Non-stick material, method for producing the same, use of the non-stick material as a spray material and non-stick cookware

Abstract

This application provides non-stick materials and their preparation methods, applications of non-stick materials as spray coating raw materials, and non-stick cookware. The non-stick material comprises a composite metal oxide with an amorphous structure, wherein the metal elements in the composite metal oxide include iron ions and titanium ions with different valence states. The non-stick material provided according to the embodiments of this application is a composite metal oxide with an amorphous structure and comprising iron ions and titanium ions with different valence states. It inherently has a low surface energy and possesses certain initial non-stick properties. Furthermore, the non-stick layer formed by this non-stick material does not age with prolonged use, exhibiting good physical and chemical stability. Therefore, it can possess more durable and long-lasting non-stick properties.

Description

Technical Field

[0001] This application relates to the field of non-stick cookware technology, and more specifically, to a non-stick material for cookware or cups and its preparation method, the application of the non-stick material as a spray coating raw material, 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 material 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 material and its preparation method, the application of the non-stick material as a spraying raw material, and non-stick cookware, so as to solve the problem that the layer formed by the existing non-stick material cannot have both initial non-stick and long-term non-stick properties.

[0005] According to a first aspect of this application, a non-stick material is provided for use in cookware, wherein the non-stick material comprises a composite metal oxide having an amorphous structure, and the metal elements in the composite metal oxide include iron ions and titanium ions in different valence states.

[0006] The non-stick material provided in the embodiments of this application has a low surface energy, and the non-stick layer formed therefrom has a certain initial non-stick performance. In addition, the non-stick layer formed by this non-stick material does not age with the extension of use time and has good physical and chemical stability. Therefore, it can have more durable and long-lasting non-stick performance.

[0007] In some embodiments, the iron ions of different valence states include Fe. 2+ and Fe 3+ The titanium ions of different valence states include Ti 2+ Ti 3+ Ti 4+ .

[0008] In these embodiments, the different arrangements of the aforementioned valence metal ions in the crystal lattice result in the non-stick material having an amorphous structure.

[0009] In some embodiments, the non-stick material further includes carbonized products of the binder, which are dispersed in the composite metal oxide.

[0010] In these embodiments, carbonized products of the binder are dispersed in the particles of the composite metal oxide. On the one hand, the presence of carbonized products of the binder can facilitate the connection of each particle of the matrix and ensure 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 can make the non-stick material as a whole exhibit high hardness and stability.

[0011] In some embodiments, the weight ratio of the carbonized product of the adhesive to the composite metal oxide is (0.4-3.5):(96.5-99.6). Having a suitable weight ratio of carbonized product of the adhesive to the composite metal oxide avoids excessive carbonized product of the adhesive from affecting the overall strength of the non-stick material.

[0012] In some embodiments, the non-stick material is in the form of particles, the particles of which have a porosity of 25%-55% and a pore size of 500 nanometers-4 micrometers.

[0013] In these embodiments, particles of composite metal oxides having the above-mentioned pore distribution are used as non-stick materials. They can be melt-stacked to form a non-stick layer with a three-dimensional pore structure, which can effectively adsorb and store edible oil, thereby further enhancing the non-stick properties of products with this non-stick layer.

[0014] In some embodiments, the non-stick material is a material with an amorphous phase volume ratio in the range of 30%-70%. Such a non-stick material with an amorphous phase volume ratio has low surface energy and higher wear resistance and stability.

[0015] In some embodiments, the average particle size of the non-stick material is 10 micrometers to 70 micrometers. This allows for the formation of a non-stick layer with a suitable pore structure using a non-stick material of this particle size, thereby facilitating oil retention 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.

[0016] According to a second aspect of this application, a method for preparing a non-stick material is provided, wherein the method comprises: forming a mixed slurry comprising a binder and a base material, wherein the base material comprises titanium oxide and iron oxide; spray drying the mixed slurry to obtain non-stick particles; and sintering the non-stick particles to slightly melt the base material in the non-stick particles, thereby obtaining a composite metal oxide comprising iron ions and titanium ions of different valence states and having an amorphous structure as the non-stick material.

[0017] In some embodiments, the weight ratio of the base material to the binder is (52-70):(30-48). In the mixed slurry, the weight proportion of the binder is comparable to that of the base material. Such a large amount of binder will volatilize in subsequent steps to ensure that a composite metal oxide with a three-dimensional macroporous structure can be easily formed while maintaining the overall strength of the non-stick material. This allows the non-stick layer formed through this non-stick material to retain the three-dimensional macroporous structure of the non-stick material, thereby ensuring the formation of the three-dimensional porous structure of the non-stick layer. And / or, the weight ratio of titanium oxide to iron oxide is (13-39):(13-39). Within this ratio range, titanium oxide and iron oxide can easily form a composite metal oxide through chemical reaction at the high temperature of subsequent sintering, and can minimize the impact of unreacted parts on the overall non-stick material. In addition, within this ratio range, the synergistic effect of titanium oxide and iron oxide can help increase the amorphization degree of the composite metal oxide.

[0018] In some embodiments, the binder comprises alcohol-based binders and / or cellulose-based binders. Specifically, the cellulose-based binder comprises at least one of hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose binders, and the alcohol-based binder comprises at least one of polyvinyl alcohol, polyacryl alcohol, and higher alcohols containing six or more carbon atoms. The above-described binders facilitate the bonding of individual particles of the base material, thereby facilitating the formation of the desired composite metal oxide.

[0019] In some embodiments, the sintering step includes heating the non-stick particles to 500°C-650°C at a heating rate of 15°C / min-20°C / min, holding at that temperature for 6h-8h, and then heating them to 1200°C-1250°C at a heating rate of 55°C / min-100°C / min, holding at that temperature for 12h-24h. Under these parameters, the base material in the non-stick particles can be micro-melted and form the desired composite metal oxide.

[0020] In some embodiments, the particle size of the base material is 0.05 micrometers to 5 micrometers. When the base material is in the range of 0.05 micrometers to 5 micrometers, it is easier to form the above-mentioned composite metal oxide with amorphous structure and three-dimensional macroporous structure, and the porosity of the formed composite metal oxide layer (non-stick layer) can be controlled to easily meet the requirements of locking oils.

[0021] According to a third 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 or cups, and is a non-stick material prepared according to the above-described non-stick material or a non-stick material prepared according to the above-described non-stick material preparation method.

[0022] 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 layer formed on the 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. Attached Figure Description

[0023] 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.

[0024] Figure 1 This is a scanning electron microscope image of non-stick particles provided according to an embodiment of this application;

[0025] Figure 2 This is a scanning electron microscope image of a non-stick material provided according to an embodiment of this application;

[0026] Figure 3 This is an XRD pattern of a non-stick material provided according to an embodiment of this application;

[0027] Figure 4 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;

[0028] Figure 5 yes Figure 4 Enlarged structural diagram at point I;

[0029] Figure 6 This is a schematic diagram of the cross-sectional structure of the non-stick layer and oil film layer of this application after being cut along the thickness direction;

[0030] Figure 7 This is a partial structural schematic diagram of another cooker provided according to an embodiment of this application.

[0031] Symbol explanation:

[0032] 100. Non-stick cookware; 110. Substrate; 120. Non-stick layer; 130. Transition layer; 140. Oil film layer; 150. Low surface energy material. Detailed Implementation

[0033] Example embodiments of the present invention will now be described in more detail.

[0034] Fluoropolymer coatings are common non-stick coatings in this field. However, while non-stick coatings made with fluorine-based 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 fluorine-based coatings, resulting in generally poor long-term non-stick properties. Furthermore, perfluoroalkyl and polyfluoroalkyl compounds (PFAS) are indispensable raw materials for the synthesis of fluorine-based coatings. As industry regulations on PFAS become increasingly stringent, the withdrawal of fluorine-based coatings from the non-stick cookware market is inevitable. This also means that the materials available for cookware coatings are gradually decreasing, thus creating a pressing need for developing new non-stick materials in the cookware manufacturing industry.

[0035] Currently, no material with a lower surface energy than fluorinated 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 fluorinated coatings. Ceramic coatings are liquid coatings with oil molecules as the main non-stick component. While the initial non-stick properties of the coating formed by ceramic coatings may be close to those of fluorinated coatings, the oil molecules are gradually consumed by the high temperatures during cooking, causing the non-stick effect to quickly disappear. Therefore, the long-lasting non-stick properties of ceramic coatings cannot meet the non-stick requirements of cookware.

[0036] With the development of the non-stick industry, solid spraying materials based on metals (e.g., iron, stainless steel, low-carbon steel, high-carbon steel, cast iron, and copper) or ceramics (e.g., titanium oxide, titanium nitride, titanium carbide, iron(II,III) oxide, iron oxide, ferrous oxide, aluminum oxide, chromium oxide, and nickel oxide) have emerged. These materials can form a non-stick layer, the so-called "coating-free non-stick technology." Here, "coating-free" simply means that it does not use organic coatings such as fluorinated or ceramic coatings. While the coating formed by these spraying materials is wear-resistant, cookware with this coating only achieves a non-stick effect when oily, and its initial non-stick properties are poor. It usually requires modification with materials that have good non-stick properties, such as polysiloxanes or fluorinated materials, to meet national standards for initial non-stick performance. Furthermore, the non-stick properties of these materials decrease rapidly after wear, and residual polysiloxanes can have a counterproductive effect on non-stick performance, making it even worse than before modification.

[0037] As can be seen from the above, existing non-stick materials struggle to achieve both initial and long-lasting non-stick properties. Therefore, developing new non-stick materials that combine both initial and long-lasting non-stick properties is extremely important in the cookware manufacturing industry.

[0038] According to a first aspect of this application, a non-stick material for cookware or cups is provided. The non-stick material comprises composite metal oxide particles having an amorphous structure, wherein the metal elements in the composite metal oxide include iron and titanium elements in different valence states.

[0039] In the embodiments of this application, a composite metal oxide refers to a compound containing two or more metals coexisting with oxygen. As an example, the composite metal oxide is a multi-metal oxide comprising at least iron and titanium, which has an amorphous structure, meaning that its atoms or molecules lack long-range order. This amorphous structure endows the non-stick material with some desirable properties, such as high hardness, high wear resistance, and good thermal stability.

[0040] The non-stick material provided in the embodiments of this application has a low surface energy, and the non-stick layer formed therefrom has a certain initial non-stick performance. In addition, the non-stick layer formed by this non-stick material does not age with the extension of use time and has good physical and chemical stability. Therefore, it can have more durable and long-lasting non-stick performance.

[0041] In some embodiments, iron in different valence states includes +2 and +3 valence states, and titanium in different valence states includes at least two of +2, +3, and +4 valence states.

[0042] In these embodiments, the different arrangements of the iron and titanium elements in the crystal lattice in the above-mentioned valence states enable the non-stick material to have an amorphous structure, which is beneficial to the manufacturing, formation and stability of composite metal oxides.

[0043] According to this application, the composite metal oxide has an amorphous structure and includes iron and titanium elements in different valence states. In some embodiments, the composite metal oxide is composed of FeTiO3, Fe2TiO5, and Fe3Ti3O3. 10 Composite metal oxides formed from various forms of oxides, such as Fe. For this iron-titanium-containing oxide, the general formula Fe... (a+b) Ti (c+d) O eTo illustrate, as examples, let a represent the number of iron atoms with a valence of +2, b represent the number of iron atoms with a valence of +3, c represent the number of titanium atoms with a valence of +2, d represent the number of titanium atoms with a valence of +4, and e represent the number of oxygen atoms with a valence of +2, where 2a + 3b + 2c + 4d = 2e. As further examples, let a represent the number of iron atoms with a valence of +2, b represent the number of iron atoms with a valence of +3, c represent the number of titanium atoms with a valence of +2, d represent the number of titanium atoms with a valence of +3, and e represent the number of oxygen atoms with a valence of +2, where 2a + 3b + 2c + 3d = 2e. As further examples, a represents the number of iron atoms with a valence of +2, b represents the number of iron atoms with a valence of +3, c represents the number of titanium atoms with a valence of +3, d represents the number of titanium atoms with a valence of +4, and e represents the number of oxygen atoms with a valence of +2, where 2a + 3b + 3c + 4d = 2e.

[0044] According to this application, the composite metal oxide is composed of FeTiO3, Fe2TiO5, and Fe3Ti3O4. 10 Composite metal oxides formed from various oxides in different forms, such as K2Ti3O7, Na2Ti3O7, CaTiO3, and MgTiO3.

[0045] In some embodiments, the oxide containing iron, titanium, and alkali metal elements is represented by the general formula Fe. (a+b) Ti (c+d) X f O e To illustrate, as examples, let a represent the number of iron atoms with a valence of +2, b represent the number of iron atoms with a valence of +3, c represent the number of titanium atoms with a valence of +2, d represent the number of titanium atoms with a valence of +4, e represent the number of oxygen atoms with a valence of +2, X represent an alkali metal element, and f represent the number of X atoms with a valence of +1, where 2a + 3b + 2c + 4d + f = 2e. As further examples, let a represent the number of iron atoms with a valence of +2, b represent the number of iron atoms with a valence of +3, c represent the number of titanium atoms with a valence of +2, d represent the number of titanium atoms with a valence of +3, e represent the number of oxygen atoms with a valence of +2, X represent an alkali metal element, and f represent the number of X atoms with a valence of +1, where 2a + 3b + 2c + 3d + f = 2e. As further examples, a represents the number of iron atoms with a valence of +2, b represents the number of iron atoms with a valence of +3, c represents the number of titanium atoms with a valence of +4, d represents the number of titanium atoms with a valence of +3, e represents the number of oxygen atoms with a valence of +2, X represents an alkali metal element, and f represents the number of X atoms with a valence of +1, where 2a + 3b + 4c + 3d + f = 2e.

[0046] In other embodiments, the oxide containing iron, titanium, and alkaline earth metal elements is expressed as Fe... (a+b) Ti (c+d) Y g O e To illustrate, as examples, a represents the number of iron atoms with a valence of +2, b represents the number of iron atoms with a valence of +3, c represents the number of titanium atoms with a valence of +2, d represents the number of titanium atoms with a valence of +4, e represents the number of oxygen atoms with a valence of +2, Y represents an alkaline earth metal element, and g represents the number of Y atoms with a valence of +2. The equation is 2a + 3b + 2c + 4d + 2g = 2e. As further examples, a represents the number of iron atoms with a valence of +2, b represents the number of iron atoms with a valence of +3, c represents the number of titanium atoms with a valence of +3, d represents the number of titanium atoms with a valence of +4, e represents the number of oxygen atoms with a valence of +2, Y represents an alkaline earth metal element, and g represents the number of Y atoms with a valence of +2, where 2a + 3b + 3c + 4d + 2g = 2e. As yet another example, a represents the number of iron atoms with a valence of +2, b represents the number of iron atoms with a valence of +3, c represents the number of titanium atoms with a valence of +3, d represents the number of titanium atoms with a valence of +2, e represents the number of oxygen atoms with a valence of +2, Y represents an alkaline earth metal element, and g represents the number of Y atoms with a valence of +2, where 2a + 3b + 3c + 2d + 2g = 2e.

[0047] In the embodiments of this application, the metal elements in the composite metal oxide include iron and titanium elements in different valence states. Here, iron and titanium elements in different valence states serve as constituent elements in the composite metal oxide, and they work synergistically. For example, iron and titanium elements in different valence states interact and chemically combine at high temperatures (e.g., redox reactions) to form a composite metal oxide with an amorphous structure. This helps to improve the non-stick properties and other physicochemical properties of the non-stick material.

[0048] In some embodiments, the metal elements in the composite metal oxide also include soluble metal elements and / or metal elements capable of reacting with fatty acids in oils. Specifically, the soluble metal elements are water-soluble metal elements, including potassium and / or sodium. Metal elements capable of reacting with fatty acids in oils include calcium and / or magnesium. When the non-stick material includes water-soluble metal elements (e.g., potassium, sodium), the formed non-stick layer also includes water-soluble metal elements. These water-soluble metal elements dissolve and exchange during product use, creating nanoscale cavities on the surface of the non-stick layer, thereby forming a micro / nano hydrophobic structure. This results in better non-stick properties when wetted by oil molecules. Furthermore, when the non-stick material includes metallic elements (e.g., calcium, magnesium) capable of reacting with fatty acids in oils, the resulting non-stick layer naturally also includes metallic elements capable of reacting with fatty acids in oils. This makes the non-stick layer more readily react with fatty acids in oils (which are oil molecules) in subsequent processes, forming a fatty acid salt modified layer on the surface of the non-stick layer, thereby further improving non-stick properties. It should be noted that only specific examples of water-soluble metallic elements and metallic elements capable of reacting with fatty acids in oils are shown here. However, those skilled in the art will understand that other water-soluble metallic elements and metallic elements capable of reacting with fatty acids in oils can achieve technical effects comparable to those described in this application.

[0049] In some embodiments, the non-stick material further includes carbonized products of the binder dispersed in the composite metal oxide. Specifically, the carbonized products of the binder are dispersed between adjacent particles of the composite metal oxide.

[0050] In these embodiments, carbonized products of the binder are dispersed in the particles of the composite metal oxide. On the one hand, the presence of carbonized products of the binder can facilitate the connection of each particle of the matrix and ensure 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 can make the non-stick material as a whole exhibit high hardness and stability.

[0051] 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.

[0052] In some embodiments, the weight ratio of the carbonized product of the binder to the composite metal oxide in the non-stick material is (0.4-3.5):(96.5-99.6). This suitable weight ratio of the carbonized product of the binder to the composite metal oxide prevents excessive carbonized product of the binder from affecting the overall strength of the non-stick material.

[0053] In some embodiments, the non-stick material is granular with a three-dimensional macroporous 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 macroporous structure, which facilitates the formation of a non-stick layer with three-dimensional pores.

[0054] In these embodiments, a composite metal oxide with a three-dimensional macroporous structure is used as a non-stick material. It can form a non-stick layer with a three-dimensional porous structure through melt 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.

[0055] In some embodiments, the non-stick material obtained by spray drying and sintering is a material with an amorphous phase volume ratio in the range of 30%-65%. Such a non-stick material with an amorphous phase volume ratio has low surface energy and higher wear resistance and stability.

[0056] In other embodiments, the non-stick material after high-temperature sintering can be subjected to rapid cooling, preventing the atoms or molecules inside from arranging into an ordered crystal structure, thereby further increasing the amorphization degree of the non-stick material and better achieving the goal of improving non-stick properties. Specifically, the rapid cooling process includes heating the non-stick layer and rapidly exposing it to a low-temperature environment to achieve rapid cooling, preventing the material in the non-stick layer from crystallizing and thus tending towards an amorphous transformation. Specifically, the non-stick layer is sintered (sintering temperature of 1200℃-1400℃, sintering time of 4h) and then cooled at a cooling rate of 80℃ / s-100℃ / s. As an example, the amorphous phase volume ratio of the non-stick material is 35%-70%.

[0057] In summary, the amorphous phase volume ratio of the non-stick material according to this application is 30%-70%, and in the preferred embodiment, the amorphous phase volume ratio of the non-stick material is 50%-70%.

[0058] In some embodiments, the non-stick material is granulated powder particles with an average particle size of 10 to 70 micrometers. In a preferred embodiment, the particles of the non-stick material have a normal distribution, with a D50 of 25 to 35 micrometers. This allows for the formation of a non-stick layer with a suitable pore structure using the non-stick material of this particle size, thereby facilitating oil retention 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 substrate.

[0059] According to a second aspect of this application, a method for preparing a non-stick material is provided. The method includes: step S101, forming a mixed slurry comprising a binder and a base material, wherein the base material comprises titanium oxide and iron(III) oxide. Step S102, spray-drying the mixed slurry to obtain non-stick particles. Step S103, sintering the non-stick particles to allow the titanium oxide and iron(III) oxide in the base material of the non-stick particles to be micro-fused and chemically bonded, thereby obtaining a composite metal oxide comprising iron and titanium elements of different valence states and having an amorphous structure as a non-stick material.

[0060] According to the method for manufacturing non-stick materials provided in the embodiments of this application, by spray drying and then sintering a mixed slurry including a binder and a base material, a composite metal oxide with an amorphous structure containing iron and titanium elements in different valence states can be formed as a non-stick material. This non-stick material has low surface energy, and the non-stick layer formed therefrom has good initial non-stick properties. In addition, the non-stick layer formed by this non-stick material does not age with prolonged use and has good physical and chemical stability, thus possessing more durable and long-lasting non-stick performance. Furthermore, the composite metal oxide has a three-dimensional macroporous structure and is in the form of microspheres. The non-stick layer formed by this non-stick material can retain the three-dimensional macroporous structure of the microspheres as much as possible, thereby forming a non-stick layer with a corresponding three-dimensional pore structure. The non-stick layer with a corresponding three-dimensional pore structure easily adsorbs oil molecules, thereby exhibiting superior non-stick performance due to the oil film non-stick principle.

[0061] The method for preparing non-stick materials according to this application will be described in detail below.

[0062] Provide adhesive

[0063] According to this application, as some embodiments, the adhesive includes alcohol-based adhesives and / or cellulose-based adhesives. As other examples, the adhesive includes oleophilic adhesives.

[0064] 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 alcohol adhesives containing six or more carbon atoms. However, this application is not limited to these, and appropriate adhesives can be selected according to actual needs.

[0065] It should be noted that the binder according to this application may volatilize or carbonize during the subsequent sintering process. Whether it 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 carbon, leaving only 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, during this process, the binder in the non-stick particles will transform into a gaseous state, leaving pores on the non-stick particles.

[0066] Provide base material

[0067] According to this application, the base material includes titanium oxide and iron oxide, which at least form a mixed slurry with a binder and can be formed into a composite metal oxide with an amorphous structure by spray drying (powder granulation). Here, titanium oxide and iron oxide refer to substances, not components. In these embodiments, titanium and iron are non-toxic and harmless metals and can form stable insoluble oxides. The electron configuration of titanium is 1s. 2 2s 2 2p 6 3s 2 3p 6 3D 2 4s 2 (2 / 8 / 10 / 2), the ferroelectron configuration is 1s 2 2s 2 2p 6 3s 2 3p 6 3D 6 4s 2 (2 / 8 / 14 / 2) Titanium and iron are both transition metals, and their electron configurations are similar in the periodic table. Therefore, these two elements readily form composite metal oxides (multi-component oxides) in oxides. Secondly, titanium has an atomic radius of 0.145 nanometers, while iron has an atomic radius of approximately 0.124 nanometers. Due to the significant difference in atomic radii, the two atoms occupy different volumes in the crystal lattice, leading to lattice distortion rather than a complete and standard lattice arrangement. This results in composite oxides exhibiting certain amorphous properties, further enhancing their non-stick properties.

[0068] In some embodiments, the base material is titanium dioxide and iron(III) oxide. In other embodiments, in addition to titanium dioxide and iron(III) oxide, the base material may also include water-soluble metal oxides and / or metal oxides capable of reacting with fatty acids in oils. The water-soluble metal oxides are alkali metal oxides, and the metal oxides capable of reacting with fatty acids in oils are alkaline earth metal oxides. Specifically, the alkali metal oxides include potassium oxide and / or sodium oxide, and the alkaline earth metal oxides include calcium oxide and / or magnesium oxide.

[0069] In these embodiments, titanium oxide and iron oxide are used as the main materials, and water-soluble metal oxides and / or metal oxides that can react with fatty acids in oils are used as auxiliary materials. By introducing auxiliary materials with larger dimensions than titanium and iron as part of the base material, lattice distortion can be further aggravated, which is conducive to the formation of composite metal oxides with obvious amorphous characteristics.

[0070] In a preferred embodiment, the base material is titanium oxide, iron oxide, potassium oxide, sodium oxide, calcium oxide, and magnesium oxide. Specifically, titanium has an atomic radius of 0.145 nm, iron approximately 0.124 nm, calcium 0.223 nm, magnesium 0.160 nm, sodium 0.186 nm, and potassium 0.236 nm. The significant difference in atomic radii between titanium and iron results in different volumes occupied by the two atoms in the crystal lattice, leading to lattice distortion rather than a complete and standard lattice arrangement. This gives the composite oxide a certain amorphous characteristic. Furthermore, the introduction of alkali metals and alkaline earth metals with larger atomic radii further exacerbates the lattice distortion, making it even more conducive to forming a composite oxide with prominent amorphous characteristics (a higher proportion of amorphous volume or a greater degree of amorphization). During the sintering process, titanium oxide, iron oxide, potassium and sodium oxides and calcium and magnesium oxides undergo semi-melting, which allows the titanium, iron, potassium, sodium, calcium and magnesium atoms to recombine and form new composite oxides, thus obtaining non-stick materials of titanium iron oxide, titanium potassium oxide, titanium sodium oxide, titanium calcium oxide and titanium magnesium oxide composite oxides.

[0071] In these embodiments, the oxides in the base material, such as titanium oxide and iron oxide, can undergo a chemical reaction under the high temperature of subsequent sintering to form a composite metal oxide with an amorphous structure. Furthermore, depending on the content of the base material and binder, a composite metal oxide with the desired three-dimensional macroporous structure is formed.

[0072] In some embodiments, the base material is spherical or near-spherical, and the resulting composite metal oxide with a three-dimensional macroporous structure also exhibits a spherical shape. Specifically, it consists of micron-sized spheres (microspheres) with a relatively uniform pore distribution and high porosity. This not only facilitates the adsorption and storage of oils but also ensures the mechanical strength and wear resistance of the formed microspheres. Using multiple microspherical composite metal oxides as a non-stick material, the resulting coating allows oil molecules to easily penetrate, and the composite metal oxide effectively protects the oil molecules located relatively inside, preventing them from directly contacting heat sources and volatilizing. Furthermore, the composite metal oxide effectively reduces heat conduction and diffusion, lowering the likelihood of oil molecules directly contacting high temperatures, thereby improving the stability and safety of the non-stick material.

[0073] In some embodiments, the base material is at the micrometer level, specifically, the particle size of the base material is 0.05 micrometers to 5 micrometers. When the base material is in the range of 0.05 micrometers to 5 micrometers, it is easier to form the aforementioned composite metal oxide with amorphous structure and three-dimensional macroporous structure, and the porosity of the formed composite metal oxide layer (non-stick layer) can be controlled to easily meet the requirements of locking oils. It should be noted that the particle size of the above-mentioned material can be the maximum length of each particle, rather than specifically limiting the material to have a spherical or near-spherical shape. For example, but not limited to, when the material has an elliptical shape, the particle size of the material can refer to the length of its major axis. It should be noted that the micrometer-level base material can be obtained by crushing and grinding, or it can be obtained commercially, and this application does not impose any restrictions on it.

[0074] In a preferred embodiment, the particle size of the base material forming the mixed slurry exhibits a normal distribution. The base material is a mixture of multiple particles, and the particle size R of the mixture has multiple distribution ranges. These multiple distribution ranges include a first distribution range R1, a second distribution range R2, and a third distribution range R3. Specifically, 0.05 μm ≤ R1 ≤ 0.1 μm, the second distribution range is 0.1 μm < R2 ≤ 1 μm, and the third distribution range is 1 μm < R3 ≤ 5 μm. Based on the total volume of the base material in the mixture being 100%, the volume percentage of the base material with particle sizes in the first distribution range is 20%-40%, the volume percentage of the base material with particle sizes in the second distribution range is 35%-65%, and the volume percentage of the base material with particle sizes in the third distribution range is 10%-25%.

[0075] Forming a mixed slurry

[0076] According to this application, the method for preparing the non-stick material further includes the step of forming a mixed slurry. Specifically, the step of forming the mixed slurry includes providing a base material and a binder, and then ball milling the base material and the binder together to form the mixed slurry.

[0077] Specifically, the base material and binder are added to a ball mill jar, and deionized water is added as the grinding medium. Grinding is carried out for 4-8 hours to obtain a uniformly dispersed slurry containing the base material and binder. The binder in the slurry enhances the bonding force between the particles forming the composite metal oxide, creating a stable particle stack. This gives the composite metal oxide a certain mechanical strength, ensuring the stability of the subsequent non-stick layer formation and preventing breakage that could affect the formation of the three-dimensional porous structure of the composite metal oxide layer (non-stick layer). It should be noted that a certain amount of dispersant may also be included in the slurry formation step to facilitate more uniform dispersion of the base material particles within the slurry.

[0078] In some embodiments, the mixed slurry includes a base material and a binder, with a weight ratio of (52-70):(30-48). In the mixed slurry, the weight proportion of the binder is roughly equal to that of the base material. Such a large amount of binder will evaporate in subsequent steps to ensure that a composite metal oxide with a three-dimensional macroporous structure is easily formed while maintaining the overall strength of the non-stick material. This allows the formation of a non-stick layer through this non-stick material to retain the three-dimensional macroporous structure of the non-stick material, thereby ensuring the formation of the three-dimensional porous structure of the non-stick layer.

[0079] According to this application, the weight percentage of each oxide in the base material is such that each oxide in the base material can react as fully as possible under the influence of high temperature to form a composite metal oxide.

[0080] In some embodiments, the base material is titanium dioxide and iron oxide (Fe3O4). As an example, the weight ratio of titanium dioxide to iron oxide is (13-39):(13-39). Within this ratio range, titanium dioxide and iron oxide can readily form a composite metal oxide through chemical reaction at the high temperatures of subsequent sintering, and can minimize the impact of unreacted portions on the overall non-stick material. Furthermore, within this ratio range, the synergistic effect of titanium dioxide and iron oxide can help increase the amorphization degree of the composite metal oxide.

[0081] In other embodiments, the base material includes titanium dioxide and iron oxide (Fe3O4), and may also include water-soluble metal oxides and / or metal oxides capable of reacting with fatty acids in oils. For example, the water-soluble metal oxide can be an alkali metal oxide, and the metal oxide capable of reacting with fatty acids in oils can be an alkaline earth metal oxide. Considering the safety of the reaction and the subsequent effects of the composite metal oxides, the water-soluble metal oxides may include potassium oxide and / or sodium oxide, also referred to as potassium-sodium oxides; the metal oxides capable of reacting with fatty acids in oils include calcium oxide and / or magnesium oxide, also referred to as alkaline earth metal oxides. In a preferred embodiment, the base material includes titanium dioxide, iron oxide, water-soluble metal oxides, and metal oxides capable of reacting with fatty acids in oils. For example, the ratio of titanium dioxide, iron oxide, water-soluble metal oxides, and metal oxides capable of reacting with fatty acids in oils is (13-39):(13-39):(1-2):(1-2). This proportion of each substance allows for the formation of a composite metal oxide with a higher volume of amorphous phase, which is beneficial for improving non-stickiness. As a specific example, the ratio of titanium oxide, iron oxide, alkali metal oxide and alkaline earth metal oxide is (13-39):(13-39):(1-2):(1-2).

[0082] It should be noted that in the above embodiments, the melting point of alkali metal oxides is relatively low. When the base material includes sodium oxide and potassium oxide, the overall melting point of the base material is lower, which is beneficial for the base material to be in a slightly molten state during the sintering process.

[0083] Spray drying to form non-sticky granules

[0084] After pulping, the mixed slurry is spray-dried. According to some embodiments of this application, a spray drying device (such as a pressure spray dryer, centrifugal spray dryer, etc.) is used to atomize the mixed slurry into fine droplets. The atomized droplets come into contact with hot air, causing the solvent (water) to evaporate rapidly, and the particles of the base material and the binder to form a microsphere-like basic structure. 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 undergo a brief residence during their descent, ultimately forming wet microspheres (non-sticky particles).

[0085] According to this application, the particle size, pore size, and distribution of microspheres can be controlled by adjusting the process parameters of spray drying (e.g., atomizing disc rotation speed and hot air temperature). As an example, during the high-speed movement of the atomizing disc, controlling its rotation speed can disperse the mixed slurry into fine and uniform droplets, improving the forming quality and consistency of the microspheres. In some embodiments, the rotation speed of the atomizing disc can be controlled within the range of 4000 rpm to 15000 rpm, preferably within the range of 6000 rpm to 12000 rpm. According to some embodiments of this application, the hot air temperature can be controlled within the range of 60°C to 100°C, the drying tower temperature can be controlled within the range of 100°C to 400°C, and the brief residence time of the droplets within the drying tower can be controlled within 5 seconds to 15 seconds. The relatively low temperature of the hot air can reduce the loss of the binder, allowing the moisture in the pre-formed wet microspheres to evaporate and retain enough binder, thus ensuring that the microspheres with a porous structure can be formed during the subsequent sintering process by means of the evaporation or carbonization of the binder.

[0086] Sintering of the spray-dried non-stick particles

[0087] According to this application, the base material itself does not possess pores. By using a mixed slurry comprising the base material and binder, which is then spray-dried and sintered at high temperature, a foundation can be laid for the subsequent formation of a three-dimensional macroporous structure, thereby forming microspheres with a three-dimensional macroporous structure and an amorphous structure. Here, the base material slightly melts during the high-temperature sintering process, and its physical state gradually changes from solid to semi-solid or viscous. In this way, the various base materials diffuse into each other and chemically bond to form the composite metal oxide according to this application.

[0088] According to the preparation method of the non-stick material of this application, the non-stick particles obtained after spray drying are sintered.

[0089] According to some embodiments of this application, the spray-dried microspheres can be heated to a temperature above the carbonization temperature at a high heating rate under an inert atmosphere such as nitrogen or argon, and held for a long time to allow as much binder as possible to carbonize during the process. 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 20°C-30°C, and the heating rate is 15°C / min-20°C / min. The high heating rate allows the binder to volatilize at this stage. The temperature is then raised to 500°C-650°C at a heating rate of 15°C / min-20°C / min and held for 6-8 hours to carbonize the binder in the spray-dried microspheres as much as possible. Then, the temperature is increased to 1200℃-1250℃ at a heating rate of 55℃ / min-100℃ / min, and then held for 12h-24h. During this process, titanium oxide and iron oxide interact, such as through diffusion and reaction, thereby changing the original crystal structure and forming a composite metal oxide with an amorphous structure. Furthermore, the particles of adjacent matrix materials interact to interlock at the contact points, resulting in volume shrinkage and the creation of pores between the particles. The final material, a carbonized product with a certain three-dimensional macroporous structure and composite metal oxide and binder, serves as a non-stick material. Additionally, during sintering, the contacting matrix materials interlock at the contact points after sintering to form microspheres, ensuring sufficient bonding between the microsphere particles to guarantee their stability in subsequent processes.

[0090] In these embodiments, under inert atmospheres such as nitrogen and argon, with a faster heating rate, higher sintering temperature, and longer sintering time, a small portion of the binder volatilizes, leaving pores, while most of the binder carbonizes, forming a high-carbon-content material (the carbonization product of the binder). Furthermore, adjacent particles interact to form a material with a composite metal oxide particle stack and carbonization products dispersed in the composite metal oxide.

[0091] As an example, the carbonization temperature of the binder in this application is approximately between 350℃ and 600℃. Under the influence of subsequent sintering temperature and time, most of the binder will volatilize, leaving pores in the non-stick material, while a small portion of the binder will form carbonization products. Since the carbonization products of the binder are mainly composed of non-polar carbon elements and have a certain degree of oleophilicity, the non-stick layer of non-stick cookware formed by this type of non-stick material is more easily filled by oil molecules.

[0092] In some embodiments, 90% of the binder evaporates, while 10% of the binder carbonizes. Specifically, this is defined by the weight ratio of the carbonized binder products to the composite metal oxide in the non-stick material. For example, in the non-stick material, the weight ratio of the carbonized binder products to the composite metal oxide is (0.4-3.5):(96.5-99.6). Therefore, the resulting non-stick layer contains both composite metal oxide and carbonized binder products, with the carbonized binder products adhering to a portion of the surface of the composite metal oxide particles. Continuing with the example above, in the non-stick layer, the weight ratio of the carbonized binder products to the base material is (0.4-3.5):(96.5-99.6).

[0093] 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 microspheres, making the non-stick layer formed therefrom easier to fill with oil molecules.

[0094] According to this application, composite metal oxides (e.g., composites of iron titanium oxide, potassium titanium oxide, sodium titanium oxide, calcium titanium oxide, and magnesium titanium oxide) can be formed as non-stick materials through spray drying and high-temperature sintering. Since iron has +2 and +3 valences, and titanium has +2 and +4 valences, and both alkali metals (valent 1) and alkaline earth metals (valent 2) are present, various oxide forms may be obtained during the formation of the composite oxide. The main forms include FeTiO3, Fe2TiO5, and Fe3Ti3O3. 10 Composite oxides formed by various oxides of different forms, such as K2Ti3O7, Na2Ti3O7, CaTiO3 and MgTiO3, exhibit an irregular and disordered state in their microscopic lattice arrangement, and generally present amorphous characteristics.

[0095] Figure 1 This is a scanning electron microscope image of non-stick particles provided according to an embodiment of this application. Figure 2 This is a scanning electron microscope (SEM) image of a non-stick material provided according to an embodiment of this application. (Refer to...) Figure 1 It can be seen that the non-stick particles do not have obvious pores before sintering. (Refer to...) Figure 2 It can be seen that after sintering, the composite metal oxide has a distinct three-dimensional macroporous structure, and the pores of the three-dimensional macroporous structure are generally uniformly distributed.

[0096] Figure 3 This is an XRD pattern of a non-stick material provided according to an embodiment of this application. For example... Figure 3As shown, the characteristic peaks are not particularly obvious, and there are many disordered impurity peaks, indicating poor crystallinity. This suggests that the composite metal oxide generally has low crystallinity and exhibits amorphous characteristics. Based on conventional full-spectrum fitting methods, the amorphous phase volume ratio of the non-stick material is calculated to be 60%.

[0097] According to the method for manufacturing non-stick materials of this application, the sintered microspheres can be sieved after the sintering step to obtain microspheres with different particle size ranges. Microsphere powders with different particle size ranges can be sieved as needed for application in different products. For example, the sintered powder can be vibrated and sieved to obtain spherical or near-spherical microspheres with a particle size of 10μm-45μm.

[0098] According to the method for manufacturing non-stick materials of this application, the final microsphere particles are not simply a single particle in a quantitative sense, but can be multiple particles aggregated together. The particle size of the final microsphere particles is not smaller than the original particle size of the various powders.

[0099] In some embodiments, the non-stick material is in the form of micron-sized particles. For example, the average particle size of the non-stick material is 10 to 70 microns, with a D50 (median particle size) of 25 to 35 microns. If the average particle size of the non-stick powder is greater than 10 microns, it is prone to clogging the powder feeding tube, and the powder melt is insufficient, resulting in reduced adhesion of the non-stick layer and decreased coating quality. If the average particle size of the non-stick powder is less than 70 microns, the powder has poor flowability, and the flight speed during spraying is insufficient, leading to over-melting and reduced deposition efficiency and coating quality.

[0100] According to this application, the microspheres formed by spray drying have pores inside or between the particles, allowing gas or liquid to pass through. Furthermore, the pores in the three-dimensional macroporous structure of the microspheres formed by spray drying are mostly open or interconnected pores (i.e., through-pores), with a few being closed pores. This ensures the oil storage capacity of the formed non-stick layer. As an example, the volume percentage of through-pores is approximately 80%-90%, with the remainder being closed pores.

[0101] Using microspheres as a non-stick material, during the spraying process to form a non-stick layer, the microspheres are only micro-melted on their surface, allowing them to stack on the substrate to form the non-stick layer. The non-stick layer retains the three-dimensional macroporous structure of the microspheres as much as possible, resulting in a non-stick layer with a three-dimensional porous structure. The pores of this three-dimensional porous structure match oil molecules, easily adsorbing them and locking them in place with a certain adhesion force, allowing for slow release of the oil molecules. This results in excellent non-stick performance due to the oil film non-stick principle. Furthermore, the base material forming this non-stick material is very small, at the micrometer level, and has a large specific surface area when bonding with the substrate, ensuring strong adhesion. The base material also has good wear resistance, acting as a protector for oil molecules, thus ensuring a continuous and stable oil film on non-stick cookware with this non-stick layer, guaranteeing long-lasting non-stick performance.

[0102] According to a third aspect of this application, a non-stick layer is provided for use in cookware or cups, wherein the non-stick layer is formed by spraying the non-stick material described above.

[0103] In some embodiments, the non-stick layer comprises a composite metal oxide layer with an amorphous structure, wherein the metal elements in the composite metal oxide layer include iron and titanium elements in different valence states. Here, the composite metal oxide layer itself has a low surface energy, thus possessing certain initial non-stick properties. Furthermore, the composite metal oxide layer does not age with prolonged use, exhibiting good physical and chemical stability. Therefore, it can possess more durable and long-lasting non-stick properties.

[0104] In some embodiments, the material further includes carbonized products of the binder dispersed in the composite metal oxide layer.

[0105] In these embodiments, carbonized products of the binder are dispersed in the composite metal oxide layer. On the one hand, the presence of carbonized products of the binder can facilitate the connection of each particle of the composite metal oxide, 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 can enable the non-stick material to exhibit high hardness and stability as a whole.

[0106] In some embodiments, in the non-adhesive layer, the weight ratio of the carbonization product of the adhesive to the composite metal oxide is (0.4-3.5):(96.5-99.6).

[0107] According to this application, the non-stick layer can be formed by thermal spraying a non-stick material, wherein the non-stick material is a microsphere with a three-dimensional macroporous structure. During the thermal spraying process, the surface of the microspheres of the non-stick material is heated and integrally deposited on the substrate to form a non-stick layer. Therefore, the formed non-stick layer can possess a finer pore structure than the three-dimensional macroporous structure of the non-stick material, and itself exhibits a three-dimensional pore structure. It can be understood that the three-dimensional pore structure in the non-stick layer is largely determined by the three-dimensional macroporous structure of the microspheres.

[0108] As an example, the formed non-stick layer has a three-dimensional porous structure with a porosity of 5%-30% and a pore size of 500 nanometers-4 micrometers, preferably 500 nanometers-1 micrometer. More specifically, the three-dimensional porous structure includes multiple macropores located between microspheres and multiple micropores located inside the microspheres. The macropores have a size of 900 nanometers-4 micrometers, and the micropores have a size of 500 nanometers-900 nanometers. The macropores allow oil molecules or oil to easily enter the non-stick layer, while the micropores allow oil molecules or oil to be easily retained. This ensures the non-stick performance of the non-stick cookware with the non-stick layer due to the stable release of the oil film.

[0109] In some embodiments, thermal spraying includes flame spraying, arc spraying, and plasma spraying. Taking plasma spraying as an example, the specific parameters are: powder feeding speed 10g / min-25g / min, spraying distance 150mm-200mm, arc current 350A-500A, voltage 50V-70V, hydrogen pressure 0.6MPa-0.8MPa, hydrogen flow rate 200L / h-300L / h, argon pressure 1.0MPa-1.5MPa, argon flow rate 1000L / h-2000L / h, and workpiece linear speed 25m / min-35m / min.

[0110] In some embodiments, the thickness of the non-stick layer is in the range of 10 micrometers to 150 micrometers, which ensures the long-lasting non-stick performance of the non-stick cookware with the non-stick layer.

[0111] According to this application, after the non-stick layer is obtained by spraying, it can be polished to make the surface bright and smooth, making it easy to stir-fry. If needed, edible oil can be applied to the surface of the non-stick layer, followed by baking at 250℃-350℃ to season the pan and enhance its non-stick and rust-preventing properties.

[0112] According to some embodiments of this application, the non-stick layer can be directly used as the inner coating of non-stick cookware, and the obtained non-stick layer can also be modified to further enhance its non-stick properties. The specific methods for modifying the non-stick layer will be described below.

[0113] According to this application, when the non-stick material includes water-soluble metal elements (e.g., potassium, sodium), the formed non-stick layer also includes water-soluble metal elements. These water-soluble metal elements dissolve and exchange during product use, creating nanoscale vacancies on the surface of the non-stick layer, thereby forming a micro-nano hydrophobic structure. This results in better non-stick properties when wetted by oil molecules. Furthermore, when the non-stick material includes metal elements capable of reacting with fatty acids in oils (e.g., calcium, magnesium), the formed non-stick layer naturally includes these metal elements as well. This facilitates the reaction between the non-stick layer and fatty acids in the oil, and the resulting fatty acid salts deposit on the surface of the non-stick layer, further enhancing its non-stick properties. Therefore, the surface of the non-stick layer includes a fatty acid salt-modified layer formed by the reaction of the metal elements in the non-stick layer.

[0114] Modifying non-stick coatings with silane materials

[0115] In the embodiments of this application, before modification, the non-stick layer can be treated with an acid or alkali solution to increase the surface roughness of the non-stick layer, thereby providing more binding sites for the modified material.

[0116] According to this application, the method for manufacturing the non-stick layer further includes the step of modifying the non-stick layer with a silane-based material. The step of modifying the non-stick layer with a silane-based material includes providing a modification solution comprising the silane-based material and water. The step of providing the modification solution comprising the silane-based material includes preparing the modification solution comprising the silane-based material and water. Here, by grafting a low surface energy material onto the non-stick layer, the overall non-stick performance of the non-stick layer is further improved.

[0117] In an exemplary embodiment, the step of preparing a modified solution comprising a silane material and water includes providing a silane material, providing an aqueous solvent, and mixing the silane material with the aqueous solvent to obtain a modified solution comprising the silane material and water. The volume ratio of the silane material to the solvent is 1:20 to 1:100.

[0118] In some embodiments, silane materials may include fluorosilane materials or silane coupling agents. For example, fluorosilane materials include at least one of perfluorodecyltrimethoxysilane, perfluorooctyltriethoxysilane, perfluorododecyltrimethoxysilane, and trifluoropropylmethylsilane. Silane coupling agents include at least one of γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, sulfur-containing silane coupling agents, epoxy-based silane coupling agents, and γ-ureidopropyltriethoxysilane. Since the above-mentioned silane materials have low solubility in water, the modified solution may also include organic solvents, specifically ester solvents and / or alcohol solvents. Organic solvents can increase the solubility of silane materials and, to some extent, inhibit the hydrolysis rate of the modified solution containing silane materials and water. Specifically, ester solvents include ethyl acetate, and alcohol solvents include ethanol, butanediol, etc.

[0119] According to this application, the step of modifying the non-stick layer with a silane-based material includes contacting and reacting a modification solution comprising a silane-based material and water with at least a portion of the surface of the non-stick layer to form a modified layer on the non-stick layer, thereby obtaining a silane-based material-modified non-stick layer as the non-stick layer of this application.

[0120] In the embodiments of this application, silane-based materials can act on at least a portion of the surface of the non-stick layer. This at least a portion of the surface can be the surface on which the product operates during use. Taking a cookware as an example, the non-stick layer is formed on the entire inner surface of the cookware, and the operating surface can be the area on the non-stick layer corresponding to the bottom wall region of the inner surface of the cookware. Of course, the at least a portion of the surface can also be the entire surface of the product, for example, the entire outer surface of the non-stick layer.

[0121] In this embodiment, the silane-modified non-stick layer (modified layer) is a product obtained by reacting the hydrolysis product of the silane-based material with the non-stick layer. The modifying solution can at least contact at least a portion of the outer surface of the non-stick layer, thereby forming a modified layer on the surface of the non-stick layer. Alternatively, the modifying solution can penetrate the surface pores of the non-stick layer to contact the inner wall of the corresponding pores, thereby forming a modified layer on the inner wall of the pores. Here, surface pores refer to pores / cavities existing in a region at a certain depth from the outer surface of the non-stick layer. In this case, the modified layer can exist not only on the outer surface of the non-stick layer but also on the inner wall of the surface pores of the non-stick layer.

[0122] According to this application, the non-stick layer and the modified layer thereon are bonded by at least chemical bonds, which have a certain degree of bonding strength, thus ensuring that they are not easily detached during use.

[0123] According to this application, a modified solution comprising a silane-based material is brought into contact with and reacts with a non-stick layer to obtain a non-stick coating having at least a modified layer on its surface. The contact can refer to immersing the non-stick layer in a modified solution comprising a silane-based material and water. Specifically, the surface of the non-stick layer has silanol groups. During the contact process, the silane-based material first hydrolyzes to generate a siloxane-based material. Subsequently, the generated siloxane-based material undergoes a dehydration reaction with the silanol groups on the surface of the non-stick layer to form a modified layer, thereby obtaining a silane-modified non-stick layer. This silane-modified non-stick layer exhibits extremely strong hydrophobicity, low surface energy, and a large contact angle, resulting in superior initial non-stick properties.

[0124] According to this application, the modified solution including silane materials can be stably hydrolyzed in an acidic environment. In an exemplary embodiment, the pH value of the modified solution of silane materials is not greater than 7. Dilute hydrochloric acid can be added to the modified solution to obtain a modified solution with a predetermined pH value.

[0125] According to this application, the hydrolysis of silane-based materials can be ensured by heating. Specifically, an ultrasonic method can be used to bring at least a portion of the surface of the non-stick layer into contact with a modified solution containing silane-based materials under heated conditions. For example, ultrasonic vibration can be used, with the vibration frequency set to 20 kHz-50 kHz, and the temperature heated to 50°C-80°C for 5 min-8 min.

[0126] Modifying the non-stick coating using rapid cooling method

[0127] According to this application, before the rapid cooling treatment, the amorphous phase volume ratio of the non-stick layer is 30%-50%. After the rapid cooling treatment, the amorphous phase volume ratio of the non-stick layer increases, specifically to 50%-70%. Here, by increasing the amorphous phase volume ratio (degree of amorphization) of the non-stick layer, the overall non-stick performance of the non-stick layer is further improved.

[0128] In some embodiments, the rapid cooling process involves heating the non-stick layer and then quickly exposing it to a low-temperature environment to achieve rapid cooling, preventing the material in the non-stick layer from crystallizing and thus causing it to transition to amorphous state. Specifically, the non-stick layer is sintered (at a temperature of 1200°C-1400°C for 4 hours) and then cooled at a rate of 80°C / s-100°C / s.

[0129] According to a fourth aspect of this application, a non-stick cookware is provided, wherein, as Figures 4 to 6 As shown, the non-stick cookware includes a substrate 110 and a non-stick layer 120 formed on the inner surface of the substrate 110, wherein the non-stick layer 120 is formed by spraying according to the above-mentioned non-stick material.

[0130] In some embodiments, the non-stick layer has a porous structure that can be filled with oil molecules.

[0131] In these embodiments, the pore structure of the non-stick layer is suitable for the filling and locking of oil molecules. When oil molecules are filled into the pore structure of the non-stick layer, the oil molecules can be slowly released from the pore structure to optimize the non-stick properties of the non-stick layer.

[0132] According to this application, the cookware coating can have various structural forms. In some embodiments, the inner surface of the substrate is a rough surface, which can be obtained by sanding the inner surface of the substrate, and the non-stick layer is formed directly on the inner surface of the substrate. In other embodiments, the inner surface of the substrate has an uneven structure. As an example, the uneven structure is at the micrometer level and consists of multiple bumps with a height of 100μm-500μm, a width of 200μm-400μm, and a spacing of 200μm-400μm between adjacent bumps. The non-stick layer is formed at least in the recesses of the uneven structure. A non-stick layer placed in the recesses between adjacent bumps is less likely to be damaged by a spatula, thus improving the non-stick life of the product. Alternatively, the non-stick layer can fill the recesses of the uneven structure and cover the surface of the uneven structure, thus forming a tenon-and-mortise connection between the non-stick layer and the substrate, resulting in higher adhesion. In still other embodiments, a rough transition layer is provided between the substrate and the non-stick layer, which can further enhance the adhesion between the coating and the substrate. As an example, a rough transition layer can be formed by thermally spraying a metallic material onto the surface of a substrate.

[0133] The following describes a method for manufacturing a non-stick cookware according to this application with specific embodiments.

[0134] Provide matrix

[0135] 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. The substrate 110 can have a shape corresponding to its function, for example, such as... Figure 4 As shown, when the non-stick cookware 100 is a non-stick pan, the base 110 can have a conventional pan shape. It should be understood that... Figure 4 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).

[0136] In some embodiments, the inner surface of the substrate is a rough surface or an uneven structure. Taking a rough surface as an example, it can be obtained by sanding the inner surface of the substrate. For example, the roughness of the rough surface is Ra value in the range of 3μm-6μm. Taking an uneven structure as an example, a substrate with an uneven structure can be prepared by etching, laser engraving, stamping, etc.

[0137] Forming a transition layer (optional)

[0138] 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 coating 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, titanium alloys, iron, iron alloys, aluminum, aluminum alloys, zinc, zinc alloys, copper, copper alloys, zirconium, and zirconium alloys.

[0139] Form a non-stick layer

[0140] According to this application, the non-stick layer can be formed by applying a non-stick material using the above-described thermal spraying method.

[0141] Provide oil molecules

[0142] According to this application, to further optimize non-stick properties, oil molecules or oils can be added at the factory. This further optimizes the non-stick performance of the non-stick layer. Furthermore, during subsequent use, oils generated during cooking can replenish the three-dimensional porous structure, forming a continuous and stable oil film to maintain the non-stick properties. Below, an embodiment according to this application will be described using the filling of oil molecules as an example.

[0143] According to this application, the oil molecules can be selected from at least one of methyl oil molecules, dimethyl oil molecules, hydroxyl oil molecules, hydrogen-containing oil molecules, and polyether-modified oil molecules. These oil molecules possess specific viscosity and surface tension, making them more readily absorbed into the three-dimensional porous structure of the non-stick layer. In this case, the oil molecules are adsorbed or bonded to the three-dimensional porous structure of the non-stick layer. Furthermore, by weight percentage, the oil molecules comprise 20%-30% low molecular weight oil molecules, 40%-60% medium molecular weight oil molecules, and 20%-30% high molecular weight oil molecules, wherein the low molecular weight oil molecules have a molecular weight between 500 and 1000, the medium molecular weight oil molecules have a molecular weight between 3000 and 6000, and the high molecular weight oil molecules have a molecular weight between 12000 and 30000.

[0144] In these embodiments, high molecular weight oil molecules bond more firmly to the structure formed by the accumulation of the base material, resulting in a slower release rate. Low molecular weight oil molecules exhibit better free movement, thus providing better non-stick properties. Medium molecular weight oil molecules balance free movement and strong bonding. Therefore, by combining low, medium, and high molecular weight oil molecules, the likelihood of oil molecules entering the non-stick layer is further increased. Furthermore, oil molecules with different bonding strengths can be continuously released at various stages of use, achieving a better non-stick effect. As an example, the bonding force between oil molecules and the non-stick layer is approximately 10 kPa-25 kPa. Such a bonding force ensures the continuous release of oil molecules, preventing premature or inability to release them.

[0145] According to this application, an oil-based impregnation layer is used to obtain a non-stick cookware in which the oil molecules are incorporated into the porous structure of the non-stick layer. As an example, in the cookware coating, based on the total weight of the coating (100%), the weight of the oil molecules accounts for 5%-10% of the total weight of the coating, with the remainder being the non-stick layer formed by microspheres. As an example, the impregnation time of the oil molecules into the non-stick layer can be 15-30 minutes, and the temperature can be 80℃-120℃. Then, excess oil molecules on the surface are wiped dry, followed by drying at 280℃-340℃ for 3-6 minutes.

[0146] According to a fifth aspect of this application, a cookware is provided, specifically relating to a non-stick cookware. The non-stick cookware includes a substrate and a non-stick layer, the non-stick layer being disposed on the substrate. The non-stick layer includes the non-stick layer provided according to the above embodiments or includes a non-stick layer formed by spraying the non-stick material provided in the above embodiments.

[0147] Figure 4 This is a schematic diagram of the cross-sectional structure of a non-stick cookware provided in the embodiment of this application after being cut along the thickness direction. Figure 5 yes Figure 4 A magnified structural diagram at point I. (Refer to...) Figure 4 and Figure 5 The non-stick cookware 100 may include a substrate 110 and a non-stick layer 120.

[0148] In some embodiments, the substrate can be made of conventional metal materials. The non-stick material belongs to the category of ceramic materials, and its bonding strength with the metal substrate is relatively poor. In order to increase the bonding strength between the non-stick layer and the substrate, in some embodiments, the non-stick cookware further includes a transition layer 130, which is made of metal material, and is disposed between the substrate 110 and the non-stick layer 120.

[0149] In an exemplary embodiment, the transition layer can be prepared using a metallic material by thermal spraying or cold spraying. The transition layer material is selected from conventional metallic materials, such as at least one of titanium, titanium alloys, iron, iron alloys, aluminum, aluminum alloys, zinc, zinc alloys, copper, copper alloys, zirconium, and zirconium alloys. Titanium or titanium alloys are preferred, as they ensure bonding strength and provide high overall strength.

[0150] In an exemplary embodiment, the thickness of the transition layer is in the range of 10 micrometers to 80 micrometers.

[0151] According to this application, non-stick cookware with this coating can form a uniform oil film as oil film layer 140 during cooking to ensure corrosion resistance. Combining the oil film layer 140, which includes oils or oil molecules, with the amorphous coating not only ensures corrosion resistance but also further achieves good non-stick properties without the use of fluorine or ceramic coatings. The oil film layer 140 can also be formed during the cookware manufacturing process, sealing the surface pores of the non-stick layer. In an exemplary embodiment, the oil film layer 140 includes oils or oil molecules; the filled oils or oil molecules are protected by the pores and are not easily damaged by use, thereby further ensuring the sealing effect and improving corrosion resistance. Additionally, the non-stick properties can be further enhanced.

[0152] In some embodiments, one side (lower surface) of the non-stick layer is connected to the transition layer or the substrate, and the other side (upper surface) of the non-stick layer can directly serve as the inner surface of the non-stick cookware. To further enhance the non-stick performance of the cookware, in other embodiments, one side (lower surface) of the non-stick layer is connected to the transition layer or the substrate, and oils or oil molecules fill the surface pores of the non-stick layer from the other side (upper surface) to serve as part of the inner surface of the non-stick cookware.

[0153] like Figure 4 As shown, the inner surface of the non-stick cookware is formed with an alternating structure of non-stick layer and oil film layer. It can be understood that after oil or oil molecules fill the surface pores of the non-stick layer 120 to form the oil film layer 140, the non-stick layer 120 and the oil film layer 140 are distributed alternately to form the inner surface of the non-stick cookware. The non-stick layer 120 can be continuous, while the oil film layer 140 is a collective term for multiple discontinuous sublayers.

[0154] In some embodiments, the formed non-stick layer may have a thickness of 10 micrometers to 150 micrometers.

[0155] In some embodiments, the substrate has a rough structure, and the non-stick layer formed on it using a conventional spraying method is also stacked on the substrate in an uneven manner. Correspondingly, the non-stick layer is also uneven.

[0156] like Figure 7As shown, the non-stick cookware includes a substrate 110 and a non-stick layer 120 laminated on the substrate 110. The surface of the non-stick layer 120 has an uneven structure, and the recesses of the uneven structure are filled with a low surface energy material 150. The non-stick layer 120 includes a composite metal oxide with an amorphous structure, and the metal elements in the composite metal oxide layer include iron and titanium elements in different valence states.

[0157] In these embodiments, by forming a non-stick layer with an uneven surface structure using a non-stick material including composite metal oxides, it is possible to meet the needs of manufacturing patterned metal cookware on the one hand, and to obtain non-stick cookware with better non-stick performance when combined with low surface energy materials on the other hand.

[0158] In this application, the vertical distance h between the highest point of the protrusion and the lowest point of the recess in the concave-convex structure is 0.05mm-0.3mm, the top width w1 of the protrusion is 1mm-3mm, and the bottom width w2 of the protrusion is 3mm-4mm.

[0159] Here, the low surface energy material can be an oil molecule, a fluorine coating, or a ceramic coating; this application does not impose any restrictions on this. The low surface energy material can fill the entire recess or be at a predetermined distance from the opening of the recess. Here, the predetermined distance is no greater than the vertical distance h, and can be 0.03mm-0.25mm.

[0160] According to a sixth 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 or cups, and the non-stick material is the non-stick material provided in the above embodiments.

[0161] 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.

[0162] Example 1

[0163] The cookware according to Example 1 is manufactured by the following method.

[0164] 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, thereby obtaining a cookware base with a thickness of 1.5 cm and a surface roughness of 4 micrometers. Here, the cookware base has a bottom planar structure and a wall structure. The bottom planar structure is beneficial for stability when placed on a countertop and is suitable for use on an induction cooker, at least forming the subsequent non-stick layer on the bottom planar structure.

[0165] Step S20: Prepare a non-stick material with an average particle size of 50 micrometers. Specifically, a base material with an average particle size of 0.05-0.1 micrometers (a mixture of titanium dioxide and iron oxide in a 1:1 weight ratio) and polyvinyl alcohol are mixed in a 60:40 weight ratio to form a slurry. The slurry is then spray-dried to obtain non-stick particles. The resulting non-stick particles are then heated to 600°C at a heating rate of 18°C / min and held at that temperature for 7 hours. Finally, the temperature is increased to 1230°C at a heating rate of 70°C / min and held at that temperature for 18 hours for sintering. During sintering, the base material slightly melts, and the various oxides undergo chemical reactions to form a composite metal oxide with an amorphous structure, which serves as the non-stick material according to this application.

[0166] Step S30: Apply a non-stick coating.

[0167] 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: powder feed rate 13 g / min, spraying distance 160 mm, arc current 400 A, voltage 60 V, hydrogen pressure 0.7 MPa, hydrogen flow rate 250 L / h, argon pressure 1.2 MPa, argon flow rate 1500 L / h, and workpiece linear speed 30 m / min. The non-stick material powder is formed on the inner surface of the cookware substrate by plasma spraying, resulting in a non-stick layer with a thickness of 65 μm, thus completing the manufacture of the cookware of Example 1.

[0168] Example 2

[0169] Except in step S20, where a different base material (in this embodiment, the base material is a mixture of titanium oxide and iron oxide in a weight ratio of 39:13) is used to replace the base material of Example 1, the cookware of Example 2 is manufactured using the same method as in Example 1.

[0170] Example 3

[0171] Except in step S20, where a different base material (in this embodiment, the base material is a mixture of titanium oxide and iron oxide in a weight ratio of 13:39) is used to replace the base material of Example 1, the cookware of Example 3 is manufactured using the same method as in Example 1.

[0172] Example 4

[0173] Except that in step S20, a different base material (in this embodiment, the base material is a mixture of titanium oxide, iron oxide, and potassium oxide in a weight ratio of 26:26:1.5) is used to replace the base material of Example 1, the cookware of Example 4 is manufactured using the same method as in Example 1.

[0174] Example 5

[0175] Except that in step S20, a different base material (in this embodiment, the base material is a mixture of titanium oxide, iron oxide, and sodium oxide in a weight ratio of 26:26:1.5) is used to replace the base material of Example 1, the cookware of Example 5 is manufactured using the same method as in Example 1.

[0176] Example 6

[0177] Except that in step S20, a different base material (in this embodiment, the base material is a mixture of titanium oxide, iron oxide, and calcium oxide in a weight ratio of 26:26:1.5) is used to replace the base material of Example 1, the cookware of Example 6 is manufactured using the same method as in Example 1.

[0178] Example 7

[0179] Except that in step S20, a different base material (in this embodiment, the base material is a mixture of titanium oxide, iron oxide, and magnesium oxide in a weight ratio of 26:26:1.5) is used to replace the base material of Example 1, the cookware of Example 7 is manufactured using the same method as in Example 1.

[0180] Example 8

[0181] Except in step S20, where a different base material (in this embodiment, the base material is a mixture of titanium oxide, iron tetroxide, sodium oxide, and calcium oxide in a weight ratio of 26:26:1.5:1.5) is used to replace the base material of Example 1, the cookware of Example 8 is manufactured using the same method as in Example 1.

[0182] Example 9

[0183] Except in step S20, where a different base material (in this embodiment, the base material is a mixture of titanium oxide, iron oxide, sodium oxide, and magnesium oxide in a weight ratio of 26:26:1.5:1.5) is used to replace the base material of Example 1, the cookware of Example 9 is manufactured using the same method as in Example 1.

[0184] Example 10

[0185] Except in step S20, where a different base material (in this embodiment, the base material is a mixture of titanium oxide, iron tetroxide, potassium oxide, and calcium oxide in a weight ratio of 26:26:1.5:1.5) is used to replace the base material of Example 1, the cookware of Example 10 is manufactured using the same method as in Example 1.

[0186] Example 11

[0187] Except in step S20, where a different base material (in this embodiment, the base material is a mixture of titanium oxide, iron tetroxide, potassium oxide, and magnesium oxide in a weight ratio of 26:26:1.5:1.5) is used to replace the base material of Example 1, the cookware of Example 11 is manufactured using the same method as in Example 1.

[0188] Example 12

[0189] Except for the step of adding silicone oil molecules to the non-stick layer and curing it after step S30 (curing time is 5 min, curing temperature is 350°C), the cookware of Example 12 was manufactured using the same method as in Example 1.

[0190] Example 13

[0191] Except after step S30, when silane-based materials are grafted onto the non-stick layer of Example 1 (specifically, at least a portion of the surface of the initial non-stick layer is brought into contact with a modified solution containing N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane under ultrasonic conditions using an ultrasonic method, with the vibration frequency set to 30 kHz and the temperature heated to 60°C for 6 min), the cookware of Example 13 is manufactured using the same method as in Example 1.

[0192] Example 14

[0193] Except after step S30, when silane-based materials are grafted onto the non-stick layer of Example 8 (specifically, by using an ultrasonic method to bring at least a portion of the surface of the initial non-stick layer into contact with a modified solution containing N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane under ultrasonic conditions, with the vibration frequency set at 30 kHz and the temperature heated to 60°C for 6 min), the cookware of Example 14 is manufactured using the same method as in Example 8.

[0194] Example 15

[0195] Except after step S30, when silane-based materials are grafted onto the non-stick layer of Example 1 (specifically, by using an ultrasonic method to bring at least a portion of the surface of the initial non-stick layer into contact with a modified solution containing perfluorodecyltrimethoxysilane under ultrasonic conditions, with a vibration frequency of 30 kHz and heating to 60°C for 6 min), the cookware of Example 15 is manufactured using the same method as in Example 1.

[0196] Example 16

[0197] Except after step S30, when grafting silane-based materials onto the non-stick layer of Example 8 (specifically, using an ultrasonic method to bring at least a portion of the surface of the initial non-stick layer into contact with a modified solution containing perfluorodecyltrimethoxysilane under ultrasonic conditions, with a vibration frequency of 30 kHz, heating to 60°C for 6 min), the cookware of Example 16 was manufactured using the same method as in Example 8.

[0198] Example 17

[0199] Except for forming a 40 μm thick transition layer on the cookware substrate with titanium alloy before step S20, the cookware of Example 17 was manufactured using the same method as in Example 1.

[0200] Example 18

[0201] Except that in step S30, the outer surface of the cookware substrate is placed at room temperature and not in an environment of circulating cooling air gas, the cookware of Example 18 is manufactured using the same method as in Example 1.

[0202] Example 19

[0203] Except for step S20, in which the non-stick material of Example 1 is sintered (sintering temperature is 1400°C, sintering time is 4h), and then cooled at a cooling rate of 80°C / s, and the sintered material is used to replace the non-stick material of Example 1, the cookware of Example 19 is manufactured using the same method as Example 1.

[0204] Example 20

[0205] Except for step S20, in which the non-stick material of Example 8 is sintered (sintering temperature is 1400°C, sintering time is 4h), and then cooled at a cooling rate of 80°C / s, and the sintered material is used to replace the non-stick material of Example 1, the cookware of Example 20 is manufactured using the same method as Example 8.

[0206] Comparative Example 1

[0207] Except that in step S20, a different material (the material in this comparative example is a mixture 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.

[0208] Comparative Example 2

[0209] Except that in step S20, a different material (the material in this comparative example is a mixture 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 being 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.

[0210] Comparative Example 3

[0211] Except that in step S20, a different amorphous material (the material in this comparative example is 45 wt% titanium dioxide, 45 wt% iron oxide + ferrous oxide, 5 wt% calcium oxide + magnesium oxide, and the balance being phosphorus, carbon, and silicon) was used to replace the non-stick material of Example 1, the cookware of Comparative Example 3 was manufactured using the same method as in Example 1.

[0212] Comparative Example 4

[0213] Except for replacing the non-stick material of Example 1 with a different material (ferrous aluminum magnesium titanate in this comparative example) in step S20, the cookware of Comparative Example 4 was manufactured using the same method as in Example 1.

[0214] Comparative Example 5

[0215] Except that in step S20, the material (a mixture of TiO2 and Fe3O4) obtained by sintering the non-stick particles at a temperature of 200°C was used instead of the non-stick material of Example 1, the cookware of Comparative Example 5 was manufactured using the same method as in Example 1.

[0216] Test methods and evaluation criteria, test results

[0217] I. The degree of amorphization of the non-stick materials in Examples 1 to 11, 19 and 20 and the materials in Comparative Examples 1 to 5 was tested, and the test results are shown in Table 1 below.

[0218] Amorphousness testing method: XRD testing was used, followed by analysis and calculation using a conventional full-spectrum fitting method to obtain the amorphousness of the sample. 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 (i.e., the amorphousness) of the corresponding material.

[0219] Table 1 Test Results

[0220]

[0221]

[0222] As can be seen from Table 1, the non-stick material in the embodiments of this application is a non-stick material with a certain volume ratio of amorphous phase.

[0223] II. The coatings of the cookware obtained in Examples 1-20 and Comparative Examples 1-5 were subjected to performance tests, and the results are recorded in Table 2 below. The specific performance test methods are as follows:

[0224] Test methods and evaluation criteria

[0225] 1. Amorphousness test method: Refer to the amorphousness test method in non-stick materials.

[0226] 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.

[0227] 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.

[0228] 4. Hardness Testing Method and Evaluation Standard: The Vickers hardness test method is used to test the Vickers hardness of the cookware coating. The unit of hardness value is HV. A higher hardness value indicates a harder sample, stronger resistance to abrasion from metal spatulas and food, and less susceptibility to wear. However, excessive hardness may lead to cracking. Generally, the desired hardness of the non-stick coating is no less than 200 HV and no more than 600 HV.

[0229] 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 goniometry method, and the surface energy of the samples was calculated using the OWRK method. Here, the samples are the coatings corresponding to the examples and comparative examples, and it is expected that the measured surface energy value of the samples will not exceed 100 dynes.

[0230] Table 2 Results Test Table

[0231]

[0232]

[0233] As shown in Table 2, the non-stick layer obtained in this application exhibits excellent initial and long-lasting non-stick properties, and possesses suitable hardness, preventing cracking caused by excessive coating hardness. By sealing the coating formed through the thermal spraying process, a lower surface energy than fluorine coatings can be obtained, ensuring initial non-stick properties. By controlling the spraying process (i.e., placing the outer surface of the cookware in a cooling gas environment during plasma spraying), the degree of amorphization of the non-stick layer can be increased to a certain extent, resulting in a relatively low surface energy and thus ensuring good long-lasting non-stick performance.

[0234] 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.

Claims

1. A non-stick material, characterized in that, The non-stick material includes a composite metal oxide having an amorphous structure, the composite metal oxide serving as a main body of the non-stick material, metal elements in the composite metal oxide including iron ions of different valence states and titanium ions of different valence states, the composite metal oxide including FeTiO3, Fe2TiO5, and Fe3Ti3O 10 .

2. The non-stick material of claim 1, wherein, The non-stick material further comprises carbonized products of the binder dispersed in the composite metal oxide.

3. The non-stick material of claim 2, wherein, The weight ratio of the carbonized products of the binder and the composite metal oxide is (0.4-3.5):(96.5-99.6).

4. The non-stick material of claim 1, wherein, The non-stick material is in the form of particles, and the porosity of the particles of the non-stick material is 25%-55% and the pore size is 500 nanometers-4 micrometers.

5. The non-stick material of claim 1, wherein, The non-stick material is a material with an amorphous phase volume ratio in the range of 30%-70%; and / or, The average particle size of the non-stick material is 10 micrometers to 70 micrometers.

6. A method for producing a non-stick material, characterized by, The preparation method of the non-stick material comprises: forming a mixed slurry comprising a binder and a base material, the base material comprising titanium oxide and magnetite; spray drying the mixed slurry to obtain non-stick particles; sintering the non-stick particles so that the base material in the non-stick particles is micro-fused and chemically bonded, thereby obtaining a composite metal oxide comprising different valence state iron ions and different valence state titanium ions and having an amorphous structure as the non-stick material, the composite metal oxide as the main body of the non-stick material.

7. The method of claim 6, wherein the non-stick material is prepared by The weight ratio of the base material and the binder is (52-70):(30-48); and / or, the weight ratio of the titanium oxide and the magnetite is (13-39):(13-39); and / or, the particle size of the base material is 0.05 micrometers-5 micrometers.

8. The method of claim 6, wherein the non-stick material is prepared by The binder comprises an alcohol-based binder and / or a cellulose-based binder.

9. The method of claim 8, wherein the non-stick material is prepared by The cellulose-based binder comprises at least one of a methylol cellulose-based binder, a hydroxyethyl cellulose-based binder, and a hydroxypropyl cellulose-based binder, and the alcohol-based binder comprises at least one of a polyvinyl alcohol-based binder, a polypropylene alcohol-based binder, and a higher alcohol-based binder containing six or more carbon atoms.

10. The method of claim 6, wherein the non-stick material is prepared by The sintering step comprises: heating the non-stick particles to 500℃-650℃ at a heating rate of 15℃ / min-20℃ / min, holding for 6h-8h, and then heating to 1200℃-1250℃ at a heating rate of 55℃ / min-100℃ / min, holding for 12h-24h.

11. The method of claim 6, wherein the non-stick material is prepared by, The composite metal oxide includes FeTi03, Fe2Ti05, and Fe3Ti3O 10 .

12. Use of a non-stick material as a sprayable raw material, characterized in that The non-stick material is used as a spraying raw material for cookware or cupware, and is the non-stick material according to any one of claims 1-5 or the non-stick material prepared by the preparation method according to any one of claims 6-11.

13. A non-stick cookware characterized by, The non-stick cookware comprises a base and a non-stick layer formed on the base, the non-stick layer having a pore structure filled with oil molecules, wherein the non-stick layer is formed of a non-stick material according to any one of claims 1-5 or prepared by the preparation method according to any one of claims 6-11.

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