CN114477301B - Non-stick material, preparation method and application thereof - Google Patents
Non-stick material, preparation method and application thereof Download PDFInfo
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- CN114477301B CN114477301B CN202210179840.3A CN202210179840A CN114477301B CN 114477301 B CN114477301 B CN 114477301B CN 202210179840 A CN202210179840 A CN 202210179840A CN 114477301 B CN114477301 B CN 114477301B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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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 metallate 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 disclosed by the application, the non-stick material has better non-stick performance and good scratch resistance, so that the non-stick material has longer non-stick service 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 of the cooker is mainly fluorine paint, the main component of the existing non-stick material is organic fluorine resin material, and the organic fluorine resin material generally has the following defects:
1. is easy to scratch: because the fluororesin is a high polymer material, the hardness is lower, and the surface is easy to scratch when the hard food (such as shells and the like) is stir-fried, so that the cooker base material is exposed.
2. Not resistant to high temperatures: the fluororesin is a high molecular resin, and the fluororesin is easy to be denatured under the high temperature condition for a long time under the high temperature environment to cause failure.
3. The use experience is poor: the hardness is low and is easy to damage, so that the method is not suitable for the conditions of stir-frying, stir-frying and the like, and the use experience is poor.
Therefore, improvements to existing non-stick materials are needed to improve scratch resistance and non-stick effect of non-stick coatings so that a longer non-stick lifetime can be achieved.
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 of poor scratch resistance and short non-stick life caused by a non-stick coating formed by the non-stick material in the prior art.
According to a first aspect of the present application there is provided a non-stick material comprising at least one complex metal cation metallate powder, the complex metal cation metallate having an amorphous structure, the complex metal cations in the complex metal cation metallate comprising at least two metal cations.
In an embodiment, the complex metal cation metallate comprises at least one of complex metal cation titanate, complex metal cation chromate, complex metal cation manganate, complex metal cation ferrite, complex metal cation meta-aluminate, complex metal cation tungstate, complex metal cation molybdate, and complex metal cation vanadate.
In an embodiment, the metal cations 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.
In an embodiment, in each of the complex metal cation metallates, 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, and the sum of the number percentages of all complex metal cations is 100%.
In an embodiment, the particle size of the non-stick material powder is 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 metal acid salt powder, in the non-stick material, the weight of the metal 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 metal acid salt 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, the method comprising melting at least two metal cation metallate powders to obtain corresponding melts; processing the molten liquid in an atomization powder preparation mode to obtain corresponding composite metal cation metal acid salt powder, wherein the composite metal cation metal acid salt has an amorphous structure; wherein, in the metal cation metal acid salts of different types, the metal acid radical ions are the same, and the metal cations are different; the non-stick material comprises at least one complex metal cation metallate powder.
In an embodiment, the absolute value of the difference in radius of any two of the metal cations is greater than or equal to 0.1 times the radius of the hydrogen atom.
In an embodiment, in each of the complex metal cation metallates, 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, and the sum of the number percentages of all complex metal cations is 100%.
In an embodiment, the metal cation metallate comprises at least one of titanate, chromate, manganate, ferrite, meta-aluminate, tungstate, molybdate, and vanadate.
In an embodiment, the metal cations 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.
In an embodiment, the processing the molten liquid by adopting an atomization powder preparation method comprises the steps of performing atomization processing on the molten liquid, wherein the molten liquid is subjected to primary cooling at a cooling speed of 300K/s-450K/s and is dispersed into liquid drops; and (3) cooling the liquid drops for the second time at a cooling speed of 600K/s-1000K/s to obtain the composite metal cation metal acid salt powder.
According to a third aspect of the present application there is provided the use of a non-stick material as a spray 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 thereof, 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 application.
Detailed Description
The inventive concept 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, the non-stick material with certain strength can be realized by taking the metal acid salt as the non-stick material, so that the anti-scratch performance and the non-stick service life are better.
However, the non-stick material needs to have not only a certain strength but also a proper non-stick property, and the metal acid salt is usually in a crystal structure, and the non-stick effect is general, and the metal acid salt needs to be treated in order to improve the non-stick effect.
The inventor finds that the composite metal cation metal acid salt with an amorphous structure is prepared by taking metal acid salt as a framework component, adopting the same metal acid salt of different metal cations as raw materials for smelting and mixing, and cooling. By designing the combination of the raw materials, the duty ratio of the metal cations in the raw materials and the number of the metal cations in the raw materials, the composite metal cation metallate powder can have a higher degree of amorphization. Because the amorphous structure has lower surface energy than the crystal structure, the composite metal cation metal acid salt powder with the amorphous structure can be used as the non-stick material to realize the purpose of cooking non-stick. In addition, the material with the amorphous structure has certain hardness, and can further improve the scratch resistance of the product formed by the non-stick material.
In addition, the inventors have found that in the method for producing a non-stick material, the powder having a higher degree of amorphization can be obtained by controlling the cooling rate during the melting of the complex metal cation metal acid salt powder to form a powder, and by maintaining the solid solution phase of the complex metal cation metal acid salt in a rapid cooling manner, thereby preventing crystallization.
The inventive concept of the present application will be described in detail 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 complex metal cation metallate powder. Wherein the complex metal cation metallate has an amorphous structure, and the complex metal cations in the complex 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 crystal 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 of the present application, one of the above-mentioned complex metal cation metal acid salts may be used as the non-stick material, or a mixture of the above-mentioned complex metal cation metal acid salts may be used as the non-stick material, and the complex metal cation metal acid salts may be mixed arbitrarily to be used as the non-stick material.
Fig. 1 is an XRD pattern of a non-stick material according to an embodiment of the application. Specifically, it may be Al 2 Fe(TiO 3 ) 4 As shown in FIG. 1, the characteristic peaks are not particularly pronounced, the hetero peaks are numerous and disordered, the crystallinity is poor, al 2 Fe(TiO 3 ) 4 The powder showed an amorphous trend, and the amorphous phase content was 87% calculated according to the conventional full spectrum fitting method. In the present application, the amorphous content of the complex metal cation metallate powder is not less than 50%, preferably not less than 65%. The effect of improving the non-tackiness is generally that the amorphous phase content of less than 50%, whereas the non-tackiness can be improved to a great extent by the amorphous phase content of greater than or equal to 50%.
In addition, according to the present application, the metal cations do not include the metal cations in the metal acid ions.
In an embodiment, the species of the complex metal cation metallate may include at least one of complex metal cation titanate, complex metal cation chromate, complex metal cation manganate, complex metal cation ferrite, complex metal cation meta-aluminate, complex metal cation tungstate, complex metal cation molybdate, and complex metal cation vanadate. The metal cations in each of the complex metal cation metallates may include at least two 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. Illustratively, when a complex metal cation salt of Macid, the complex metal cation salt of Macid may comprise aluminum iron Macid or may comprise aluminum iron magnesium Macid. The chemical formula of the aluminum iron magnesium M acid can be Al x Fe y Mg z (MO 3 ) w Wherein 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 z is more than 0 and less than or equal to 3,w, and is determined by the valence state and the mole number of metal cations. The chemical formula of the aluminum iron M acid can beAl x Fe y (MO 3 ) w Wherein 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,w, and is determined by the valence state and the mole number of metal cations. Specifically, the chemical formula of the aluminum iron magnesium titanate can be Al x Fe y Mg z (TiO 3 ) w Wherein, when Fe 3+ When 3x+3y+2z=2w, or when Fe 2+ When 3x+2y+2z=2w.
In an embodiment, in each of the complex metal cation metallates, 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, and the sum of the number percentages of all complex metal cations is 100%.
In the application, in the process of forming the coating by adopting the non-stick material, under the condition of ensuring that the coating can be formed, the flight time is shortened as much as possible, so that more amorphous structures can be reserved in the non-stick material. I.e., the degree of melting of the complex metal cation metallate powder is controlled so that it retains more amorphous phase during the formation of the coating. Specifically, the surface of the composite metal cation metallate powder having an amorphous structure is melted while the inside is incompletely melted, and a non-stick coating having an amorphous structure can be formed, thereby ensuring a non-stick effect.
In practical use, it has been found that, due to the high melting point and poor thermal conductivity of the complex metal cation metal salt powder, when sprayed as a non-stick material, the surface of the complex metal cation metal salt powder melts and the interior is hardly completely melted 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 is slightly affected when sprayed onto the product. In order to improve the bonding force, the non-stick material may include a metal material in addition to the complex metal cation metallate powder on the premise of ensuring non-stick property. Wherein, the metal material forms a film layer on the surface of the composite metal cation metal acid salt 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 based on the total weight of the non-stick material, and the balance is the composite metal cation metal acid salt powder.
According to the non-stick material disclosed by the application, the melting point of the metal material is relatively low, and the heat conductivity is good, so that the metal material can be completely melted in a short time, and the metal material can serve as an adhesive on the surface of the composite metal cation metal acid salt powder by compounding the metal material and the composite metal cation metal acid salt powder to form the non-stick material, so that the binding force between the metal material and a product in the subsequent spraying process can be improved on the premise of ensuring the non-stick property.
In an exemplary embodiment, the metallic material may include at least one of iron and its alloys, zinc and its alloys, aluminum and its alloys, titanium and its alloys, chromium and its alloys, nickel and its alloys, cobalt and its alloys, copper and its alloys, zirconium and its alloys, molybdenum and its alloys, and vanadium and its alloys. However, those skilled in the art can select other suitable materials as binders to promote the bonding of the complex cationic metal salts to the coating formed by the product in light of the teachings of the present application.
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 for preparing a non-stick material, which may comprise the steps of:
and step S101, melting at least two metal cation metallate powders to obtain corresponding melt.
Step S102, treating 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 the metal cation metal acid salts of different types, the metal acid radical ions are the same, and the metal cations are different. The non-stick material comprises at least one complex metal cation metallate powder.
According to the preparation method of the non-stick material, the same metal acid salt of different metal cations is adopted to form the molten liquid, and the molten liquid is treated by an atomization powder preparation method, so that the composite metal cation metal acid salt powder with an amorphous structure can be formed. 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 metal acid salts are usually solid solution phases, which are divided into substitutional solid solutions and interstitial solid solutions, and the solid solutions have lattice distortion effects. The method comprises the steps of forming molten liquid by adopting at least two metal cation metallate powders, processing the molten liquid by an atomization powder preparation method, and forming the low-surface-energy composite metal cation metallate powder by continuously cooling the molten liquid.
The method of preparing a non-stick material according to the present application may include a step of preparing a raw material, which may include at least two metal cation metallate powders. In an embodiment, the raw material has a uniform size and has a spheroid shape so that both can be sufficiently melted in the step of performing melting. According to the present application, the particle size of the powder of the raw material may be selected according to the difference of the melting point, and exemplary, the powder having the melting point of 1000 to 1200 c, the particle size of the selected powder is 300 to 500 mesh, the powder having the melting point of 1200 to 1500 c, the particle size of the selected powder is 500 to 800 mesh, and the higher the melting point, the finer the powder. The corresponding particle size powder can be obtained by ball milling of the raw materials.
The raw material for forming the composite metal cation metal acid salt takes 'metal acid salt' as a framework component, and the composite metal cation metal acid salt also has good hardness and oxidation resistance because the metal acid salt has high hardness and oxidation resistance. Further, non-stick materials formed with at least one complex metal cation metallate also have superior properties. In the raw material of the present application, the metal cation metallate may include at least one of titanate, chromate, manganate, ferrite, meta-aluminate, tungstate, molybdate, vanadate, silicate, and phosphate. The metal cations 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 raw materials according to the application can be obtained commercially or by synthetic methods known in the art.
The preparation method of the raw material according to the present application may be achieved by the following steps, and in particular, the preparation method of the raw material may include: chemical precipitation, liquid phase synthesis, hydrothermal method, solvothermal method and high-temperature solid phase synthesis. The corresponding raw materials are obtained through the method and are purified for later use.
According to the method for preparing a non-stick material of the present application, after the raw materials are selected, the combination of the respective raw materials can be designed such that the metal cations between the raw materials have a relatively large radius difference, thereby enabling to increase the degree of amorphization of the formed complex metal cation metallate. Among the raw materials, the absolute value of the 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.
In addition, according to the present application, the metal cations do not include the metal cations in the metal acid ions.
In addition, in order to enhance the degree of amorphization of the complex metal cation metallate, it is possible to design a combination of individual raw materials forming one complex metal cation metallate, and it is also possible to facilitate formation of a disordered amorphous phase by providing a large variety of metal cations.
In addition, the number ratio of the metal cations in the raw materials can be set so that the finally formed composite metal cation metallate has a certain content of metal cations.
Any two metal cations can be present in the starting material in a molar ratio of between 1:9 and 9:1. According to the present application, in each of the complex metal cation metallates, the percentage of the number of any one metal cation to the total number of complex metal cations is 10% or more, based on the total number of complex metal cations, and the sum of the percentages of the numbers of all complex metal cations is 100%.
Illustratively, the complex metal cation metallate is formed by a first metal cation metallate and a second metal cation metallate, wherein the number of first metal cations is greater than or equal to 10% of the total number of complex metal cations and the number of second metal cations is greater than or equal to 90% of the total number of complex metal cations based on the total number of complex metal cations.
Specifically, feTiO in an amount of 4mol 3 And 3mol of Al 2 (TiO 3 ) 3 Formation of Al 2 Fe(TiO 3 ) 4 In the case that the amount of aluminum ions is 60% of the total amount of aluminum ions among the aluminum ions, the amount of iron ions is 40% of the total amount of aluminum 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 crystal distortion energy is too high to keep the crystal structure, the disordered amorphous phase is easy to form, by setting each metal cation in the raw materials to have a certain duty ratio, in the process of forming the composite metal cation metal acid salt, the proper quantity duty ratio of the metal cations can play a role of the metal cations as doping ions, so that the crystal structure of the metal acid salt is damaged through a plurality of kinds of metal cations, the amorphous structure is easier to form, and further, the lower surface energy can be obtained to improve the non-stick performance.
According to the method for preparing the composite metal cation metallate of the application, the composite metal cation metallate can be obtained by melting two kinds of metallate powder and preparing powder by atomizing, and can also be obtained by melting more kinds of metallate powder and preparing powder by atomizing. The preparation method of the composite metal cation metal acid salt formed by more metal acid salts is different in that more raw materials are added only in the melting process, and other methods are the same as the preparation method of the composite metal cation metal acid salt formed by two metal acid salts. For convenience of description, the method for preparing the non-stick material of the present application will be described below by taking two kinds of metal acid salts as examples to form a complex metal cation metal acid salt.
According to the method for producing a non-stick material of the present application, after two metal cation metallate powders are prepared, next, the two powders are smelted. Specifically, in order to avoid oxidation, the smelting process needs to be performed under the protection of inert atmosphere, the metal cation metal salt powder with a relatively high melting point is heated to be completely melted, then other metal cation metal salt powder with a relatively low melting point is slowly added, and sufficient stirring is needed in the smelting process, so that corresponding molten liquid is obtained. According to the application, the feeding sequence of the powder can be performed according to the sequence from high to low melting point, so that the powder with relatively high melting point can be sufficiently melted, and the operation time can be reduced, thereby improving the working efficiency. According to the application, the preset smelting temperature can be in the range of 1500-2000 ℃, and the smelting time can be 4-8 hours, so that the smelting can be completely carried out.
Then, the powder is prepared by adopting a high-pressure water atomization mode, the molten liquid is put into a water atomization device, and the molten liquid is cooled for the first time at a certain cooling speed under the impact of high-pressure water flow or water mist pressure and is dispersed into liquid drops. Then, the droplets are cooled for the second time at a certain cooling rate, thereby obtaining the complex metal cation metallate powder. According to the present application, the melt is subjected to two cooling stages and by controlling the appropriate cooling rate, the droplets do not reach the formation of a complete crystal structure, thereby tending to form the composite metal cation metalloate powder in an amorphous form. By controlling the proper water pressure to crush the molten liquid to different degrees, the composite metal cation metal acid salt powder with proper granularity can be obtained.
The composite metal cation metal acid salt powder obtained in the past also has a certain amount of moisture, and therefore, the powder needs to be subjected to operations such as drying to remove the moisture. The preparation method of the non-stick material according to the application further comprises the steps of dehydrating and drying the preliminarily obtained composite metal cation metallate powder, thereby obtaining the composite metal cation metallate powder in the form of particles. Since the step of drying is performed at a relatively low temperature, oxidation and the like are not liable to occur, the step of shielding by an inert gas can be omitted during the drying process, and the cost can be saved.
As an example, in step S201, under the protection of argon, high-melting ferrous titanate is added into a high-frequency induction furnace, heated to be molten, then magnesium titanate with a relatively low melting point is added, the melting temperature can be 1700-1900 ℃, and the melting time can be 3-5 h, so that a molten liquid is prepared.
Step S202, a high-pressure water pump is started in advance, and the high-pressure water atomization device starts to work. Pouring the molten liquid obtained in the step S201 into a tundish of a water atomization device, and enabling the molten liquid in the tundish to enter the atomizer through a discharge spout at the bottom of the tundish through beam current. Under the pressure of high-pressure water of the atomizer, the molten liquid is continuously broken up and formed into fine liquid drops, and then falls into cooling liquid in the water atomization device to be quickly solidified into composite metal cation metallate powder. According to an exemplary embodiment of the present application, in order to avoid interference of impurities and oxygen, the high pressure water is purified water, the water pressure is 45MPa to 75MPa, the flow rate of the water is 1500L/min to 3000L/min, inert gas for protection, such as argon, etc., may be added into the atomizer, the pressure is 0.4MPa to 0.6MPa, and the flow rate is 30L/min to 50L/min.
And step S203, dehydrating and drying the atomized composite metal cation metallate powder, wherein the drying temperature is 150-200 ℃.
After the non-stick material is prepared, a powder of a suitable particle size is selected for application to the product to form a non-stick coating. Here, the particle size of the non-stick material powder is in the range of 200 mesh to 800 mesh. The powder size of more than 800 meshes is undersized, the spraying utilization rate is low, and the cost is wasted. The powder with the size smaller than 200 meshes is difficult to melt in the process of spraying, cannot be well adhered to the surface of a product, and can lead to rough surface of a final coating, difficult to carry out after-treatment and relatively poor texture.
In the application, in the process of forming the coating by adopting the non-stick material, under the condition of ensuring that the coating can be formed, the flight time is shortened as much as possible, so that more amorphous structures can be reserved in the non-stick material. I.e., the degree of melting of the complex metal cation metallate powder is controlled so that it retains more amorphous phase during the formation of the coating. Specifically, the surface of the composite metal cation metallate powder having an amorphous structure is melted while the inside is incompletely melted, and a non-stick coating having an amorphous structure can be formed, thereby ensuring a non-stick effect.
In practical use, it has been found that, due to the high melting point and poor thermal conductivity of the complex metal cation metal salt powder, when sprayed as a non-stick material, the surface of the complex metal cation metal salt powder melts and the interior is hardly completely melted 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 is slightly affected when sprayed onto the product.
For this reason, in order to improve the bonding force with the product, the non-stick material according to the present application may improve the bonding force with the product by an appropriate metal material. In the following, another method for preparing the non-stick powder of the present application will be described with reference to specific examples.
In an embodiment, the non-stick material may include a metallic material in addition to the at least one composite metal cation metal acid salt powder, the metallic material forming a film layer on the surface of the composite metal cation metal acid salt powder. The weight ratio of the metal material is lower than 3%, the effect of improving the binding force is difficult to achieve, and the weight ratio of the metal material is higher than 10%, but the non-stick effect of the finally formed coating can be 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 metallate powder.
According to the present application, the metal material and the above-obtained complex metal cation metal acid salt may be mixed in a certain ratio to form a non-stick material. However, in order to ensure that the metal material as the "binder" can exert a better effect in the non-stick material, the metal material may be compounded with the complex metal cation metal acid salt powder so that the metal material is deposited on the surface of the complex metal cation metal acid salt powder to form the non-stick material. Illustratively, a 1 μm to 3 μm film of metallic material may be formed on the surface of the complex metal cation metallate powder by 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 metal acid salt. The specific steps for preparing the non-stick material according to the application are as follows:
s301, sequentially ultrasonically cleaning the composite metal cation metallate powder with acetone, deionized water and absolute ethyl alcohol, drying and then placing the powder in a substrate holder container.
S302, transferring the cleaned powder from the base container to a sample stage of the magnetron sputtering equipment, rapidly closing the vacuum chamber, and vacuumizing to 8.0x10 degrees -4 Pa. Opening an argon bottle tank, opening an air valve, introducing argon, setting the argon flow to be 60sccm through 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 0.5Pa.
S303, adjusting the power of the corresponding metal target, opening the total baffle, and starting sputtering the metal layer.
S304, naturally cooling the composite non-stick material prepared by the process in a vacuum cavity to room temperature to form the non-stick material according to the embodiment of the application.
According to the non-stick material, the melting point of the metal material is relatively low, and the heat conductivity is good, so that the metal material can be completely melted in a short time, the metal material can serve as a binder on the surface of the composite metal cation metal acid salt powder by compounding the metal material and the composite metal cation metal acid salt powder to form the non-stick material, and the binding force between the metal material and a product in the subsequent spraying process 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 an embodiment of the third aspect of the present application there is also provided the use of a non-stick material as a spray feedstock.
Based on the non-stick material of each embodiment, powder with proper particle size can be screened out from the obtained non-stick material to be suitable for different products, and the products according to the embodiment of the application can be containers, cookware and the like.
After the non-stick powder is selected, in a specific application, a thermal spraying mode, taking a supersonic plasma spraying method as an example, can be used for simply describing the spraying mode of the application: step S301, pretreatment of the product surface, including pretreatment modes such as degreasing and cleaning, sand blasting and roughening after surface shot blasting, and the like, so as to enhance the binding force between the product and the non-stick coating. And step S302, placing the 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, loading powder of 200-800 meshes of non-stick materials into a powder feeder, wherein the powder feeding speed is 20-50g/min; the spraying distance is 80-100mm; 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 1000-1500L/min. Under the above parameters, the high pressure plasma flame flow formed at the muzzle heats the surface of the non-stick material to melt, and then rapidly cools and deposits on the surface of the product at a cooling rate of 180-200K/S, forming a 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) having an average particle diameter of 500 mesh 3 ) As the first metal cation metal acid salt powder, magnesium titanate powder (MgTiO) having an average particle diameter of 500 mesh 3 ) As a second metal cation metallate 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 to be molten, 200mol of magnesium titanate powder with relatively low melting point is added, 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 by adopting a water atomization powder preparation mode, so as to obtain non-sticky powder.
The high-pressure water pump is started in advance, so that the high-pressure water atomization device starts to work. Setting working parameters of an atomizer in advance: the high-pressure water is purified water, the water pressure is 60MPa, the flow rate of the water is 2000L/min, the argon protection is started, the pressure of the argon is 0.5MPa, and the flow rate of the argon is 40L/min. After the above work is ready, the melt obtained in step S20 is poured into a tundish of the water atomizing device, and the melt in the tundish passes through the beam and enters the atomizer through a discharge spout at the bottom of the tundish. Under the action of pure 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 to be quickly solidified into composite metal cation metal acid salt powder.
And step S40, drying the formed composite metal cation metal acid salt powder to remove the moisture contained in the powder, wherein the drying temperature is 180 ℃, so that the composite metal cation metal acid salt powder in a particle form is obtained as a non-stick material.
Example 2
Except that three raw materials were prepared in step S10 of supplying the raw materials and sequentially formed into corresponding melts at a molar ratio of 10:8:3 { i.e., aluminum titanate powder (Al was added on the basis of example 1 2 (TiO 3 ) 3 ) And (3) adopt andmethod of example 1 the non-stick material of example 2 was prepared in the same manner.
Example 3
Except that four raw materials were prepared in step S10 of supplying the raw materials and the four raw materials were formed into a melt in a molar ratio of 30:21:7:8 in order { i.e., aluminum titanate powder (Al was added on the basis of example 1 2 (TiO3) 3 ) And copper titanate powder (CuTiO) 3 ) The non-stick material of example 3 was prepared by the same method as that of example 1.
Example 4
Except for using zirconium ferrite Zr 3 (FeO 3 ) 4 And zinc ferrite Zn 3 (FeO 3 ) 2 The non-stick material of example 4 was prepared in the same manner as in example 1, except that instead of the ferrous titanate powder and the magnesium titanate powder, a melt was formed in a molar ratio of 1:1 in sequence.
Example 5
The non-stick material was formed by physical vapor deposition using 5% by weight copper and 95% by weight of the complex metal cation metallate powder obtained in example 1.
Example 6
The non-stick material was formed by physical vapor deposition using 5% by weight of aluminum and 95% by weight of the complex metal cation metallate powder obtained in example 1.
Example 7
The non-stick materials used in examples 1 and 4 were used in accordance with 1:1, and a non-stick material formed by mixing the materials in a weight ratio.
Comparative example 1
Ferrous titanate powder is used as the non-stick material.
Comparative example 2
Magnesium titanate powder is used as a non-stick material.
Comparative example 3
A coating material formed of a fluororesin was used as the non-stick material.
Table 1 parameters of examples and comparative examples of the present application
Performance index test
(1) The non-stick materials of examples 1-7 and comparative examples 1-2 were tested for the degree of amorphization as follows:
the amorphous degree testing method comprises the following steps: XRD testing was used and analytical calculations were performed using conventional full spectrum fitting methods to obtain the degree of amorphism of the samples. The conventional full spectrum fitting method comprises the following steps: firstly, finding a crystalline phase with the same chemical structure as an 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 peak position and intensity of the amorphous phase; secondly, firstly fitting the spectral line of the pure amorphous phase to determine the grain size and microscopic strain; finally, the grain size and microscopic strain were fixed and this phase was included in a conventional Rietveld quantitative calculation to obtain the amorphous content (i.e., the degree of amorphization) and recorded in table 2 below.
Table 2 amorphization degree test data for examples of the present application and comparative examples
| Sequence 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:
the pretreated pan base material (made of 304 stainless steel) is selected, and the outer surface of the base material is placed in a circulating cooling air gas environment, wherein the temperature of cooling air is minus 15 ℃. Then powder of the non-stick material with 400 meshes is filled into a powder feeder, and the parameters are set as follows: powder feeding speed is 30g/min; the spraying distance is 90mm; arc current 550A; the pressure of hydrogen is 0.3MPa, the flow rate of hydrogen is 8L/min, the pressure of argon is 3MPa, the flow rate of argon is 1200L/min, and non-stick material powder is sprayed on the surface of a base material to form a pot with a corresponding non-stick coating.
The fluororesin was not resistant to high temperature, usually, after being prepared into a coating, it was sprayed with an air spray gun and then sintered into a non-stick coating, so that comparative example 3 was applied to a cooker by air spraying, the spray gun caliber was 1.2mm, the atomization pressure was 0.3MPa, and it was sintered at a sintering temperature of 420 ℃ for 7 minutes.
Performance tests were performed on the cookware obtained above and recorded in table 3 below, and the specific performance test method is as follows:
(1) initial tack free test method: the method for testing the non-tackiness of the omelette in GB/T32095.2-2015 is an initial non-tackiness test and is divided into a grade I, a grade II and a grade III, wherein the grade I non-tackiness is optimal, and the grade III non-tackiness is worst.
(2) Persistent tack-free test method: the duration tack free test method in GB/T32388-2015 is in times, the higher the times are, the longer the service life is, the tack free result is evaluated once for 500 times, and the times when the test method is used to III grade are recorded.
(3) The hardness testing method comprises the following steps: GB/T4340.1-2009 metal material Vickers hardness test method, with the unit being HV.
TABLE 3 Performance index test data for examples of the present application and comparative examples
| Sequence number | Initial non-tackiness | Durable non-stick | Vickers hardness of |
| 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 summary, the non-stick coating obtained from the non-stick material according to the present application can realize that the cooker has a non-stick effect, can be permanently non-stick and has a long non-stick life. In addition, according to the present application, the coating obtained from the non-stick material has a good scratch resistance, and the cooker can be cleaned using a spatula, a scouring pad, a wire ball, or the like.
Although embodiments of the present application have been described in detail hereinabove, various modifications and variations may be made to the embodiments of the application by those skilled in the art without departing from the spirit and scope of the application. It will be appreciated that those skilled in the art will appreciate that such modifications and variations will still fall within the spirit and scope of the embodiments of the application as defined by the appended claims.
Claims (12)
1. A non-stick material, characterized in that the non-stick material comprises at least one composite metal cation metallate powder, the composite metal cation metallate has an amorphous structure, the composite metal cations in the composite metal cation metallate comprise at least two of magnesium ions, aluminum ions, calcium ions, titanium ions, manganese ions, iron ions, copper ions, zinc ions, gallium ions and zirconium ions, and the composite metal cation metallate comprises at least one of composite metal cation titanate, composite metal cation chromate, composite metal cation manganate, composite metal cation ferrite, composite metal cation meta-aluminate, composite metal cation tungstate, composite metal cation molybdate and composite metal cation vanadate.
2. The non-stick material of claim 1 wherein the composite metal cation metallate powder has an amorphous content of not less than 50%.
3. The non-stick material of claim 2 wherein the composite metal cation metallate powder has an amorphous content of not less than 65%.
4. The non-stick material of claim 1, wherein in each of the complex metal cation metallates, the percentage of any one metal cation based on the total number of complex metal cations is greater than or equal to 10% of the total number of complex metal cations, and the sum of the percentages of all complex metal cations is 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 cation 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 cation 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 preparing a non-stick material, the method comprising:
melting at least two metal cation metallate powders to obtain corresponding melt;
processing the molten liquid in an atomization powder preparation mode to obtain corresponding composite metal cation metal acid salt powder, wherein the composite metal cation metal acid salt has an amorphous structure;
wherein, in the metal cation metal acid salts of different types, the metal acid radical ions are the same, and the metal cations are different;
the non-stick material comprises at least one composite metal cation metallate powder, the composite metal cation metallate comprises at least one of composite metal cation titanate, composite metal cation chromate, composite metal cation manganate, composite metal cation ferrite, composite metal cation meta-aluminate, composite metal cation tungstate, composite metal cation molybdate and composite metal cation vanadate, and the metal cation of the composite metal cation metallate comprises at least two of magnesium ion, aluminum ion, calcium ion, titanium ion, manganese ion, iron ion, copper ion, zinc ion, gallium ion and zirconium ion.
9. The method for producing a non-stick material according to claim 8, wherein the absolute value of the difference in radius of any two of the metal cations is 0.1 times or more the radius of the hydrogen atom.
10. The method for producing a non-stick material according to claim 8, wherein in each of the complex metal cation metallates, the percentage of any one metal cation to the total number of complex metal cations is 10% or more, and the sum of the percentages of all complex metal cations is 100%, based on the total number of complex metal cations.
11. The method for preparing a non-stick material according to claim 8, wherein the step of treating the molten liquid by atomizing to obtain powder comprises the steps of:
subjecting the melt to an atomization treatment in which the melt is first cooled at a cooling rate of 300-450K/s and dispersed into droplets;
and (3) cooling the liquid drops for the second time at a cooling speed of 600-1000K/s to obtain the composite metal cation metal acid salt powder.
12. Use of a non-stick material as a spray raw material, characterized in that the non-stick material is a non-stick material according to any one of claims 1 to 7 or a non-stick material as a cookware prepared by the method of preparing a non-stick material according to any one of claims 8 to 11.
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