Non-stick material and method for its production, non-stick coating and non-stick cookware

Abstract

The application provides a non-stick material and a preparation method thereof, a non-stick coating and a non-stick cooker. The non-stick material comprises mixed particles of a multi-metal cation titanate and an auxiliary material, wherein the auxiliary material is magnetite and titanium suboxide or titanium suboxide, the mixed particles have an amorphous structure, and the weight percentage of the multi-metal cation titanate is 80-90%, the weight percentage of the magnetite is 0-10%, and the weight percentage of the titanium suboxide is 10-20% based on 100% of the total weight of the mixed particles. The non-stick material can ensure that the cooker has excellent initial non-stickness, persistent non-stickness, hardness and anti-impact properties.

Description

Technical Field

[0001] This application relates to the field of non-stick materials technology, specifically to a non-stick material and its preparation method, a non-stick coating, and non-stick cookware. Background Technology

[0002] Existing non-stick cookware materials are mainly fluoropolymer coatings, whose main component is organic fluoropolymer resin. Although this material has some excellent properties, it also has some obvious drawbacks.

[0003] First, fluoropolymer materials have low hardness and are easily scratched. During cooking, especially when stir-frying hard foods, the surface of the cookware is easily scratched, exposing the base material. This not only affects the appearance of the cookware but may also have a negative impact on the cooking results.

[0004] Secondly, due to its low hardness, fluoropolymer materials are not well-suited for stir-frying and other high-heat cooking conditions, resulting in a poor user experience. This limits their application in the high-end cookware market to some extent.

[0005] To overcome these shortcomings, some cookware uses a plasma-sprayed coating of inorganic ceramic, which improves scratch resistance to some extent. However, the bonding strength between the inorganic ceramic coating and the substrate is a common problem. When subjected to external impacts (such as mechanical shock and thermal shock), the coating is prone to cracking and peeling, which also affects the lifespan of the cookware and its cooking performance.

[0006] Therefore, it is necessary to develop new non-stick materials to meet the various requirements of cookware, such as initial non-stick properties, long-term non-stick properties, hardness, and resistance to external impacts. Summary of the Invention

[0007] Therefore, the purpose of this application is to provide a non-stick material and its preparation method, a non-stick coating, and non-stick cookware to meet the needs of cookware in terms of initial non-stickness, long-term non-stickness, hardness, and resistance to external impact.

[0008] According to a first aspect of this application, a non-stick material is provided, wherein the non-stick material comprises mixed particles of a polymetallic cationic titanate and an auxiliary material, wherein the auxiliary material is magnetite and titanium suboxide, or titanium suboxide, wherein the mixed particles have an amorphous structure, and based on the total weight of the mixed particles as 100%, the weight percentage of the polymetallic cationic titanate is 80%-90%, the weight percentage of the magnetite is 0%-10%, and the weight percentage of the titanium suboxide is 10%-20%.

[0009] According to the non-stick material provided in this application, the non-stick material includes polymetallic cationic titanate, and its content indicates that it constitutes the main component of the non-stick material. Belonging to ceramic materials and possessing an amorphous structure, the non-stick material exhibits overall amorphous properties. Since amorphous structures possess lower surface energy, better hardness, chemical stability, and thermal stability compared to crystalline structures, using materials with amorphous structures, including polymetallic cationic titanates, as non-stick materials can meet the requirements of cookware for initial non-stickness, long-term non-stickness, hardness, and resistance to external impacts. The non-stick material also includes auxiliary materials such as magnetite and titanium suboxide. This mixture of substances facilitates stress release within the coating, preventing the non-stick layer from peeling off due to mechanical or thermal shocks during use. Furthermore, due to the porosity of the non-stick material particles and the different thermal expansion coefficients of various materials, the coating formed by this non-stick material easily forms uniform small pores during cooling, resulting in a non-stick coating with a porous structure capable of storing oil. Therefore, the non-stick coating can further enhance the non-stick properties of cookware due to the oil film effect.

[0010] In this embodiment, the particle size of the non-stick material is 300-500 mesh.

[0011] In these embodiments, the non-stick material has a relatively small and uniform particle size, which helps to form a dense and uniform non-stick coating on the substrate surface. Furthermore, the particle size of the non-stick material ensures proper spraying by the plasma spraying equipment, thereby guaranteeing the quality of the non-stick coating.

[0012] In this embodiment, the non-stick material is black.

[0013] In these embodiments, the black non-stick material does not cause a color change after spraying, thus forming a black non-stick coating. The black non-stick coating can weaken the contrast of the charred color change during use, improving the user's visual experience.

[0014] In the embodiments, the volume percentage of the amorphous phase in the non-stick material is 80%-98%.

[0015] In these embodiments, the non-stick material has a high proportion of amorphous phase, thus exhibiting excellent properties such as hardness, wear resistance, corrosion resistance, and toughness. Therefore, it can maintain the stability of its structure and performance when facing harsh environments such as high temperature and chemical corrosion, thereby extending the service life of the non-stick coating.

[0016] According to a second aspect of this application, a method for preparing a non-stick material is provided, wherein the method comprises solid-state sintering a block comprising raw materials magnetite and titanium dioxide to obtain a non-stick block; cooling the non-stick block and then pulverizing it to obtain a non-stick material comprising mixed particles formed of polymetallic cationic titanate and auxiliary materials, wherein the auxiliary materials are magnetite and titanium dioxide, or titanium dioxide, wherein the mixed particles have an amorphous structure, and based on the total weight of the mixed particles as 100%, the weight percentage of the polymetallic cationic titanate is 80%-90%, the weight percentage of the magnetite is 0%-10%, and the weight percentage of the titanium dioxide is 10%-20%.

[0017] According to the preparation method of the non-stick material provided in this application, the non-stick material includes a polymetallic cationic titanate, and its content indicates that it constitutes the main component of the non-stick material. Belonging to ceramic materials and possessing an amorphous structure, the non-stick material exhibits overall amorphous properties. Since the amorphous structure has lower surface energy, better hardness, chemical stability, and thermal stability compared to the crystalline structure, using a material with an amorphous structure, including a polymetallic cationic titanate, as a non-stick material can meet the requirements of cookware for initial non-stickness, long-term non-stickness, hardness, and resistance to external impact. The non-stick material also includes auxiliary materials such as magnetite and titanium suboxide. This mixture of various substances facilitates the release of internal stress in the coating, preventing the non-stick layer from peeling off due to mechanical or thermal shock during use. Furthermore, due to the porosity of the non-stick material particles and the different coefficients of thermal expansion of different materials, the coating formed by this non-stick material easily forms uniform small pores during cooling, giving the non-stick coating a porous structure capable of storing oil. Therefore, the non-stick coating can further enhance the non-stickness of cookware due to the oil film effect.

[0018] In this embodiment, based on the total weight of the raw magnetite as 100%, the main components of the raw magnetite include 90%-95% iron(III) oxide, 0.1%-1% silicate minerals, and the balance being harmless metal ions.

[0019] In these embodiments, the raw material magnetite with the above chemical composition provides a solid foundation for manufacturing high-performance non-stick cookware materials through the synergistic effect between its components.

[0020] In the embodiments, the method for preparing the non-stick material further includes at least acid washing and roasting of natural magnetite powder to obtain the raw material magnetite.

[0021] In these embodiments, the pickling and high-temperature roasting steps can remove harmful metal ions from natural magnetite as much as possible to obtain raw magnetite suitable for cookware according to this application.

[0022] In an embodiment, the solid-state sintering of the bulk material comprising raw magnetite and titanium oxide includes: treating the bulk material comprising raw magnetite and titanium oxide at 1100℃-1400℃ for 8h-20h.

[0023] In these embodiments, solid-state sintering is performed under the above parameters. Most of the raw material magnetite reacts with titanium dioxide to generate a polymetallic cationic titanate (at least three metal cations) with an amorphous structure suitable for use as a non-stick material for cookware. At the same time, titanium dioxide loses oxygen under the reducing atmosphere and high temperature of solid-state sintering to form sub-titanium dioxide. Since the raw material magnetite has a coarser particle size than titanium dioxide, its reaction rate during solid-state sintering is slower than that of titanium dioxide. In this case, under the limitation of the amount of raw material magnetite and titanium dioxide in the raw materials, a small portion of magnetite may remain in the final product and be uniformly dispersed with sub-titanium dioxide among the above-mentioned polymetallic cationic titanate particles.

[0024] In an embodiment, cooling the non-stick block includes cooling the non-stick block under air-cooling conditions of 20°C / min to 50°C / min.

[0025] In these embodiments, placing the non-stick block under the above air-cooling conditions results in a relatively fast cooling rate, allowing the non-stick block to quickly reach the required temperature. This helps to refine the grain structure of the material and improve its mechanical and physical properties.

[0026] In the embodiments, the mass ratio of the raw materials magnetite and titanium oxide is 2:3-2:5.

[0027] In these embodiments, the mass ratio of raw materials magnetite and titanium dioxide is 2:3 to 2:5, which facilitates the formation of a non-stick material of mixed particles according to the present application.

[0028] In this embodiment, the particle size of the raw material magnetite is 500-2000 mesh; the particle size of the titanium oxide is 1000-2000 mesh.

[0029] In these embodiments, precise control of the particle size of the raw materials magnetite and titanium dioxide can optimize the preparation process of the non-stick material, so that the obtained non-stick material contains various components (e.g., polymetallic cationic titanates and auxiliary materials) and has a suitable weight ratio range, so that the non-stick material properties are more prominent, such as hardness and non-stickiness.

[0030] In one embodiment, the magnetite comprises a black metal oxide that is magnetic.

[0031] In these embodiments, a black non-stick coating can be easily formed, which can weaken the contrast of the charred color during use and improve the user's visual experience.

[0032] According to a third aspect of this application, a non-stick coating is provided, wherein the non-stick coating is formed by thermal spraying of the non-stick material provided in the above embodiments, or by thermal spraying of the non-stick material prepared by the method for preparing the non-stick material provided in the above embodiments.

[0033] According to a fourth aspect of this application, a non-stick cookware is provided, wherein the non-stick cookware includes a substrate and a non-stick coating formed on the substrate according to the various embodiments described above.

[0034] In one embodiment, the surface of the non-stick coating is filled with grease or silicone oil.

[0035] In these embodiments, the surface of the non-stick coating is filled with grease or silicone oil, thus optimizing non-stick properties by forming an "oil film." In addition, the pores are filled with grease or silicone oil, which can prevent corrosion from corrosive media and ensure the corrosion resistance of the coating on non-stick cookware. Detailed Implementation

[0036] The inventive concept of this application will be described in more detail below.

[0037] Natural magnetite, with its main chemical component being Fe3O4, is a natural mineral with an inverse spinel crystal structure and generally low non-stick properties. If it were to be used as a non-stick material, at least the requirements for non-stick properties and food safety would need to be addressed.

[0038] The inventors discovered through research that by removing impurities from natural magnetite to obtain raw magnetite, and then forming a mixture of raw magnetite (i.e., the impurity-removed magnetite) and titanium dioxide into a block, the block is subjected to solid-state sintering to obtain a non-sticky block. The non-sticky block is then cooled and pulverized to obtain a non-sticky material consisting of mixed particles of polymetallic cationic titanate and auxiliary materials. Specifically, during the solid-state sintering process, by controlling the sintering temperature and time, the raw magnetite and titanium dioxide particles undergo a chemical reaction to form a polymetallic cationic titanate with an amorphous structure. Simultaneously, under the reducing atmosphere and high temperature of the solid-state sintering, titanium dioxide loses some oxygen, forming sub-titanium oxide. It should be noted that due to differences in particle size and raw material dosage, the raw magnetite may not fully participate in the reaction; some of the raw magnetite and the formed sub-titanium oxide will be uniformly dispersed among the polymetallic cationic titanate particles, forming a non-sticky block. The auxiliary materials are magnetite and titanium suboxide, or titanium suboxide alone. Here, the magnetite refers to the unreacted portion of the raw magnetite, and the titanium suboxide comprises Ti₂O₃, Ti₃O₄, and Ti₄O₇, wherein the titanium suboxide comprises 60%-80% Ti₄O₇, with the balance being Ti₂O₃ and Ti₃O₄. It should be noted that this application does not impose excessive limitations on Ti₂O₃ and Ti₃O₄, as their proportion range has minimal impact on the overall performance of the material.

[0039] According to this application, polymetallic cationic titanate is the main component of the non-stick material and possesses an amorphous structure. Therefore, the non-stick material exhibits overall amorphous properties. Since the amorphous structure has lower surface energy compared to the crystalline structure, using a material with an amorphous structure, including polymetallic cationic titanate, as a non-stick material achieves the purpose of non-stick cooking. The non-stick material also includes auxiliary materials such as magnetite and titanium suboxide. This mixture of multiple substances facilitates stress release within the coating, preventing the non-stick layer from peeling off due to mechanical or thermal shock during use. Furthermore, due to the porosity of the non-stick material particles and the different coefficients of thermal expansion of various materials, the coating formed by this non-stick material easily forms uniform small pores during cooling. This results in a non-stick coating with a porous structure capable of storing oil, further enhancing the non-stick properties of the cookware due to the oil film effect. In addition, the non-stick material is a ceramic material, possessing improved hardness and stability. Therefore, it ensures the cookware's scratch resistance and high-temperature resistance, guaranteeing long-lasting non-stick properties.

[0040] In addition, the inventors also discovered that by controlling the cooling rate during the cooling process of the non-stick block, it is possible to prevent the atoms or molecules in the material from forming a long-range ordered crystal structure, and to further freeze them into a disordered state, thereby further improving the amorphization degree of the non-stick material.

[0041] The inventive concept of this application will now be described in detail with reference to exemplary embodiments.

[0042] According to a first aspect of this application, a method for preparing a non-stick material for cookware is provided, wherein the method for preparing the non-stick material includes:

[0043] Step S101: The block containing raw materials magnetite and titanium oxide is placed in a high-temperature environment for solid-state sintering to obtain a partially solid-state sintered non-stick block.

[0044] Step S102: Cool the non-stick block and then pulverize it to obtain a non-stick material comprising mixed particles of polymetallic cationic titanate and auxiliary materials, wherein the auxiliary materials are magnetite and titanium suboxide, or titanium suboxide, wherein the mixed particles have an amorphous structure, and based on the total weight of the mixed particles as 100%, the weight percentage of polymetallic cationic titanate is 80%-90%, the weight percentage of magnetite is 0%-10%, and the weight percentage of titanium suboxide is 10%-20%.

[0045] According to the non-stick material preparation method provided in the embodiments of this application, during the solid-state sintering process, most of the raw material magnetite reacts with titanium dioxide to generate a polymetallic cationic titanate (at least three metal cations) with an amorphous structure suitable for use as a non-stick material for cookware. At the same time, titanium dioxide loses oxygen under the influence of the reducing atmosphere and high temperature of solid-state sintering to form sub-titanium dioxide. In some embodiments, since the particle size of the raw material magnetite is coarser than that of titanium dioxide, the rate of solid-state reaction is slower than that of titanium dioxide. Under the limitation of the amount of raw material magnetite and titanium dioxide in the raw materials, a small portion of magnetite may remain in the final product and be uniformly dispersed with sub-titanium dioxide among the above-mentioned polymetallic cationic titanate particles.

[0046] According to this application, polymetallic cationic titanate is the main component of the non-stick material and possesses an amorphous structure. Therefore, the non-stick material exhibits overall amorphous properties. Since the amorphous structure has a lower surface energy compared to the crystalline structure, using a material with an amorphous structure, including polymetallic cationic titanate, as a non-stick material can achieve the purpose of non-stick cooking. In addition, the non-stick material also includes titanium suboxide, or auxiliary materials such as magnetite and titanium suboxide. This mixture of multiple substances facilitates stress release within the coating, preventing the non-stick layer from peeling off due to mechanical or thermal shock during use. Furthermore, because the particles of the non-stick material themselves possess porosity, and due to the different coefficients of thermal expansion of different materials, the coating formed by this non-stick material easily forms uniform small pores during cooling. This results in a non-stick coating with a porous structure capable of storing oil, thus further enhancing the non-stick properties of the cookware due to the oil film effect. Moreover, the non-stick material is a ceramic material, possessing improved hardness and stability. Therefore, it can ensure excellent properties in terms of initial non-stickness, long-term non-stickness, hardness, and resistance to external impacts.

[0047] According to this application, the main components of the raw material magnetite include iron oxide, harmless metal ions (iron ions, aluminum ions, titanium ions, vanadium ions, magnesium ions, zinc ions and calcium ions) and silicate minerals. For example, the harmless metal ions in the raw material magnetite will react with titanium oxide to obtain polymetallic cationic titanates as reaction products. As an example, polymetallic cationic titanates may include calcium magnesium zinc titanate or vanadium aluminum calcium titanate.

[0048] In some embodiments, the non-stick material comprises mixed particles of polymetallic cationic titanate, magnetite, and titanium suboxide. It is understood that the non-stick material, containing mixed particles of polymetallic cationic titanate, magnetite, and titanium suboxide, may also contain unavoidable impurities. For example, based on the total weight of the mixed particles as 100%, the weight percentage of polymetallic cationic titanate is 80%-90%, the weight percentage of magnetite is 0%-10%, and the weight percentage of titanium suboxide is 10%-20%. It should be noted that in the case where the non-stick material contains unavoidable impurities, the weight percentage of the unavoidable impurities is no greater than 1%. In non-stick materials, polymetallic cationic titanates constitute 80%-90% by weight, forming the main component. Their amorphous nature and low surface energy endow the non-stick material with excellent non-stick properties. Magnetite accounts for 0%-10% by weight, indicating that it may or may not be present in the non-stick material. Magnetite has high hardness and density. In the absence of magnetite, the mechanical properties of the coating are ensured by the polymetallic cationic titanates. The presence of magnetite further enhances the mechanical properties of the coating, making the magnetite-containing non-stick material more robust and durable under external pressure or impact, less prone to deformation or damage. Titanium suboxide accounts for 10%-20% by weight. Its unique chemical properties and surface structure help reduce the contact between food and cookware surfaces, lowering the likelihood of food adhesion. In addition, although magnetite and titanium suboxide constitute a small proportion of the non-stick material, their differences among the various materials in the non-stick material create a porous structure that can retain oil. Furthermore, they facilitate the release of internal stress in the coating, preventing the non-stick coating from peeling off due to mechanical or thermal shock during use. It should be noted that magnetite and titanium suboxide are the mixed particles that form the non-stick material, not specific components.

[0049] Provide raw material magnetite

[0050] As is well known, cookware, as a cooking utensil, has its inner surface in direct contact with food. Therefore, the coating material must be non-toxic and harmless, meeting food safety standards. However, natural magnetite contains many impurities that make cookware unsuitable. For example, the main components of natural magnetite include iron oxide (Fe3O4), harmful metal ions (chromium, manganese, nickel, cobalt, copper, mercury, and lead ions), harmless metal ions (e.g., iron, aluminum, titanium, vanadium, magnesium, zinc, and calcium ions), and silicate minerals (quartz, calcium silicate, and sodium silicate, etc.). Of these, based on the total weight of natural magnetite (100%), iron oxide accounts for 50%-70%, silicate minerals for 10%-20%, harmful metal ion compounds for 0.1%-1%, and the remainder is harmless metal ion compounds. The excessive amount of harmful heavy metals in this material renders it unsuitable for food safety standards. Therefore, according to this application, natural magnetite needs to be pretreated to remove harmful impurities, resulting in raw magnetite that is safe and non-toxic, meeting food safety standards, and suitable as a raw material for non-stick coatings of cookware. In an exemplary embodiment, the raw magnetite is black and comprises: iron(III) oxide, harmless metal ions (e.g., iron, aluminum), and silicate minerals (quartz, calcium silicate, sodium silicate, etc.). Based on the total weight of the raw magnetite (100%), it comprises 90%-95% iron(III) oxide, 0.1%-1% silicate minerals, and the remainder harmless metal ions (e.g., iron ions, aluminum ions, titanium ions, vanadium ions, magnesium ions, zinc ions, and calcium ions). First, iron(III) oxide, as the main component of the raw magnetite, ensures the stability, hardness, and wear resistance of the coating, effectively resisting scratches and abrasions during cooking. Second, the presence of silicate minerals also has a positive impact on the coating's performance. Silicate minerals have good high-temperature resistance, enhancing the stability of the coating under high-temperature cooking environments. Furthermore, silicate minerals may participate in the coating formation process, improving the bonding strength between the coating and the substrate and reducing the risk of coating cracking and peeling. Finally, although the remaining harmless metal ions are present in low amounts, they may play a role in regulating the properties of the coating, enabling the final coating to have a higher degree of weathering and further optimizing the coating's non-stick properties, hardness, and resistance to external impacts.

[0051] In some embodiments, the method for preparing non-stick materials further includes removing impurities from natural magnetite to obtain raw magnetite. Thus, the raw magnetite meets food hygiene requirements and is suitable as a non-stick material for cookware.

[0052] Specifically, the impurity removal process for natural magnetite includes:

[0053] Primary grinding: Natural magnetite is crushed using a coarse grinding equipment to reduce the particle size to between 100μm and 300μm, which facilitates subsequent processing.

[0054] Primary magnetic separation: Magnetic separation equipment is used to treat the crushed and coarsely ground magnetite. The equipment uses magnetic differences to separate magnetic minerals from non-magnetic minerals, extracting the magnetic minerals (mainly magnetite).

[0055] Secondary grinding: The magnetite particles that have undergone one magnetic separation are ground into particles with a size between 25μm and 48μm using a grinding equipment.

[0056] Secondary magnetic separation: Magnetic separation equipment is used to treat the crushed and coarsely ground magnetite. Magnetic separation can remove silicate minerals (sodium silicate, calcium silicate).

[0057] Three-stage grinding: The impurity-removed magnetite is ground to make its particles even smaller, to 10μm-25μm.

[0058] Flotation: The powder after two magnetic separations is then subjected to flotation to remove impurities. Flotation utilizes the difference in affinity between different parts of the mineral and air bubbles. By injecting air bubbles into the flotation cell, silicate particles combine with the air bubbles and float to the surface, while magnetic magnetite particles sink to the bottom, thus achieving separation.

[0059] Acid washing: The flotation magnetite is washed with hydrochloric acid solution, the mass concentration of which is 8%-20%, so that the target metal ions (e.g., chromium ions, nickel ions, cobalt ions, copper ions) in the natural magnetite are dissolved. Then, through multiple water washing, filtration and drying, most of the harmful metal ions are removed to separate magnetite with higher purity.

[0060] High-temperature roasting: The high-purity magnetite obtained by acid washing is heated until it melts and kept at that temperature for 1-2 hours to volatilize harmful metal ions such as mercuric chloride and lead chloride, thus obtaining the final raw material magnetite.

[0061] In these embodiments, the pickling and high-temperature roasting steps can remove harmful metal ions from natural magnetite as much as possible, so as to obtain raw magnetite that can be used in accordance with this application.

[0062] Provide titanium dioxide

[0063] Titanium oxide (TiO2) includes various crystal forms, such as rutile, anatase, and perovskite. This application does not limit the crystal form of titanium oxide. In a preferred embodiment, the titanium oxide is rutile. Rutile TiO2 exhibits thermodynamic stability at temperatures below its melting point, possesses excellent wear resistance, and is suitable for forming non-stick coatings. It should be noted that other types of TiO2 can irreversibly transform into rutile TiO2 during solid-state sintering. Therefore, choosing rutile as the starting material can, to some extent, avoid structural changes and performance losses that may occur during phase transformation, thus facilitating the manufacture of the non-stick material of this application.

[0064] Raw material selection for forming lumps

[0065] In some embodiments, when the mass ratio of raw magnetite to titanium oxide in the raw material is the theoretically complete weight ratio for chemical reaction, regardless of the particle size of the raw magnetite and titanium oxide, the raw magnetite and titanium oxide will partially react to form a polymetallic cationic metal salt, while the titanium oxide will partially convert to sub-titanium oxide, with a remaining portion of raw magnetite, thereby enabling the formation of a non-stick material according to this application composed of polymetallic cationic metal salt, raw magnetite, and sub-titanium oxide.

[0066] In other embodiments, when there is a significant excess of titanium oxide in the raw material, controlling the particle size of the raw material can, to a certain extent, suppress the formation of polymetallic cationic titanates through solid-phase sintering. Specifically, when the particle sizes of the raw materials magnetite and titanium oxide are set to be comparable, for example, both being 1000-2000 mesh, due to the excess titanium oxide, all the raw material magnetite will react with the titanium oxide to form polymetallic cationic titanates. Simultaneously, the remaining titanium oxide will be converted into sub-titanium oxide, thereby enabling the formation of the non-stick material composed of polymetallic cationic titanates and sub-titanium oxide according to this application. When the particle size of the raw magnetite is significantly larger than that of titanium dioxide, for example, the particle size of the raw magnetite can be 500-1000 mesh (which can be converted to 13μm-25μm), and the particle size of titanium dioxide can be 1000-2000 mesh (which can be converted to 6.5μm-13μm). In this case, the raw magnetite and titanium dioxide will partially react to form a polymetallic cation metalate. At the same time, the titanium dioxide will be partially converted into sub-titanium dioxide. The raw magnetite powder has a coarse particle size and a slow reaction rate in the solid-phase reaction. The titanium dioxide powder is fine and in excess, and can uniformly coat the magnetite in the solid-phase reaction, but only partially reacts. In this case, the raw magnetite that cannot react in time will be retained, thereby ensuring that the formed non-stick material is a mixture of polymetallic cation metalates, raw magnetite, and sub-titanium dioxide particles, which can form the non-stick material according to this application.

[0067] As an example, the weight ratio of raw materials magnetite and titanium dioxide can be 2:3 to 2:5, in which case the titanium dioxide is in a suitable or excessive state, thereby forming the non-stick material according to this application.

[0068] According to this application, the raw material can be spherical or near-spherical in shape, which facilitates diffusion and contact between particles during solid-state sintering, ensuring mass transfer efficiency between particles and the formation rate of sintering necks. For example, spherical particles have a larger contact area and a smaller contact angle, which is beneficial for the formation of sintering necks and mass transfer. Secondly, due to their regular shape and good flowability, spherical particles have more uniform and denser contact between particles, making it easier to form a compact packing structure, thereby obtaining a high-density sintered body. In addition, sintered bodies made from spherical particles typically have higher strength and hardness, and possess better mechanical properties.

[0069] Formation of lumps consisting of raw materials magnetite and titanium dioxide

[0070] According to this application, forming a block comprising raw materials magnetite and titanium dioxide includes uniformly mixing the mixture with a volatile binder and forming the block by pressing. As an example, the pressing pressure is 20 MPa-100 MPa, and the pressing holding time is 2 min-5 min. As an example, the binder accounts for 1%-10% of the total weight of the mixed raw materials magnetite and titanium dioxide, and the binder includes at least one of low-melting-point polyethylene glycol, polyvinyl alcohol, and liquid paraffin.

[0071] Partial solid-state sintering of the bulk material yields a non-stick bulk.

[0072] In some embodiments, the bulk material is subjected to solid-state sintering to obtain a partially solid-state sintered non-stick bulk. During the preparation of the non-stick material, a bulk material comprising raw materials magnetite and titanium dioxide is used. By controlling the sintering temperature, time, and reducing atmosphere, it is ensured that the raw materials can be partially sintered and fused into a polymetallic cation metal salt. Simultaneously, under the influence of the reducing atmosphere and temperature, oxygen from some of the titanium dioxide escapes, forming sub-titanium dioxide that can be used to improve non-stickiness. Additionally, due to the influence of particle size, a certain amount of raw material magnetite may remain in the final non-stick bulk. As an example, solid-state sintering is carried out in a vacuum furnace. Specifically, the bulk material is placed in a vacuum furnace and treated at a controlled temperature of 1100°C-1400°C for 8-20 hours under a continuous reducing atmosphere (e.g., carbon monoxide or hydrogen, preferably carbon monoxide) to heat the bulk material and form a partially sintered non-stick bulk. During solid-state sintering, the binder volatilizes, so there is no binder in the non-stick bulk. As some examples, the non-stick bulk material consists of mixed particles of polymetallic cationic titanate, magnetite, and titanium suboxide. As other examples, the non-stick bulk material consists of mixed particles of polymetallic cationic titanate and titanium suboxide. In these examples, the magnetite is partially unreacted raw magnetite, and the titanium suboxide comprises 60%-80% Ti4O7 and the balance being Ti2O3 and Ti3O4.

[0073] According to this application, the obtained non-stick bulk material possesses sufficient amorphousness to ensure that the non-stick material obtained after subsequent processing has non-stick properties suitable for use in cookware. As an example, the amorphous phase volume fraction of the non-stick bulk material is 80%-90%.

[0074] In this application, most of the raw materials in the bulk material undergo solid-state sintering, while a small portion does not. As an example, based on the total weight of the bulk material as 100%, 80%-90% of the bulk material undergoes a solid-state reaction, with the remainder being the portion of the bulk material that does not undergo a solid-state reaction. Thus, in the final non-stick material mixed particles, the weight percentage of polymetallic cationic titanate is 80%-90%, with the remainder being the magnetite and titanium suboxide.

[0075] In some embodiments, the preparation method of the non-stick material further includes performing phase analysis, microstructure observation and non-stick performance testing on the obtained non-stick bulk material to verify whether it has achieved the expected effect of partial sintering.

[0076] Cooling the non-stick block

[0077] According to this application, the cooling process of the non-stick bulk can be controlled to increase the volume ratio of the amorphous phase in the final non-stick material. Of course, this application may also not control the cooling process. For example, it can be cooled to room temperature in the furnace. This is because the non-stick bulk formed by the aforementioned method already has a sufficient volume ratio of the amorphous phase.

[0078] The following description will focus solely on controlling the cooling process of the non-stick block.

[0079] In some embodiments, cooling the non-stick bulk can also help control the crystallization process of the non-stick material, avoid unnecessary chemical reactions, and ensure the quality and performance of the final product. In some embodiments, cooling the non-stick bulk includes placing it under air cooling conditions of 20°C / min-50°C / min. When the non-stick bulk is cooled under air cooling conditions of 20°C / min-50°C / min, the cooling rate is relatively fast, which helps to quickly reach the required temperature for rapid forming and helps to refine the grain structure of the material, improving its mechanical and physical properties. In some embodiments, the amorphous phase volume fraction of the non-stick material is 85%-95%, which is approximately 5% higher than the aforementioned percentage.

[0080] In these embodiments, under the aforementioned air-cooling conditions, the non-stick bulk material can be cooled and, upon crushing, forms a reaction product comprising the raw material magnetite and titanium dioxide, a polymetallic cationic titanate, unreacted raw material magnetite (hereinafter referred to as magnetite), and sub-titanium dioxide. After the non-stick bulk material is crushed, the unreacted raw material magnetite and sub-titanium dioxide are dispersed between the particles of the polymetallic cationic titanate.

[0081] Crushed

[0082] According to this application, after cooling, the non-stick block obtained by cooling is crushed and ground, and then screened to obtain the non-stick material according to this application. Specifically, it is first crushed into small pieces using a jaw crusher, then ground to a suitable particle size using a Raymond mill, ball mill, or other grinding methods, and finally screened to obtain granular non-stick material.

[0083] According to a second aspect of this application, a non-stick material is provided, wherein the non-stick material comprises mixed particles of a polymetallic cationic titanate and an auxiliary material, wherein the auxiliary material comprises magnetite and titanium suboxide, or comprises titanium suboxide, wherein the mixed particles have an amorphous structure, and based on the total weight of the mixed particles being 100%, the weight percentage of the polymetallic cationic titanate is 80%-90%, the weight percentage of the magnetite is 0%-10%, and the weight percentage of the titanium suboxide is 10%-20%.

[0084] According to the non-stick material of this application, the non-stick material includes polymetallic cationic titanate, and its content indicates that it constitutes the main component of the non-stick material. Belonging to ceramic materials and possessing an amorphous structure, the non-stick material exhibits overall amorphous properties. Since amorphous structures possess lower surface energy, better hardness, chemical stability, and thermal stability compared to crystalline structures, using materials with amorphous structures, including polymetallic cationic titanate, as non-stick materials can meet the requirements of cookware for initial non-stickness, long-term non-stickness, hardness, and resistance to external impacts. The non-stick material also includes auxiliary materials such as magnetite and titanium suboxide. This mixture of substances facilitates the release of internal stress in the coating, preventing the non-stick layer from peeling off due to mechanical or thermal shocks during use. Furthermore, due to the different coefficients of thermal expansion of different materials, during the cooling process, uniform small pores form around the uniformly dispersed magnetite and titanium suboxide particles in the non-stick material, giving the non-stick coating a porous structure capable of storing oil. Therefore, the non-stick coating can further enhance the non-stickness of cookware due to the oil film effect.

[0085] In some embodiments, the sub-titanium oxide comprises Ti2O3, Ti3O4, and Ti4O7, wherein the sub-titanium oxide comprises 60%-80% Ti4O7 and the balance Ti2O3 and Ti3O4.

[0086] In some embodiments, the resulting non-stick material has a particle size of 300-500 mesh. A particle size range of 300-500 mesh means that the non-stick material has relatively small and uniform particle size, which helps to form a dense and uniform non-stick coating on the substrate surface. Furthermore, this particle size of non-stick material ensures proper spraying by the plasma spraying equipment, thereby guaranteeing the quality of the non-stick coating.

[0087] In some embodiments, the non-stick material is black, the black color primarily due to the iron oxide in its composition. The black non-stick material does not change color after spraying, thus forming a black non-stick coating. This black coating weakens the contrast of the charred discoloration during use, enhancing the user's visual experience.

[0088] In some embodiments, the amorphous phase volume ratio of the non-stick material is 80%-98%. The non-stick material has a high proportion of amorphous phase, and the material exhibits excellent performance in terms of surface energy, hardness, wear resistance, corrosion resistance and toughness. Therefore, it can maintain the stability of its structure and performance when facing harsh environments such as high temperature and chemical corrosion, thereby extending the service life of the non-stick coating.

[0089] According to a third aspect of this application, a non-stick coating is provided for use in cookware, wherein the non-stick coating is formed by thermal spraying using the non-stick material employed in the various embodiments described above.

[0090] According to this application, the non-stick coating is an inorganic titanate-based coating, which has high hardness and high temperature resistance, and can resist scratches and high-temperature deformation. It also possesses good corrosion resistance.

[0091] In some embodiments, the surface pores of the non-stick coating can be used to store oil, thereby improving the non-stick properties of cookware with the coating by storing oil and optimizing corrosion resistance by closing the pores.

[0092] In some embodiments, the surface energy of the non-stick coating is 35 to 80 dynes.

[0093] In some embodiments, the porosity of the non-stick coating is 10% to 25%, and / or the pore size of the non-stick coating is 0.1 μm to 8 μm, such that the pore structure is suitable for oil storage and optimizes non-stick properties.

[0094] In some embodiments, the hardness of the non-stick coating is 400HV to 800HV, which ensures the hardness and wear resistance of the cookware and guarantees that the coating can remain non-stick for a long time.

[0095] In some embodiments, the volume percentage of the amorphous phase in the non-stick coating is 80%-95%.

[0096] In some embodiments, the non-stick coating is black, which can weaken the contrast of the charred color during use and improve the user's visual experience.

[0097] In some embodiments, the non-stick coating is a ceramic coating. Ceramic coatings are more brittle than coatings formed from metal materials and are easily polished during use, thus ensuring that the cookware remains clean and new during use.

[0098] According to a fourth aspect of this application, a non-stick cookware is provided, wherein the non-stick cookware includes a substrate and a non-stick coating formed on the substrate.

[0099] According to this application, the non-stick material is a ceramic material, while the cookware substrate is generally a metal material. Therefore, the adhesion between the non-stick material and the cookware substrate is slightly weaker. To improve the adhesion between the two, in some embodiments, the non-stick cookware also includes a base coat made of a metal material, wherein the base coat is formed between the substrate and the non-stick coating. In exemplary embodiments, the metal material may include at least one of iron and its alloys, zinc and its alloys, aluminum and its alloys, titanium and its alloys, chromium and its alloys, nickel and its alloys, cobalt and its alloys, copper and its alloys, zirconium and its alloys, molybdenum and its alloys, and vanadium and its alloys. However, those skilled in the art can also select other suitable materials as binders under the guidance of this application to improve the adhesion between the non-stick material and the coating formed on the product.

[0100] According to this application, a method for preparing a non-stick cookware is provided, wherein the method for preparing a non-stick cookware includes:

[0101] A non-stick coating is formed on the substrate by thermal spraying of a non-stick material.

[0102] The preparation method of the non-stick cookware of this application will be described in detail below.

[0103] Provide matrix

[0104] According to this application, the substrate can be made of commonly used materials. Exemplarily, the material can be stainless steel, titanium, aluminum, their corresponding alloys, and composite materials. The substrate can have a shape corresponding to its function; for example, when the non-stick cookware is a non-stick pan, the substrate can have a conventional pan shape.

[0105] According to this application, the substrate can be pretreated, for example, by grinding, sandblasting, pickling, etc. The substrate surface has a certain roughness; in an exemplary embodiment, the Ra value of the roughness can be in the range of 3μm-5μm.

[0106] Provide non-stick materials

[0107] According to this application, the non-stick material can be prepared by the methods for preparing non-stick materials described in the above embodiments of this application, which will not be repeated here.

[0108] Form a non-stick coating

[0109] According to this application, the non-stick coating can at least partially cover the inner surface of the substrate, meaning that the non-stick coating can cover the bottom surface or the entire inner surface of the substrate. The non-stick coating may be formed by spraying a non-stick material with a certain amorphous phase volume ratio as provided in the embodiments of this application, thereby having improved non-stick properties (initial non-stick and durable non-stick) and hardness.

[0110] According to some embodiments of this application, the non-stick material powder can possess a certain degree of amorphousness, for example, 80%-95%. The non-stick material powder can retain its amorphous nature to form a non-stick coating with a certain amorphous phase volume ratio. Specifically, during the spraying process, only the surface of the non-stick material is micro-melted, causing the individual particles to connect with each other, thereby obtaining a non-stick coating with an amorphous phase volume ratio of 80%-95%. This amorphous phase volume ratio is obtained by the material itself possessing amorphous properties and retaining them after spraying.

[0111] In an exemplary embodiment, the spraying is thermal spraying, specifically plasma spraying. The process parameters for plasma spraying can be: powder feed rate 20g / min-50g / min; spraying distance 80mm-100mm; arc current 450A-650A; voltage 50V-70V; hydrogen pressure 0.2MPa-0.4MPa, hydrogen flow rate 6L / min-15L / min; argon pressure 2.5MPa-4.0MPa, argon flow rate 1000L / min-1500L / min; spraying angle 45°-80°; and workpiece temperature at room temperature.

[0112] Conventional ceramic powders are dense, and the pores in the coating originate from powder stacking. These pores are typically closed pores, meaning they are not interconnected. After coating formation, the depth is limited to a small surface area, resulting in limited oil storage capacity. According to this application, the non-stick material comprises mixed particles of polymetallic cationic titanate and auxiliary materials, and the particle surface itself contains pores. By performing thermal spraying on the non-stick material powder within the aforementioned process parameters, a non-stick coating of suitable thickness with amorphous properties and a porous structure can be formed on the surface of the substrate. For example, the formed non-stick coating can have a thickness of 40 μm to 100 μm. For example, the pores in the porous structure are interconnected, possessing a certain depth, greatly enhancing the oil storage effect. As an example, the porosity of the formed non-stick coating can be 10% to 25%, and the pore size can be 0.1 μm to 8 μm. This non-stick coating has properties similar to those of the non-stick material, thus exhibiting good non-stick properties, improved hardness, and the desired porosity for oil storage. In other words, the amorphous non-stick coating conceived according to the present invention can retain the various properties of the aforementioned non-stick materials and can exhibit properties superior to those of non-stick materials due to spraying, such as, but not limited to, non-stickiness and hardness.

[0113] Plasma-sprayed inorganic ceramic coatings generally suffer from adhesion strength issues. This is because, firstly, inorganic ceramics typically have high melting points and poor thermal conductivity, making it difficult for the powder to completely melt during plasma spraying; only the surface of the powder particles melts, resulting in fewer bonding points between particles and making them prone to breakage. Secondly, inorganic ceramics themselves have high hardness and poor toughness, making them prone to releasing stress through cracking when deformed. Based on these two points, ceramic coatings are susceptible to external impacts (mechanical and thermal shocks), leading to coating cracking and detachment. However, by performing thermal spraying on the non-stick material powder within the process parameters of this application, a non-stick coating that resists certain external impacts can be formed on the substrate surface. This is because the non-stick material, in the form of a mixture of various substances, facilitates bonding between particles and promotes the release of internal stress within the coating, thus preventing detachment due to mechanical and thermal shocks during use.

[0114] According to other embodiments of this application, the non-stick material powder itself has a certain degree of amorphousness, for example, it can be 80%-95%. The non-stick material is used, and the spraying process is controlled to form a non-stick coating with a relatively high amorphous phase volume ratio. Exemplarily, the amorphous phase volume ratio in the non-stick coating is 83%-98%. This amorphous phase volume ratio is about 3% higher than in the aforementioned embodiments. This is because the various components of the non-stick material itself form a more complex titanate structure during the spraying process, and the degree of amorphization tends to increase, thereby enabling the non-stick coating to exhibit relatively superior properties.

[0115] According to this application, controlling the spraying process includes intervening to a certain extent during the formation of a non-stick coating using a non-stick material. Specifically, the substrate includes a first surface and a second surface facing away from each other. The steps of controlling the spraying process include: cooling the second surface of the substrate, and spraying a non-stick material onto the first surface of the substrate, thereby forming a non-stick coating with an amorphous phase volume ratio of 83%-98% on the first surface of the substrate. The step of cooling the second surface of the substrate includes applying cold air to the second surface of the substrate and controlling the temperature of the cold air at -15℃ to 0℃. Then, the non-stick material is sprayed onto the first surface of the substrate, thereby forming a non-stick coating with a predetermined amorphous phase volume ratio on the first surface of the substrate, resulting in a non-stick coating with low surface energy and good non-stick properties. It should be noted that the first surface can be an inner surface and the second surface can be an outer surface. Of course, this application does not impose excessive limitations on this. It is understood that those skilled in the art, under the guidance of this application, can make the first surface an outer surface and the second surface an inner surface according to actual usage requirements.

[0116] In an exemplary embodiment, the step of applying cooling includes placing the second surface of the substrate in an environment of cooling gas. The temperature of the cooling gas is -15°C to 0°C, and the flow rate of the cooling gas is 2000 L / h to 4000 L / h.

[0117] Pore ​​oil storage

[0118] According to this application, the titanium oxide and magnetite dispersed between the particles of the polymetallic cation metal salt not only help to enhance the overall stability and hardness of the non-stick material, but also ensure the formation of a coating with an oil-retaining porous structure, thereby further improving the non-stick performance.

[0119] According to this application, due to the different coefficients of thermal expansion of different materials, uniform small pores will be formed around the magnetite powder and titanium suboxide particles during the cooling process, making the surface structure of the non-stick coating more dense. It can be understood that the surface of the non-stick coating has a pre-set pore structure, which is conducive to the storage of grease or silicone oil and will make the non-stick properties better.

[0120] According to this application, the surface of the non-stick coating can be filled with grease or silicone oil to form an "oil film" on the surface of the non-stick coating, thereby achieving non-stick properties. Furthermore, filling the pores with grease or silicone oil can prevent erosion by corrosive media and ensure corrosion resistance. In some embodiments, before filling the pore structure with grease or silicone oil, the inner surface of the substrate can be polished with a 120-grit silicon carbide grinding wheel to achieve a surface roughness Ra of 4μm-6μm. Then, it can be sanded with a scouring pad using both forward and reverse rotation until the roughness Ra is less than 2μm. Following ultrasonic cleaning to remove dust and drying, the surface of the non-stick coating will achieve good roughness and cleanliness, providing favorable conditions for subsequent grease or silicone oil filling operations.

[0121] In some embodiments, silicone oil can be applied to the surface of the non-stick coating, allowing it to penetrate the surface pores of the non-stick coating, and then sintered at a first predetermined temperature for a first predetermined time, thereby forming a surface seal in the non-stick coating. In an exemplary embodiment, the silicone oil can be polydimethyl silicone oil. After coating, the cookware coated with polydimethyl silicone oil can be placed in a sintering furnace for curing, wherein the first predetermined curing temperature is 300℃-400℃, and the first predetermined curing time is 3-10 minutes.

[0122] In other embodiments, the non-stick coating can be immersed in grease at a second predetermined temperature for a second predetermined time, allowing the grease to penetrate the surface pores of the non-stick coating and form a surface seal. In an exemplary embodiment, the grease may include edible oil (peanut oil, rapeseed oil) or palm oil. The edible oil or palm oil is heated to a second predetermined temperature and maintained for a second predetermined time to form a sealing layer on the non-stick coating, wherein the second predetermined temperature is 80℃-100℃ and the second predetermined time is 10-30 minutes.

[0123] According to this application, by filling with grease or silicone oil, an "oil film" is formed on the surface of the non-stick coating. It should be noted that silicone oil is better than grease in optimizing non-stick properties. For example, before silicone oil treatment, the non-stick coating can have a surface energy of 40 to 80 dynes. Although this is lower than the surface energy of fluoropolymer non-stick coatings (18 to 25 dynes), after grease or silicone oil treatment, the surface energy can be reduced to 35 to 40 dynes, thus achieving non-stick properties close to those of fluoropolymer non-stick coatings. By filling with grease or silicone oil, a sealing layer is formed on the surface of the non-stick coating, preventing corrosive media from penetrating, thereby improving the corrosion resistance of the cookware coating.

[0124] 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 embodiments.

[0125] Example 1

[0126] Step S10: Prepare the cookware base. Specifically, the composite titanium sheet is deep-drawn, surface-washed with alkali to remove oil, dried, and sandblasted to obtain a cookware base with a thickness of 1.5cm.

[0127] Step S20: Provide non-stick material.

[0128] Step S21: Prepare a non-stick material with an average particle size of 500 mesh, wherein the amorphous phase of the non-stick material accounts for 83% of the volume, and based on the total weight of the mixed particles as 100%, the weight percentage of calcium magnesium zinc titanate is 80%, the weight percentage of magnetite is 10%, and the weight percentage of titanium suboxide is 10%.

[0129] Step S30: Spray non-stick material onto the cookware substrate.

[0130] The outer surface of the cookware substrate was placed in a circulating cooling air environment with a temperature of -15°C. Then, 400-mesh non-stick material powder was loaded into a powder feeder with the following parameters set: powder feeding speed 30 g / min; spraying distance 90 mm; arc current 550 A; voltage 60 V; hydrogen pressure 0.3 MPa, hydrogen flow rate 8 L / min; argon pressure 3 MPa, argon flow rate 1200 L / min; and spraying angle 60°. The non-stick material powder was sprayed onto the inner surface of the cookware substrate, resulting in a 65 μm thick non-stick coating, thus completing the manufacture of the cookware in Example 1.

[0131] Example 2

[0132] Except in step S20, where a different non-stick material is used instead of the non-stick material of Example 1 (the non-stick material of this example has an amorphous phase volume ratio of 83%, and based on the total weight of the mixed particles of 100%, the weight ratio of calcium magnesium zinc titanate is 80%, the weight ratio of magnetite is 5%, and the weight ratio of titanium suboxide is 15%), the cookware of Example 2 is manufactured using the same method as in Example 1.

[0133] Example 3

[0134] Except in step S20, where a different non-stick material is used to replace the non-stick material of Example 1 (the non-stick material in this example has an amorphous phase volume ratio of 83%, and based on the total weight of the mixed particles being 100%, the weight ratio of calcium magnesium zinc titanate is 80%, and the weight ratio of titanium suboxide is 20%), the cookware of Example 3 is manufactured using the same method as in Example 1.

[0135] Example 4

[0136] Except in step S20, where a different non-stick material is used instead of the non-stick material of Example 1 (the non-stick material of this example has an amorphous phase volume ratio of 88%, and based on the total weight of the mixed particles of 100%, the weight ratio of calcium magnesium zinc titanate is 85%, the weight ratio of magnetite is 5%, and the weight ratio of titanium suboxide is 10%), the cookware of Example 4 is manufactured using the same method as in Example 1.

[0137] Example 5

[0138] Except in step S20, where a different non-stick material is used instead of the non-stick material of Example 1 (the non-stick material in this example has an amorphous phase volume ratio of 88%, and with the total weight of the mixed particles being 100%, the weight ratio of calcium magnesium zinc titanate is 85%, and the weight ratio of titanium suboxide is 15%), the cookware of Example 5 is manufactured using the same method as in Example 1.

[0139] Example 6

[0140] Except in step S20, where a different non-stick material is used instead of the non-stick material of Example 1 (the non-stick material in this example has an amorphous phase volume ratio of 93%, and based on the total weight of the mixed particles of 100%, the weight ratio of calcium magnesium zinc titanate is 90%, and the weight ratio of titanium suboxide is 15%), the cookware of Example 6 is manufactured using the same method as in Example 1.

[0141] Example 7

[0142] Except in step S20, where a different non-stick material is used instead of the non-stick material of Example 1 (the non-stick material of this example has an amorphous phase volume ratio of 96%, and based on the total weight of the mixed particles of 100%, the weight ratio of polymetallic cationic titanate is 85%, the weight ratio of magnetite is 5%, and the weight ratio of titanium suboxide is 10%), the cookware of Example 7 is manufactured using the same method as in Example 1.

[0143] Example 8

[0144] Except in step S20, where a different non-stick material is used instead of the non-stick material of Example 1 (the non-stick material of this example has an amorphous phase volume ratio of 96%, and based on the total weight of the mixed particles of 100%, the weight ratio of the polymetallic cationic titanate is 85%, and the weight ratio of the sub-titanium oxide is 15%), the cookware of Example 8 is manufactured using the same method as in Example 1.

[0145] Example 9

[0146] Except in step S20, where a different non-stick material is used instead of the non-stick material of Example 1 (the non-stick material of this example has an amorphous phase volume ratio of 98%, and based on the total weight of the mixed particles of 100%, the weight ratio of polymetallic cationic titanate is 85%, the weight ratio of magnetite is 5%, and the weight ratio of titanium suboxide is 10%), the cookware of Example 9 is manufactured using the same method as in Example 1.

[0147] Example 10

[0148] Except in step S20, where a different non-stick material is used instead of the non-stick material of Example 1 (the non-stick material of this example has an amorphous phase volume ratio of 98%, and based on the total weight of the mixed particles of 100%, the weight ratio of the polymetallic cationic titanate is 85%, and the weight ratio of the titanium suboxide is 15%), the cookware of Example 10 is manufactured using the same method as in Example 1.

[0149] Example 11

[0150] Except in step S30, where the outer surface of the cookware substrate is not placed in a circulating cooling air environment, the cookware of Example 11 is manufactured using the same method as in Example 1.

[0151] Example 12

[0152] Except that in step S21, a 300-mesh non-stick material is used instead of the non-stick material of Example 1, the cookware of Example 12 is manufactured using the same method as that of Example 1.

[0153] Example 13

[0154] Except that in step S21, a 400-mesh non-stick material is used instead of the non-stick material of Example 1, the cookware of Example 13 is manufactured using the same method as Example 1.

[0155] Example 14

[0156] Except for filling the non-stick coating obtained in Example 1 with silicone oil, the cookware of Example 14 was manufactured using the same method as in Example 1.

[0157] Example 15

[0158] Except for filling the non-stick coating obtained in Example 1 with edible oil, the cookware of Example 15 was manufactured using the same method as in Example 1.

[0159] Comparative Example 1

[0160] Except that in step S20, natural magnetite 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.

[0161] Comparative Example 2

[0162] Except for replacing the non-stick material of Example 1 with a different material (magnesium ferrous titanate in this comparative example) in step S20, the cookware of Comparative Example 2 was manufactured using the same method as that of Example 1.

[0163] Comparative Example 3

[0164] Except for replacing the non-stick material of Example 1 with a different material (ferrous magnesium aluminum titanate in this comparative example) in step S20, the cookware of Comparative Example 3 was manufactured using the same method as in Example 1.

[0165] Comparative Example 4

[0166] Except for replacing the non-stick material of Example 1 with a different material (ferrous magnesium aluminum copper titanate in this comparative example) in step S20, the cookware of Comparative Example 4 was manufactured using the same method as in Example 4.

[0167] Comparative Example 5

[0168] Except for replacing the non-stick material of Example 1 with a different material (magnetite powder, the raw material of this application) in step S20, the cookware of Comparative Example 5 was manufactured using the same method as in Example 1.

[0169] Comparative Example 6

[0170] Except for replacing the non-stick material of Example 1 with a different material (titanium suboxide in this comparative example) in step S20, the cookware of Comparative Example 6 was manufactured using the same method as in Example 1.

[0171] Test methods and evaluation criteria, test results

[0172] Regarding the above Example The coatings of the cookware obtained in Examples 1 to 15 and Comparative Examples 1 to 6 were subjected to performance tests, and the results are recorded in Table 1 below. The specific performance test methods are as follows:

[0173] I. Testing Methods and Evaluation Criteria

[0174] 1. Amorphousness Testing Method: XRD testing is used, followed by analysis and calculation using a conventional full-spectrum fitting method to obtain the degree of amorphization of the coating. The steps of the conventional full-spectrum fitting method are as follows: First, a crystalline phase with the same chemical structure as the amorphous phase is found. It is assumed that the amorphous phase is a tiny grain of this crystalline phase, and this crystalline phase can be used to establish a model of the peak position and intensity of the amorphous phase. Second, the spectrum of the pure amorphous phase is fitted to determine the grain size and microstrain. Finally, the grain size and microstrain are fixed, and this phase is included in the traditional Rietveld quantitative calculation to obtain the volume fraction of the amorphous phase in the coating (i.e., the degree of amorphization).

[0175] 2. Initial non-stick test method: GB / T32095.2-2015 test method for non-stick properties of fried eggs. This method is for initial non-stick properties and is divided into three levels: I, II and III. Level I has the best non-stick properties and Level III has the worst non-stick properties.

[0176] 3. Durable non-stick test method: The durable non-stick test method in GB / T32388-2015, the unit is the number of times. The higher the number of times, the longer the life. 500 times is used to evaluate the non-stick result once. The number of times is recorded until the use reaches level III.

[0177] 4. Hardness Testing and Evaluation Standards: The Vickers hardness test method is used to test the Vickers hardness of the cookware coating. The unit of hardness value is HV. For hardness testing, the higher the measured hardness value, the harder the sample. When the sample is a non-stick coating, the higher the hardness, the harder the non-stick coating, the stronger its resistance to abrasion from metal spatulas and food, and the less easily it is worn away, thus resulting in a longer service life. Generally speaking, it is expected that the hardness of the non-stick coating is not less than 200 HV.

[0178] 5. Surface Energy Testing and Evaluation Standards: Under a temperature condition of 20°C, the contact angles of water and ethylene glycol on the sample surfaces were measured using a SINDIN SDC-200SH contact angle meter according to the antegrade method, and the surface energy of the samples was calculated using the OWRK method. Here, the sample refers to the coating of the cookware obtained in the examples and comparative examples. For surface energy testing, it is expected that the measured surface energy value of the sample will not exceed 100 dynes.

[0179] 6. Mechanical Impact Test and Evaluation Standard: A 500g steel ball is dropped freely from a height of 10cm onto the coating surface of the cookware. Observe whether the surface cracks or peels off. If not, continue dropping the ball 5cm until the coating cracks or peels off, and record the height at which this phenomenon occurs. For the mechanical impact test, the expected mechanical impact value of the sample is not less than 30cm.

[0180] 7. Thermal shock test: Dry-heat the cookware on a gas stove over high heat until any point on the bottom reaches 450℃, then quickly immerse it in 50L of room temperature (25±2℃) tap water. Repeat this process until the coating cracks and peels off. Record the number of times this occurs. The more times this happens, the better the properties of the cookware coating.

[0181] II. Test Results

[0182] Table 1 Test Results

[0183]

[0184] As shown in Table 1, the non-stick coating on the surface of the cookware has a good degree of amorphization. The higher the degree of amorphization, the higher the hardness, the better the wear resistance, and the stronger the long-lasting non-stick properties. Since the surface of the non-stick coating is filled with grease, on the one hand, it can improve the non-stick properties (initial non-stick and long-lasting non-stick), and on the other hand, it can further seal the pores and improve the corrosion resistance of the cookware.

[0185] As can be seen from Examples 1, 12 and 13, non-stick materials with larger particle sizes have better long-lasting non-stick properties. This is because larger particle sizes can form suitable surface roughness structures, which can protect the surface grease layer and ensure longer-lasting non-stick properties.

[0186] As can be seen from Examples 1 and 11, by controlling the spraying process (i.e., placing the outer surface of the cookware in a cooling gas environment during the plasma spraying process), the degree of amorphization of the non-stick coating can be increased to a certain extent, resulting in a relatively low surface energy and thus ensuring good and durable non-stick performance.

[0187] In summary, according to this application, the coating of the cookware has excellent initial non-stick properties, long-lasting non-stick properties, hardness, and resistance to external impacts, thus making the cookware more durable.

[0188] The coating on cookware in comparison obviously cannot simultaneously possess multiple properties such as initial non-stickness, long-lasting non-stickness, hardness, and resistance to external impacts. Therefore, the cookware is less durable.

[0189] While the invention has been specifically shown and described with reference to exemplary embodiments thereof, those skilled in the art will understand that various changes in form and detail may be made herein without departing from the spirit and scope of the invention as defined by the claims and their equivalents. The embodiments should be considered in a descriptive sense and not for limiting purposes only. Therefore, the scope of the invention is not defined by the specific embodiments thereof, but by the claims, and all differences within that scope will be construed as included in the invention.

[0190] While embodiments of this application have been described in detail above, those skilled in the art can make various modifications and variations to the embodiments of this application without departing from the spirit and scope of this application. However, it should be understood that, in the view of those skilled in the art, these modifications and variations will still fall within the spirit and scope of the embodiments of this application as defined in the claims.

Claims

1. A non-stick material, characterized in that, The non-stick material comprises particles in the form of a mixture of polymetallic cationic titanate and auxiliary materials. The polymetallic cationic titanate has an amorphous structure, and the auxiliary materials are dispersed between the polymetallic cationic titanate. The auxiliary materials are magnetite and titanium suboxide, or titanium suboxide. The particles in the form of the mixture have an amorphous structure. Based on the total weight of the particles in the form of the mixture as 100%, the weight percentage of the polymetallic cationic titanate is 80%-90%, the weight percentage of the magnetite is 0%-10%, and the weight percentage of the titanium suboxide is 10%-20%.

2. The non-stick material according to claim 1, characterized in that, The particle size of the non-stick material is 300-500 mesh.

3. The non-stick material according to claim 2, characterized in that, The non-stick material includes at least one of the following characteristics: The non-stick material is black in color; The non-stick material has an amorphous phase volume ratio of 80%-98%; The metal ions in the polymetallic cationic titanate include iron ions, aluminum ions, titanium ions, vanadium ions, magnesium ions, zinc ions, and calcium ions.

4. A method for preparing a non-stick material, characterized in that, The method for preparing the non-stick material includes: Solid-state sintering of a block of raw materials, including magnetite and titanium dioxide, yields a non-stick block. The non-stick bulk material is cooled and then pulverized to obtain a non-stick material comprising particles in the form of a mixture of polymetallic cationic titanates and auxiliary materials. The auxiliary materials are magnetite and titanium suboxide, or titanium suboxide. The particles in the mixed form have an amorphous structure. Based on the total weight of the particles in the mixed form as 100%, the weight percentage of the polymetallic cationic titanate is 80%-90%, the weight percentage of the magnetite is 0%-10%, and the weight percentage of the titanium suboxide is 10%-20%.

5. The method for preparing the non-stick material according to claim 4, characterized in that, The method for preparing the non-stick material further includes: The natural magnetite powder is subjected to at least acid washing and roasting treatment to obtain the raw magnetite.

6. The method for preparing the non-stick material according to claim 4, characterized in that, Based on the total weight of the raw magnetite as 100%, the main components of the raw magnetite include 90%-95% iron(III) oxide, 0.1%-1% silicate minerals, and the balance being harmless metal ions.

7. The method for preparing the non-stick material according to claim 4, characterized in that, The solid-state sintering of the bulk material comprising raw materials magnetite and titanium dioxide includes: The bulk material, consisting of raw magnetite and titanium dioxide, is treated at 1100℃-1400℃ for 8-20 hours.

8. The method for preparing the non-stick material according to claim 4, characterized in that, The cooling of the non-stick block includes: The non-stick block was cooled under air cooling conditions of 20℃ / min-50℃ / min.

9. The method for preparing the non-stick material according to claim 4, characterized in that, The mass ratio of the raw materials, magnetite and titanium dioxide, is 2:3 to 2:

5.

10. The method for preparing the non-stick material according to claim 4, characterized in that, The particle size of the raw material magnetite is 500-2000 mesh; and / or The titanium oxide has a particle size of 1000-2000 mesh.

11. A non-stick coating, characterized in that, The non-stick coating is formed by thermal spraying of the non-stick material according to any one of claims 1 to 3, or by thermal spraying of the non-stick material prepared by the method of preparing the non-stick material according to any one of claims 4 to 10.

12. A non-stick cookware, characterized in that, The non-stick cookware includes a substrate and a non-stick coating according to claim 11 formed on the substrate.

13. The non-stick cookware according to claim 12, characterized in that, The surface of the non-stick coating is filled with grease or silicone oil.

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