CN114477301A - Non-stick material and preparation method and application thereof - Google Patents
Non-stick material and preparation method and application thereof Download PDFInfo
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- CN114477301A CN114477301A CN202210179840.3A CN202210179840A CN114477301A CN 114477301 A CN114477301 A CN 114477301A CN 202210179840 A CN202210179840 A CN 202210179840A CN 114477301 A CN114477301 A CN 114477301A
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- C01—INORGANIC CHEMISTRY
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- C01G49/00—Compounds of iron
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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Abstract
The application provides a non-stick material, a preparation method and application thereof. Wherein the non-stick material comprises at least one composite metal cation metalate powder, the composite metal cation metalate has an amorphous structure, and the composite metal cations in the composite metal cation metalate comprise at least two metal cations. According to the non-stick material, the non-stick material has good non-stick performance and good scratch resistance, and therefore has a long non-stick life.
Description
Technical Field
The application relates to the technical field of non-stick materials, in particular to a non-stick material, a preparation method of the non-stick material and application of the non-stick material.
Background
The existing non-stick material for kitchenware is mainly fluorine paint, the main component of which is organic fluororesin material, and the organic fluororesin material generally has the following disadvantages:
1. is easy to be scratched: since fluororesin is a high molecular material, its hardness is low, and when hard food (such as seashell) is stir-fried, its surface is easily scratched and exposed out of the base material of the cooker.
2. No high temperature resistance: the fluororesin is a high molecular resin, and is easy to deform under long-time high-temperature conditions to cause failure in a high-temperature environment.
3. The use experience is poor: the hardness is low, so that the stir-frying machine is easy to damage, cannot be suitable for conditions such as stir-frying and stir-frying, and is poor in use experience.
Therefore, there is a need for improvement of the existing non-stick materials to improve the scratch resistance and non-stick effect of the non-stick coating to enable a longer non-stick life.
Disclosure of Invention
Therefore, the application aims to provide a non-stick material, a preparation method and application thereof, so as to solve the problems that a non-stick coating formed by the non-stick material in the prior art is poor in scratch resistance and short in non-stick life caused by a non-stick effect.
According to a first aspect of the present application, there is provided a non-stick material comprising at least one powder of a composite metal cationic metallate having an amorphous structure, wherein the composite metal cations in the composite metal cationic metallate comprise at least two metal cations.
In an embodiment, the complex metal cationic metalate comprises at least one of a complex metal cationic titanate, a complex metal cationic chromate, a complex metal cationic manganate, a complex metal cationic ferrite, a complex metal cationic meta-aluminate, a complex metal cationic tungstate, a complex metal cationic molybdate, and a complex metal cationic vanadate.
In an embodiment, the metal cation comprises at least one of magnesium, aluminum, calcium, selenium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, yttrium, zirconium, niobium, molybdenum, technetium, indium, tin, antimony, hafnium, tantalum, and tungsten.
In an embodiment, in each of the complex metal cation metalates, the percentage of the number of any one metal cation to the total number of complex metal cations is greater than or equal to 10% based on the total number of complex metal cations, the sum of the percentages of the number of all complex metal cations being 100%.
In embodiments, the non-stick material powder has a particle size in the range of 200 mesh to 800 mesh.
In an embodiment, the non-stick material further comprises a metal material, the metal material forms a film layer on the surface of the composite metal cation metalate powder, and the weight of the metal material in the non-stick material accounts for 3% -10% of the total weight of the non-stick material, based on the total weight of the non-stick material, and the balance is the composite metal cation metalate powder.
In an embodiment, the metallic material comprises at least one of iron and its alloys, zinc and its alloys, aluminum and its alloys, titanium and its alloys, chromium and its alloys, nickel and its alloys, cobalt and its alloys, copper and its alloys, zirconium and its alloys, molybdenum and its alloys, and vanadium and its alloys.
According to a second aspect of the present application, there is provided a method of preparing a non-stick material, said method comprising melting at least two metal cationic metalate powders to obtain corresponding melts; processing the molten liquid in an atomization powder preparation mode to obtain corresponding composite metal cation metallate powder, wherein the composite metal cation metallate has an amorphous structure; wherein, in different kinds of metal cation metalates, the metal acid radical ions are the same, and the metal cations are different; the non-stick material includes at least one composite metal cationic metallate powder.
In embodiments, the absolute value of the difference in radii for any two of the metal cations is greater than or equal to 0.1 times the radius of a hydrogen atom.
In an embodiment, in each of the complex metal cation metalates, the percentage of the number of any one metal cation to the total number of complex metal cations is greater than or equal to 10% based on the total number of complex metal cations, the sum of the percentages of the number of all complex metal cations being 100%.
In an embodiment, the metal cation metalate comprises at least one of a titanate, a chromate, a manganate, a ferrite, a meta-aluminate, a tungstate, a molybdate, and a vanadate.
In an embodiment, the metal cation comprises at least one of magnesium, aluminum, calcium, selenium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, yttrium, zirconium, niobium, molybdenum, technetium, indium, tin, antimony, hafnium, tantalum, and tungsten.
In an embodiment, the processing of the melt by atomizing powder comprises atomizing the melt, wherein in the atomizing, the melt is firstly cooled at a cooling speed of 300-450K/s and is dispersed into liquid drops; and carrying out secondary cooling on the liquid drops at a cooling speed of 600K/s-1000K/s to obtain the composite metal cation metalate powder.
According to a third aspect of the present application, there is provided the use of a non-stick material as feedstock for a spray application, said non-stick material being used as a non-stick material for cookware.
Drawings
The above and other objects and features of the present application will become more apparent from the following description of the embodiments taken in conjunction with the accompanying drawings, in which:
FIG. 1 is an XRD pattern of a non-stick material according to an embodiment of the present application.
Detailed Description
The inventive concepts of the present application will be described more fully hereinafter.
Compared with metal materials, the metal acid salt has the advantages of higher hardness, melting point, better oxidation resistance and long-term high-temperature invariance. Therefore, a non-stick material having a certain strength can be realized by using a metal acid salt as the non-stick material, thereby realizing better scratch resistance and non-stick life.
However, the non-stick material needs to have not only certain strength but also proper non-stick performance, and the metalate is generally in a crystal structure, so that the non-stick effect is general, and the metalate needs to be treated in order to improve the non-stick effect.
The inventor researches and discovers that the metal salt is used as a framework component, the same metal salt with different metal cations is used as a raw material to be smelted and mixed, and the metal salt is cooled to prepare the composite metal cation metal salt with an amorphous structure. By designing the combination of the raw materials, the proportion of the metal cations in the raw materials and the number of the metal cations in the raw materials, the composite metal cation metalate powder can have a high degree of amorphization. Because the amorphous structure has lower surface energy compared with the crystal structure, the non-stick material can achieve the purpose of cooking non-stick by adopting the composite metal cation metallate powder with the amorphous structure as the non-stick material. In addition, the material with the amorphous structure has certain hardness, and the scratch resistance of a product formed by the non-stick material can be further improved.
Furthermore, the inventors have found that, in the method for producing a non-stick material, the composite metal cationic metalate powder is melted to form a powder, and the solid solution phase of the composite metal cationic metalate is kept stable by controlling the cooling rate in a rapid cooling manner, and crystallization is prevented, so that a powder with a higher degree of amorphization can be obtained.
The inventive concept of the present application will be described in detail below with reference to exemplary embodiments.
According to a first aspect of the present application there is provided a non-stick material comprising at least one composite metal cationic metalate powder. The composite metal cation metallate has an amorphous structure, and the composite metal cations in the composite metal cation metallate comprise at least two metal cations.
According to the non-stick material of the present application, since the amorphous structure has a lower surface energy than the crystalline structure, it can be used as a non-stick material having a non-stick effect. In addition, the composite metal cation metallate with the amorphous structure also has certain hardness, so that the scratch resistance of the non-stick material can be improved, and the non-stick service life can be prolonged.
According to the non-stick material, the composite metal cation metalate can be used as the non-stick material, or the mixture of the multiple composite metal cation metalates can be used as the non-stick material, and the multiple composite metal cation metalates can be used as the non-stick material after being randomly mixed, so that the combination mode and the mixing ratio of the non-stick material are not limited in the application.
FIG. 1 is an XRD pattern of a non-stick material according to an embodiment of the present application. Specifically, it may be Al2Fe(TiO3)4As shown in FIG. 1, the XRD pattern of (A) was not particularly clear, with many and random peaks, poor crystallinity, and Al2Fe(TiO3)4The powder shows amorphous tendency, and the amorphous phase content is 87 percent according to the calculation of a conventional full-spectrum fitting method. In the present application, the amorphous content of the composite metal cationic metalate powder is not less than 50%, preferably not less than 65%. A content of the amorphous phase of less than 50% promotes the non-tackiness effect, whereas a content of the amorphous phase of greater than or equal to 50% can promote the non-tackiness property to a large extent.
It is noted that, according to the present application, the metal cation does not include the metal cation in the metallate ion.
In an embodiment, the species of the complex metal cation metalate may include at least one of a complex metal cation titanate, a complex metal cation chromate, a complex metal cation manganate, a complex metal cation ferrite, a complex metal cation metaaluminate, a complex metal cation tungstate, a complex metal cation molybdate, and a complex metal cation vanadate. The metal cation in each complex metal cation metalate can include at least two of magnesium, aluminum, calcium, selenium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, yttrium, zirconium, niobium, molybdenum, technetium, indium, tin, antimony, hafnium, tantalum, and tungsten. Illustratively, when a complex metal cation M acid salt, the complex metal cation M acid salt may include M aluminum iron or may include M aluminum iron magnesium. The chemical formula of the M aluminum-iron-magnesium alloy can be AlxFeyMgz(MO3)wWherein x is more than 0 and less than or equal to 3, y is more than or equal to 1 and less than or equal to 6, z is more than 0 and less than or equal to 3, and w is determined by the valence state and the mole number of the metal cation. The M aluminum ferric oxide can be AlxFey(MO3)wWherein x is more than 0 and less than or equal to 3, y is more than or equal to 1 and less than or equal to 6, and w is determined by the valence state and the mole number of the metal cation. Specifically, the aluminum iron magnesium titanate may have the chemical formula AlxFeyMgz(TiO3)wWherein, when is Fe3+When 3x +3y +2z is 2w, or when Fe2+When 3x +2y +2z is 2 w.
In an embodiment, in each of the complex metal cation metalates, the percentage of the number of any one metal cation to the total number of complex metal cations is greater than or equal to 10% based on the total number of complex metal cations, the sum of the percentages of the number of all complex metal cations being 100%.
In the application, in the process of forming the coating by adopting the non-stick material, the flight time is shortened as far as possible under the condition of ensuring that the coating can be formed, so that more amorphous structures can be remained in the non-stick material. I.e., the degree of melting of the composite metal cationic metallate powder is controlled such that it retains more amorphous phase during the formation of the coating. Specifically, the non-stick coating with the amorphous structure can be formed by melting the surface of the composite metal cation metallate powder with the amorphous structure and not completely melting the inside of the composite metal cation metallate powder, so that the non-stick effect is ensured.
In practical applications, it is found that, due to the high melting point and poor thermal conductivity of the composite metal cationic metalate powder, when the powder is sprayed as a non-stick material, the surface of the composite metal cationic metalate powder will melt and the interior of the powder will hardly melt completely in a short flight time (the time taken for the powder to pass from the spray gun to the product), and the bonding strength with the product will be slightly affected when the powder is sprayed on the product. On the premise of ensuring non-stickiness, in order to improve the binding force, the non-stick material may include a metal material in addition to the composite metal cationic metallate powder. Wherein the metal material forms a film layer on the surface of the composite metal cation metallate powder. And in the non-stick material, the weight of the metal material accounts for 3% -10% of the total weight of the non-stick material, and the balance is the composite metal cation metalate powder.
According to the non-stick material, the metal material is relatively low in melting point and good in thermal conductivity, so that the metal material can be completely melted in a short time, the non-stick material is formed by compounding the metal material and the composite metal cation metallate powder, the metal material can serve as an adhesive on the surface of the composite metal cation metallate powder, and the bonding force between the non-stick material and a product during subsequent spraying can be improved on the premise of ensuring the non-stick property.
In an exemplary embodiment, the metal material may include at least one of iron and its alloy, zinc and its alloy, aluminum and its alloy, titanium and its alloy, chromium and its alloy, nickel and its alloy, cobalt and its alloy, copper and its alloy, zirconium and its alloy, molybdenum and its alloy, and vanadium and its alloy. However, those skilled in the art can also select other suitable materials as the binder under the teaching of the present application to improve the binding force of the composite metal cationic metalate to the coating formed by the product.
Hereinafter, the preparation method of the non-stick material of the present application will be described in detail with reference to examples.
Embodiments according to the second aspect of the present application also provide a method of preparing a non-stick material, which may include the steps of:
step S101, melting at least two kinds of metal cation metalate powder to obtain corresponding molten liquid.
And S102, processing the molten liquid in an atomization powder preparation mode to obtain corresponding composite metal cation metalate powder, wherein the composite metal cation metalate has an amorphous structure. Wherein, in different kinds of metal cation metalates, the metalate ions are the same, and the metal cations are different. The non-stick material includes at least one composite metal cationic metallate powder.
According to the preparation method of the non-stick material, the same metal acid salt with different metal cations is adopted to form molten liquid, the molten liquid is processed by an atomization powder preparation method, composite metal cation metal acid salt powder with an amorphous structure can be formed, and the amorphous structure has lower surface energy compared with a crystal structure, so that the non-stick material with a better non-stick effect can be realized. In addition, the composite metal cation metallate with the amorphous structure also has certain hardness, so that the scratch resistance of the non-stick material can be improved, and the non-stick service life can be prolonged.
According to the present application, the metalate is often in the solid solution phase, which is divided into substitutional and interstitial solid solutions, which have lattice distortion effects. Adopt at least two kinds of metal cation metallate powder to form the melt, process the melt through the method of atomizing powder process, in the in-process that constantly cools off the formation powder, because the radius of different cations is different, different cations occupy each lattice position with equal chance, lead to the crystal lattice to take place the distortion, the size difference of different cations makes the lattice distortion can too high and can not keep crystal structure to the crystal lattice collapses and forms amorphous structure, and then forms the compound metal cation metallate powder of low surface energy of this application.
The method of making a non-stick material according to the present application may include the step of preparing a starting material, which may include at least two metal cationic metalate powders. In an embodiment, the raw material has a size of a uniform size and has a spheroidal shape so that each can be sufficiently melted in the step of performing melting. According to the application, the selection of the powder particle size of the raw material can be selected according to the melting point, and exemplarily, the powder with the melting point between 1000 ℃ and 1200 ℃, the powder with the selectable particle size between 300 ℃ and 1500 ℃, and the powder with the selectable particle size between 1200 ℃ and 1500 ℃ are 500-800 meshes, wherein the higher the melting point is, the finer the powder is. The raw materials can be used for obtaining powder with corresponding particle size by means of ball milling.
According to the application, the raw material for forming the composite metal cation metallate takes the metallate as a framework component, and the composite metal cation metallate has high hardness and oxidation resistance due to the fact that the metallate has high hardness and oxidation resistance. Further, the non-stick material formed from at least one complex metal cation metallate also has superior properties. In the raw material of the present application, the metal cation metalate may include at least one of titanate, chromate, manganate, ferrite, metaaluminate, tungstate, molybdate, vanadate, silicate and phosphate. The metal cation may include at least one of magnesium ion, aluminum ion, calcium ion, selenium ion, titanium ion, vanadium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion, gallium ion, germanium ion, yttrium ion, zirconium ion, niobium ion, molybdenum ion, technetium ion, indium ion, tin ion, antimony ion, hafnium ion, tantalum ion, and tungsten ion. The starting materials according to the present application can be obtained either commercially or by synthetic methods known in the art.
The preparation method of the raw material according to the present application can be realized by the following steps, and specifically, the preparation method of the raw material can comprise the following steps: chemical precipitation, liquid phase synthesis, hydrothermal, solvothermal, and high temperature solid phase synthesis. The corresponding raw materials obtained by the method are purified for later use.
According to the preparation method of the non-stick material, after the raw materials are selected, the combination of the raw materials can be designed, so that the metal cations between the raw materials have relatively large radius difference, and the non-crystallization degree of the formed composite metal cation metalate can be improved. In the raw materials, an absolute value of a difference in radius of the metal cation between any two raw materials may be greater than or equal to 0.1 times the radius of the hydrogen atom.
It is noted that, according to the present application, the metal cation does not include the metal cation in the metallate ion.
In addition, in order to increase the degree of amorphization of the complex metal cation metalate, it is possible to facilitate the formation of a disordered amorphous phase by providing a large number of types of metal cations in addition to designing the combination of the respective raw materials forming one complex metal cation metalate.
In addition, the ratio of the number of metal cations in the raw material can be set so that the finally formed composite metal cation metalate has a certain content of metal cations.
The molar ratio of any two metal cations in the starting material may be between 1:9 and 9: 1. According to the application, in each of the complex metal cation metalates, the percentage of the number of any one metal cation to the total number of complex metal cations is greater than or equal to 10% based on the total number of complex metal cations, the sum of the percentages of the number of all complex metal cations being 100%.
Illustratively, the composite metal cationic metalate is formed from a first metal cationic metalate and a second metal cationic metalate, wherein the percentage of the number of first metal cations to the total number of composite metal cations is greater than or equal to 10% and the percentage of the number of second metal cations to the total number of composite metal cations is greater than or equal to 90%, based on the total number of composite metal cations.
In particular, 4mol of FeTiO3And 3mol of Al2(TiO3)3Formation of Al2Fe(TiO3)4In the case where the number of aluminum ions is 60% of the total number of aluminum iron ions, the number of iron ions is 40% of the total number of aluminum iron ions.
According to the preparation method of the non-stick material, the larger the radius difference of the metal cations in the raw materials is, the larger the size difference is, the higher the lattice distortion energy is, the crystal structure cannot be maintained, the more disordered amorphous phase is easily formed, and by setting each metal cation in the raw materials to have a certain proportion, in the process of forming the composite metal cation metalate, the proper quantity proportion of the metal cations can play a role of the metal cations as doping ions, so that the crystal structure of the metalate is damaged by more kinds of metal cations, the amorphous structure is easily formed, and further, the lower surface energy can be obtained to improve the non-stick performance.
According to the preparation method of the composite metal cation metal salt, the composite metal cation metal salt can be obtained by melting two kinds of metal salt powder and preparing powder by atomization, and can also be obtained by melting more kinds of metal salt powder and preparing powder by atomization. The method for preparing the composite metal cation metalate formed by more metalate is different in that more raw materials are added in the melting process, and the other method is the same as the method for preparing the composite metal cation metalate formed by two metalate. For convenience of description, the preparation method of the non-stick material of the present application will be described below by taking the formation of a composite metal cation metalate from two metalates as an example.
According to the method for preparing the non-stick material of the present application, after preparing the two metal cation metalate powders, next, the two powders will be melted. Specifically, in order to avoid oxidation, the melting process needs to be performed under the protection of an inert atmosphere, the metal cation metalate powder with a relatively high melting point is heated to be completely melted, then other metal cation metalate powder with a relatively low melting point is slowly added, and sufficient stirring needs to be performed in the melting process, so as to obtain a corresponding molten liquid. According to this application, the reinforced order of powder can go on from high to low order according to the melting point to make the powder that the melting point is higher relatively can fully melt, and then can reduce the time of operation and promote work efficiency. According to the application, the preset melting temperature can be in the range of 1500-2000 ℃, and the melting time can be 4-8 h, so that the melting can be completely carried out.
And then, pulverizing by adopting a high-pressure water atomization mode, putting the molten liquid into an atomization device, and dispersing the molten liquid into liquid drops after carrying out primary cooling on the molten liquid at a certain cooling speed under the impact of high-pressure water flow or water mist pressure. Then, the droplets are subjected to secondary cooling at a cooling rate to obtain composite metal cation metalate powder. According to the present application, the melt undergoes two cooling stages and, by controlling the appropriate cooling rate, the droplets do not have time to form a complete crystal structure, thereby tending to form amorphous complex metal cationic metalate powders. By controlling the proper water pressure, the molten liquid is crushed to different degrees, so that the composite metal cation metalate powder with proper granularity can be obtained.
The preliminarily obtained powder of the composite metal cation metalate also has a certain moisture content, and therefore, the powder needs to be dried to remove the moisture content. The preparation method of the non-stick material further comprises the steps of dehydrating and drying the preliminarily obtained composite metal cation metalate powder, so as to obtain the composite metal cation metalate powder in a granular form. Since the drying step is performed at a relatively low temperature, oxidation and the like are not likely to occur, and therefore, the step of inert gas protection can be omitted during the drying process, and the cost can be saved.
As an example, in step S201, under the protection of argon gas, ferrous titanate with a high melting point is added into a high-frequency induction furnace, heated and melted, and then magnesium titanate with a relatively low melting point is added, wherein the melting temperature may be 1700 ℃ to 1900 ℃, and the melting time may be 3h to 5h, so as to prepare a melt.
Step S202, the high-pressure water pump is started in advance, and the high-pressure water atomization device starts to work. And (4) pouring the molten liquid obtained in the step (S201) into a tundish of a water atomization device, wherein the molten liquid in the tundish enters an atomizer through a discharge spout at the bottom of the tundish after passing through a beam. Under the pressure of the high-pressure water of the atomizer, the molten liquid is broken continuously and formed into fine liquid drops, and then the fine liquid drops fall into the cooling liquid in the water atomization device to be rapidly solidified into composite metal cation metallate powder. According to the exemplary embodiment of the present application, in order to avoid interference of impurities and oxygen, the high pressure water is pure water, the water pressure is 45MPa to 75MPa, the flow rate of water is 1500L/min to 3000L/min, inert gas for protection, such as argon, etc., may be added to the atomizer, the pressure is 0.4MPa to 0.6MPa, and the flow rate is 30L/min to 50L/min.
Step S203, dehydrating and drying the composite metal cation metallate powder obtained by atomization, wherein the drying temperature is 150-200 ℃.
After the non-stick material is prepared, a powder of the appropriate particle size is selected for application to the product to form the non-stick coating. Here, the non-stick material powder has a particle size in the range of 200 mesh to 800 mesh. The undersize powder with the size higher than 800 meshes has low spraying utilization rate and wastes cost. The powder with the size less than 200 meshes is difficult to melt in the process of spraying, cannot be well attached to the surface of a product, and can cause the surface of a final coating to be rough, the post-treatment is difficult to carry out, and the texture is relatively poor.
In the application, in the process of forming the coating by adopting the non-stick material, the flight time is shortened as far as possible under the condition of ensuring that the coating can be formed, so that more amorphous structures can be remained in the non-stick material. I.e., the degree of melting of the composite metal cationic metallate powder is controlled such that it retains more amorphous phase during the formation of the coating. Specifically, the non-stick coating with the amorphous structure can be formed by melting the surface of the composite metal cation metallate powder with the amorphous structure and not completely melting the inside of the composite metal cation metallate powder, so that the non-stick effect is ensured.
In practical applications, it is found that, due to the high melting point and poor thermal conductivity of the composite metal cationic metalate powder, when the powder is sprayed as a non-stick material, the surface of the composite metal cationic metalate powder will melt and the interior of the powder will hardly melt completely in a short flight time (the time taken for the powder to pass from the spray gun to the product), and the bonding strength with the product will be slightly affected when the powder is sprayed on the product.
For this reason, in order to improve the bonding force with the product, according to the non-stick material of the present application, the bonding force of the non-stick material with the product may be improved by a suitable metal material. In the following, another method for preparing a non-stick powder according to the present application will be described with reference to specific examples.
In embodiments, the non-stick material may include a metallic material that forms a film layer on the surface of at least one composite metal cationic metalate powder in addition to the at least one composite metal cationic metalate powder. The weight ratio of the metal material is less than 3%, the effect of improving the binding force is difficult to achieve, and the weight ratio of the metal material is more than 10%, but the non-stick effect of the finally formed coating is affected. Therefore, in the non-stick material, the weight of the metal material accounts for 3% -10% of the total weight of the non-stick material, and the balance is the composite metal cation metalate powder.
According to the application, the metal material and the above-obtained composite metal cationic metalate may be mixed in a certain ratio to form a non-stick material. However, in order to ensure that the metal material as the "adhesive" can exert a better effect in the non-stick material, the metal material may be compounded with the composite metal cationic metalate powder so that the metal material is deposited on the surface of the composite metal cationic metalate powder to form the non-stick material. Illustratively, a metal material film layer with the thickness of 1 μm to 3 μm can be formed on the surface of the composite metal cation metalate powder by means of physical vapor deposition. Specifically, a metal material is used as a target material, and a magnetron sputtering physical vapor deposition process is adopted to deposit a metal material film layer on the surface of each powder of the composite metal cation metallate. The specific steps for preparing the non-stick material according to the present application are as follows:
s301, ultrasonically cleaning and drying the composite metal cation metallate powder by using acetone, deionized water and absolute ethyl alcohol in sequence, and then placing the cleaned and dried powder into a base container.
S302, transferring the cleaned powder from the base container to a sample stage of a magnetron sputtering device, rapidly closing a vacuum chamber, and vacuumizing to 8.0 × 10-4Pa. Opening an argon bottle, opening an air valve, introducing argon, setting the argon flow to be 60sccm by adjusting a gas flowmeter, setting the substrate temperature to be 200 ℃, adjusting a gate valve of a molecular pump, and setting the sputtering air pressure to be 0.5 Pa.
And S303, adjusting the power of the corresponding metal target, opening the total baffle and starting sputtering the metal layer.
And S304, naturally cooling the composite non-stick material prepared by the process in a vacuum cavity, and cooling to room temperature to form the non-stick material according to the embodiment of the application.
According to the non-stick material, the metal material is relatively low in melting point and good in thermal conductivity, so that the metal material can be completely melted in a short time, the non-stick material is formed by compounding the metal material and the composite metal cation metallate powder, the metal material can serve as a binder on the surface of the composite metal cation metallate powder, and the binding force between the non-stick material and a product during subsequent spraying can be improved on the premise of ensuring the non-stick property.
Hereinafter, the application of the non-stick material of the present application will be described in detail with reference to examples.
According to embodiments of the third aspect of the present application, there is also provided the use of a non-stick material as a feedstock for spraying.
Based on the non-stick material of each embodiment, in the obtained non-stick material, powder with a proper particle size can be screened out to be suitable for different products, and the product according to the embodiment of the application can be a container, a pot and the like.
After the non-stick powder is selected, in a specific application, a thermal spraying mode can be adopted, and a supersonic plasma spraying method is taken as an example, and the spraying mode of the application is briefly described as follows: step S301, product surface pretreatment, including degreasing cleaning, surface shot blasting, sand blasting, coarsening and other pretreatment modes, is carried out to enhance the bonding force between the product and the non-stick coating. And S302, placing one surface of the product opposite to the spraying surface in a circulating cooling air gas environment, wherein the temperature of cooling gas is between minus 20 ℃ and minus 10 ℃. Step S303, powder of the non-stick material with 200-800 meshes is filled into a powder feeder, and the powder feeding speed is 20-50 g/min; the spraying distance is 80-100 mm; arc current 450-650A; the hydrogen pressure is 0.2-0.4MPa, the hydrogen flow is 6-15L/min, the argon pressure is 2.5-4.0MPa, and the argon flow is 1000-. Under the parameters, the surface of the non-stick material is heated to be molten by the high-pressure plasma flame flow formed at the muzzle, and then the non-stick material is rapidly cooled at the cooling speed of 180-200K/S and deposited on the surface of the product to form the non-stick coating.
The present application will be described in detail with reference to examples, but the scope of the present application is not limited to the examples.
Example 1
The non-stick material according to example 1 was prepared by the following method.
Step S10, providing a raw material. Providing ferrous titanate powder (FeTiO) with an average particle size of 500 mesh3) Magnesium titanate powder (MgTiO) having an average particle diameter of 500 mesh as first metal cation metalate powder3) As a second metal cation metalate powder.
Step S20, preparing a melt.
Under the protection of argon, 900mol of ferrous titanate powder with high melting point is added into a high-frequency induction furnace, heated and melted, and then 200mol of magnesium titanate powder with relatively low melting point is added, wherein the melting temperature can be 1800 ℃, and the melting time can be 3 hours, so that molten liquid is prepared.
And step S30, treating the molten liquid in a water atomization powder preparation mode to obtain non-sticky powder.
And starting the high-pressure water pump in advance to enable the high-pressure water atomization device to start working. Setting working parameters of the atomizer in advance: the high-pressure water is purified water with the water pressure of 60MPa and the water flow of 2000L/min, the argon protection is started, the argon pressure is 0.5MPa, and the argon flow is 40L/min. After the above operation is prepared, the melt obtained in step S20 is poured into a tundish of a water atomization apparatus, and the melt in the tundish flows through a nozzle at the bottom of the tundish and enters an atomizer. Under the action of the purified water of the atomizer, the molten liquid is continuously crushed and forms fine liquid drops, and the fine liquid drops fall into the cooling liquid in the water atomization device and are rapidly solidified into composite metal cation metallate powder.
And step S40, drying the formed composite metal cation metalate powder to remove the moisture contained in the composite metal cation metalate powder, wherein the drying temperature is 180 ℃, and thus the composite metal cation metalate powder in a particle form is obtained and used as a non-stick material.
Example 2
Except that three raw materials were prepared and sequentially formed into corresponding ones at a molar ratio of 10:8:3 in step S10 of providing raw materialsIn addition to the melt { i.e., in addition to example 1, aluminum titanate powder (Al) was added2(TiO3)3) Prepare the non-stick material of example 2 using the same procedure as example 1.
Example 3
In addition to preparing four raw materials and melting the four raw materials in sequence at a molar ratio of 30:21:7:8 in step S10 of providing raw materials { i.e., adding aluminum titanate powder (Al) on the basis of example 1 }2(TiO3)3) And copper titanate powder (CuTiO)3) Prepare the non-stick material of example 3 using the same procedure as example 1.
Example 4
Except for using zirconium ferrite Zr3(FeO3)4And zinc ferrite Zn3(FeO3)2The non-stick material of example 4 was prepared in the same manner as in example 1, except that ferrous titanate powder and magnesium titanate powder were replaced and molten solutions were formed in the order of molar ratio of 1: 1.
Example 5
The non-stick material was formed by physical vapor deposition using 5 weight percent copper and 95 weight percent of the composite metal cationic metalate powder obtained in example 1.
Example 6
The non-stick material was formed by physical vapor deposition using 5 weight percent aluminum and 95 weight percent of the composite metal cationic metalate powder obtained in example 1.
Example 7
The non-stick materials of example 1 and example 4 were used as described in 1:1 by weight ratio to form a non-stick material.
Comparative example 1
Ferrous titanate powder is used as the non-stick material.
Comparative example 2
Magnesium titanate powder is used as the non-stick material.
Comparative example 3
The coating formed by the fluororesin is used as a non-stick material.
Table 1 parameters of the examples and comparative examples of the present application
Performance index testing
(1) The non-crystallizing degree of the non-stick materials of examples 1-7 and comparative examples 1-2 was tested as follows:
the amorphous degree test method comprises the following steps: and (4) carrying out analysis calculation by adopting XRD test and a conventional full spectrum fitting method to obtain the amorphization degree of the sample. The steps of the conventional full-spectrum fitting method are as follows: firstly, finding a crystalline phase with the same chemical structure as the amorphous phase, and assuming that the amorphous phase is a tiny crystal grain of the crystalline phase, the crystalline phase can be used for establishing a model of the peak position and the intensity of the amorphous phase; secondly, fitting a spectral line of a pure amorphous phase to determine the grain size and the microscopic strain; finally, by fixing the grain size and microscopic strain, and including this phase in a conventional Rietveld quantitative calculation, the amorphous content (i.e., degree of amorphization) was obtained and reported in table 2 below.
TABLE 2 data of the amorphization degree test for the examples and comparative examples of the present application
| Serial number | Degree of amorphization |
| Example 1 | 88％ |
| Example 2 | 92％ |
| Example 3 | 94％ |
| Example 4 | 86％ |
| Example 5 | 77％ |
| Example 6 | 75％ |
| Example 7 | 87％ |
| Comparative example 1 | - |
| Comparative example 2 | - |
| Comparative example 3 | - |
(2) The non-stick materials of examples 1-7 and comparative examples 1-2 were applied to cookware using the same spray conditions, as follows:
selecting a pretreated cookware base material (made of 304 stainless steel), and placing the outer surface of the base material in a circulating cooling air gas environment, wherein the temperature of cooling gas is below 15 ℃. Then 400-mesh powder of non-stick material is loaded into a powder feeder, and the setting parameters are as follows: the powder feeding speed is 30 g/min; the spraying distance is 90 mm; arc current 550A; and spraying non-stick material powder on the surface of the base material to form the cookware with the corresponding non-stick coating, wherein the hydrogen pressure is 0.3MPa, the hydrogen flow is 8L/min, the argon pressure is 3MPa, and the argon flow is 1200L/min.
The fluorine resin does not resist high temperature, and is generally prepared into coating, then sprayed by an air spray gun and sintered into a non-stick coating, so that the comparative example 3 adopts an air spraying mode to be applied to a cooker, the caliber of the spray gun is 1.2mm, the atomization pressure is 0.3MPa, and the fluorine resin is sintered for 7min at the sintering temperature of 420 ℃.
The pot obtained above was subjected to performance testing and recorded in table 3 below, the specific performance testing method was as follows:
firstly, an initial non-adhesiveness test method: the non-stickiness test method of the fried egg in GB/T32095.2-2015 is an initial non-stickiness test and comprises a first non-stickiness test, a second non-stickiness test and a third non-stickiness test, wherein the first non-stickiness test is the best, and the third non-stickiness test is the worst.
② a method for testing lasting inadhesion: the method for testing the permanent non-stick property in GB/T32388-2015 is characterized in that the unit is times, the higher the times is, the longer the service life is, the 500 times are used for evaluating the non-stick result once, and the times when the non-stick result is used to the grade III are recorded.
Hardness testing method: GB/T4340.1-2009 Vickers hardness test method for metal materials, the unit is HV.
Table 3 performance index test data of the examples and comparative examples of the present application
| Serial number | Initial non-tackiness | Permanent tack-free property | Vickers hardness |
| Example 1 | Ⅱ | 84000 | 550 |
| Example 2 | Ⅱ | 88000 | 620 |
| Example 3 | Ⅱ | 90000 | 660 |
| Example 4 | Ⅱ | 82000 | 530 |
| Example 5 | Ⅱ | 76000 | 480 |
| Example 6 | Ⅱ | 73000 | 450 |
| Example 7 | Ⅱ | 83000 | 540 |
| Comparative example 1 | Ⅲ | - | 380 |
| Comparative example 2 | Ⅲ | - | 350 |
| Comparative example 3 | Ⅰ | 15000 | - |
In conclusion, the non-stick coating obtained from the non-stick material according to the present application enables cookware to have a non-stick effect, to be permanently non-stick and to have a longer non-stick life. In addition, according to the present application, the coating obtained from the non-stick material has a good scratch resistance and allows the cookware to be cleaned using a shovel, a scouring pad or a steel wool or the like.
Although the embodiments of the present application have been described in detail above, those skilled in the art may make various modifications and alterations to the embodiments of the present application without departing from the spirit and scope of the present application. It will be understood that those skilled in the art will recognize modifications and variations as falling within the spirit and scope of the embodiments of the application as defined by the claims.
Claims (14)
1. A non-stick material comprising at least one powder of a composite metal cationic metallate, said composite metal cationic metallate having an amorphous structure, wherein the composite metal cations in said composite metal cationic metallate comprise at least two metal cations.
2. The non-stick material of claim 1 wherein the complex metal cationic metalate comprises at least one of a complex metal cationic titanate, a complex metal cationic chromate, a complex metal cationic manganate, a complex metal cationic ferrite, a complex metal cationic meta-aluminate, a complex metal cationic tungstate, a complex metal cationic molybdate, and a complex metal cationic vanadate.
3. The non-stick material of claim 2 wherein the metal cations include at least one of magnesium ions, aluminum ions, calcium ions, selenium ions, titanium ions, vanadium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions, zinc ions, gallium ions, germanium ions, yttrium ions, zirconium ions, niobium ions, molybdenum ions, technetium ions, indium ions, tin ions, antimony ions, hafnium ions, tantalum ions, and tungsten ions.
4. The non-stick material of claim 1 wherein in each complex metal cation metalate, the percentage of the number of any metal cation to the total number of complex metal cations is greater than or equal to 10% based on the total number of complex metal cations, the sum of the percentages of the number of all complex metal cations being 100%.
5. The non-stick material of claim 1 wherein the non-stick material powder has a particle size in the range of 200 mesh to 800 mesh.
6. The non-stick material of claim 1 further comprising a metallic material forming a film layer on the surface of the composite metal cationic metallate powder, wherein the weight of the metallic material in the non-stick material is 3% -10% of the total weight of the non-stick material, based on the total weight of the non-stick material, and the balance is the composite metal cationic metallate powder.
7. The non-stick material of claim 6 wherein the metallic material comprises at least one of iron and its alloys, zinc and its alloys, aluminum and its alloys, titanium and its alloys, chromium and its alloys, nickel and its alloys, cobalt and its alloys, copper and its alloys, zirconium and its alloys, molybdenum and its alloys, and vanadium and its alloys.
8. A method of making a non-stick material, the method comprising:
melting at least two kinds of metal cation metallate powder to obtain corresponding molten liquid;
processing the molten liquid in an atomization powder preparation mode to obtain corresponding composite metal cation metallate powder, wherein the composite metal cation metallate has an amorphous structure;
wherein, in different kinds of metal cation metalates, the metal acid radical ions are the same, and the metal cations are different;
the non-stick material includes at least one composite metal cationic metallate powder.
9. The method of claim 8 wherein the absolute value of the difference in the radii of any two of said metal cations is greater than or equal to 0.1 times the radius of a hydrogen atom.
10. The method of claim 8 wherein the percentage of the number of any one metal cation to the total number of complex metal cations in each complex metal cation metalate is greater than or equal to 10% based on the total number of complex metal cations, the sum of the percentages of the number of all complex metal cations being 100%.
11. The method of making the non-stick material of claim 8 wherein the metal cation metalate comprises at least one of a titanate, a chromate, a manganate, a ferrite, a meta-aluminate, a tungstate, a molybdate, and a vanadate.
12. The method of making the non-stick material of claim 9 wherein the metal cations include at least one of magnesium, aluminum, calcium, selenium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, yttrium, zirconium, niobium, molybdenum, technetium, indium, tin, antimony, hafnium, tantalum, and tungsten.
13. The method of claim 8 wherein said melt is processed by atomizing to form a powder comprising:
atomizing the molten liquid, wherein in the atomizing treatment, the molten liquid is firstly cooled at a cooling speed of 300-450K/s and is dispersed into liquid drops;
and carrying out secondary cooling on the liquid drop at the cooling speed of 600-1000K/s to obtain the composite metal cation metalate powder.
14. Use of a non-stick material as feedstock for spraying, said non-stick material being a non-stick material according to any of claims 1 to 7 or a non-stick material obtained by a method of preparation of a non-stick material according to any of claims 8 to 13 as non-stick material for cookware.
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