Non-stick layer and method for producing same, non-stick cookware and method for producing same

Abstract

The application provides a non-stick layer and a preparation method thereof, a non-stick cooker and a manufacturing method thereof. The preparation method of the non-stick layer comprises spraying a non-stick material to form an initial non-stick layer, wherein the initial non-stick layer comprises a composite metal oxide layer with an amorphous structure, metal elements in the composite metal oxide layer include iron elements with different valence states and titanium elements with different valence states, and the initial non-stick layer is modified by a silane material, so as to obtain the non-stick layer. The non-stick layer provided in the embodiments of the application has good initial non-stickness and durable and persistent non-stickness.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of cookware non-stick technology, and more particularly to a non-stick layer and a preparation method thereof, a non-stick cookware and a manufacturing method thereof. BACKGROUND

[0002] In the art, fluorine coating is a common non-stick coating. However, the non-stick coating manufactured by using fluorine coating has excellent initial non-stick property, but is easily damaged by a spatula and is easily aged or decomposed at high temperature during use. These problems have seriously affected the service life of the coating formed by fluorine coating, resulting in the general persistent non-stick property of the coating formed by fluorine coating.

[0003] Therefore, it is still a problem to be solved to develop a layer formed by a non-stick material which has both initial non-stick property and persistent non-stick property. SUMMARY

[0004] Therefore, the present application aims to provide a non-stick layer and a preparation method thereof, a non-stick cookware and a manufacturing method thereof, so as to solve the problem that the layer formed by the existing non-stick material cannot have both initial non-stick property and persistent non-stick property.

[0005] According to a first aspect of the present application, a method for preparing a non-stick layer is provided, which comprises spraying a non-stick material to form an initial non-stick layer, wherein the initial non-stick layer comprises a composite metal oxide layer having an amorphous structure, metal elements in the composite metal oxide layer include iron elements of different valence states and titanium elements of different valence states, and water-soluble metal elements and / or metal elements capable of reacting with fatty acids in grease; and modifying the initial non-stick layer with a silane-based material to obtain the non-stick layer.

[0006] According to the method for preparing a non-stick layer provided by the embodiments of the present application, the composite metal oxide layer having an amorphous structure is used as the material for forming the initial non-stick layer, the initial non-stick layer formed by the material has low surface energy and has certain initial non-stick property. In addition, the initial non-stick layer formed by the non-stick material will not age with the extension of use time, and has good physical and chemical stability, so as to have more durable persistent non-stick property. In addition, the initial non-stick layer is modified with a silane-based material, and the non-stick layer obtained has strong hydrophobicity, low surface energy and large contact angle due to the grafted silane-based material, so that the non-stick property of the non-stick layer is better.

[0007] In some embodiments, the water-soluble metal element comprises potassium element and / or sodium element, and the metal element capable of reacting with fatty acid in oil and fat comprises calcium element and / or magnesium element. In the case that the non-stick material comprises metal element capable of reacting with fatty acid in oil and fat (e.g., calcium element, magnesium element), the initial non-stick layer formed also naturally comprises metal element capable of reacting with fatty acid in oil and fat, so that the initial non-stick layer is prone to react with fatty acid in oil and fat as oil molecules in subsequent processes, and the formed fatty acid salt is deposited on the surface of the non-stick layer to further assist in providing non-stick property.

[0008] In some embodiments, the iron element of different valence comprises +2 valence and +3 valence, and the titanium element of different valence comprises at least two of +2 valence, +3 valence and +4 valence.

[0009] In these embodiments, the arrangement of the above-mentioned iron element and titanium element of different valence in the crystal lattice is different, which can make the non-stick material have an amorphous structure and be conducive to the formation and stability of the composite metal oxide.

[0010] In some embodiments, the initial non-stick layer further comprises carbonized product of a binder, and the carbonized product of the binder is dispersed in the composite metal oxide layer.

[0011] In these embodiments, the carbonized product of the binder is dispersed in the particles of the composite metal oxide. On the one hand, the presence of the carbonized product of the binder can facilitate the connection between the particles of the base body and ensure the bonding force inside each particle of the non-stick material; on the other hand, the carbonized product of the binder can be used as a connecting bridge between the particles of the base body, so that the non-stick material as a whole has high hardness and stability.

[0012] In some embodiments, the weight ratio of the carbonized product of the binder to the composite metal oxide is (0.4-3.5):(96.5-99.6). With a suitable weight ratio of the carbonized product of the binder to the composite metal oxide, the overall strength of the non-stick material can be avoided from being affected by too much carbonized product of the binder.

[0013] In some embodiments, the non-stick material is in a granular form, and the porosity of the particles of the non-stick material is 25%-55% and the pore size is 500 nanometers-4 micrometers.

[0014] In these embodiments, the particles of the composite metal oxide with the above-mentioned pore distribution are used as the non-stick material, which can be stacked by melting to form a non-stick layer with a three-dimensional pore structure, so that the non-stick layer can well adsorb and store edible oil, thereby further enhancing the non-stick property of the product with the non-stick layer.

[0015] In some embodiments, the initial non-stick layer has a porosity of 5-30% and a pore size of 500 nm-4 microns.

[0016] In these embodiments, the particles of the composite metal oxide having the above pore distribution are used as the non-stick material, which can be stacked by melting to form a non-stick layer having a three-dimensional pore structure, thus being able to well adsorb and store edible oil, thereby further enhancing the non-stick performance of the product provided with the non-stick layer.

[0017] In some embodiments, the silane-based material includes at least one of gamma-aminopropyltriethoxysilane, N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane, sulfur-containing silane coupling agent, epoxy-based silane coupling agent, gamma-ureidopropyltriethoxysilane, perfluorodecyltrimethoxysilane, perfluorooctyltriethoxysilane, perfluorododecyltrimethoxysilane, and trifluoropropylmethylsilane.

[0018] In these embodiments, the modified material has strong hydrophobicity, low surface energy, and a large contact angle, thus being able to obtain a non-stick layer with better non-stick performance.

[0019] In some embodiments, the step of modifying the initial non-stick layer with the silane-based material includes contacting and reacting a modification solution including the silane-based material and water with at least part of the surface of the initial non-stick layer, thereby obtaining a silane-based material-modified initial non-stick layer as the non-stick layer.

[0020] In these embodiments, in the above manner, the low surface energy material-silane-based material is grafted on the initial non-stick layer, so that the overall non-stick performance of the initial non-stick layer is further enhanced.

[0021] In some embodiments, the silane-based material-modified initial non-stick layer is a product after the hydrolysis product of the silane-based material reacts with the initial non-stick layer.

[0022] In these embodiments, the product after the hydrolysis product of the silane-based material reacts with the initial non-stick layer is grafted on the initial non-stick layer, which can further enhance the overall non-stick performance of the initial non-stick layer.

[0023] In some embodiments, the method of preparing the non-stick layer further includes impregnating the non-stick layer with oil molecules, thereby obtaining a non-stick layer combined with oil molecules, thus being able to further optimize the non-stick performance by means of the oil film non-stick principle.

[0024] According to a second aspect of the present application, a non-stick layer is provided, wherein the non-stick layer comprises a composite metal oxide layer having an amorphous structure, metal elements in the composite metal oxide layer include iron elements of different valence states and titanium elements of different valence states, and a silane-based material formed on the composite metal oxide layer.

[0025] In some embodiments, the non-stick layer has an amorphous phase volume fraction of 50%-70%, so that the non-stick layer with the amorphous phase volume fraction has low surface energy and higher wear resistance and stability.

[0026] According to a third aspect of the present application, a manufacturing method of a non-stick cookware is provided, wherein the manufacturing method of the non-stick cookware comprises: forming a mixed slurry comprising a binder and a base, the base comprising titanium oxide and magnetite, and a water-soluble metal oxide and / or a metal oxide capable of reacting with fatty acids in grease; spray drying the mixed slurry to obtain non-stick particles; sintering the non-stick particles so that the base in the non-stick particles is slightly fused, thereby obtaining a composite metal oxide comprising iron elements of different valence states and titanium elements of different valence states and having an amorphous structure as a non-stick material; forming an initial non-stick layer on a substrate by spraying the non-stick material on the substrate; and modifying the initial non-stick layer with a silane-based material, thereby obtaining the non-stick layer.

[0027] In some embodiments, the weight ratio of the base to the binder is (52-70):(30-48), and in the mixed slurry, the weight fraction of the binder is comparable to that of the base, so that a large amount of binder can be volatilized in the subsequent steps to ensure that the composite metal oxide having a three-dimensional macro-pore structure is easily formed while ensuring the overall strength of the non-stick material, so that the formation of the non-stick layer by the non-stick material can retain the three-dimensional macro-pore structure of the non-stick material, thereby ensuring the formation of the three-dimensional pore structure of the non-stick layer. And / or, the weight ratio of the titanium oxide to the magnetite is (13-39):(13-39), and within this ratio range, the titanium oxide and the magnetite can easily form a composite metal oxide through a chemical reaction at a high temperature in the subsequent sintering process, and can minimize the impact of unreacted portions on the overall non-stick material. In addition, within this ratio range, the synergistic effect of titanium oxide and magnetite can help to increase the amorphous degree of the composite metal oxide.

[0028] In some embodiments, the binder includes an alcohol-based binder and / or a cellulose-based binder, in particular, the cellulose-based binder includes at least one of a hydroxymethyl cellulose-based binder, a hydroxyethyl cellulose-based binder, and a hydroxypropyl cellulose-based binder, and the alcohol-based binder includes at least one of a polyvinyl alcohol-based binder, a polypropylene glycol-based binder, and a higher alcohol-based binder containing six or more carbon atoms. The above-mentioned binder can facilitate the connection of the individual particles of the base material, thereby facilitating the formation of the intended composite metal oxide.

[0029] In some embodiments, the particle size of the base material is 0.05 microns to 5 microns. When the base material is in the range of 0.05 microns to 5 microns, it is easier to form the above-mentioned composite metal oxide having an amorphous structure and a three-dimensional macro-pore structure, and the porosity of the formed composite metal oxide layer (non-stick layer) can be controlled to easily meet the needs of locking oil.

[0030] In some embodiments, the sintering step includes heating the non-stick particles to 500°C to 650°C at a heating rate of 15°C / min to 20°C / min, holding for 6h to 8h, and then heating to 1200°C to 1250°C at a heating rate of 55°C / min to 100°C / min, holding for 12h to 24h. Under this parameter, the base material in the non-stick particles can be slightly melted, and the intended composite metal oxide can be formed.

[0031] According to a fourth aspect of the present application, a non-stick cookware is provided, wherein the non-stick cookware includes the non-stick layer according to the above description or is manufactured by the manufacturing method of the non-stick cookware according to the above description. BRIEF DESCRIPTION OF DRAWINGS

[0032] The above-mentioned and / or other features and aspects of the inventive concept will become apparent and easy to understand from the description of the embodiments, taken in conjunction with the accompanying drawings.

[0033] Figure 1 is a scanning electron microscope image of a non-stick particle according to an embodiment of the present application;

[0034] Figure 2 is a scanning electron microscope image of a non-stick material according to an embodiment of the present application;

[0035] Figure 3 is an XRD spectrum of a non-stick material according to an embodiment of the present application;

[0036] Figure 4 is a cross-sectional structure schematic diagram of a non-stick cookware according to an embodiment of the present application after being cut along the thickness direction;

[0037] Figure 5 is Figure 4 is an enlarged structure schematic diagram at I in FIG.

[0038] Figure 6 is a schematic diagram of a cross-sectional structure of the non-stick layer and the oil film layer of the present application after being cut along the thickness direction;

[0039] Figure 7 is a schematic diagram of a partial structure of another non-stick cookware provided according to an embodiment of the present application.

[0040] Symbol explanation:

[0041] 100, non-stick cookware; 110, base body; 120, non-stick layer; 130, transition layer; 140, oil film layer; 150, low surface energy material. DETAILED DESCRIPTION

[0042] Example embodiments of the inventive concept will be described in more detail below. Although example embodiments of the inventive concept are described below, it should be understood that the inventive concept can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that the inventive concept can be more thoroughly understood and so that the scope of the inventive concept can be conveyed completely to those skilled in the art.

[0043] In the art, fluorine coating is a common non-stick material. However, the non-stick coating made by using fluorine coating has excellent initial non-stickiness, but is easily damaged by a spatula and is easily aged or decomposed at high temperature during use. These problems have seriously affected the service life of the coating formed by fluorine coating, resulting in that the long-lasting non-stickiness of the coating formed thereby is generally poor. In addition, perfluoroalkyl and polyfluoroalkyl compounds (PFAS) are indispensable raw materials for synthetic fluorine coating. As the control of perfluoroalkyl and polyfluoroalkyl compounds (PFAS) in the industry gradually becomes strict, it is inevitable that fluorine coating will exit the stage of non-stick cookware, which also means that the materials that can be used for cookware coating are gradually decreasing, so there is still an urgent need to develop new non-stick materials in the field of cookware manufacturing.

[0044] At present, no material with lower surface energy than fluorine coating has been found, but the demand for non-stick in the cookware industry has always existed, and ceramic coating is the most promising material to replace fluorine coating at present. Ceramic coating is a liquid coating with oil molecules as the main non-stick component. Although the initial non-stickiness of the coating formed thereby can approach that of fluorine coating, the oil molecules will be continuously consumed and lose non-stick effect quickly due to high temperature during high-temperature cooking, and therefore, the long-lasting non-stickiness of ceramic coating cannot meet the demand for non-stick of cookware.

[0045] With the development of the non-stick industry, solid spraying materials mainly made of metal (e.g., iron, stainless steel, low-carbon steel, high-carbon steel, cast iron, and copper, etc.) or ceramic (e.g., titanium oxide, titanium nitride, titanium carbide, magnetite, iron oxide, ferrous oxide, aluminum oxide, chromium oxide, and nickel oxide, etc.) have emerged, which can form a non-stick layer without organic materials, i.e., so-called "coating-free non-stick technology". Here, coating-free means that it does not use organic coatings such as fluorine coatings or ceramic coatings. Although the coating formed by the above spraying materials is wear-resistant, the cookware with the coating only has the effect of cooking non-stick in the state of having oil, and its initial non-stick property is poor, and usually needs to be modified with a material with good non-stick property, such as polysiloxane or fluorinated material, to meet the initial non-stick property required by the national standard. In addition, the non-stick property of such materials decreases quickly after wear, and the residual polysiloxane has a negative effect on the non-stick property, which is worse than before modification.

[0046] As can be seen from the above, the existing non-stick materials are difficult to achieve both initial non-stick property and durable non-stick property. Therefore, developing new non-stick materials with both initial non-stick property and durable non-stick property plays an extremely important role in the field of cookware manufacturing.

[0047] According to a first aspect of the present application, a non-stick material for cookware or cupware is provided. The non-stick material includes composite metal oxide particles with an amorphous structure, wherein the metal elements in the composite metal oxide include iron elements of different valences and titanium elements of different valences.

[0048] In the embodiments of the present application, the 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 including at least iron and titanium, which has an amorphous structure, meaning that the arrangement of atoms or molecules has no long-range order. The amorphous structure endows the non-stick material with some good properties, such as high hardness, high wear resistance, and good thermal stability.

[0049] According to the non-stick material provided in the embodiments of the present application, the non-stick material itself has a relatively low surface energy, and the non-stick layer formed by the non-stick material has certain initial non-stick performance. In addition, the non-stick layer formed by the non-stick material does not age with the extension of use time, and has good physical and chemical stability, so it can have more durable non-stick performance.

[0050] In some embodiments, the iron elements of different valences include +2 valence and +3 valence, and the titanium elements of different valences include at least two of +2 valence, +3 valence, and +4 valence.

[0051] In these embodiments, the different arrangements of the iron elements and titanium elements in the lattice in different valence states enable the non-stick material to have an amorphous structure and facilitate the manufacture, formation and stability of the composite metal oxide.

[0052] According to the present application, the composite metal oxide has an amorphous structure and includes iron elements in different valence states and titanium elements in different valence states. In some embodiments, the composite metal oxide is a composite metal oxide formed by FeTiO3, Fe2TiO5, Fe3Ti3O10 and other oxides in different forms. For the iron-titanium-containing oxide, it is described by the general formula Fe(a+b)Ti(c+d)Oe, as some examples, a is the number of iron atoms with a valence of +2, b is the number of iron atoms with a valence of +3, c is the number of titanium atoms with a valence of +2, d is the number of titanium atoms with a valence of +4, and e is the number of oxygen atoms with a valence of +2, wherein 2a+3b+2c+4d=2e. As other examples, a is the number of iron atoms with a valence of +2, b is the number of iron atoms with a valence of +3, c is the number of titanium atoms with a valence of +2, d is the number of titanium atoms with a valence of +3, and e is the number of oxygen atoms with a valence of +2, wherein 2a+3b+2c+3d=2e. As yet other examples, a is the number of iron atoms with a valence of +2, b is the number of iron atoms with a valence of +3, c is the number of titanium atoms with a valence of +3, d is the number of titanium atoms with a valence of +4, and e is the number of oxygen atoms with a valence of +2, wherein 2a+3b+3c+4d=2e.

[0053] According to the present application, the composite metal oxide is a composite metal oxide formed by FeTiO3, Fe2TiO5, Fe3Ti3O10, K2Ti3O7, Na2Ti3O7, CaTiO3 and MgTiO3 and other oxides in different forms.

[0054] In some embodiments, the oxide containing iron, titanium, and an alkali metal element is described by the general formula Fe(a+b)Ti(c+d)XfOe, where a is the number of iron atoms having a valence of +2, b is the number of iron atoms having a valence of +3, c is the number of titanium atoms having a valence of +2, d is the number of titanium atoms having a valence of +4, e is the number of oxygen atoms having a valence of +2, X is the alkali metal element, and f is the number of X atoms having a valence of +1, where 2a + 3b + 2c + 4d + f = 2e. As other examples, a is the number of iron atoms having a valence of +2, b is the number of iron atoms having a valence of +3, c is the number of titanium atoms having a valence of +2, d is the number of titanium atoms having a valence of +3, e is the number of oxygen atoms having a valence of +2, X is the alkali metal element, and f is the number of X atoms having a valence of +1, where 2a + 3b + 2c + 3d + f = 2e. As yet other examples, a is the number of iron atoms having a valence of +2, b is the number of iron atoms having a valence of +3, c is the number of titanium atoms having a valence of +4, d is the number of titanium atoms having a valence of +3, e is the number of oxygen atoms having a valence of +2, X is the alkali metal element, and f is the number of X atoms having a valence of +1, where 2a + 3b + 4c + 3d + f = 2e.

[0055] In other embodiments, the oxide containing iron, titanium, and an alkaline earth metal element is described by the general formula Fe(a+b)Ti(c+d)YgOe, where a is the number of iron atoms having a valence of +2, b is the number of iron atoms having a valence of +3, c is the number of titanium atoms having a valence of +2, d is the number of titanium atoms having a valence of +4, e is the number of oxygen atoms having a valence of +2, Y is the alkaline earth metal element, and g is the number of Y atoms having a valence of +2, where 2a + 3b + 2c + 4d + 2g = 2e. As other examples, a is the number of iron atoms having a valence of +2, b is the number of iron atoms having a valence of +3, c is the number of titanium atoms having a valence of +3, d is the number of titanium atoms having a valence of +4, e is the number of oxygen atoms having a valence of +2, Y is the alkaline earth metal element, and g is the number of Y atoms having a valence of +2, where 2a + 3b + 3c + 4d + 2g = 2e. As yet other examples, a is the number of iron atoms having a valence of +2, b is the number of iron atoms having a valence of +3, c is the number of titanium atoms having a valence of +3, d is the number of titanium atoms having a valence of +2, e is the number of oxygen atoms having a valence of +2, Y is the alkaline earth metal element, and g is the number of Y atoms having a valence of +2, where 2a + 3b + 3c + 2d + 2g = 2e.

[0056] In the embodiments of the present application, the metal elements in the composite metal oxide include iron elements in different valence states and titanium elements in different valence states. Here, the iron elements in different valence states and the titanium elements in different valence states, as constituent elements in the composite metal oxide, synergistically act, for example, the iron elements in different valence states and the titanium elements in different valence states interact with each other and chemically combine (for example, redox reaction) at high temperature to form the composite metal oxide with amorphous structure, thus helping to improve the non-stick performance and other physical and chemical properties of the non-stick material.

[0057] In some embodiments, the metal elements in the composite metal oxide further include soluble metal elements and / or metal elements capable of reacting with fatty acids in oil and fat. Specifically, the soluble metal elements are water-soluble metal elements, and specifically include potassium elements and / or sodium elements. The metal elements capable of reacting with fatty acids in oil and fat include calcium elements and / or magnesium elements. In the case where the non-stick material includes water-soluble metal elements (for example, potassium elements, sodium elements), the initial non-stick layer formed also includes water-soluble metal elements, which are dissolved and exchanged during the use of the product, so that some nanoscale cavities are generated on the surface of the initial non-stick layer, thereby forming a micro-nano hydrophobic structure, so that better non-stick performance can be generated under the infiltration of oil molecules. In addition, in the case where the non-stick material includes metal elements capable of reacting with fatty acids in oil and fat (for example, calcium elements, magnesium elements), the initial non-stick layer formed also naturally includes metal elements capable of reacting with fatty acids in oil and fat, so that the initial non-stick layer is prone to react with fatty acids in oil and fat as oil molecules in the subsequent process, and the formed fatty acid salt is deposited on the surface of the non-stick layer to further assist in providing non-stick performance. It should be noted that only some specific examples of water-soluble metal elements and metal elements capable of reacting with fatty acids in oil and fat are shown here, but those skilled in the art can understand that other water-soluble metal elements and metal elements capable of reacting with fatty acids in oil and fat can achieve the same technical effects as the present application.

[0058] In some embodiments, the non-stick material further includes carbonized products of the binder, and the carbonized products of the binder are dispersed in the composite metal oxide. Specifically, the carbonized products of the binder are dispersed between adjacent particles of the composite metal oxide.

[0059] In these embodiments, the particles of the composite metal oxide have the carbonized products of the binder dispersed therein, on the one hand, the presence of the carbonized products of the binder can facilitate the connection between the particles of the matrix and ensure the bonding force inside each particle of the non-stick material; on the other hand, the carbonized products of the binder can serve as a connecting bridge between the particles of the matrix, so that the non-stick material as a whole exhibits high hardness and stability.

[0060] Specifically, the carbonized product of the binder is oleophilic, so that the initial non-stick layer formed by the non-stick material can ensure the oleophilicity during subsequent use, which is conducive to the locking of oil molecules, thereby further improving the non-stick performance of the non-stick layer based on the oil film non-stick principle.

[0061] 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). The carbonized product of the binder and the composite metal oxide have a suitable weight ratio, so that the excessive carbonized product of the binder can be avoided to affect the overall strength of the non-stick material.

[0062] In some embodiments, the non-stick material is in a granular form and has a three-dimensional macro-pore structure, and the porosity of a single particle of the non-stick material is 25%-55% and the pore size is 500 nm-4 μm. The pores are interconnected in a natural and irregular arrangement to form a three-dimensional macro-pore structure, which is conducive to the formation of an initial non-stick layer with three-dimensional pores.

[0063] In these embodiments, the composite metal oxide with a three-dimensional macro-pore structure is used as the non-stick material, which can form an initial non-stick layer with a three-dimensional pore structure by melting and stacking, so that the initial non-stick layer can well adsorb and store edible oil, thereby further enhancing the non-stick performance of a product with the initial non-stick layer.

[0064] 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%, so that the non-stick material with an amorphous phase volume ratio has low surface energy and higher wear resistance and stability.

[0065] In other embodiments, the non-stick material after high-temperature sintering can also be subjected to quenching treatment, so that the atoms or molecules in the interior of the non-stick material do not have time to arrange into an ordered crystal structure, and the degree of amorphization of the non-stick material is further improved to better achieve the purpose of improving non-stickness. Specifically, the specific method of quenching treatment includes heating the initial non-stick layer and rapidly exposing it to a low-temperature environment to achieve rapid cooling, so that the material in the initial non-stick layer does not have time to crystallize, thereby tending to amorphous transformation. Specifically, the initial non-stick layer is sintered (sintering temperature: 1200°C-1400°C, sintering time: 4 h), and then cooled at a cooling rate of 80°C / s-100°C / s. As an example, the amorphous phase volume ratio of the non-stick material is 35%-70%.

[0066] In summary, the amorphous phase volume ratio of the non-stick material according to the present application is 30%-70%, and in preferred embodiments, the amorphous phase volume ratio of the non-stick material is 50%-70%.

[0067] In some embodiments, the non-stick material is granulated powder particles with an average particle size of 10 microns to 70 microns. In preferred embodiments, the granulated powder particles of the non-stick material are normally distributed with a D50 of 25 microns to 35 microns. In this way, on the one hand, the initial non-stick layer formed by the non-stick material of this particle size can have a suitable pore structure, thereby facilitating oil storage and improving non-stickiness; on the other hand, the granulated powder particles themselves have a large specific surface area, which can ensure the bonding force between the initial non-stick layer and the substrate.

[0068] According to a second aspect of the present application, a method for preparing a non-stick material is provided. The method for preparing the non-stick material comprises: step S101, forming a mixed slurry comprising a binder and a base material, the base material comprising titanium oxide and magnetite. Step S102, spray drying the mixed slurry to obtain non-stick particles. Step S103, sintering the non-stick particles, so that the titanium oxide and the magnetite in the base material in the non-stick particles are micro-fused and chemically bonded, thereby obtaining a composite metal oxide comprising different valence states of iron elements and different valence states of titanium elements and having an amorphous structure as the non-stick material.

[0069] According to the method for preparing a non-stick material provided by the embodiments of the present application, by performing spray drying on the mixed slurry comprising a binder and a base material, and then sintering, a composite metal oxide having an amorphous structure and containing different valence states of iron elements and different valence states of titanium elements can be formed as a non-stick material. The non-stick material has a low surface energy, and the initial non-stick layer formed therefrom has good initial non-stickiness. In addition, the initial non-stick layer formed by the non-stick material does not age with the extension of use time, and has good physical and chemical stability, so it has more durable and persistent non-stick performance. Furthermore, the composite metal oxide has a three-dimensional macro-pore structure and is in the form of microspheres. The initial non-stick layer formed by the non-stick material can retain the three-dimensional macro-pore structure of the microspheres as much as possible, thereby forming an initial non-stick layer having a corresponding three-dimensional pore structure. The initial non-stick layer having a corresponding three-dimensional pore structure is easy to adsorb oil molecules, thereby being able to exhibit more excellent non-stick performance due to the oil film non-stick principle.

[0070] In the following, the method for preparing a non-stick material according to the present application will be described in detail.

[0071] Providing a binder

[0072] According to the present application, as some embodiments, the binder comprises an alcohol-based binder and / or a cellulose-based binder. As another example, the binder comprises an oleophilic binder.

[0073] Specifically, the cellulose-based binder includes 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 can include at least one of a polyvinyl alcohol-based binder, a polypropylene glycol-based binder, and other higher alcohol-based binders containing six or more carbon atoms. However, the present application is not limited thereto, but a suitable binder can be selected according to actual needs.

[0074] It is to be noted that the binder according to the present application is volatilized or carbonized in the subsequent sintering process, and whether it is volatilized or carbonized depends largely on the heating rate, sintering temperature, and time of the subsequent sintering stage. Here, carbonization is a process in which, at high temperatures, an organic substance removes hydrogen, oxygen, and the like other than carbon as a low molecular compound through thermal decomposition, and only the remaining carbon is obtained. Volatilization is a process in which an organic substance is converted from a liquid state to a gaseous state after reaching the boiling point, that is, in this process, the binder in the non-stick particles is converted into a gaseous state and leaves pores on the non-stick particles.

[0075] Providing a base

[0076] According to the present application, the base material includes titanium oxide and magnetite, which at least forms a mixed slurry with the binder and can form a composite metal oxide having an amorphous structure through spray drying (powder granulation). Here, titanium oxide and magnetite refer to substances, not ingredients. In these embodiments, titanium and iron are non-toxic and harmless metals, and can form stable insoluble oxides. The electronic configuration of titanium is 1s22s2 2p 6 3s2 3p 6 3d2 4s2(2 / 8 / 10 / 2), the electronic configuration of iron 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 metal elements, and their electronic layer configurations have similarities in the periodic table, so these two elements are prone to form composite metal oxides (multi-component oxides) in oxides. Secondly, the atomic radius of titanium is 0.145 nanometers, and the atomic radius of iron is about 0.124 nanometers. Due to the significant difference in atomic radius between the two elements, the volume occupied by the two atoms is different in the crystal lattice arrangement, resulting in lattice distortion rather than forming a complete and standard lattice arrangement, so that the composite oxide formed has certain amorphous characteristics, further improving the non-stick performance.

[0077] In some embodiments, the base material is titanium oxide and magnetite. In other embodiments, the base material can include water-soluble metal oxides and / or metal oxides capable of reacting with fatty acids in oil and fat in addition to titanium oxide and magnetite. The water-soluble metal oxides are alkali metal oxides, and the metal oxides capable of reacting with fatty acids in oil and fat 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.

[0078] In these embodiments, titanium oxide and magnetite serve as the main material, and water-soluble metal oxides and / or metal oxides capable of reacting with fatty acids in oil and fat serve as the auxiliary material. By introducing an auxiliary material with a larger size than titanium and iron elements as part of the base material, lattice distortion can be further intensified, thereby facilitating the formation of a composite metal oxide with obvious amorphous characteristics.

[0079] In preferred embodiments, the base material is titanium oxide, magnetite, potassium oxide, sodium oxide, calcium oxide, and magnesium oxide. Among them, the atomic radius of titanium is 0.145 nanometers, the atomic radius of iron is about 0.124 nanometers, the atomic radius of calcium is 0.223 nanometers, the atomic radius of magnesium is 0.160 nanometers, the atomic radius of sodium is 0.186 nanometers, and the atomic radius of potassium is 0.236 nanometers. There is a significant difference in atomic radius between titanium and iron, and the volume occupied by the two atoms in the lattice arrangement is different, resulting in lattice distortion rather than complete and standard lattice arrangement. Therefore, the composite oxide has certain amorphous characteristics. The introduction of alkali metals and alkaline earth metals with larger atomic radii further intensifies the lattice distortion, which is more conducive to the formation of a composite oxide with prominent amorphous characteristics (a larger proportion of amorphous volume or a greater degree of amorphization). During sintering, titanium oxide, magnetite, potassium-sodium oxide, and calcium-magnesium oxide undergo semi-melting, causing titanium, iron, potassium, sodium, calcium, and magnesium atoms to reorganize and form new composite oxides, i.e., the composite oxides of titanium-iron oxide, titanium-potassium oxide, titanium-sodium oxide, titanium-calcium oxide, and titanium-magnesium oxide.

[0080] In these embodiments, the oxides in the base material, such as titanium oxide and magnetite, can undergo chemical reactions and form composite metal oxides with amorphous structures under the influence of high temperatures during subsequent sintering. Furthermore, under the influence of the contents of the base material and the binder, composite metal oxides with the desired three-dimensional macro-pore structure are formed.

[0081] In some embodiments, the base material is spherical or spheroid, and the composite metal oxide with three-dimensional macro-pore structure formed thereby is also spherical. Specifically, the composite metal oxide is micron-sized (microspheres), and the microspheres have a relatively uniform pore distribution and a high open porosity, which is conducive to the adsorption and storage of oil and ensures the mechanical strength and wear resistance of the microspheres. When the composite metal oxide in the form of microspheres is used as a non-stick material, the coating formed thereby can ensure that oil molecules can easily enter, and the composite metal oxide can effectively protect the oil molecules inside from direct contact with heat sources and volatilization. In addition, the composite metal oxide can effectively reduce the conduction and diffusion of heat, reducing the possibility of direct contact of oil molecules with high temperature, thereby improving the stability and safety of the non-stick material.

[0082] In some embodiments, the base material is micron-sized, specifically, the particle size of the base material is 0.05 microns to 5 microns. When the particle size of the base material is in the range of 0.05 microns to 5 microns, it is easier to form the composite metal oxide with amorphous structure and three-dimensional macro-pore structure described above, and the porosity of the composite metal oxide layer (initial non-stick layer) formed thereby can be controlled to meet the requirements of locking oil. It should be noted that the particle size of the material described above can be the maximum length of each particle, and is not specifically limited to the shape of the material being spherical or spheroid. 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 the major axis. It should be noted that the micron-sized base material can be obtained by crushing and grinding, or can be obtained by commercial means, and the present application does not make too many limitations on this.

[0083] In preferred embodiments, the particle size of the base material forming the mixed slurry is normally distributed, and the base material is a mixture of multiple particles, and the particle size R of the mixture has multiple distribution intervals. The multiple distribution intervals include a first distribution interval R1, a second distribution interval R2, and a third distribution interval R3, wherein 0.05 microns ≤ R1 ≤ 0.1 microns, the second distribution interval is 0.1 microns < R2 ≤ 1 micron, and the third distribution interval is 1 micron < R3 ≤ 5 microns. Based on the total volume of the base material in the mixture being 100%, the volume fraction of the base material with a particle size in the first distribution interval is 20%-40%, the volume fraction of the base material with a particle size in the second distribution interval is 35%-65%, and the volume fraction of the base material with a particle size in the third distribution interval is 10%-25%.

[0084] Forming a mixed slurry

[0085] According to the present application, the method for preparing the non-stick material further comprises a step of forming a mixed slurry. Specifically, the step of forming a mixed slurry comprises providing a base material, a binder, and then ball-milling the base material and the binder to form a mixed slurry.

[0086] Specifically, the base material and the binder are added into a ball mill tank, and deionized water is added as a grinding medium, and grinding is performed for 4-8 hours to obtain a mixed slurry of the base material and the binder uniformly dispersed. The binder in the mixed slurry can enhance the binding force between the particles of the composite metal oxide to form a stable particle stack, so that the composite metal oxide has a certain mechanical strength to ensure the stability of the initial non-stick layer in the subsequent formation, and to avoid breaking and affecting the formation of the three-dimensional pore structure of the composite metal oxide layer (initial non-stick layer). It should be noted that in the step of forming the mixed slurry, a certain amount of dispersant can also be included, so that the individual particles of the base material are more easily and uniformly dispersed in the mixed slurry.

[0087] In some embodiments, the mixed slurry includes the base material and the binder, and the weight ratio of the base material to the binder is (52-70):(30-48). In the mixed slurry, the weight ratio of the binder to the base material is comparable, and such a large amount of binder will volatilize in the subsequent step to ensure that the composite metal oxide with a three-dimensional macro-pore structure is easily formed while ensuring the overall strength of the non-stick material, so that the initial non-stick layer formed by the non-stick material can retain the three-dimensional macro-pore structure of the non-stick material, thereby ensuring the formation of the three-dimensional pore structure of the initial non-stick layer.

[0088] According to the present application, the weight ratio of each oxide in the base material can enable each oxide in the base material to react as fully as possible to form a composite metal oxide under the influence of high temperature.

[0089] In some embodiments, the base material is titanium oxide and magnetite. As an example, the weight ratio of titanium oxide to magnetite is (13-39):(13-39), and within this ratio range, titanium oxide and magnetite can easily form a composite metal oxide through chemical reaction under the high temperature of subsequent sintering, and can as much as possible reduce the influence of unreacted parts on the overall non-stick material. In addition, within this ratio range, the synergistic effect of titanium oxide and magnetite can help to increase the degree of amorphization of the composite metal oxide.

[0090] In some embodiments, the base material includes titanium oxide and ferric oxide, and can further include a water-soluble metal oxide and / or a metal oxide capable of reacting with fatty acids in the oil and fat. As an example, the water-soluble metal oxide can be an alkali metal oxide, and the metal oxide capable of reacting with fatty acids in the oil and fat can be an alkaline earth metal oxide. In some embodiments, the water-soluble metal oxide can include potassium oxide and / or sodium oxide, which can also be referred to as potassium-sodium oxide, and the metal oxide capable of reacting with fatty acids in the oil and fat can include calcium oxide and / or magnesium oxide, which can also be referred to as alkaline earth metal oxide. In some embodiments, the base material includes titanium oxide, ferric oxide, a water-soluble metal oxide, and a metal oxide capable of reacting with fatty acids in the oil and fat. As an example, the ratio of titanium oxide, ferric oxide, water-soluble metal oxide, and metal oxide capable of reacting with fatty acids in the oil and fat can be (13-39):(13-39):(1-2):(1-2), respectively, to form a composite metal oxide with a higher volume fraction of amorphous phase in an amorphous structure to facilitate the improvement of non-stickiness.

[0091] It should be noted that in the above embodiments, the melting point of the alkali metal oxide is relatively low, and when the base material includes sodium oxide and potassium oxide, the overall melting point of the base material can be relatively low, thereby facilitating the base material to be in a slightly molten state during the sintering process.

[0092] Spray drying to form tack-free granules

[0093] After the pulp is prepared, the mixed pulp is subjected to spray drying. According to some embodiments of the present application, a spray drying device (such as a pressure spray dryer, a centrifugal spray dryer, etc.) is used to atomize the mixed pulp into fine droplets. The atomized droplets are contacted with hot air, and the solvent (water) is rapidly evaporated, and the particles of the base material form a microspherical basic structure with the binder. As an example, the mixed pulp can be delivered to a high-speed spinning atomization disc to form droplets, and then the droplets are blown into a drying tower using hot air. The droplets are temporarily stopped during the descending process, and finally form wet microspheres (non-stick particles).

[0094] According to the present application, by adjusting the process parameters of spray drying (e.g. atomizing disc rotation speed and hot air temperature), the particle size, pore size and distribution, etc. of the microspheres can be controlled. As an example, during high-speed movement of the atomizing disc, by controlling the rotation speed of the atomizing disc, the mixed slurry can be dispersed 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 in the range of 4000 rpm-15000 rpm, preferably, in the range of 6000 rpm-12000 rpm. According to some embodiments of the present application, the temperature of the hot air can be controlled in the range of 60°C-100°C, the temperature of the drying tower can be controlled in the range of 100°C-400°C, and the short residence time of the droplets in the drying tower can be controlled to be 5 seconds-15 seconds. The relatively low temperature of the hot air can reduce the loss of the binder, so that the water in the resulting pre-formed wet microspheres is volatilized and enough binder is retained, thereby ensuring that the microspheres with pore structure can be formed by means of volatilization or carbonization of the binder in the subsequent sintering process.

[0095] Sintering the tack-free granules after spray drying

[0096] According to the present application, the base material itself does not have pores, and the use of a mixed slurry including the base material and the binder by spray drying and high-temperature sintering can lay the foundation for subsequent formation of a three-dimensional macro-pore structure, thereby forming a microsphere with a three-dimensional macro-pore structure and an amorphous structure. Here, the base material is slightly fused during high-temperature sintering, and its physical state gradually changes from solid to semi-solid or viscous. In this way, each base material diffuses and chemically combines to form a composite metal oxide according to the present application.

[0097] According to some embodiments of the present application, the spray-dried microspheres can be heated to a temperature above the carbonization temperature at a high heating rate in an inert atmosphere such as nitrogen, argon, etc., and kept for a long time, so that as much binder as possible is carbonized in this process. As an example, the non-stick particles are placed in a sintering furnace in an inert atmosphere such as nitrogen, argon, etc., the initial sintering temperature is 20-30°C, the heating rate is 15-20°C / min, a larger heating rate can make the binder volatilize at this stage, and the temperature is raised to 500-650°C at a heating rate of 15-20°C / min, and kept for 6-8h, so that the binder in the spray-dried microspheres is carbonized as much as possible. Then, the temperature is raised to 1200-1250°C at a heating rate of 55-100°C / min, and then kept for 12-24h, in this process, titanium oxide and magnetite interact with each other, such as diffusion, reaction, etc., thereby changing the original crystal structure and forming a composite metal oxide with amorphous structure. In addition, the adjacent base particles interact with each other to interlock at the contact part, and the volume shrinks to leave pores between the particles, and the final material with a certain three-dimensional macro-pore structure and containing the carbonized product of the binder and the composite metal oxide serves as the non-stick material. In addition, in the sintering process, the base particles in contact with each other interlock at the contact part after sintering to form microspheres, so that the particles in the microspheres have a strong enough binding force to ensure the stability of the microspheres in the subsequent process.

[0098] In these embodiments, in an inert atmosphere such as nitrogen, argon, etc., at a faster heating rate, a higher sintering temperature and a longer sintering time, a small amount of binder will volatilize, leaving pores, and most of the binder will be carbonized to form a material with a high carbon content (carbonized product of the binder), and the adjacent particles will interact with each other to form a material with a stack of composite metal oxide particles and carbonized products dispersed in the composite metal oxide.

[0099] As an example, the carbonization temperature of the binder of the present application is approximately 350-600°C, and under the influence of the subsequent sintering temperature and time, most of the binder will volatilize to leave pores in the non-stick material, and a small amount of binder will form a carbonized product. Since the carbonized product of the binder is mainly composed of non-polar carbon elements, it has a certain lipophilicity, and the initial non-stick layer of the cookware formed by such non-stick material is more easily filled with oil molecules.

[0100] In some embodiments, 90% of the binder is volatilized, and 10% of the binder is carbonized. Specifically, the weight ratio of the carbonized product of the binder to the composite metal oxide in the non-stick material is defined as (0.4-3.5):(96.5-99.6), for example. Thus, the initial non-stick layer formed has the composite metal oxide and the carbonized product of the binder, and the carbonized product of the binder is attached to part of the surface of the composite metal oxide particles. Continuing with the above example, the weight ratio of the carbonized product of the binder to the base material in the initial non-stick layer is (0.4-3.5):(96.5-99.6).

[0101] In these embodiments, the non-stick material also has a small amount of the carbonized product of the binder, which has a certain lipophilicity due to the fact that the carbonized product of the binder is mainly composed of non-polar carbon elements, thereby further improving the lipophilicity of the microspheres as a whole, and making the initial non-stick layer formed therefrom more easily filled with oil molecules.

[0102] According to the present application, the composite metal oxide (for example, a composite of iron oxide titanium, potassium oxide titanium, sodium oxide titanium, calcium oxide titanium, and magnesium oxide titanium) can be formed as a non-stick material by spray drying and high-temperature sintering. Since iron has +2 and +3 valence, titanium has +2 and +4 valence, and there are +1 alkali metal and +2 alkaline earth metal elements, various forms of oxides can be obtained during the formation of the composite oxide, and the main forms include FeTiO3, Fe2TiO5, Fe3Ti3O 10 , K2Ti3O7, Na2Ti3O7, CaTiO3, and MgTiO3. The composite oxide formed by various forms of oxides has an irregular disordered state in the microcrystalline lattice arrangement, and the whole presents an amorphous characteristic.

[0103] Figure 1 is a scanning electron microscope image of a non-stick particle according to an embodiment of the present application. Figure 2 is a scanning electron microscope image of a non-stick material according to an embodiment of the present application. Referring to Figure 1 It can be seen that, before sintering, the non-stick particle does not have obvious pores, referring to Figure 2 It can be seen that, after sintering, the composite metal oxide has obvious three-dimensional macro-pore structure, and the pores of the three-dimensional macro-pore structure are generally uniformly distributed.

[0104] Figure 3 is an XRD spectrum of a non-stick material according to an embodiment of the present application. As Figure 3As shown, the characteristic peaks are not particularly obvious, the impurity peaks are numerous and chaotic, and the crystallinity is poor. It can be seen that the crystallinity of the composite metal oxide is generally poor and has amorphous characteristics. According to the conventional full spectrum fitting method, the volume fraction of the amorphous phase of the non-stick material is 60%.

[0105] According to the method for manufacturing the non-stick material, the sintered microsphere particles can be sieved after the sintering step, so as to obtain microspheres in different particle size intervals. The microsphere powder in different particle size intervals can be sieved as needed for application in different products. For example, the sintered powder is sieved by a vibrating screen to obtain spherical or spherical microspheres with a particle size of 10 μm-45 μm.

[0106] According to the method for manufacturing the non-stick material, the finally formed microsphere particles are not only one particle in the sense of quantity, but also can be a plurality of particles aggregated together. The particle size of the finally formed microsphere particles is not less than the particle size of the original various powders.

[0107] In some embodiments, the non-stick material is in the form of micrometer-level particles. As an example, the average particle size of the non-stick material is 10-70 microns, and the D50 (median particle size) is 25-35 microns. If the average particle size of the non-stick powder is greater than 10 microns, the powder feeding pipe is easily clogged, and the powder is not sufficiently melted, the initial non-stick layer has reduced bonding strength, and the coating quality is reduced. If the average particle size of the non-stick powder is less than 70 microns, the powder flowability is poor, and the flight speed is not sufficient during the spraying process, which easily over-melts, reduces the deposition efficiency and coating quality.

[0108] According to the present application, there are pores inside or between the microsphere particles after spray drying, which can allow gas or liquid to pass through, and the pores of the three-dimensional macro-porous structure in the microspheres formed by spray drying are mostly open pores or connected pores, i.e. through holes, and a small number of closed pores, so as to ensure the oil storage capacity of the formed initial non-stick layer. As an example, the volume fraction of the through holes is about 80%-90%, and the balance is closed pores.

[0109] According to the present application, the microspheres are used as the non-stick material, and when the non-stick layer is formed by spraying, the microspheres are only slightly melted on the surface so as to be stacked on the substrate to form the non-stick layer. The three-dimensional macro-pore structure of the microspheres can be retained in the non-stick layer as much as possible, so that the non-stick layer with the three-dimensional pore structure is formed. The pores of the non-stick layer with the three-dimensional pore structure match the oil molecules, are easy to adsorb the oil molecules, and can lock the oil molecules with a certain adhesion, so that the oil molecules can be slowly released, thereby being able to play excellent non-stick performance due to the oil film non-stick principle. In addition, the base material for forming the non-stick material is small, in the order of microns, and has a large specific surface area when combined with the substrate, so as to be able to ensure the bonding force with the substrate. The base material has good wear resistance, and can act as a protective body for the oil molecules, so as to be able to ensure that the cookware with the non-stick layer has a sustained and stable oil film to ensure long-lasting non-stick performance.

[0110] According to a third aspect of the present application, a non-stick layer is provided for a cookware or a cup, and a method for preparing the non-stick layer comprises:

[0111] Spraying a non-stick material to form an initial non-stick layer, wherein the initial non-stick layer comprises a composite metal oxide layer with an amorphous structure, and the metal elements in the composite metal oxide layer include iron elements with different valence states and titanium elements with different valence states;

[0112] Modifying the initial non-stick layer with a silane-based material, thereby obtaining a non-stick layer with a silane-based material modification layer.

[0113] In the embodiments of the present application, the initial non-stick layer comprises a composite metal oxide layer with an amorphous structure, and the metal elements in the composite metal oxide layer include iron elements with different valence states and titanium elements with different valence states. Here, the composite metal oxide layer itself has a low surface energy and has a certain initial non-stick performance. In addition, the composite metal oxide layer will not age with the extension of the use time, and has good physical and chemical stability, so as to be able to have more durable and long-lasting non-stick performance. Furthermore, the initial non-stick layer is modified with a silane-based material, and the silane-based material can be grafted on the initial non-stick layer. Since the silane-based material has strong hydrophobicity, low surface energy, and a large contact angle, a non-stick layer with better non-stick performance can be obtained.

[0114] In some embodiments, the carbonized product of the binder is dispersed in the composite metal oxide layer.

[0115] In these embodiments, the carbonized product of the binder is dispersed in the composite metal oxide layer, on one hand, the presence of the carbonized product of the binder can facilitate the connection of the individual particles of the composite metal oxide, ensuring the bonding force inside the individual particles of the non-stick material; on the other hand, the carbonized product of the binder as the connecting bridge between the individual particles can make the non-stick material as a whole present higher hardness and stability.

[0116] In some embodiments, in the initial non-stick layer, the weight ratio of the carbonized product of the binder to the composite metal oxide is (0.4-3.5):(96.5-99.6).

[0117] According to the present application, the initial non-stick layer can be formed by thermal spraying of the non-stick material, wherein the non-stick material is microspheres having a three-dimensional macro-pore structure. In the process of thermal spraying, the surface of the microspheres of the non-stick material is heated and further densely packed on the substrate as a whole to form the initial non-stick layer, thus the initial non-stick layer formed can have a more detailed pore structure than the three-dimensional macro-pore structure of the non-stick material and itself presents a three-dimensional pore structure. It can be understood that the three-dimensional pore structure in the initial non-stick layer is largely determined by the three-dimensional macro-pore structure of the microspheres.

[0118] As an example, in the initial non-stick layer formed, having a three-dimensional pore structure, the porosity of the initial non-stick layer is 5%-30% and the pore size is 500 nanometers-4 microns. Preferably, the pore size is 500 nanometers-1 micron. More specifically, the three-dimensional pore structure includes a plurality of large pores between the microspheres and a plurality of small pores inside the microspheres, the size of the large pores is 900 nanometers-4 microns, and the size of the small pores is 500 nanometers-900 nanometers. The large pores can make oil molecules or oil easily enter the initial non-stick layer, and the small pores can make oil molecules or oil easily remain, so as to ensure the non-stick performance of the cookware having the initial non-stick layer due to the stable release of the oil film.

[0119] In some embodiments, the thermal spraying includes flame spraying, arc spraying and plasma spraying. Taking plasma spraying as an example, the specific parameters are: powder feeding speed 10 g / min-25 g / min, spraying distance 150 mm-200 mm, arc current 350 A-500 A, voltage 50 V-70 V, hydrogen pressure 0.6 MPa-0.8 MPa, hydrogen flow 200 L / h-300 L / h, argon pressure 1.0 MPa-1.5 MPa, argon flow 1000 L / h-2000 L / h, workpiece linear speed 25 m / min-35 m / min.

[0120] In some embodiments, the thickness of the initial non-stick layer is in the range of 10 microns-150 microns, which can ensure the long-lasting non-stick performance of the cookware having the initial non-stick layer.

[0121] According to the present application, after the initial non-stick layer is obtained by spraying, the initial non-stick layer after spraying can be polished and ground to make the surface smooth and bright, which is convenient for stir-frying. According to the needs, edible oil can be used to coat the surface of the initial non-stick layer, and then baking treatment is performed at 250-350°C, which plays a role of maintaining the pot and improving the non-stick and anti-rust properties.

[0122] According to the present application, in the case that the non-stick material includes water-soluble metal elements (for example, potassium elements, sodium elements), the initial non-stick layer formed also includes water-soluble metal elements, which will be dissolved and exchanged in the process of product use, so that some nanoscale cavities are generated on the surface of the initial non-stick layer, thereby forming a micro-nano hydrophobic structure, so that better non-stick property can be generated under the infiltration of oil molecules. In addition, in the case that the non-stick material includes metal elements (for example, calcium elements, magnesium elements) that can react with fatty acids in oil, the initial non-stick layer formed also naturally includes metal elements that can react with fatty acids in oil, so that the initial non-stick layer is easy to react with fatty acids in oil, and the formed fatty acid salt is deposited on the surface of the initial non-stick layer, which can further assist in providing non-stick property. Therefore, the surface of the non-stick layer includes a fatty acid salt modified layer formed by reacting with the metal elements in the initial non-stick layer.

[0123] According to some embodiments of the present application, the initial non-stick layer can be directly used as the inner coating of the non-stick cookware, and the obtained initial non-stick layer can also be modified to further increase the non-stick property of the initial non-stick layer. In the following, specific ways of modifying the initial non-stick layer will be specifically introduced.

[0124] Activating the surface of the initial tack-free layer

[0125] According to the present application, after the step of forming the initial non-stick layer by spraying the non-stick material, the step of surface modification can be directly performed, or the surface of the initial non-stick layer can be activated before the step of surface modification.

[0126] According to the present application, the method of preparing a non-stick coating further comprises, prior to the step of modifying the initial non-stick layer with a fluoro-silane based material, activating the surface of the initial non-stick layer so as to increase the surface roughness of the initial non-stick layer to provide more binding sites for the modifying material. The step of activating the surface of the initial non-stick layer comprises treating the initial non-stick layer with an acid solution so as to activate the surface of the initial non-stick layer to generate at least silicon hydroxyl groups and / or form a plurality of etched grooves to provide more reactive groups (e.g. silicon hydroxyl groups) and / or specific surface area for the subsequent step of modifying. In particular, activating the surface of the initial non-stick layer with an acid solution can increase the number of silicon hydroxyl groups on the surface of the initial non-stick layer to facilitate the subsequent step of modifying. On the other hand, treating with an acid can displace the dissolution of metal (e.g. calcium, magnesium, sodium, potassium, iron and titanium) on the surface of the initial non-stick layer to cause etching of the surface of the initial non-stick layer to form a plurality of etched grooves to increase the micro-roughness of the surface of the initial non-stick layer and increase the specific surface area for the subsequent step of modifying to optimize the non-stick property. In addition, treating with an acid can also increase the size of the surface layer pores. +

[0127] In an exemplary embodiment, the step of treating the initial non-stick layer with an acid solution comprises providing an acid solution comprising hydrogen peroxide and hydrochloric acid, placing the initial non-stick layer in the acid solution and maintaining at a predetermined temperature for a predetermined time to activate the surface of the initial non-stick layer to generate at least silicon hydroxyl groups. The surface activation covers the entire surface that is accessible to the acid solution, in particular, the inner surface of the surface layer pores and the outer surface of the initial non-stick layer.

[0128] In the acid solution, concentrated hydrochloric acid and hydrogen peroxide are used in a volume ratio of 6:4 to 8:2. In particular, the concentrated hydrochloric acid and hydrogen peroxide are mixed in a volume ratio of 6:4 to 8:2 to form a mixed acid, the non-stick material is soaked in the mixed acid and maintained at 80°C to 120°C for 20 minutes to 50 minutes to activate the surface of the non-stick material to generate silicon hydroxyl groups and / or form a plurality of etched grooves.

[0129] In some embodiments, after the step of treating the initial non-stick layer with an acid solution and prior to the step of modifying the initial non-stick layer with a fluoro-silane based material, the method of preparing a non-stick coating further comprises placing the initial non-stick layer with the acid solution attached in a basic solution to remove the acid solution from the surface of the initial non-stick layer and then cleaning the initial non-stick layer for use. Exemplarily, the basic solution comprises sodium hydroxide solution, sodium bicarbonate solution.

[0130] Modifying the initial tack-free layer with silane-based materials

[0131] ​According to the present application, the method for preparing the non-stick layer further comprises a step of modifying the initial non-stick layer with a silane material. Specifically, the step of modifying the initial non-stick layer with a silane material comprises a step of providing a modifying solution comprising a silane material and water. The step of providing the modifying solution comprising the silane material comprises a step of preparing the modifying solution comprising the silane material and water. Here, the overall non-stick property of the initial non-stick layer is further improved by grafting a low surface energy material on the initial non-stick layer.

[0132] In an exemplary embodiment, the step of preparing the modifying solution comprising the silane material and water comprises providing the silane material, providing an aqueous solvent, mixing the silane material with the aqueous solvent, thereby preparing the modifying solution comprising the silane material and water. Here, the volume ratio of the silane material to the solvent is 1:20-1:100.

[0133] In some embodiments, the silane material can comprise a fluoro-silane material or a silane coupling agent. For example, the fluoro-silane material can comprise at least one of perfluorodecyltrimethoxysilane, perfluorooctyltriethoxysilane, perfluorododecyltrimethoxysilane, and trifluoropropylmethylsilane. For example, the silane coupling agent can comprise at least one of γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, a sulfur-containing silane coupling agent, an epoxy-based silane coupling agent, and γ-ureidopropyltriethoxysilane. The solubility of the above-mentioned silane material in water is not high, and therefore the modifying solution can further comprise an organic solvent, specifically an ester solvent and / or an alcohol solvent. The organic solvent can increase the solubility of the silane material and can inhibit the hydrolysis rate of the modifying solution comprising the silane material and water to a certain extent. Specifically, the ester solvent can comprise ethyl acetate, and the alcohol solvent can comprise ethanol, ethylene glycol, and the like.

[0134] According to the present application, the step of modifying the initial non-stick layer with a silane material comprises contacting and reacting the modifying solution comprising the silane material and water with at least part of the surface of the initial non-stick layer to form a modified layer on the initial non-stick layer, thereby obtaining the silane material-modified initial non-stick layer as the non-stick layer of the present application.

[0135] In the embodiments of the present application, the silane material can act on at least part of the surface of the initial non-stick layer. Here, the at least part of the surface can be the active surface of the product in use. For example, the initial non-stick layer is formed on the entire inner surface of a pot, and the active surface can be the area of the initial non-stick layer corresponding to the bottom wall area of the inner surface of the pot. Of course, the at least part of the surface can also be the entire surface of the product, for example, the entire outer surface of the initial non-stick layer.

[0136] In the embodiments of the present application, the initial non-stick layer modified by the silane material (modified layer) is a product obtained by reacting the hydrolysis product of the hydrolysis of the silane material with the initial non-stick layer. The modification solution can at least contact at least part of the outer surface of the initial non-stick layer, so as to form the modified layer on the surface of the initial non-stick layer. Of course, the modification solution can also enter the surface layer pores of the initial non-stick layer to contact the inner wall surface of the corresponding pores, so as to form the modified layer on the inner wall surface of the pores. Here, the surface layer pores refer to the pores / holes existing in a region of a certain depth from the outer surface of the initial non-stick layer inward. In this case, the modified layer can exist not only on the outer surface of the initial non-stick layer, but also on the inner wall surface of the surface layer pores of the initial non-stick layer.

[0137] According to the present application, at least a chemical bond is used between the initial non-stick layer and the modified layer located thereon, and has a certain bonding firmness, so as to ensure that it is not easy to fall off during use.

[0138] According to the present application, the modification solution comprising the silane material is contacted and reacted with the initial non-stick layer, so as to obtain the initial non-stick layer with at least a surface having a modified layer. Wherein, the contact can refer to soaking the initial non-stick layer in the modification solution comprising the silane material and water. Specifically, the surface of the initial non-stick layer has a silicon hydroxyl group, and in the process of contact, first, the silane material can be hydrolyzed to generate a siloxane material, and then the generated siloxane material reacts with the silicon hydroxyl group on the surface of the initial non-stick layer to form a modified layer, so as to obtain the initial non-stick layer modified by the silane material. The initial non-stick layer modified by the silane material has extremely strong hydrophobicity, low surface energy and large contact angle, so that the initial non-stick property of the initial non-stick layer is better.

[0139] According to the present application, the modification solution comprising the silane material can be stably hydrolyzed in an acidic environment. In an exemplary embodiment, the pH value of the modification solution of the silane material is not greater than 7, and dilute hydrochloric acid can be added to the modification solution to obtain a modification solution with a predetermined pH value.

[0140] According to the present application, the hydrolysis of the silane material can be ensured by heating. Specifically, the at least part of the surface of the initial non-stick layer can be contacted with the modification solution comprising the silane material under heating, for example, by ultrasonic vibration, and the vibration frequency is set to 20KHz-50KHz, and heated to 50℃-80℃ for 5min-8min.

[0141] Modifying the initial tack-free layer with a quenching process

[0142] According to the present application, the initial non-stick layer has an amorphous phase volume fraction of 30%-50% before quenching. After quenching, the initial non-stick layer has an amorphous phase volume fraction of 50%-70%. Here, the non-stick property of the initial non-stick layer is further improved by increasing the amorphous phase volume fraction (amorphization degree) of the initial non-stick layer.

[0143] In some embodiments, for a specific quenching method, the initial non-stick layer can be heated and quickly exposed to a low-temperature environment to achieve rapid cooling, so that the material in the initial non-stick layer does not have time to crystallize, thereby tending to amorphous transition. Specifically, the initial non-stick layer is sintered (sintering temperature: 1200-1400°C, sintering time: 4h), and then cooled at a cooling rate of 80-100°C / s, thereby obtaining a non-stick layer with an amorphous phase volume fraction of 50%-70%.

[0144] According to a fourth aspect of the present application, a non-stick cookware is provided, wherein, as shown in Figures 4 to 6 the non-stick cookware includes a base 110 and a non-stick layer 120 formed on the inner surface of the base 110, wherein the non-stick layer 120 is obtained by spraying a non-stick material according to the above description and modifying it by a silane-based material.

[0145] In some embodiments, the non-stick layer has a pore structure that can be filled with oil molecules.

[0146] In these embodiments, the pore structure of the non-stick layer is a structure suitable for oil molecules to fill and lock, and when the pore structure of the non-stick layer is filled with oil molecules, the oil molecules can be slowly released from the pore structure to optimize the non-stick property of the non-stick layer.

[0147] According to the present application, the cookware coating can have various structural forms. In some embodiments, the inner surface of the base is a rough surface, which can be obtained by sanding the inner surface of the base, and the non-stick layer is directly formed on the inner surface of the base. In other embodiments, the inner surface of the base has a concave-convex structure. As an example, the concave-convex structure is on the micron level, which is composed of a plurality of convex blocks, the height of the convex blocks is 100-500 μm, the width is 200-400 μm, and the distance between adjacent convex blocks is 200-400 μm. The non-stick layer is formed at least in the concave part of the concave-convex structure, and the non-stick layer is arranged in the concave part between adjacent convex blocks, which is not easily damaged by a spatula, so as to improve the non-stick life of the product, or the non-stick layer fills the concave part of the concave-convex structure and covers the surface of the concave-convex structure, so that a mortise and tenon joint is formed between the non-stick layer and the base, so that the bonding force is higher. In yet other embodiments, a rough transition layer is provided between the base and the non-stick layer, which can further improve the bonding force between the coating and the base. As an example, the rough transition layer can be formed by thermal spraying of a metal material on the surface of the base.

[0148] In the following, the manufacturing method of the non-stick cookware according to the present application will be described in specific embodiments.

[0149] Providing a base

[0150] According to the present application, the base 110 can be made of commonly used materials. As an example, the material can be stainless steel, titanium, aluminum, their corresponding alloys, and composite materials. The base 110 can have a shape corresponding to the function, for example, Figure 4 As shown in FIG. 1, when the non-stick cookware 100 is a non-stick pot, the base 110 can have a conventional pot body shape. It should be understood that, Figure 4 As shown in FIG. 1, only the main part of the non-stick pot is shown without other parts, and the non-stick pot according to the present application can also include a handle (for example, a pot handle) and other common cookware structures / components.

[0151] In some embodiments, the inner surface of the base is a rough surface, which can be obtained by sanding the inner surface of the base, or can be prepared by etching, laser engraving, stamping, etc.

[0152] Forming a transition layer (optional)

[0153] In some embodiments, a rough transition layer is provided between the base and the non-stick layer, which can further improve the bonding force between the coating and the base. As an example, the rough transition layer can be formed by thermal spraying of a metal material on the surface of the base. Specifically, the metal material can include at least one of titanium, titanium alloy, iron, iron alloy, aluminum, aluminum alloy, zinc, zinc alloy, copper, copper alloy, zirconium, and zirconium alloy.

[0154] Forming a tack-free layer

[0155] According to the present application, the non-stick layer can be prepared by the method for preparing a non-stick layer provided in the above embodiments.

[0156] Providing oil-based molecules

[0157] According to the present application, in order to further optimize the non-stick property, the prepared non-stick layer can be filled with oil molecules or oil, so that the non-stick property of the non-stick layer can be further optimized, and during subsequent use, the oil in the cooking process can also be supplemented in the three-dimensional pore structure to form a continuous and stable oil film to play the non-stick property. In the following, an embodiment according to an aspect of the present application will be described by taking filling oil molecules as an example.

[0158] According to the present 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. The above oil molecules have specific viscosity and surface tension, and are more easily entered into the three-dimensional pore structure of the non-stick layer. In this case, the oil molecules are adsorbed or bonded in the three-dimensional pore structure of the non-stick layer. In addition, the oil molecules include 20%-30% low molecular weight oil molecules, 40%-60% medium molecular weight oil molecules, and 20%-30% high molecular weight oil molecules by weight percentage, wherein the molecular weight of the low molecular weight oil molecules is between 500-1000, the molecular weight of the medium molecular weight oil molecules is between 3000-6000, and the molecular weight of the high molecular weight oil molecules is between 12000-30000.

[0159] In these embodiments, the large molecular weight oil molecules are more firmly combined with the structure formed by the accumulation of the base material, and the release speed is slower, the small molecular weight oil molecules have better free mobility, thereby having better non-stick property, and the medium molecular weight oil molecules have both free mobility and firmness. Therefore, by combining low molecular weight oil molecules, medium molecular weight oil molecules and high molecular weight oil molecules, on the one hand, the possibility of oil molecules entering the non-stick layer is further increased, and on the other hand, oil molecules with different binding forces can be continuously released at each stage of use to achieve better non-stick effect. As an example, the binding force between the oil molecules and the non-stick layer is approximately 10KPa-25KPa. Such a binding force can ensure the continuous release of oil molecules and avoid premature release or failure to release of oil molecules.

[0160] According to the present application, the oil molecules are used to impregnate the non-stick layer, so as to obtain the non-stick cookware in which the oil molecules are combined in the pore structure of the non-stick layer. Here, the oil molecules, such as oil, can be chemically combined with the metal elements on the non-stick layer to form a fatty acid salt modified layer on the non-stick layer.

[0161] As an example, in the cookware coating, the weight of the oil molecules accounts for 5%-10% of the total weight of the cookware coating, and the rest is the non-stick layer formed by the microspheres, with the total weight of the cookware coating being 100%. As an example, the time for impregnating the non-stick layer with the oil molecules can be 15 min-30 min, and the temperature can be 80℃-120℃, and then the excess oil molecules on the surface are wiped dry, and then dried at a temperature of 280℃-340℃ for 3 min-6 min.

[0162] According to the fifth aspect of the present application, a cookware is provided, in particular a non-stick cookware. The non-stick cookware includes a base and a non-stick layer, and the non-stick layer is arranged on the base. The non-stick layer includes the non-stick layer provided in the above-mentioned embodiments or includes a non-stick layer formed by spraying the non-stick material provided in the above-mentioned embodiments.

[0163] Figure 4 FIG. 1 is a schematic diagram of a cross-sectional structure of a non-stick cookware according to an embodiment of the present application. Figure 5 FIG. 2 is a schematic diagram of a cross-sectional structure of a non-stick cookware according to another embodiment of the present application. Figure 4 FIG. 3 is a schematic diagram of an enlarged structure at I in FIG. 2. Refer to FIG. 2 Figure 4 FIG. 4 is a schematic diagram of an enlarged structure at I in FIG. 2. Refer to FIG. 2 Figure 5 The non-stick cookware 100 can include a base 110 and a non-stick layer 120.

[0164] In some embodiments, the base can be made of a conventional metal material, and the non-stick material belongs to a type of ceramic material, and the bonding force between the non-stick material and the metal base is relatively poor. In order to increase the bonding force between the non-stick layer and the base, in some embodiments, the non-stick cookware further includes a transition layer 130 made of a metal material, and the transition layer 130 is arranged between the base 110 and the non-stick layer 120.

[0165] In an exemplary embodiment, the transition layer can be prepared by thermal spraying or cold spraying using a metal material. The transition layer material is selected from conventional metal materials, such as at least one of titanium, titanium alloy, iron, iron alloy, aluminum, aluminum alloy, zinc, zinc alloy, copper, copper alloy, zirconium, and zirconium alloy. Preferably, titanium or titanium alloy is used, which can ensure the bonding force and has relatively high strength.

[0166] In an exemplary embodiment, the thickness of the transition layer is in the range of 10 microns-80 microns.

[0167] 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.

[0168] 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.

[0169] 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.

[0170] In some embodiments, the formed non-stick layer may have a thickness of 10 micrometers to 150 micrometers.

[0171] 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.

[0172] like Figure 7 As shown, the non-stick cookware includes a substrate 110 and a non-stick layer 120 stacked 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.

[0173] In the embodiments, the non-stick layer with the surface having the concave-convex structure is formed by using the non-stick material including the composite metal oxide, so that on one hand, the demand for manufacturing the patterned metal cookware can be met, and on the other hand, the non-stick cookware with better non-stick performance can be obtained under the joint action of the low surface energy material.

[0174] In the present application, the vertical distance h between the highest point of the convex of the concave-convex structure and the lowest point of the concave of the concave-convex structure is 0.05 mm-0.3 mm, the top width w1 of the convex is 1 mm-3 mm, and the bottom width w2 of the convex is 3 mm-4 mm.

[0175] Here, the low surface energy material can be oil molecules, fluorine coating or ceramic coating, and the present application does not make too many limitations thereon. The low surface energy material can fill the entire concave, or can have a preset distance from the mouth of the concave, and the preset distance is not greater than the vertical distance h, and can be 0.03 mm-0.25 mm.

[0176] The present application will be described in detail below in combination with specific embodiments, but the protection scope of the present application is not limited to the described embodiments.

[0177] Example 1

[0178] The cookware according to Embodiment 1 is manufactured by the following method.

[0179] In step S10, a cookware base is prepared. Specifically, the step of preparing the cookware base includes deep drawing a stainless steel sheet, surface alkali washing to remove oil, drying, sand blasting, removing surface defects and oxide scale of the stainless steel, so as to obtain a cookware base with a thickness of 1.5 cm and a surface roughness of 4 microns. Here, the cookware base has a bottom planar structure and a wall structure, the bottom planar structure is beneficial to the stability of placing on the table top and is suitable for use on the electromagnetic oven, and at least the initial non-stick layer is formed on the bottom planar structure.

[0180] In step S20, a non-stick material with an average particle size of 0.05 microns-0.1 microns is prepared. Specifically, a base material (a mixture of titanium oxide and magnetite with a weight ratio of 1:1) with an average particle size of 0.05 microns-0.1 microns and polyvinyl alcohol are mixed at a weight ratio of 60:40 to form a mixed slurry, and the mixed slurry is spray dried to obtain non-stick particles, then the obtained non-stick particles are heated at a heating rate of 18 ℃ / min to 600 ℃, the holding time is 7 h, and finally, the heating rate is 70 ℃ / min to 1230 ℃, and the holding time is 18 h for sintering. In the process of sintering, the base material is slightly fused, and each oxide undergoes chemical reaction, so as to form the composite metal oxide with amorphous structure as the non-stick material according to the present application.

[0181] Step S30, spraying with non-stick material.

[0182] The outer surface of the pot base is placed in a circulating cooling air gas environment, wherein the temperature of the cooling gas is 5°C. The non-stick material is loaded into a powder feeder, and the spraying parameters of the plasma spraying are set as follows: powder feeding speed 13 g / min, spraying distance 160 mm, arc current 400 A, voltage 60 V, hydrogen pressure 0.7 MPa, hydrogen flow 250 L / h, argon pressure 1.2 MPa, argon flow 1500 L / h, and workpiece linear speed 30 m / min. The non-stick material powder is formed on the inner surface of the pot base by plasma spraying to obtain an initial non-stick layer with a thickness of 65 μm. The initial non-stick layer is used as the non-stick layer of the present application, thereby completing the manufacture of the pot of Example 1.

[0183] Example 2

[0184] Except that a different base material (a mixture of titanium oxide and magnetite in a weight ratio of 39:13 in the present example) is used to replace the base material of Example 1 in step S20, the pot of Example 2 is manufactured by the same method as that of Example 1.

[0185] Example 3

[0186] Except that a different base material (a mixture of titanium oxide and magnetite in a weight ratio of 13:39 in the present example) is used to replace the base material of Example 1 in step S20, the pot of Example 3 is manufactured by the same method as that of Example 1.

[0187] Example 4

[0188] Except that a different base material (a mixture of titanium oxide, magnetite and potassium oxide in a weight ratio of 26:26:1.5 in the present example) is used to replace the base material of Example 1 in step S20, the pot of Example 4 is manufactured by the same method as that of Example 1.

[0189] Example 5

[0190] Except that a different base material (a mixture of titanium oxide, magnetite and sodium oxide in a weight ratio of 26:26:1.5 in the present example) is used to replace the base material of Example 1 in step S20, the pot of Example 5 is manufactured by the same method as that of Example 1.

[0191] Example 6

[0192] Example 6 was manufactured in the same manner as Example 1 except that a different base material (a mixture of titanium oxide, magnetite and calcium oxide in a weight ratio of 26:26:1.5) was used in place of the base material of Example 1 in step S20.

[0193] Example 7

[0194] Example 7 was manufactured in the same manner as Example 1 except that a different base material (a mixture of titanium oxide, magnetite and magnesium oxide in a weight ratio of 26:26:1.5) was used in place of the base material of Example 1 in step S20.

[0195] Example 8

[0196] Example 8 was manufactured in the same manner as Example 1 except that a different base material (a mixture of titanium oxide, magnetite, sodium oxide, calcium oxide in a weight ratio of 26:26:1.5:1.5) was used in place of the base material of Example 1 in step S20.

[0197] Example 9

[0198] Example 9 was manufactured in the same manner as Example 1 except that a different base material (a mixture of titanium oxide, magnetite, sodium oxide, magnesium oxide in a weight ratio of 26:26:1.5:1.5) was used in place of the base material of Example 1 in step S20.

[0199] Example 10

[0200] Example 10 was manufactured in the same manner as Example 1 except that a different base material (a mixture of titanium oxide, magnetite, potassium oxide, calcium oxide in a weight ratio of 26:26:1.5:1.5) was used in place of the base material of Example 1 in step S20.

[0201] Example 11

[0202] Example 11 was manufactured in the same manner as Example 1 except that a different base material (a mixture of titanium oxide, magnetite, potassium oxide, magnesium oxide in a weight ratio of 26:26:1.5:1.5) was used in place of the base material of Example 1 in step S20.

[0203] Example 12

[0204] Example 12 was manufactured in the same manner as Example 1, except that after step S30, a step of adding a silicone oil molecule to the initial non-stick layer and curing (curing time: 5 min, curing temperature: 350°C) was added.

[0205] Example 13

[0206] Example 13 was manufactured in the same manner as Example 1, except that after step S30, a step of grafting a silane-based material to the initial non-stick layer of Example 1 (specifically, at least a part of the surface of the initial non-stick layer was brought into contact with a modified solution containing N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane under ultrasonic conditions using an ultrasonic method, and the vibration frequency was set to 30 KHz, heated to 60°C, and the time was 6 min) was added.

[0207] Example 14

[0208] Example 14 was manufactured in the same manner as Example 8, except that after step S30, a step of grafting a silane-based material to the initial non-stick layer of Example 8 (specifically, at least a part of the surface of the initial non-stick layer was brought into contact with a modified solution containing N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane under ultrasonic conditions using an ultrasonic method, and the vibration frequency was set to 30 KHz, heated to 60°C, and the time was 6 min) was added.

[0209] Example 15

[0210] Example 15 was manufactured in the same manner as Example 1, except that after step S30, a step of grafting a silane-based material to the initial non-stick layer of Example 1 (specifically, at least a part of the surface of the initial non-stick layer was brought into contact with a modified solution containing perfluorodecyltrimethoxysilane under ultrasonic conditions using an ultrasonic method, and the vibration frequency was set to 30 KHz, heated to 60°C, and the time was 6 min) was added.

[0211] Example 16

[0212] Example 16 was manufactured in the same manner as Example 8, except that after step S30, a step of grafting a silane-based material to the initial non-stick layer of Example 8 (specifically, at least a part of the surface of the initial non-stick layer was brought into contact with a modified solution containing perfluorodecyltrimethoxysilane under ultrasonic conditions using an ultrasonic method, and the vibration frequency was set to 30 KHz, heated to 60°C, and the time was 6 min) was added.

[0213] Example 17

[0214] The pan of Example 17 was manufactured in the same manner as Example 1, except that a 40-μm-thick transition layer was formed on the pan base by a titanium alloy prior to step S20.

[0215] Example 18

[0216] The pan of Example 18 was manufactured in the same manner as Example 1, except that the outer surface of the pan base was left at room temperature in step S30, instead of being left in an environment in which the air was circulated and cooled.

[0217] Example 19

[0218] The pan of Example 19 was manufactured in the same manner as Example 1, except that the non-stick material of Example 1 was replaced with a sintered material (sintering temperature: 1400°C, sintering time: 4 h, and cooling rate: 80°C / s) in step S20.

[0219] Example 20

[0220] The pan of Example 20 was manufactured in the same manner as Example 8, except that the non-stick material of Example 8 was replaced with a sintered material (sintering temperature: 1400°C, sintering time: 4 h, and cooling rate: 80°C / s) in step S20.

[0221] Comparative Example 1

[0222] The pan of Comparative Example 1 was manufactured in the same manner as Example 1, except that a different material (a mixture of 21.06% silicon dioxide, 1.32% aluminum trioxide, 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 impurities) was used in place of the non-stick material of Example 1 in step S20.

[0223] Comparative Example 2

[0224] The pan of Comparative Example 2 was manufactured in the same manner as Example 1, except that a different material (a mixture of 30% silicon dioxide, 1.32% aluminum trioxide, 0.44% potassium oxide, 0.27% sodium oxide, 3.71% calcium oxide, 1.19% magnesium oxide, 0.45% titanium oxide, 50% iron oxide, and the balance impurities) was used in place of the non-stick material of Example 1 in step S20.

[0225] Comparative Example 3

[0226] A pot of Comparative Example 3 was manufactured by the same method as in Example 1 except that a different non-stick material (the material of this comparative example was 45wt% titanium dioxide, 45wt% iron oxide + ferrous oxide, 5wt% calcium oxide + magnesium oxide, and the balance phosphorus, carbon and silicon) was used instead of the non-stick material of Example 1 in step S20.

[0227] Comparative Example 4

[0228] A pot of Comparative Example 4 was manufactured by the same method as in Example 1 except that a different material (the material of this comparative example was magnesium aluminum titanate) was used instead of the non-stick material of Example 1 in step S20.

[0229] Comparative Example 5

[0230] A pot of Comparative Example 5 was manufactured by the same method as in Example 1 except that the material (a mixture of TiO2and 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 in step S20.

[0231] Test methods and evaluation criteria, test results

[0232] I. Test the degree of amorphization of the non-stick materials in Examples 1 to 11, 19 and 20 above and the materials in Comparative Examples 1 to 5, and show the test results in Table 1 below.

[0233] 1. Amorphization test method

[0234] Amorphization test method: XRD test and analysis calculation by conventional full spectrum fitting method were used to obtain the degree of amorphization of the sample. The steps of the conventional full spectrum fitting method are as follows: first, find a crystal phase with the same chemical structure as the amorphous phase, assume that the amorphous phase is a small crystal grain of this crystal phase, and this crystal phase can be used to establish the model of the peak position and intensity of the amorphous phase; second, fit the spectrum of pure amorphous phase first to determine the grain size and microstrain; finally, fix the grain size and microstrain, and include this phase in the traditional Rietveld quantitative calculation, and the volume fraction of the amorphous phase (i.e. the degree of amorphization) of the corresponding material can be obtained.

[0235] 2. Test results Table 1 results test table

[0236]

[0237]

[0238] As can be seen from Table 1, the non-stick material of the embodiments of the present application is a non-stick material with a certain volume ratio of amorphous phase.

[0239] II. Performance tests were conducted on the coatings of the pots obtained in Examples 1-20 and Comparative Examples 1-5 above, and the results are recorded in Table 2 below. The specific performance test methods are as follows:

[0240] 1. Amorphous degree test method

[0241] Amorphous degree test method: the test method of the above non-stick material was used.

[0242] 2. Initial non-stickiness test method

[0243] Initial non-stickiness test method: the egg frying non-stickiness test method in GB / T32095.2-2015, which is an initial non-stickiness test, is divided into levels I, II, and III, with level I being the best non-stickiness and level III being the worst non-stickiness.

[0244] 3. Persistent non-stickiness test method

[0245] Persistent non-stickiness test method: the persistent non-stickiness test method in GB / T32388-2015, with units of times, the higher the number of times, the longer the service life, the non-stickiness result is evaluated every 500 times, and the number of times until level III is recorded.

[0246] 4. Hardness test and evaluation criteria

[0247] Vickers hardness test method was used to test the Vickers hardness of the coating of the obtained pot, wherein the hardness value unit is HV. The larger the measured hardness value, the harder the sample, the stronger the resistance of the non-stick layer to the iron shovel and food material grinding ability, and the less likely to be worn. However, too hard may cause easy cracking. Generally, the hardness of the non-stick layer is expected to be not less than 200 HV and not more than 600 HV.

[0248] 5. Surface energy test and evaluation criteria

[0249] Under the temperature condition of 20°C, the contact angle of water and ethylene glycol on the surface of the sample was measured using a SINDIN SDC-200SH contact angle measuring instrument according to the goniometry method, and the OWRK method was used to calculate the surface energy of the sample. Here, the coating corresponding to the examples and comparative examples.

[0250] For surface energy testing, the measured surface energy value of the sample is expected to be not more than 100 dynes.

[0251] 6. Test results

[0252] Table 2 results test table

[0253]

[0254]

[0255] As can be seen from Table 2, the non-stick layer obtained by the present application has excellent initial non-stickiness and durable non-stickiness, and has suitable hardness, which can avoid the cracking caused by too large coating hardness. By sealing treatment of the coating formed by thermal spraying process, a lower surface energy than fluorine coating can be obtained, which ensures the initial non-stickiness. By controlling the spraying process (i.e. placing the outer surface of the pot in a cooling gas environment in the plasma spraying process), the amorphous degree of the non-stick layer can be improved to a certain extent, so that the surface energy is relatively low, thereby ensuring good durable non-stickiness.

[0256] While the application has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various changes in form and details can be made therein without departing from the spirit and scope of the application as defined by the appended claims and their equivalents. Embodiments should be considered in a descriptive sense only and not for purposes of limitation. Therefore, the scope of the application is not to be limited by specific embodiments. Rather, the scope of the application is to be defined solely by the claims.

Claims

1. A method for preparing a non-stick layer, characterized in that, The method for preparing the non-stick layer includes: A mixed slurry comprising a binder and a base material is formed, wherein the base material comprises titanium dioxide and iron oxide, as well as water-soluble metal oxides and / or metal oxides capable of reacting with fatty acids in oils; The mixed slurry is spray-dried to obtain non-sticky particles; The non-stick particles are sintered to allow the base material in the non-stick particles to be micro-melted and chemically bonded, thereby obtaining a non-stick material; A non-stick material is sprayed to form an initial non-stick layer, wherein the initial non-stick layer includes a composite metal oxide layer with an amorphous structure, the composite metal oxide layer serves as the main body of the initial non-stick layer, and the metal elements in the composite metal oxide layer include iron elements and titanium elements with different valence states, as well as water-soluble metal elements and / or metal elements that can react with fatty acids in oils. The initial non-stick layer is modified with a silane-based material to obtain the non-stick layer.

2. The method for preparing a non-stick layer according to claim 1, characterized in that, The water-soluble metal element includes potassium and / or sodium, and the metal element that can react with fatty acids in oils includes calcium and / or magnesium.

3. The method for preparing a non-stick layer according to claim 1, characterized in that, The initial non-stick layer also includes carbonized products of the adhesive, which are dispersed in the composite metal oxide layer.

4. The method for preparing a non-stick layer according to claim 3, characterized in that, The weight ratio of the carbonization product of the binder to the composite metal oxide layer is (0.4-3.5):(96.5-99.6).

5. The method for preparing a non-stick layer according to claim 1, characterized in that, The initial non-stick layer has a porosity of 5%-30% and a pore size of 500 nanometers-4 micrometers; the thickness of the initial non-stick layer is in the range of 10 micrometers-150 micrometers.

6. The method for preparing a non-stick layer according to claim 1, characterized in that, The silane materials include at least one of γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, sulfur-containing silane coupling agents, epoxy-based silane coupling agents, γ-ureopropyltriethoxysilane, perfluorodecyltrimethoxysilane, perfluorooctyltriethoxysilane, perfluorododecyltrimethoxysilane, and trifluoropropylmethylsilane.

7. The method for preparing a non-stick layer according to claim 1, characterized in that, The composite metal oxide layer includes FeTiO3, Fe2TiO5, and Fe3Ti3O 10 .

8. The method for preparing a non-stick layer according to any one of claims 1 to 7, characterized in that, The step of modifying the initial non-stick layer with a silane-based material includes: A modified solution comprising silane-based materials and water is brought into contact with at least a portion of the surface of the initial non-stick layer and reacted to obtain an initial non-stick layer modified with silane-based materials as the non-stick layer.

9. The method for preparing a non-stick layer according to claim 8, characterized in that, The initial non-stick layer modified with silane-based materials is the product of the reaction between the hydrolysis product of the silane-based material and the initial non-stick layer.

10. The method for preparing a non-stick layer according to any one of claims 1 to 7, characterized in that, The method for preparing the non-stick layer further includes: The non-stick layer is obtained by impregnating it with oil molecules, thereby creating a non-stick layer that bonds with the oil molecules.

11. A non-stick layer, characterized in that, The non-stick layer comprises an amorphous composite metal oxide layer and a silane-based material formed on the composite metal oxide layer. The composite metal oxide layer serves as the main body of the non-stick layer, and the metal elements in the composite metal oxide layer include iron and titanium elements in different valence states, as well as water-soluble metal elements and / or metal elements capable of reacting with fatty acids in oils. The composite metal oxide layer includes FeTiO3, Fe2TiO5, and Fe3Ti3O3. 10 .

12. The non-stick layer according to claim 11, characterized in that, The non-stick layer has an amorphous phase volume ratio of 50%-70%; and / or, the silane material includes at least one of γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, sulfur-containing silane coupling agent, epoxy-based silane coupling agent, γ-ureidopropyltriethoxysilane, perfluorodecyltrimethoxysilane, perfluorooctyltriethoxysilane, perfluorododecyltrimethoxysilane, and trifluoropropylmethylsilane; and / or, the water-soluble metal element includes potassium and / or sodium, and the metal element capable of reacting with fatty acids in oils includes calcium and / or magnesium.

13. The non-stick layer according to claim 11, characterized in that, The non-stick layer also includes carbonized products of the adhesive, which are dispersed in the composite metal oxide layer.

14. The non-stick layer according to claim 13, characterized in that, The weight ratio of the carbonization product of the binder to the composite metal oxide layer is (0.4-3.5):(96.5-99.6).

15. A method for manufacturing a non-stick cookware, characterized in that, The method for manufacturing the non-stick cookware includes: A mixed slurry comprising a binder and a base material is formed, wherein the base material comprises titanium dioxide and iron oxide, as well as water-soluble metal oxides and / or metal oxides capable of reacting with fatty acids in oils; The mixed slurry is spray-dried to obtain non-sticky particles; The non-stick particles are sintered to allow the base material in the non-stick particles to be micro-melted and chemically bonded, thereby obtaining a composite metal oxide with an amorphous structure containing iron and titanium elements in different valence states as a non-stick material. A non-stick material is sprayed onto the substrate to form a composite product layer with an amorphous structure on the substrate, which serves as the main body of the initial non-stick layer; The initial non-stick layer is modified with a silane-based material to obtain a non-stick cookware with a non-stick layer.

16. The method for manufacturing a non-stick cookware according to claim 15, characterized in that, The weight ratio of the base material to the binder is (52-70):(30-48); and / or, the weight ratio of the titanium oxide to the iron oxide is (13-39):(13-39).

17. The method for manufacturing a non-stick cookware according to claim 15, characterized in that, The binder includes alcohol-based binders and / or cellulose-based binders; and / or, the particle size of the base material is 0.05 micrometers to 5 micrometers.

18. The method for manufacturing a non-stick cookware according to claim 15, characterized in that, The sintering step includes: The non-stick granules are heated to 500℃-650℃ at a heating rate of 15℃ / min-20℃ / min and held for 6h-8h. Then, the temperature is increased to 1200℃-1250℃ at a heating rate of 55℃ / min-100℃ / min and held for 12h-24h.

19. A non-stick cookware, characterized in that, The nonstick cookware includes a substrate and a nonstick layer formed on the substrate according to any one of claims 11 to 14, or a nonstick cookware manufactured by the method of manufacturing a nonstick cookware according to any one of claims 15 to 18.

20. The non-stick cookware according to claim 19, characterized in that, The non-stick layer of the non-stick cookware has a porous structure that can be filled by oil molecules.

21. The non-stick cookware according to claim 19, characterized in that, The thickness of the non-stick layer is in the range of 10 micrometers to 150 micrometers.

22. The non-stick cookware according to claim 19, characterized in that, The non-stick cookware also includes a transition layer made of a metal material, wherein the transition layer is disposed between the substrate and the non-stick layer.

23. The non-stick cookware according to claim 22, characterized in that, The thickness of the transition layer is in the range of 10 micrometers to 80 micrometers; and / or the metallic material includes at least one of titanium, titanium alloy, iron, ferroalloy, aluminum, aluminum alloy, zinc, zinc alloy, copper, copper alloy, zirconium, and zirconium alloy.

24. The non-stick cookware according to claim 19, characterized in that, The surface of the non-stick layer has an uneven structure, and the depressions of the uneven structure are filled with a low surface energy material.

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