CN111202435A

CN111202435A - Quasicrystal coating, preparation method thereof and cooking utensil

Info

Publication number: CN111202435A
Application number: CN201811299742.3A
Authority: CN
Inventors: 万鹏; 曹达华; 陈炜杰; 钟春发; 屈雪平
Original assignee: Foshan Shunde Midea Electrical Heating Appliances Manufacturing Co Ltd
Current assignee: Foshan Shunde Midea Electrical Heating Appliances Manufacturing Co Ltd
Priority date: 2018-11-02
Filing date: 2018-11-02
Publication date: 2020-05-29

Abstract

The invention provides a quasicrystalline coating, a preparation method thereof and a cooking utensil. The quasicrystalline coating comprises: the quasi-crystal base layer is provided with a plurality of pores on the outer surface; a filler material filled within at least a portion of the pores. Therefore, the filling material is filled in partial pores of the quasicrystal base layer, so that external impurities can be prevented from entering the pores of the quasicrystal base layer to influence the non-adhesiveness and the wear resistance of the quasicrystal coating; moreover, the filling material is filled in the pores of the quasicrystal base layer, so that the filling material cannot be damaged when an external device used in the process of using the quasicrystal coating layer is in contact with the outer surface of the quasicrystal base layer. Therefore, the quasicrystalline coating of the present application has good non-stick and wear resistance, as well as long service life.

Description

Quasicrystal coating, preparation method thereof and cooking utensil

Technical Field

The invention relates to the technical field of quasi-crystal, in particular to a quasi-crystal coating, a preparation method thereof and a cooking utensil.

Background

At present, in order to achieve non-stickiness during cooking, domestic and foreign cookers and inner pots are all provided with non-stick coatings on the inner sides of the inner pots. The most widely used organic fluororesin coating is one having poor durability, and is likely to come off after long-term use, and also to decompose perfluorooctanoic acid (PFOA) or the like harmful to the human body at high temperatures. The quasicrystal has the advantages of high hardness, high corrosion resistance, wear resistance, low surface energy and the like, and the non-adhesiveness of the quasicrystal can be compared favorably with a Teflon (Teflon) coating. However, the pores in the quasicrystalline coating cannot be avoided in the process of spraying to form the quasicrystalline coating, so that residues in food can be accumulated in the pores during cooking, and the non-stickiness of the quasicrystalline coating is reduced.

Therefore, research on quasicrystalline coatings is awaited.

Disclosure of Invention

The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a quasicrystalline coating, which has the advantages of good non-stick property, good wear resistance or long service life.

In one aspect of the invention, the invention provides a quasicrystalline coating. According to an embodiment of the invention, the quasicrystalline coating comprises: the quasi-crystal base layer is provided with a plurality of pores on the outer surface; a filler material filled within at least a portion of the pores. Therefore, the filling material is filled in partial pores on the outer surface of the quasicrystal base layer, so that external impurities can be prevented from entering the pores of the quasicrystal base layer to influence the non-adhesiveness and the wear resistance of the quasicrystal coating; moreover, the filling material is filled in the pores of the quasicrystal base layer, so that the filling material cannot be damaged when an external device used in the process of using the quasicrystal coating layer is in contact with the outer surface of the quasicrystal base layer. Therefore, the quasicrystalline coating of the present application has good non-stick and wear resistance, as well as long service life.

According to an embodiment of the invention, a plurality of said voids are filled with said filler material.

According to an embodiment of the invention, the filler material comprises silicon dioxide.

According to the embodiment of the invention, the particle size of the quasicrystal particles forming the quasicrystal base layer is greater than or equal to 10 nanometers and less than 150 micrometers.

According to the embodiment of the invention, the outer surface of the quasicrystalline substrate is provided with a concave-convex structure, and the height of the protrusions in the concave-convex structure is smaller than the particle sizes of the quasicrystalline particles (1/2-2/3).

According to an embodiment of the invention, the height of the protrusion is larger than the thickness of the filling material within the aperture.

According to an embodiment of the invention, the size of the pores is between 5 and 40 microns.

According to an embodiment of the invention, the quasicrystalline coating further comprises: an aperture-sealing layer formed from a filler material, the aperture-sealing layer disposed on an outer surface of the quasicrystalline substrate.

According to an embodiment of the invention, the thickness of the orifice sealing layer is less than 10 microns at a maximum.

According to an embodiment of the present invention, the quasicrystalline substrate comprises: a first quasicrystalline base layer; the second quasicrystal base layer is arranged on the outer surface of the first quasicrystal base layer, the outer surface of the first quasicrystal base layer is provided with a plurality of pores, the particle size of first quasicrystal particles forming the first quasicrystal base layer is larger than that of second quasicrystal particles forming the second quasicrystal base layer, and the filling material is filled in at least one part of the pores.

According to the embodiment of the invention, the particle size of at least 90% of the quasi-crystal particles in the first quasi-crystal particles is larger than 80 microns and smaller than 150 microns, and the particle size of at least 90% of the quasi-crystal particles in the second quasi-crystal particles is larger than or equal to 10 nanometers and smaller than or equal to 80 microns.

According to an embodiment of the present invention, the quasicrystalline substrate layer satisfies one of the following conditions: the content of the quasicrystal is 20-90 wt%; a porosity of 0.1% or more and 20% or less; the thermal conductivity is 0.1W/mK to 3W/mK; the thickness is 10-500 μm.

In another aspect of the invention, the invention provides a method of making a quasicrystalline coating as described above. According to an embodiment of the invention, the method comprises: spraying the quasicrystal particles to form a quasicrystal base layer; and carrying out hole sealing treatment on the outer surface of the quasicrystal base layer so as to obtain the quasicrystal coating. Therefore, the preparation method is simple, easy to implement and suitable for industrial production, and the filling material is formed in partial pores of the quasicrystal base layer by sealing the quasicrystal base layer, so that external impurities can be prevented from entering the pores of the quasicrystal base layer to influence the non-adhesiveness and the wear resistance of the quasicrystal coating; moreover, because the filling material is filled in the pores of the quasicrystal base layer, the filling material cannot be damaged when an external appliance used is in contact with the outer surface of the quasicrystal base layer in the use process of the quasicrystal coating, and the quasicrystal coating has good non-adhesiveness and wear resistance and long service life.

According to an embodiment of the present invention, the quasicrystalline particles are prepared by the following steps: mixing raw materials including at least two of aluminum, iron, copper, chromium, titanium, nickel and zirconium, and smelting to form an alloy ingot; and carrying out atomization powder preparation treatment on the alloy ingot in vacuum or protective atmosphere so as to obtain the quasicrystal particles.

According to an embodiment of the invention, the alloy ingot comprises one or more of an Al-Cu-Fe alloy, an Al-Cu-Fe-Cr alloy, a Ti-Fe alloy or a Ti-Ni-Zr alloy.

According to an embodiment of the invention, the raw material comprises aluminum, copper, iron and chromium, the aluminum, copper, iron and chromium being in atomic number ratios (60-70): (15-25): (5-15): (5-15) and smelting to form an alloy ingot; and carrying out atomization powder preparation treatment on the alloy ingot in vacuum or protective atmosphere so as to obtain the quasicrystal particles.

According to the embodiment of the invention, before the sealing treatment is performed on the outer surface of the quasicrystal base layer, the method further comprises the following steps: and annealing the quasicrystal base layer in a protective atmosphere or a vacuum environment.

According to an embodiment of the present invention, the sealing treatment includes: coating a sealant on the outer surface of the quasicrystal base layer; and carrying out a crosslinking reaction on the hole sealing agent.

According to an embodiment of the present invention, the hole sealing agent is selected from at least one of a silane coupling agent and a nano-silica precursor.

According to the embodiment of the invention, the flowing-out time of the hole sealing agent is 8-12 seconds by using a No. two viscosity cup of a rock field.

According to the embodiment of the invention, the crosslinking reaction is completed under the condition of heating at 150-200 ℃ for 5-20 min.

In yet another aspect of the present invention, the present invention provides a cooking appliance. According to an embodiment of the invention, the cooking appliance comprises the aforementioned quasicrystalline coating. Because the filling material is filled in partial pores on the outer surface of the quasicrystal base layer, food residues can be prevented from being accumulated in the pores of the quasicrystal base layer, and the non-adhesiveness and the wear resistance of the quasicrystal coating are influenced; moreover, because the filling material is filled in the pores of the quasicrystal base layer, the filling material cannot be damaged when an external appliance is in contact with the outer surface of the quasicrystal base layer in the cooking process of the quasicrystal coating, so that the quasicrystal coating has good non-adhesiveness and wear resistance, and when the cooking appliance cooks food, the food cannot stick to a pot, so that the taste and the attractiveness of the food are improved, and the service life of the cooking appliance is longer. Moreover, it will be understood by those skilled in the art that the cooking appliance has all the features and advantages of the quasicrystalline coating described above and will not be described in detail herein.

Drawings

FIG. 1 is a flow chart of a method for producing a quasicrystalline coating in one embodiment of the present invention.

FIG. 2 is a flow chart of a method for preparing a quasicrystalline coating in another embodiment of the present invention.

FIG. 3 is a flow chart of a method for preparing a quasicrystalline coating in yet another embodiment of the present invention

Detailed Description

The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

It should be noted that the quasicrystalline substrate is formed by quasicrystalline material, and there are gaps, i.e. the above-mentioned pores, between the crystal grains of the quasicrystalline material. The term "outer surface" as used herein refers to the exposed surface of the quasicrystalline substrate layer during use of the quasicrystalline coating, such as when the quasicrystalline coating is used in a cooking appliance, the outer surface of the quasicrystalline substrate layer refers to the inner surface of a cookware, the surface that comes into contact with food.

According to the embodiment of the invention, in order to better avoid the foreign matters from being accumulated in the pores of the quasicrystal base layer, a plurality of pores at the outer surface of the quasicrystal base layer are filled with the filling material. Therefore, external impurities can be better prevented from entering and being gathered in the pores of the quasicrystal base layer, and the non-adhesiveness of the quasicrystal coating is further improved.

According to an embodiment of the invention, the filler material comprises silicon dioxide in order to ensure the safety of use of the quasicrystalline coating. From this, the quasi-crystal coating is friendly to the environment, and the safety in utilization is high, and when this quasi-crystal coating was applied to cooking utensil, the quasi-crystal coating had better high temperature resistance, also did not have any potential safety hazard when culinary art under high temperature, and filling material also can not receive the influence of high temperature.

According to the embodiment of the invention, the outer surface of the quasicrystalline substrate layer is provided with the concave-convex structure, and the height of the convex in the concave-convex structure is smaller than the particle sizes of the quasicrystalline particles (1/2) - (2/3). Therefore, the height of the protrusions on the outer surface of the quasicrystal base layer is appropriate, so that external appliances can be prevented from contacting with the filling material, and the protrusions can be prevented from being too high and affecting the non-adhesiveness of the quasicrystal coating.

According to an embodiment of the present invention, the protrusion height is greater than the thickness of the filling material for higher protection of the filling material from the outside. Therefore, external appliances can be better prevented from contacting the filling material, and the filling material is prevented from being damaged.

According to an embodiment of the present invention, the shape of the pores is selected from at least one of a cube, a sphere, a hemisphere, a cylinder, and a cone. Therefore, the filling material with different shapes is filled into the pores on the outer surface of the quasicrystal base layer, and the combination of the pores and the filling material is improved.

According to an embodiment of the invention, the size of the pores is between 5 and 40 microns. Because the surface energy of the quasicrystal is lower, the non-stick performance is good, the raw material for forming the filling material is difficult to coat in the pores, and the capillary adsorption effect can be formed on the filling material within the size range of the pores of the quasicrystal, so that the filling material is easy to adsorb in the pores.

According to an embodiment of the present invention, the quasicrystalline coating further comprises an aperture sealing layer formed of a filling material, the aperture sealing layer being disposed on an outer surface of the quasicrystalline base layer. Thereby, the pores of the entire outer surface of the quasicrystalline substrate can be filled with the filler particles.

According to the embodiment of the invention, in the using process, in order to avoid peeling of the hole sealing layer on the protrusions of the concave-convex structure and further cause the extraction of the filling material in the pores, the maximum thickness of the hole sealing layer is less than 10 microns. In some embodiments of the present invention, the thinnest sealing layer is located on the protrusions, i.e., the thickness of the sealing layer on the protrusions is less than 10 microns. Therefore, the thickness of the filling material on the bulge is small, the peeling phenomenon cannot occur, and the filling material in the hole cannot be pulled out by the filling material on the bulge.

According to the embodiment of the invention, in order to improve the compactness of the quasicrystal substrate, the particle size of the quasicrystal particles forming the quasicrystal substrate is greater than or equal to 10 nanometers and less than 150 micrometers, such as 10 nanometers, 50 nanometers, 100 nanometers, 200 nanometers, 300 nanometers, 400 nanometers, 500 nanometers, 700 nanometers, 900 nanometers, 1 micrometer, 5 micrometers, 10 micrometers, 20 micrometers, 50 micrometers, 80 micrometers, 100 micrometers, 120 micrometers, 140 micrometers or 150 micrometers. Therefore, the quasicrystal base layer has good compactness, is beneficial to improving the non-adhesiveness of the quasicrystal coating, and ensures that the protrusion height of the outer surface of the quasicrystal base layer is appropriate; and the quasi-crystal particles within the particle size range prevent the roughness of the quasi-crystal base layer from being relatively large, namely, the protrusions on the outer surface are too high, so that the non-adhesiveness of the quasi-crystal coating is reduced, and prevent the protrusions on the outer surface of the quasi-crystal base layer from being relatively too low, so that the filling material is likely to contact with an external appliance in the using process of the quasi-crystal coating, and the filling material is further damaged.

According to the embodiment of the invention, in order to obtain a denser quasicrystal coating and improve the utilization rate of quasicrystal particles, the quasicrystal base layer comprises: a first quasicrystalline base layer; the second quasicrystal base layer is arranged on the outer surface of the first quasicrystal base layer, the outer surface of the first quasicrystal base layer is provided with a plurality of pores, the particle size of first quasicrystal particles forming the first quasicrystal base layer is larger than that of second quasicrystal particles forming the second quasicrystal base layer, and the filling material is filled in at least one part of the pores. Therefore, the first quasicrystal base layer formed by the large-particle-size first quasicrystal particles can further improve the utilization rate of the quasicrystal particles, and the first quasicrystal base layer has certain porosity which can further reduce the thermal conductivity of the coating, so that the surface temperature of the whole quasicrystal coating is more uniform, the non-adhesiveness of the coating can be improved, and moreover, the preparation cost of the large-particle-size quasicrystal particles is lower, so that the consumption cost of the whole process is reduced; however, the porosity has a great influence on the corrosion resistance, so that a second more dense quasi-crystal base layer is sprayed on one surface of the first quasi-crystal base layer, so that the corrosion resistance and the compactness of the quasi-crystal coating finally obtained are improved, and the quasi-crystal coating formed by the quasi-crystal particles with small particle sizes is better in non-stickiness.

According to the embodiment of the invention, in order to obtain a denser quasicrystal coating and improve the utilization rate of quasicrystal particles, at least 90% of the quasicrystal particles in the first quasicrystal particles have particle sizes larger than 80 micrometers and smaller than 150 micrometers, and at least 90% of the quasicrystal particles in the second quasicrystal particles have particle sizes larger than or equal to 10 nanometers and smaller than or equal to 80 micrometers. Therefore, the quasicrystal coating with good compactness, corrosion resistance, non-adhesiveness and other properties can be obtained, the production cost of the quasicrystal coating can be reduced, and meanwhile, the outer surface of the quasicrystal base layer can be ensured to be provided with the protrusions with proper height.

According to an embodiment of the present invention, the quasicrystalline substrate layer satisfies one of the following conditions:

the content of the quasicrystal is 20 wt% to 90 wt%, for example, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt% or 90 wt%. Therefore, the quasi-crystal coating can be ensured to have better non-adhesiveness;

the porosity is greater than or equal to 0.1% and less than or equal to 20%, such as 0.1%, 0.5%, 1.0%, 5%, 7%, 10%, 13%, 15%, 18%, or 20%. Therefore, stress concentration can be reduced and cracks of the quasicrystal base layer can be avoided due to reasonable pores in the quasicrystal base layer, but when the porosity in the quasicrystal base layer is greater than 20%, the hardness and the wear resistance of the quasicrystal base layer can be greatly reduced, so that the durability of the quasicrystal base layer is reduced;

the thermal conductivity is 0.1W/mK to 3W/mK, such as 0.1W/mK, 0.5W/mK, 1.0W/mK, 1.5W/mK, 2.0W/mK, 2.5W/mK or 3W/mK. When the quasicrystal base layer is arranged on the metal base body, as the thermal conductivity of the metal base body is very high, if the thermal conductivity of low-carbon steel exceeds 50W/mK, when the quasicrystal base layer is applied to a pot, a pot body and the pot bottom generate temperature difference to cause the bottom pasting and the pot sticking, the thermal conductivity of the quasicrystal base layer is lower and ranges from 0.1W/mK to 3W/mK, therefore, the quasicrystal base layer is coated on the metal base body and equivalently a protective layer is arranged on the surface of the pot, the heat is uniformly distributed on the surface of the pot due to the characteristic of low thermal conductivity of the quasicrystal base layer, and the problem;

the thickness is 10 microns to 500 microns, such as 10 microns, 20 microns, 50 microns, 75 microns, 100 microns, 125 microns, 150 microns, 175 microns, 200 microns, 250 microns, 300 microns, 350 microns, 400 microns, 450 microns, or 500 microns. Because the quasicrystal base layer has the characteristics of high hardness and high wear resistance, when cleaning tools such as an iron shovel, a scouring pad and the like are used for cleaning for a long time, the quasicrystal base layer cannot be damaged and fall off, and the pot body can be endowed with permanent non-adhesiveness, but the thickness of the quasicrystal base layer has great influence on the heat conductivity of the surface of the pot body, the quasicrystal base layer cannot be uniformly heated when being too thin, the outer surface structure of the quasicrystal base layer is loose and the pores are increased when the quasicrystal base layer is too thick, and the coating hardness, the wear resistance and the non-adhesiveness are reduced, so the thickness of the quasicrystal base layer in the embodiment of the invention is 10-500 micrometers, and thus, the quasicrystal coating can be ensured to have a good uniform heating effect, and the problems of the loose outer surface structure.

In another aspect of the invention, the invention provides a method of making a quasicrystalline coating as described above. According to an embodiment of the present invention, referring to fig. 1, the method includes:

s100: and spraying the quasicrystal particles to form a quasicrystal base layer.

According to the embodiment of the present invention, the specific material of the substrate is not limited as long as it has sufficient strength to allow the quasicrystalline particles to be sprayed on the surface thereof. In some embodiments of the invention, the substrate is a metal substrate of (low) carbon steel, aluminum alloy, stainless steel or iron, or a ceramic substrate or a metal composite substrate. Therefore, the substrate has enough strength to bear the pressure during spraying, so that the quasicrystal coating can be applied to the pot body or the inner container of the cooking utensil and is arranged on the inner surface of the pot body or the inner container to be directly contacted with food, and the non-stick performance of the pot body or the inner container is improved. According to an embodiment of the present invention, referring to fig. 2, the quasicrystalline particles are prepared by the following steps:

s110: mixing raw materials including at least two of aluminum, iron, copper, chromium, titanium, nickel and zirconium, and smelting to form an alloy ingot;

according to an embodiment of the invention, the alloy ingot comprises one or more of an Al-Cu-Fe alloy, an Al-Cu-Fe-Cr alloy, a Ti-Fe alloy or a Ti-Ni-Zr alloy. Thus, the quasicrystal content is high.

According to the embodiment of the invention, the aluminum, the copper, the iron and the chromium are mixed according to the atomic number ratio of (60-70): (15-25): (5-15): (5-15) and smelting to form an alloy ingot. The quasicrystal base layer prepared by mixing aluminum, copper, iron and chromium has higher quasicrystal content which can reach 20-90%, so that the finally obtained quasicrystal coating has better non-adhesiveness.

According to the embodiment of the invention, the quasicrystal obtained by the method has five-time rotational symmetry or ten-time rotational symmetry characteristics. Therefore, the quasicrystal has the special quasi-periodic arrangement characteristics, the crystal grains of the quasicrystal cannot be arranged in the whole space, and the coating surface formed by the quasicrystal is provided with the concave-convex structure with micron-scale or micro-nanometer-scale gaps formed by the crystal grains, so that the structure can play an excellent hydrophobic role and has a good non-sticking effect.

According to an embodiment of the present invention, the grain shape of the quasicrystal is an icosahedron or a rhombohedral shape (ten-order quasicrystal). Therefore, when the quasicrystal contains the crystal grains with the shapes of icosahedron or rhombohedra, the quasicrystal has a more compact structure, so that the quasicrystal has higher hardness, wear resistance, scratch resistance, corrosion resistance, longer service life and better non-stick performance, and the coating containing the quasicrystal has better service performance.

S120: and carrying out atomization powder preparation treatment on the alloy ingot in vacuum or protective atmosphere so as to obtain quasicrystal particles.

According to an embodiment of the present invention, in the atomization pulverization process, the alloy ingot is melted into a liquid at 1000 to 1200 ℃, and then the melted liquid is impacted or otherwise broken into fine droplets by a rapidly moving fluid (atomizing medium), followed by condensation into a solid powder, i.e., quasicrystalline particles. Therefore, the method has mature process, is easy to operate and is easy for industrial production.

According to embodiments of the present invention, in addition to the above-mentioned methods of the present application, a person skilled in the art may obtain the quasicrystalline particles by a conventional preparation method in the art, such as a conventional casting method, a rapid solidification method, a mechanical alloying method, a deep undercooling preparation technique, a gas atomization method, a czochralski method, a float zone method, a magnetron sputtering or vapor deposition method, and the like.

According to an embodiment of the invention, before the thermal spraying, further comprising: and spheroidizing the crystal particles. Therefore, the powder yield of the quasicrystal particles is improved in the subsequent spraying step. According to the embodiment of the invention, in order to ensure that the projections are formed on the outer surface of the quasicrystal base layer and further improve the powder yield of the raw material during spraying, the particle size of the quasicrystal particles is greater than or equal to 10 nanometers and less than 150 micrometers, and specifically, the quasicrystal particles with the particle size of greater than or equal to 10 nanometers and less than 150 micrometers can be obtained by screening (for example, screening by using a screen of 50-200 meshes) after spheroidizing. Therefore, the powder discharging rate of the quasicrystal particles is optimal during spraying, the outer surface of the formed quasicrystal base layer is provided with protrusions with proper height, if the particle size of the quasicrystal particles is too large, the powder discharging is not facilitated, the size of the quasicrystal particles which can not be melted during spraying is larger, if the quasicrystal particles which can not be melted are sprayed on the outer surface of the primary coating, the protrusions on the surface of the quasicrystal base layer are too high, the non-adhesiveness of the quasicrystal coating can be relatively reduced, if the particle size of the quasicrystal particles is too small, the protrusion height on the outer surface of the quasicrystal base layer is too low, the filling material is likely to be contacted with an external appliance in.

According to the embodiment of the invention, in order to improve the adhesion of the quasicrystalline particles on the substrate, a step of cleaning the surface of the substrate may be further included before spraying, and the specific method for cleaning is not limited as long as the stain, oil stain or rust on the surface of the substrate can be cleaned to meet the requirement of spraying. In the embodiment of the invention, the surface of the substrate can be cleaned and dried by adopting the modes of alcohol, trichloroethylene or pure water and ultrasonic waves, and the like, and the surface of the substrate cannot have rust and the like before spraying, so that the adhesion of the quasicrystal particles on the substrate can be greatly improved after the spraying after the cleaning. In some embodiments of the present invention, after the cleaning step, the surface of the substrate may be subjected to sand blasting to roughen the surface of the substrate in order to further improve the adhesion of the quasicrystalline particles on the substrate and prolong the service life of the quasicrystalline coating.

According to the embodiment of the invention, the specific manner of spraying to form the quasicrystalline substrate is not limited, and the quasicrystalline substrate can be cold spraying or thermal spraying. In some embodiments of the present invention, the application employs thermal spraying, i.e., heating quasicrystalline particles to a molten or semi-molten state and spraying them at high velocity onto the substrate surface to form a firmly attached quasicrystalline substrate layer, the thermal spraying being selected from plasma spraying, flame spraying (e.g., oxy-ethylene flame powder spraying, oxy-acetylene flame wire spraying, oxy-acetylene flame spray welding, supersonic flame spraying), or arc spraying. Therefore, the method not only has mature process, easy operation and easy industrial production, but also can obtain the quasicrystal substrate with better performance. The quasi-crystal base layer is prepared in a spraying mode, the outer surface of the quasi-crystal base layer has certain roughness, so that the outer surface has a protruding structure, and after filling particles are formed in the subsequent process, the filling particles in the pores of the quasi-crystal base layer can be protected from being influenced by external appliances due to the protruding structure.

According to the embodiment of the invention, when the plasma spraying is adopted, the plasma spraying is completed under at least one of the following conditions: the power is 15-50 KW, such as 15KW, 20KW, 25KW, 30KW, 35KW, 40KW or 50KW, the main air flow is 40-60L/min, such as 40L/min, 45L/min, 50L/min, 55L/min or 60L/min, the auxiliary air flow is 10-30L/min, such as 10L/min, 15L/min, 20L/min, 25L/min or 30L/min, and the powder feeding amount is 10-20 g/min, such as 10g/min, 15g/min or 20 g/min. Therefore, the quasicrystal base layer with better performance can be formed. It should be noted that, since aluminum (Al) is partially ablated during plasma spraying, the content of Al in the raw material is higher than that in the final quasicrystalline base layer.

According to an embodiment of the present invention, referring to fig. 3, after the thermal spraying and before the sealing process, the method further includes step S130: and annealing the crystal base layer in a protective atmosphere or a vacuum environment. In the annealing process, the amorphous phase converted by spraying in the quasicrystal base layer is converted into quasicrystal again at high temperature, and the quasicrystal crystal seed in the quasicrystal base layer also grows up in the annealing process to form quasicrystal crystal grains, so the quasicrystal content in the quasicrystal base layer can be greatly improved by annealing treatment, the non-adhesiveness of the quasicrystal coating is greatly improved, and the problem that in the thermal spraying process, due to the fact that the flame temperature is extremely high, most of the quasicrystal grains can undergo the melting and solidification processes, and most of the quasicrystal is converted into the amorphous phase in the process, and the quasicrystal content in the quasicrystal base layer.

According to the embodiment of the invention, in order to obtain the quasicrystal base layer with higher quasicrystal content on the basis of ensuring the quality of the quasicrystal base layer, the annealing temperature is 600 ℃ to 800 ℃, such as 600 ℃, 650 ℃, 700 ℃, 750 ℃ or 800 ℃, and it is noted that the annealing temperature refers to the heat preservation temperature in the annealing process. Therefore, annealing within the temperature range can not only convert the amorphous phase in the primary coating, which is converted by spraying, into quasicrystal at high temperature, but also enable the quasicrystal crystal seeds in the primary coating to grow into quasicrystal crystal grains, and furthermore, the quality of the quasicrystal base layer cannot be influenced; if the temperature is lower than 600 ℃, the speed of converting the amorphous phase into the quasicrystal is relatively slow, and long time is consumed to completely convert the amorphous phase into the quasicrystal, so that the quasicrystal content in the quasicrystal coating is improved compared with that of the quasicrystal base layer before annealing treatment; if the temperature is higher than 800 ℃, although the content of the quasicrystal in the quasicrystal base layer can be greatly increased, in the annealing process, the quasicrystal base layer has relatively high thermal stress, and the quasicrystal base layer is cracked due to the high thermal stress, so that the quality and the service performance of the quasicrystal base layer are seriously influenced, and the non-adhesiveness of the finally obtained quasicrystal coating is also influenced.

S200: and carrying out hole sealing treatment on the outer surface of the crystal base layer so as to obtain the quasi-crystal coating.

According to an embodiment of the present invention, in order to secure edible safety of the quasicrystalline coating layer, the sealing agent for sealing treatment is selected from at least one of a silane coupling agent and a nano-silica precursor. Therefore, the two hole sealing agents are converted into inorganic particles after hole sealing treatment, namely inorganic silicon (silicon oxide grids are formed after the silane coupling agent reacts and are disordered silicon dioxide; nano silicon dioxide particles are formed after the nano silicon dioxide precursor reacts) is filled in the holes in the quasicrystal base layer, so that external impurities are prevented from entering the holes in the quasicrystal base layer to influence the non-adhesiveness of the quasicrystal base layer, the non-adhesiveness and the service life of the quasicrystal coating are further improved, the silicon dioxide is environment-friendly and high in use safety, when the quasicrystal coating is applied to cooking appliances, the quasicrystal coating has good high-temperature resistance, no potential safety hazard is caused during cooking at high temperature, the filling material is not influenced, and the safety of food is guaranteed.

According to an embodiment of the present invention, the sealing treatment includes:

s210: and coating the hole sealing agent on the outer surface of the quasicrystal base layer.

The specific method of coating is not limited according to the embodiment of the present invention, and those skilled in the art can flexibly select the method according to actual requirements. In the embodiment of the invention, a spin coating method is adopted, so that the sealant can be uniformly coated on the outer surface of the quasicrystal base layer, the pores on the outer surface of the quasicrystal base layer are filled with the inorganic silicon obtained by conversion after hole sealing treatment, and further, external impurities can be better prevented from entering and being gathered in the pores of the quasicrystal base layer, and the non-adhesiveness of the quasicrystal coating is further improved.

According to the embodiment of the invention, in the preparation process, the sealant is inevitably coated on the protrusion structure on the outer surface of the quasi-crystal base layer, so that the hole sealing layer formed by filling particles is formed on the outer surface of the quasi-crystal base layer, and thus, the pores on the outer surface of the quasi-crystal base layer are ensured to be filled with the filling particles, but when the hole sealing layer on the protrusion is contacted with an external appliance for a long time, the thicker hole sealing layer can generate a peeling phenomenon, and then the filling material in the pores is pulled out, so that in order to prevent the peeling phenomenon, the thickness of the hole sealing layer on the protrusion is thinner, in the preparation process, the smaller the viscosity of the sealant is, the thinner the thickness of the hole sealing layer on the protrusion is, and in addition, the thickness can be controlled by adjusting the rotary eccentricity of rotary coating. Therefore, the thickness of the hole sealing layer on the protrusion is controlled within 10 micrometers by the two methods, so that the hole sealing layer on the protrusion can be prevented from peeling, and the filling material in the hole can be prevented from being pulled out by the hole sealing layer on the protrusion.

According to the embodiment of the invention, the viscosity of the sealant is tested by using a viscosity cup No. II of a rock field, and the flowing-out time of the sealant is 8 seconds to 12 seconds (the longer the flowing-out time is, the larger the viscosity is). Therefore, the hole sealing agent can enter pores, so that the hole sealing agent is firmly combined with the quasicrystal base layer; if the viscosity of the sealant is too high, the fluidity is relatively poor, and further the filling material may not completely fill the pores on the outer surface of the quasicrystalline base layer; due to the hydrophobicity of the quasicrystalline coating, if the viscosity of the sealant is too low, the wetting of the sealant is relatively unfavorable, and the effect of filling the pores of the filler material is still affected.

S220: so that the hole sealing agent generates a cross-linking reaction. Wherein the crosslinking reaction is completed under the condition of heating at 150-200 ℃ for 5-20 min. Therefore, the hole sealing agent is converted into inorganic silicon after cross-linking reaction to form silica grids or nano silica which is filled in the pores of the quasicrystal base layer. Taking silane coupling agent as an example, the silane coupling agent is cross-linked to form silica grids, so that disordered silicon dioxide is obtained.

According to the embodiment of the invention, the method for preparing the quasicrystal coating is simple, easy to implement and suitable for industrial production, and the filling material is formed in part or all of the pores on the outer surface of the quasicrystal base layer by sealing the quasicrystal base layer, so that external impurities can be prevented from entering the pores of the quasicrystal base layer to influence the non-adhesiveness and the wear resistance of the quasicrystal coating; moreover, as the filling material is filled in the pores of the quasicrystal base layer, the filling material cannot be damaged when an external appliance used in the use process is in contact with the outer surface of the quasicrystal base layer; and when the quasicrystal base layer formed by thermal spraying has certain roughness on the surface, namely the surface of the quasicrystal base layer is provided with protrusions, so that an external appliance used in the use process of the quasicrystal coating is in contact with the protrusions of the quasicrystal base layer, the filling material in the pores can be further protected from being damaged by the external appliance, and the quasicrystal coating is further ensured to have good non-adhesiveness and wear resistance and long service life.

According to the embodiment of the present invention, the method for preparing a quasi-crystal coating can be used for preparing the quasi-crystal coating, wherein the requirements of the alignment crystal substrate layer, the hole sealing layer and the filling material are the same as those described above, and detailed description is omitted here.

In yet another aspect of the present invention, the present invention provides a cooking appliance. According to an embodiment of the invention, the cooking appliance comprises the aforementioned quasicrystalline coating. Because the filling material is filled in partial or all pores on the outer surface of the quasicrystal base layer, food residues can be prevented from being accumulated in the pores of the quasicrystal base layer, and the non-adhesiveness and the wear resistance of the quasicrystal coating are influenced; moreover, because the filling material is filled in the pores of the quasicrystal base layer, the filling material cannot be damaged when the cooking utensil is in contact with the outer surface of the quasicrystal base layer in the cooking process, so that the quasicrystal coating has good non-adhesiveness and wear resistance, the food cannot stick to a pot when the cooking utensil cooks the food, the taste and the attractiveness of the food are improved, and the service life of the cooking utensil is longer. Moreover, it will be understood by those skilled in the art that the cooking appliance has all the features and advantages of the quasicrystalline coating described above and will not be described in detail herein.

According to the embodiment of the invention, the specific type of the cooking appliance is not limited, and those skilled in the art can flexibly select according to actual needs:

in some embodiments of the present invention, the cooking appliance is a pot comprising: a pot body; the quasi-crystal coating is arranged on the inner surface of at least one part of the cookware body, and the outer surface of the quasi-crystal base layer in the quasi-crystal coating is far away from the cookware body. The pot is at least one selected from a frying pan, a stew pan and a milk pan.

In other embodiments of the present invention, the cooking appliance includes an inner container, the inner container including: a liner body; the quasi-crystal coating is arranged on the inner surface of at least one part of the liner body, and the outer surface of the quasi-crystal base layer in the quasi-crystal coating is far away from the liner body. The cooking appliance is any cooking appliance with an inner container, for example, the inner container can be an inner container of an electric cooker or an autoclave.

Of course, it will be understood by those skilled in the art that the cooking appliance includes the necessary structures or components of the conventional cooking appliance, such as the wok, in addition to the quasicrystal coating and the body, and the handle, etc.; taking an electric cooker as an example, the electric cooker comprises a cooker body, a base, a steam valve, a cooker cover, an electric heating plate, an operation interface and other structures or components besides the inner container.

Examples

Example 1

The steps for preparing the quasicrystalline coating are as follows:

1. according to the atomic number ratio, Al: cu: fe: cr 64: 20: 8: 8, smelting aluminum, copper, iron and chromium to form an alloy ingot;

2. atomizing to prepare powder: and preparing the quasicrystal particles by adopting powder preparation equipment in a vacuum or protective atmosphere environment.

3. Spheroidizing: and spheroidizing and screening the quasicrystal particles to obtain the quasicrystal particles with the particle size of more than or equal to 10 nanometers and less than 150 micrometers.

4. Cleaning the surface of a substrate: cleaning and drying the surface of the matrix by adopting modes of alcohol, trichloroethylene or pure water and ultrasonic waves, so that the surface of the matrix has no rust before plasma spraying, and then performing sand blasting to coarsen the surface of the matrix.

5. Plasma spraying: and (2) spraying the surface of the substrate by adopting plasma spraying to form a quasicrystal base layer, wherein the spraying power is 15-50 KW, the main air flow is 40-60L/min, the auxiliary air flow is 10-30L/min, and the powder delivery amount is 10-20 g/min.

6. Annealing: and annealing the quasicrystal base layer in vacuum or protective atmosphere at 600-800 ℃.

7. Hole sealing treatment: selecting a silane coupling agent as a hole sealing agent, uniformly coating the hole sealing agent on the outer surface of the quasicrystal base layer by using a rotary coating method, and drying at 150-200 ℃ for 5-20 minutes to react the hole sealing agent to obtain the quasicrystal coating.

Comparative example 1

The steps for preparing the quasicrystalline coating are as follows:

6. Annealing: and annealing the quasicrystal base layer in vacuum or protective atmosphere at the annealing temperature of 600-800 ℃ to obtain the quasicrystal coating.

The substrates in example 1 and comparative example 1 were all mild steel, 25.4 mm in diameter and 4 mm thick; the hydrophobic angle of the quasicrystalline coatings obtained in example 1 and comparative example 1 was measured using a hydrophobic angle tester and the results are shown in Table 1, wherein the larger the hydrophobic angle, the better the non-tackiness, which was measured using the fried egg non-tackiness test method and standard according to the standard in GB/T32095-. The non-tackiness of the quasicrystalline coatings obtained just as prepared in example 1 and comparative example 1, respectively, and the non-tackiness of the quasicrystalline coatings after six months of use, respectively, were measured by the above-mentioned test methods

Table 1 test results of quasicrystalline coatings obtained in example 1 and comparative example 1

Through detection, after the quasicrystalline coating in the comparative example 1 is used for a period of time, external pollutants are accumulated in pores of the quasicrystalline coating, and the non-adhesiveness of the quasicrystalline coating is influenced.

In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.

Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims

1. A quasicrystalline coating, comprising:

the quasi-crystal base layer is provided with a plurality of pores on the outer surface;

a filler material filled within at least a portion of the pores.

2. The quasicrystalline coating according to claim 1, characterized in that a plurality of said voids are filled with said filler material.

3. The quasicrystalline coating according to claim 1, characterized in that the filler material comprises silicon dioxide.

4. The quasicrystalline coating according to claim 1, characterized in that the particle size of the quasicrystalline particles forming the quasicrystalline base layer is greater than or equal to 10 nm and less than 150 μm.

5. The quasicrystalline coating layer according to claim 4, characterized in that the quasicrystalline substrate layer has a relief structure on its outer surface, and the height of the projections in the relief structure is smaller than (1/2) - (2/3) of the particle size of the quasicrystalline particles.

6. The quasicrystalline coating according to claim 1, wherein the height of the protrusions is greater than the thickness of the filler material within the pores.

7. The quasicrystalline coating according to claim 1, characterized in that the size of the pores is between 5 and 40 microns.

8. The quasicrystalline coating of claim 1, further comprising: an aperture-sealing layer formed from a filler material, the aperture-sealing layer disposed on an outer surface of the quasicrystalline substrate.

9. The quasicrystalline coating according to claim 8, characterized in that the thickness of the capping layer is less than 10 microns at maximum.

10. The quasicrystalline coating according to claim 1, wherein the quasicrystalline base layer comprises:

a first quasicrystalline base layer;

a second quasicrystal base layer disposed on an outer surface of the first quasicrystal base layer, the outer surface of the first quasicrystal base layer having a plurality of the pores,

wherein the grain size of the first quasicrystal grains forming the first quasicrystal base layer is larger than that of the second quasicrystal grains forming the second quasicrystal base layer, and the filling material is filled in at least one part of the pores.

11. The quasicrystalline coating according to claim 10, wherein at least 90% of the quasicrystalline particles in the first quasicrystalline particles have a particle size greater than 80 microns and less than 150 microns, and at least 90% of the quasicrystalline particles in the second quasicrystalline particles have a particle size greater than or equal to 10 nm and less than or equal to 80 microns.

12. The quasicrystalline coating according to claim 1, characterized in that said quasicrystalline base layer fulfils one of the following conditions:

the content of the quasicrystal is 20 to 90 weight percent;

a porosity of 0.1% or more and 20% or less;

the thermal conductivity is 0.1W/mK to 3W/mK;

the thickness is 10-500 μm.

13. A method of preparing a quasicrystalline coating as claimed in any one of claims 1 to 12, comprising:

spraying the quasicrystal particles to form a quasicrystal base layer;

and carrying out hole sealing treatment on the outer surface of the quasicrystal base layer so as to obtain the quasicrystal coating.

14. The method of claim 13, wherein the quasicrystalline particles are prepared by:

mixing raw materials including at least two of aluminum, iron, copper, chromium, titanium, nickel and zirconium, and smelting to form an alloy ingot;

and carrying out atomization powder preparation treatment on the alloy ingot in vacuum or protective atmosphere so as to obtain the quasicrystal particles.

15. The method of claim 14, wherein the alloy ingot comprises one or more of an Al-Cu-Fe alloy, an Al-Cu-Fe-Cr alloy, a Ti-Fe alloy, or a Ti-Ni-Zr alloy.

16. The method of claim 14, wherein the raw material comprises aluminum, copper, iron, and chromium in an atomic ratio of (60-70): (15-25): (5-15): (5-15) and smelting to form an alloy ingot.

17. The method according to any one of claims 13 to 16, wherein before the sealing treatment of the outer surface of the quasicrystalline substrate, further comprising: and annealing the quasicrystal base layer in a protective atmosphere or a vacuum environment.

18. The method of claim 13, wherein the sealing process comprises:

coating a sealant on the outer surface of the quasicrystal base layer;

and carrying out a crosslinking reaction on the hole sealing agent.

19. The method of claim 18, wherein the sealing agent is selected from at least one of a silane coupling agent and a nanosilica precursor.

20. The method of claim 18 or 19, wherein the flow-out time of the sealant is 8-12 seconds using a viscosity cup for petrographic field number two.

21. The method of claim 18, wherein the crosslinking reaction is performed by heating at 150-200 ℃ for 5-20 min.

22. A cooking appliance comprising the quasicrystalline coating of any one of claims 1 to 12.