into a pot bottom with a planar structure and an annular wall structure. The planar structure of the pot bottom is beneficial for stability when placed on a countertop and is suitable for use on an induction cooker.

[0171] In some embodiments, the substrate 110 may have a shape corresponding to its function, for example, such as Figure 10 As shown, when the cookware 100 is a non-stick pan, the base 110 can have a conventional pan shape. It should be understood that... Figure 10 The nonstick pan is shown only as an example of the main body and other parts are not shown. The nonstick pan according to the present invention may also include common cookware structures / components such as handles (e.g., pot handles).

[0172] In some embodiments, the inner surface of the substrate has a rough structure, which can be obtained by sanding the inner surface of the substrate. For example, the roughness of the sanded rough surface is in the range of Ra value between 3 μm and 5 μm. The rough structure can also be prepared by etching, laser engraving, stamping, etc. For example, the rough structure on the surface of the substrate 110 is composed of protrusions 111 and grooves 112. For example, refer to... Figure 10 and Figure 11 Understand the protrusions and grooves in the rough structure here. In an exemplary embodiment, the height of the protrusion 111 is H1, where 80 micrometers ≤ H1 ≤ 130 micrometers; and / or, the width of the protrusion 111 is W1, where 0.3 millimeters ≤ W1 ≤ 0.8 millimeters; the depth of the groove 112 is H2, where 80 micrometers ≤ H2 ≤ 130 micrometers; and / or, the width of the groove 112 is W2, where 3 millimeters ≤ W2 ≤ 6 millimeters; the grooves and protrusions are alternately arranged around the center of the cookware.

[0173] It should be noted that the substrate according to this application can also have a relatively flat surface from a macroscopic perspective.

[0174] In some embodiments, after the cookware is formed into a prototype, it can be polished and dewaxed / degreased to make the surface of the cookware clean and free of oil.

[0175] Forming a transition layer (optional) In some embodiments, a rough transition layer is provided between the substrate and the non-adhesive layer, which can further enhance the adhesion between the non-adhesive layer and the substrate. As an example, the rough transition layer can be formed by thermally spraying a metallic material onto the surface of the substrate. Specifically, the metallic material may include at least one of titanium, chromium, chromium alloys, titanium alloys, iron, iron alloys, aluminum, aluminum alloys, zinc, zinc alloys, copper, copper alloys, zirconium, and zirconium alloys.

[0176] Form a non-stick layer According to this application, a non-stick layer can be formed in the manner described in the above embodiments.

[0177] In some embodiments, the cookware base is a pot, and when the bottom of the pot has a flat structure, non-stick layers are stacked on the flat structure of the bottom of the pot, and the bottom of the pot has, for example, a non-stick layer. Figure 10 and Figure 11 In the case of the rough structure shown, the non-stick layer is formed in the grooves of the rough structure and is flush with or at a predetermined distance from the groove opening. Here, the predetermined distance is no more than 10 micrometers. In this way, various types of cookware can be manufactured to meet different market demands. In addition, the protrusions can protect the non-stick layer from being scratched or subjected to stress together with the non-stick layer, and also protect the non-stick layer from delamination.

[0178] Provide oil molecules or polysiloxanes According to this application, to further enhance the initial user experience, oil molecules can be added to the surface of the non-stick layer of the cookware at the time of manufacture. This further optimizes the non-stick performance of the cookware. Furthermore, during subsequent use, oil molecules generated during cooking can replenish the porous structure of the non-stick layer, forming a continuous and stable oil film to maintain its non-stick properties. As some examples, the cookware with the non-stick layer can be immersed in oil molecules, allowing the oil molecules to penetrate the porous structure of the non-stick layer or adhere to its surface, further enhancing its long-lasting non-stick performance. The immersion time can be 15-30 minutes at a temperature of 80℃-120℃. Afterward, excess oil molecules are wiped off, and the surface is dried at 280℃-340℃ for 3-6 minutes. As other examples, silane can be coated evenly onto the surface of the non-stick layer. For example, the silane can be polydimethylsiloxane or other modified low-molecular-weight dimethylsilanes. For example, low molecular weight dimethylsilane can be used as silicone oil. Specifically, polysiloxane can be selected from low molecular weight silicone oils with a number average molecular weight of 400-900, or hydroxyl-modified silicone oils. For the coating method, roller coating or air spraying can be used; this application does not impose further limitations on this. After coating, the cookware substrate coated with polysiloxane is placed on a support chain at 60℃-80℃ and heated for 5-10 minutes to accelerate the diffusion and penetration of polysiloxane into the pores of the non-stick layer. If production conditions permit, ultrasonic treatment can also be applied to enhance the penetration effect. After penetration, excess polysiloxane on the surface is wiped away with a clean, soft cloth. Then, the surface-treated cookware substrate is placed in a high-temperature oven for baking and drying. The oven temperature is set at 280℃-340℃ for 3-6 minutes to dry and cure the polysiloxane in the non-stick layer.

[0179] According to a seventh aspect of this application, a cookware is provided, specifically relating to a non-stick cookware. The cookware includes a substrate and a non-stick layer, the non-stick layer being disposed on the substrate and directly serving as the inner surface of the cookware. The non-stick layer includes the non-stick layer provided according to the various embodiments described above, or a non-stick layer formed by spraying the non-stick material provided in the various embodiments described above. (See also...) Figure 10 and Figure 11 The cookware 100 may include a base 110 and a non-stick layer 120.

[0180] In some embodiments, the cookware further includes a transition layer made of the aforementioned metallic material, wherein the transition layer is disposed between the substrate 110 and the non-stick layer 120. In an exemplary embodiment, the thickness of the transition layer is in the range of 10 micrometers to 80 micrometers. This thickness range ensures that the interlayer bonding performance between the substrate and the non-stick layer is effectively improved while minimizing the internal stress induced by the increased thickness, thereby guaranteeing the overall performance of the cookware.

[0181] According to some embodiments of this application, the surface of the non-stick layer is covered with an oil film layer or a polysiloxane layer, and the oil film layer or polysiloxane layer directly constitutes the inner surface of the cookware. This oil film layer or polysiloxane layer, by covering and sealing the micropores on the surface of the non-stick layer, can act as a physical barrier against corrosive media penetrating the interior of the cookware, thereby improving the overall non-stick performance while also protecting the covered non-stick layer. According to other embodiments of this application, an oil-based fatty acid salt modified layer is formed on the surface of the non-stick layer. For example, when the non-stick layer contains calcium and iron elements, it can react with fatty acids possessing lipophilic groups to generate fatty acid salts (such as calcium stearate) and adhere to the surface of the non-stick layer. Since the fatty acid salts themselves have lipophilic non-stick properties, the cookware with the non-stick layer can achieve a "the more you use it, the less sticky it becomes" seasoning effect.

[0182] According to the eighth aspect of this application, an application of a non-stick material as a spray coating material is provided, wherein the non-stick material is used as a spray coating material for cookware, and the non-stick material is the non-stick material provided in the above embodiments.

[0183] The present application will now be described in detail with reference to specific embodiments, but the scope of protection of the present application is not limited to the described embodiments.

[0184] Example 1 The cookware according to Example 1 is manufactured by the following method.

[0185] Step S10: Prepare the cookware base. Specifically, the steps for preparing the cookware base include deep drawing a stainless steel sheet, surface alkaline washing to remove oil, drying, and sandblasting to remove surface defects and oxide scale from the stainless steel, thereby obtaining a cookware base with a thickness of 1.5 cm and a surface roughness of 4 micrometers.

[0186] Step S20: Prepare an inorganic non-metallic compound with a median particle size of 30μm-45μm as a non-stick material. Specifically, step S20 includes step S21: Provide calcium carbonate and titanium oxide as raw materials with a median particle size of 1.5μm-2.5μm, and mix the calcium carbonate and titanium oxide at a calcium-to-titanium atomic ratio of 1:1 to obtain a mixture. Then, mix the mixed mixture with a 0.45% polyvinyl alcohol solution at a mass ratio of 1:1 to form a mixed slurry. Step S22: Perform spray drying on the mixed slurry using a centrifugal spray dryer to form non-stick particles. The inlet temperature of the centrifugal spray dryer is 280℃ and the outlet temperature is 140℃, ultimately obtaining uniform non-stick particles. Step S23: Place the granulated powder in a high-temperature electric furnace for staged degreasing treatment. First, hold at 400℃ for 180min, then heat to 800℃ and hold for 120min. Monitor the degreasing process in real time using a loss-in-weight method. After degreasing, the material is slowly heated to 1050℃ at a heating rate of 3℃ / min for high-temperature sintering. It is held at this temperature for 3 hours to allow calcium oxide and titanium dioxide to metallurgically bond and form perovskite. The heating rate is strictly controlled to prevent bubbling of the material. After the entire sintering process is completed, the furnace temperature is slowly cooled to below 150℃ before the material is removed from the furnace. The inorganic non-metallic compound obtained in step S20 is then obtained through sieving.

[0187] Step S30: Apply a non-stick coating.

[0188] The outer surface of the cookware substrate is placed in a circulating cooling air environment, where the temperature of the cooling air is 5°C. Non-stick material is loaded into a powder feeder, and the plasma spraying parameters are set as follows: current 400A, voltage 60V, hydrogen pressure 0.7MPa, hydrogen flow rate 250L / h, argon pressure 1.2MPa, argon flow rate 1500L / h, spraying distance 160mm, and workpiece linear speed 30m / min. The non-stick material powder is heated to a micro-melt state and deposited onto the inner surface of the cookware substrate, resulting in a non-stick layer with a thickness of 65μm, thus completing the manufacture of the cookware of Example 1.

[0189] In Example 1, it should be noted that when the high-temperature electric furnace is slowly heated to 880°C at a heating rate of 3°C / min, calcium carbonate is gradually decomposed into calcium oxide as the temperature rises. Heating continues at the same rate to 1050°C, and high-temperature sintering is performed at this temperature for 3 hours (during sintering, the reaction is as follows: CaO + TiO2 → CaTiO3), allowing the softened calcium oxide and titanium dioxide to react fully and form an inorganic non-metallic compound with a polycrystalline structure. The main phase of the obtained inorganic non-metallic compound is CaTiO3 with a polycrystalline structure. In the following examples, it should be noted that, apart from the different sintering temperatures applied to the non-stick particles when different raw materials are selected, there are no other differences. Here, the sintering temperature is determined based on the overall melting point of the mixture.

[0190] Example 2 Except for replacing the raw materials of Example 1 with different raw materials in step S20 (the raw materials in this embodiment are calcium oxide and titanium oxide mixed in a calcium-titanium atomic ratio of 1:1, wherein the phase of the resulting inorganic non-metallic compound is mainly CaTiO3 with a polycrystalline structure), the cookware of Example 2 is manufactured using the same method as in Example 1.

[0191] Example 3 Except for replacing the raw materials of Example 1 with different raw materials in step S20 (the raw materials in this embodiment are calcium hydroxide and titanium oxide mixed in a calcium-titanium atomic ratio of 1:1, wherein the phase of the resulting inorganic non-metallic compound is mainly CaTiO3 with a polycrystalline structure), the cookware of Example 3 is manufactured using the same method as in Example 1.

[0192] Example 4 Except for replacing the raw materials of Example 1 with different raw materials in step S20 (the raw materials in this embodiment are a mixture of calcium carbonate and titanium oxide in a calcium-titanium atomic ratio of 2:3, wherein the phase of the resulting inorganic non-metallic compound is mainly a mixture of TiO2 and CaTiO3 with a polycrystalline structure), the cookware of Example 4 is manufactured using the same method as in Example 1.

[0193] Example 5 Except for replacing the raw materials of Example 1 with different raw materials in step S20 (the raw materials in this embodiment are a mixture of calcium carbonate and titanium oxide in a calcium-titanium atomic ratio of 3:2, wherein the phase of the resulting inorganic non-metallic compound is mainly a mixture of CaO and CaTiO3 with a polycrystalline structure), the cookware of Example 5 is manufactured using the same method as in Example 1.

[0194] Example 6 Except for replacing the raw materials of Example 1 with different raw materials in step S20 (the raw materials in this embodiment are a mixture of calcium oxide and titanium oxide in a calcium-titanium atomic ratio of 2:3, wherein the phase of the resulting inorganic non-metallic compound is mainly a mixture of TiO2 and CaTiO3 with a polycrystalline structure), the cookware of Example 6 is manufactured using the same method as in Example 1.

[0195] Example 7 Except for replacing the raw materials of Example 1 with different raw materials in step S20 (the raw materials in this embodiment are a mixture of calcium oxide and titanium oxide in a calcium-titanium atomic ratio of 3:2, wherein the phase of the resulting inorganic non-metallic compound is mainly a mixture of CaO and CaTiO3 with a polycrystalline structure), the cookware of Example 7 is manufactured using the same method as in Example 1.

[0196] Example 8 Except for replacing the raw materials of Example 1 with different raw materials in step S20 (the raw materials in this example are calcium hydroxide and titanium oxide mixed in a calcium-titanium atomic ratio of 2:3, wherein the phase of the resulting inorganic non-metallic compound is mainly a mixture of TiO2 and CaTiO3 with a polycrystalline structure), the cookware of Example 8 is manufactured using the same method as in Example 1.

[0197] Example 9 Except for replacing the raw materials of Example 1 with different raw materials in step S20 (the raw materials in this example are calcium hydroxide and titanium oxide mixed in a calcium-titanium atomic ratio of 3:2, wherein the phase of the resulting inorganic non-metallic compound is mainly a mixture of CaO and CaTiO3 with a polycrystalline structure), the cookware of Example 9 is manufactured using the same method as in Example 1.

[0198] Example 10 In addition to using different raw materials in step S20 (in this embodiment, the raw material is a mixture of barium carbonate and iron(III) oxide in a 1:1 barium-iron atomic ratio, sintered at 1200°C, wherein the resulting inorganic non-metallic compound is mainly composed of BaFe with a polycrystalline structure), the raw material is used in step S20. 12 O 19 The cookware of Example 10 was manufactured using the same method as in Example 1, except for the raw materials used in Example 1.

[0199] Example 11 Except for replacing the raw materials of Example 1 with different raw materials in step S20 (the raw materials in this embodiment are a mixture of cesium oxide and manganese dioxide in a 1:1 cesium-manganese atomic ratio, sintered at 1200°C, wherein the phase of the resulting inorganic non-metallic compound is mainly CsMnO4 with a polycrystalline structure), the cookware of Example 11 is manufactured using the same method as in Example 1.

[0200] Example 12 Except for replacing the raw materials of Example 1 with different raw materials in step S20 (the raw materials in this example are lanthanum trioxide and manganese dioxide mixed in a 1:1 lanthanum-manganese atomic ratio, sintered at 1150°C, wherein the phase of the resulting inorganic non-metallic compound is mainly LaMnO3 with a polycrystalline structure), the cookware of Example 12 is manufactured using the same method as in Example 1.

[0201] Example 13 Except for replacing the raw materials of Example 1 with different raw materials in step S20 (the raw materials in this example are lanthanum trioxide and titanium dioxide mixed in a 1:1 lanthanum-titanium atomic ratio, sintered at 1100°C, wherein the phase of the resulting inorganic non-metallic compound is mainly La2Ti2O7 with a polycrystalline structure), the cookware of Example 13 is manufactured using the same method as in Example 1.

[0202] Example 14 Except for replacing the raw materials of Example 1 with different raw materials in step S20 (the raw materials in this embodiment are a mixture of yttrium trioxide and titanium dioxide in a 1:1 yttrium-titanium atomic ratio, sintered at a temperature of 1250°C, wherein the phase of the resulting inorganic non-metallic compound is mainly Y2Ti2O7 with a polycrystalline structure), the cookware of Example 14 is manufactured using the same method as in Example 1.

[0203] Comparative Example 1 Except that in step S20, a different material (the material in this comparative example is composed of 21.06% silicon dioxide, 1.32% aluminum oxide, 0.44% potassium oxide, 0.27% sodium oxide, 3.71% calcium oxide, 1.19% magnesium oxide, 0.45% titanium oxide, 69.59% iron oxide, and the balance being impurities) was used to replace the non-stick material of Example 1, the cookware of Comparative Example 1 was manufactured using the same method as in Example 1.

[0204] Comparative Example 2 Except that in step S20, a different material (the material in this comparative example is composed of 30% silicon dioxide, 1.32% aluminum oxide, 0.44% potassium oxide, 0.27% sodium oxide, 3.71% calcium oxide, 1.19% magnesium oxide, 0.45% titanium oxide, 50% iron oxide, and the balance impurities) was used to replace the non-stick material of Example 1, the cookware of Comparative Example 2 was manufactured using the same method as in Example 1.

[0205] Comparative Example 3 Except in step S20, where a different amorphous material (the material composition of this comparative example is 45 wt% titanium oxide, 45 wt% iron oxide + ferrous oxide, 5 wt% calcium oxide + magnesium oxide, and the balance being phosphorus, carbon, and silicon) is used to replace the non-stick material of Example 1, the cookware of Comparative Example 3 is manufactured using the same method as in Example 1.

[0206] Comparative Example 4 Except for replacing the non-stick material of Example 1 with a different material (the material of this comparative example is ferrous aluminum magnesium titanate with an amorphous phase volume ratio of 92%) in step S20, the cookware of Comparative Example 4 was manufactured using the same method as in Example 1.

[0207] Comparative Example 5 Except that in step S20, the non-stick material of Example 1 was replaced by a material obtained by mixing Fe3O4 and titanium oxide in an iron-titanium atomic ratio of 1:1, the cookware of Comparative Example 5 was manufactured using the same method as in Example 1.

[0208] Comparative Example 6 Except in step S20, where the non-stick material of Example 1 was replaced with a different material (the material of Comparative Example 6 is a composite metal oxide with an amorphous phase volume ratio of 68% obtained by sintering granulated powder of TiO2, Fe3O4 and CaO at 1400°C for 4 hours, wherein the weight ratio of TiO2, Fe3O4 and CaO in the granulated powder is 26:26:1.5, and the composite metal oxide contains iron in different valence states, titanium in different valence states, and calcium), the cookware of Comparative Example 6 was manufactured using the same method as in Example 1.

[0209] Comparative Example 7 Except in step S20, where calcium carbonate is replaced with Fe3O4 and the iron-titanium atomic ratio of Fe3O4 and titanium oxide is set to 1:1, the cookware of Comparative Example 7 was manufactured using the same method as in Example 1.

[0210] Test methods and evaluation criteria, test results The performance of the non-stick coatings of the cookware obtained in Examples 1-14 and Comparative Examples 1-7 was tested and recorded in Table 1 below. The specific performance testing methods are as follows: Test methods and evaluation criteria 1. Impact Toughness Test Method and Evaluation Standard: The impact toughness of the non-stick coating is tested using the steel ball impact method. Specifically, a 500g steel ball is dropped freely from different heights onto the surface of the cookware, and the cracking of the non-stick coating is checked. The impact height is gradually increased from 5cm, with 5cm intervals, until the coating shows signs of chipping, and the final impact height is recorded. This project requires that the impact toughness test value be no less than 20cm.

[0211] 2. Initial non-stickiness test method and evaluation standard: GB / T32095.2-2015 test method for non-stickiness of fried eggs. This method is an initial non-stickiness test, which is divided into grades I, II and III. Grade I has the best non-stickiness and grade III has the worst non-stickiness.

[0212] 3. Durable non-stick test method and evaluation standard: The durable non-stick test method in GB / T32388-2015 is measured in cycles. The higher the number of cycles, the longer the lifespan. 500 cycles are used to evaluate the non-stick result once. The number of cycles is recorded up to the point of use at level III.

[0213] 4. Hardness Testing Method and Evaluation Standard: The Vickers hardness test method is used to test the Vickers hardness of the non-stick coating of the cookware. The unit of hardness value is HV. A higher hardness value indicates a harder sample, stronger resistance to wear from metal spatulas and food, and less susceptibility to wear. However, excessive hardness may lead to cracking. Generally, a non-stick coating hardness of 400HV-600HV is desirable.

[0214] 5. Supplementary Adhesion Test Method and Evaluation Standard: The adhesion strength of the non-stick layer is tested using the tensile method. Specifically, axial tension is applied until the non-stick layer fails, the maximum load is recorded, and the strength is calculated. The specific steps are as follows: Use AB glue to firmly adhere the pull-out head to the surface of the cookware, and leave it for 24 hours to allow the glue to fully solidify. Then, vertically fix the cookware on the clamps of the tensile testing machine, ensuring that the tensile direction is perpendicular to the surface of the non-stick layer to avoid eccentric force. Set the tensile speed to 1 mm / min, the temperature to 23±2℃, and the humidity to 60±5%. Start the testing machine and apply an axial tensile load to the cookware at a constant rate until the non-stick layer fails (peels or breaks), thus obtaining the maximum tensile load (F) at which the coating fails. Based on the bonding area (A) between the non-stick layer and the substrate, calculate the adhesion strength (σ) of the coating using the formula σ=F / A. This project requires that the adhesion strength test value be no less than 8 MPa.

[0215] Table 1 Results Test Table

[0216] As can be seen from Table 1, and in conjunction with Examples 1 to 3, using different calcium sources (e.g., calcium carbonate, calcium oxide, calcium hydroxide) all exhibits good non-stickiness and long-lasting non-stickiness. This is because alkaline earth metal oxides and transition metal oxides can be completely converted into polycrystalline perovskites.

[0217] Based on Examples 1 / 4 / 5, 2 / 6 / 7, and 3 / 8 / 9, when the atomic ratio of alkaline earth metal element in alkaline earth metal oxide to transition metal in transition metal oxide is 1:1, the initial non-stickiness, persistent non-stickiness, impact toughness, hardness, and bonding strength are all optimal. When the atomic ratio is 2:3 or 3:2, the persistent non-stickiness, impact strength, hardness, and bonding strength are relatively inferior to the former. This is because when the atomic ratio is 1:1, the reaction completely produces an ABO3-type polycrystalline compound. However, when the ratio is 2:3 or 3:2, one of the raw materials is in excess, preventing the complete formation of a polycrystalline compound. This results in relatively lower persistent non-stickiness, impact strength, hardness, and bonding strength, particularly affecting impact toughness and bonding strength.

[0218] Compared with the amorphous materials in Comparative Examples 3 / 4 / 6 and the other crystalline materials in Comparative Examples 1 / 2 / 5, the non-stick layer of the cookware in the embodiments of this application has significantly improved impact toughness and adhesion.

[0219] As can be seen from Example 1 and Comparative Example 7, when the raw materials are selected in a combination form other than that of this application, such as transition metal oxides and transition metal oxides, their bonding and toughness cannot simultaneously meet the requirements of this project, nor can they simultaneously achieve non-stick properties. This is because they cannot form inorganic non-metallic compounds with a perovskite-type structure (ABO3 type) and a polycrystalline structure, and therefore cannot obtain cookware with the excellent properties of bonding, toughness, and non-stick properties as described in this application.

Claims

1. A non-stick coating for cookware or cups, characterized in that, The non-stick layer includes an inorganic non-metallic compound layer with a polycrystalline structure, wherein the inorganic non-metallic compound layer includes a first metal element and a second metal element, wherein the first metal element includes rare earth metal elements and / or alkaline earth metal elements, and the second metal element includes transition metal elements.

2. The non-stick layer according to claim 1, characterized in that, The inorganic non-metallic compound layer is an oxide-containing layer, and its general formula is A. x B y C z Wherein, A is the alkaline earth metal element, B is titanium among the transition metal elements, and C is oxygen, wherein 2x+2y=2z, 2x+3y=2z, or 2x+4y=2z; or, The inorganic non-metallic compound layer is an oxide-containing layer, and its general formula is A. x B y C z Wherein, A is the alkaline earth metal element, B is iron or cobalt among the transition metal elements, and C is oxygen, wherein 2x + 3y = 2z or 2x + 2y = 2z; or, The inorganic non-metallic compound layer is an oxide-containing layer, and its general formula is A. x B y C z Wherein, A is the alkaline earth metal element, B is manganese among the transition metal elements, and C is oxygen, wherein 2x+2y=2z, 2x+4y=2z, 2x+6y=2z, or 2x+7y=2z; or, The inorganic non-metallic compound layer is an oxide-containing layer, and its general formula is A. x B y C z Wherein, A is the rare earth metal element, B is titanium among the transition metal elements, and C is oxygen, wherein 3x+2y=2z, 3x+3y=2z, or 3x+4y=2z; or, The inorganic non-metallic compound layer is an oxide-containing layer, and its general formula is A. x B y C z Wherein, A is the rare earth metal element, B is iron or cobalt among the transition metal elements, and C is oxygen, wherein 3x + 3y = 2z or 3x + 2y = 2z; or... The inorganic non-metallic compound layer is an oxide-containing layer, and its general formula is A. x B y C z Wherein, A is the rare earth metal element, B is manganese among the transition metal elements, and C is oxygen, wherein 3x+2y=2z, 3x+4y=2z, 3x+6y=2z, or 3x+7y=2z; or, The inorganic non-metallic compound layer is a halide layer, and its general formula is A. x B y C z Wherein, A is the alkaline earth metal element, B is titanium among the transition metal elements, and C is a halogen element, wherein 2x+2y=z, 2x+3y=z, or 2x+4y=z; or, The inorganic non-metallic compound layer is a halide layer, and its general formula is A. x B y C z Wherein, A is the alkaline earth metal element, B is iron or cobalt among the transition metal elements, and C is a halogen element, wherein 2x + 3y = z or 2x + 2y = z; or... The inorganic non-metallic compound layer is a halide layer, and its general formula is A. x B y C z Wherein, A is the alkaline earth metal element, B is manganese among the transition metal elements, and C is a halogen element, wherein 2x+2y=z, 2x+4y=z, 2x+6y=z, or 2x+7y=z; or, The inorganic non-metallic compound layer is a halide layer, and its general formula is A. x B y C z Wherein, A is the rare earth metal element, B is titanium among the transition metal elements, and C is a halogen element, wherein 3x+2y=z, 3x+3y=z, or 3x+4y=z; or... The inorganic non-metallic compound layer is a halide layer, and its general formula is A. x B y C z Wherein, A is the rare earth metal element, B is iron or cobalt among the transition metal elements, and C is a halogen element, wherein 3x + 3y = z or 3x + 2y = z; or... The inorganic non-metallic compound layer is a halide layer, and its general formula is A. x B y C z Wherein, A is the rare earth metal element, B is manganese among the transition metal elements, and C is a halogen element, wherein 3x+2y=z, 3x+4y=z, 3x+6y=z, or 3x+7y=z; or... The inorganic non-metallic compound layer is an oxide layer with the general formula Al. x1 A2 x2 B y C z Where A1 is an alkaline earth metal, A2 is a rare earth metal, B is a transition metal, and C is oxygen, and 2x1 + 3x2 + 3y = 2z or 2x1 + 3x2 + 4y = 2z; or, The inorganic non-metallic compound layer is an oxide layer with the general formula Al. x1 A2 x2 B y C z In this equation, A1 is an alkaline earth metal element, A2 is a rare earth metal element, B is a transition metal element, and C is a halogen. In this equation, 2x1+3x2+3y=z or 2x1+3x2+4y=z.

3. The non-stick layer according to claim 1, characterized in that, The alkaline earth metal element includes at least one of calcium, strontium, and barium; the transition metal element includes at least one of titanium, manganese, iron, and cobalt; and the rare earth metal element includes at least one of lanthanum, neodymium, and yttrium.

4. The non-stick layer according to claim 1, characterized in that, The polycrystalline structure comprises micron- and / or nano-sized grains.

5. The non-stick layer according to claim 4, characterized in that, The grain has subgrains inside; and / or the grain has a layered structure.

6. The non-stick layer according to any one of claims 1 to 5, characterized in that, The inorganic non-metallic compound layer also contains carbonized products of the binder, and the mass ratio of the carbonized products of the binder to the inorganic non-metallic compound layer is (1-3):(97-99).

7. The non-stick layer according to any one of claims 1 to 5, characterized in that, The inorganic non-metallic compound layer with a polycrystalline structure accounts for no less than 80% of the total mass of the non-stick layer.

8. A method for preparing a non-stick layer, characterized in that, The method for preparing the non-stick layer includes: A mixed slurry comprising a binder, a first metal compound, and a second metal compound is formed, wherein the first metal compound comprises a rare earth metal compound and / or an alkaline earth metal compound, and the second metal compound comprises a transition metal compound. The mixed slurry is spray-dried to form non-sticky particles; The non-stick particles are sintered, causing the first and second metal compounds in the non-stick particles to react with each other, thereby obtaining a non-stick material mainly composed of inorganic non-metallic compounds with a polycrystalline structure. The non-stick material is sprayed onto a substrate to produce the non-stick layer.

9. The method for preparing the non-stick layer according to claim 8, characterized in that, The step of sintering the non-stick particles includes: The non-stick particles are sintered at a temperature of 75%-85% of their melting point; or, Heat the non-stick granules to 300℃-450℃ and hold for 2h-4h. Then, continue heating to 700℃-900℃ and hold for 1h-3h. Finally, heat to 1000℃-1100℃ at a heating rate of 1℃ / min-5℃ / min and hold for 2h-4h.

10. The method for preparing the non-stick layer according to claim 8, characterized in that, In the mixed slurry, the mass of the binder is 0.2%-0.25% of the total mass of the first metal compound and the second metal compound.

11. The method for preparing the non-stick layer according to claim 8, characterized in that, The adhesive includes alcohol-based adhesives and / or cellulose-based adhesives.

12. The method for preparing the non-stick layer according to claim 11, characterized in that, The cellulose-based binder includes at least one of hydroxymethyl cellulose binders, hydroxyethyl cellulose binders, and hydroxypropyl cellulose binders, and the alcohol-based binder includes at least one of polyvinyl alcohol binders, polyacryl alcohol binders, and alcohol binders containing six or more carbon atoms.

13. The method for preparing the non-stick layer according to claim 8, characterized in that, The median particle size of the non-stick material is 30μm-45μm; and / or, the porosity of the particles of the non-stick material is 25%-55%, and the pore size is 500 nanometers-4 micrometers.

14. A method for preparing a non-stick layer, characterized in that, The method for preparing the non-stick layer includes the following steps: A first metal compound and a second metal compound are mixed to obtain a mixture, wherein the first metal compound includes rare earth metal compounds and / or alkaline earth metal compounds, and the second metal compound includes transition metal compounds; The mixture is heated to melt it, causing the first metal compound and the second metal compound to react with each other. A cooling process is performed to obtain a non-stick material mainly composed of inorganic non-metallic compounds with a polycrystalline structure; The non-stick material is sprayed onto a substrate to produce the non-stick layer.

15. The method for preparing the non-stick layer according to claim 14, characterized in that, The step of heating the mixture for melting includes: heating the mixture to a temperature 30°C-100°C above the melting point of the metal compound with the highest melting point in the mixture, and melting at the temperature for 3-6 hours.

16. The method for preparing the non-stick layer according to claim 14, characterized in that, The cooling rate of the cooling process is controlled between 10°C / min and 20°C / min to obtain a polycrystalline structure with micron- and nano-sized grains.

17. The method for preparing the non-stick layer according to claim 14, characterized in that, The step of spraying the non-stick material onto the substrate to produce the non-stick layer includes: The inorganic non-metallic compound with a polycrystalline structure is crushed; The crushed inorganic non-metallic compound is pressed into an initial target material; The initial target material is pressed and sintered under a protective atmosphere to obtain a non-stick material that can be used as a target material. The non-stick material is physically vapor-deposited to produce the non-stick layer.

18. The method for preparing the non-stick layer according to any one of claims 8 to 17, characterized in that, When the first metal compound is an alkaline earth metal compound, the atomic ratio of the alkaline earth metal element in the first metal compound to the transition metal element in the second metal compound is 2:3-3:2; when the first metal compound is a rare earth metal compound, the atomic ratio of the rare earth metal element in the first metal compound to the transition metal element in the second metal compound is 2:3-3:2; and / or, when the first metal compound is both a rare earth metal compound and an alkaline earth metal compound, the ratio of the total number of rare earth metal elements and alkaline earth elements in the first metal compound to the number of transition metal elements in the second metal compound is 2:3-3:2; and / or, The median particle sizes of the first metal compound and the second metal compound are 1.5 μm and 2.5 μm, respectively.

19. The method for preparing the non-stick layer according to any one of claims 8 to 17, characterized in that, The first metal compound and the second metal compound react to form compounds with the same anion type.

20. The method for preparing the non-stick layer according to any one of claims 8 to 17, characterized in that, The first metal compound is selected from at least one of oxides, hydroxides, and carbonates, and the second metal compound is selected from oxides; or, the first metal compound is selected from chlorides, and the second metal compound is selected from chlorides; or, the first metal compound is selected from iodides, and the second metal compound is selected from iodides.

21. The method for preparing the non-stick layer according to any one of claims 8 to 17, characterized in that, The transition metal compound includes at least one of titanium oxide, manganese oxide, iron oxide, cobalt oxide, titanium chloride, manganese chloride, iron chloride, cobalt chloride, titanium iodide, manganese iodide, iron iodide, and cobalt iodide; and / or, the alkaline earth metal compound includes at least one of calcium oxide, calcium hydroxide, calcium carbonate, strontium oxide, strontium hydroxide, strontium carbonate, barium oxide, barium hydroxide, barium carbonate, calcium chloride, strontium chloride, barium chloride, calcium iodide, strontium iodide, and barium iodide; and / or, the rare earth metal compound includes at least one of lanthanum oxide, neodymium oxide, yttrium oxide, lanthanum chloride, neodymium chloride, yttrium chloride, lanthanum iodide, neodymium iodide, and yttrium iodide.

22. A non-stick cookware, characterized in that, The non-stick cookware includes a cookware substrate and a non-stick layer formed on the cookware substrate, wherein the non-stick layer is a non-stick layer according to any one of claims 1 to 7 or a non-stick layer prepared by the method of preparing a non-stick layer according to any one of claims 8 to 21.

23. The non-stick cookware according to claim 22, characterized in that, The non-stick layer has a porous structure, which is filled with grease and / or silicone oil.

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