CN115161580B - Non-stick coating, preparation method thereof and cookware comprising non-stick coating - Google Patents
Non-stick coating, preparation method thereof and cookware comprising non-stick coating Download PDFInfo
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- CN115161580B CN115161580B CN202111051023.1A CN202111051023A CN115161580B CN 115161580 B CN115161580 B CN 115161580B CN 202111051023 A CN202111051023 A CN 202111051023A CN 115161580 B CN115161580 B CN 115161580B
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- 238000000576 coating method Methods 0.000 title claims abstract description 177
- 239000011248 coating agent Substances 0.000 title claims abstract description 176
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000010410 layer Substances 0.000 claims abstract description 136
- 238000007751 thermal spraying Methods 0.000 claims abstract description 84
- 239000000758 substrate Substances 0.000 claims abstract description 68
- 239000000843 powder Substances 0.000 claims abstract description 63
- 238000005507 spraying Methods 0.000 claims abstract description 47
- 230000007704 transition Effects 0.000 claims abstract description 37
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 33
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- 238000002844 melting Methods 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract description 21
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- 238000000034 method Methods 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000012790 adhesive layer Substances 0.000 claims description 13
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
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- 238000007750 plasma spraying Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
- A47J36/00—Parts, details or accessories of cooking-vessels
- A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
- A47J36/025—Vessels with non-stick features, e.g. coatings
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/131—Wire arc spraying
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Food Science & Technology (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
The application provides a non-stick coating, a preparation method thereof and a pot comprising the non-stick coating, wherein the preparation method comprises the following steps: forming a thermal spray coating by thermally spraying an alloy powder on a surface of a substrate; carrying out heat preservation on the thermal spraying coating; completely melting the surface layer of the thermal spraying coating after heat preservation by adopting laser remelting, so that the thermal spraying coating is formed to comprise a melting layer and a transition layer; the melted layer is rapidly cooled to form a non-stick layer having an amorphous structure on the surface of the substrate. The non-stick coating obtained by the preparation method has good wear resistance, lasting non-stick property and good binding force with the matrix, and has low requirements on the preparation process.
Description
Technical Field
The present application relates to the field of kitchen appliances, and more particularly, to a non-stick coating, a method of preparing the same, and a pot including the same.
Background
Since the non-stick pan is used, the phenomenon that the traditional pan sticks to the food frequently occurs in the cooking process can be avoided because the non-stick pan can not stick the food to the pan bottom when cooking the food, so that the food is prevented from being burnt, and the problem of generating harmful substances caused by the burnt food can be avoided. Moreover, the non-stick pan not only reduces the cleaning difficulty of the pan, but also can fry and cook foods easily, and can avoid the traditional pan from needing more grease to prevent food from sticking to the pan, thereby reducing the oil consumption to the maximum extent, reducing the fat intake of people, and conforming to the consumption trend of modern pursuing low fat and low heat. Therefore, the non-stick pan is the first choice for many families.
Cookware in the market is mainly achieved by coating a non-stick layer on the inner surface of the cookware, wherein fluorine paint, ceramic paint and organic silicon resin paint are common non-stick layers. Although fluorine paint, ceramic paint and organic silicon resin paint can be used as non-stick layers of cookware, the problems are obvious in the use process. For example, a non-stick layer formed of a fluorine paint is not abrasion-resistant and easily decomposes out harmful substances at high temperatures; the non-adhesive layer formed by the ceramic paint has poor lasting non-adhesive property and is easy to fall off after being used for 3-6 months; the non-stick layer formed of the silicone resin coating is easily yellowing or graying under the conditions of high temperature or open flame, and the non-stick layer is reduced in hardness at high temperature, and is easily subjected to the phenomenon of "back sticking".
Disclosure of Invention
To address one or more of the above problems, the present invention provides a non-stick coating having durable non-stick and abrasion resistance.
To this end, a first aspect of the present application is to provide a method of preparing a non-stick coating.
A second aspect of the present application is to provide a non-stick coating.
A third aspect of the present application is to provide a cookware comprising a non-stick coating.
To achieve the above object, an embodiment of the first aspect of the present application provides a method for preparing a non-stick coating, including the steps of: forming a thermal spray coating by thermally spraying an alloy powder on a surface of a substrate; carrying out heat preservation on the thermal spraying coating; completely melting the surface layer of the thermal spraying coating after heat preservation by adopting laser remelting, so that the thermal spraying coating is formed to comprise a melting layer and a transition layer; the melted layer is rapidly cooled to form a non-stick layer having an amorphous structure on the surface of the substrate. The preparation method can avoid the crystallization phenomenon of the amorphous structure in the process of forming the non-stick coating containing the amorphous structure by adopting the thermal spraying of the alloy powder containing the amorphous structure, reduces the requirements of the thermal spraying process and the requirements on the raw material alloy powder selection, reduces the preparation cost to a certain extent, has simple preparation process of the non-stick coating, and is easy to realize batch production.
In some embodiments, the rapid cooling step may be performed using liquid nitrogen, wherein in the rapid cooling step, the cooling rate may be not less than 10 4 K/s. Under the condition, atoms in the melting layer can be quickly frozen down, and crystallization of the atoms in the melting layer is avoided, so that an amorphous state in the melting layer is cooled to form an amorphous structure, and finally, the non-adhesive layer containing the amorphous structure is obtained.
In some embodiments, in the maintaining step, the maintaining temperature may be 350 ℃ to 450 ℃ and the maintaining time may be at least 20 minutes. Through the heat preservation mode, the thermal stress in the thermal spraying coating is reduced, the thermal spraying coating cannot expand and contract freely due to the fact that the thermal stress is too large in the thermal spraying coating is avoided, and therefore the thermal spraying coating is prevented from cracking when the melting layer is cooled to form the non-stick layer, and finally the obtained non-stick coating is prevented from cracking, falling and other problems.
In some embodiments, the thermal spray coating may have a thickness of 100 μm to 800 μm, wherein the melt layer may be formed to have a thickness of 30% to 60% of the thermal spray coating thickness. In this embodiment, the laser remelts only the surface layer of the thermal spraying coating, and the remelted surface layer forms a molten layer, so that the problem that the thermal spraying coating and the substrate deform due to a large temperature difference between the molten layer and the substrate when the molten layer is cooled to form a non-stick layer is avoided, and therefore, the thickness of the molten layer is smaller than that of the thermal spraying coating, and the problem that the formed non-stick coating falls off in the use process due to the reduction of the binding force between the thermal spraying coating and the substrate can be prevented to a certain extent.
In some embodiments, the alloy powder may have a particle size of 300 to 800 mesh. The alloy powder with the granularity range can be heated and melted to form a thermal spraying coating during thermal spraying, and the formed thermal spraying coating has good compactness and low impurity content.
In some embodiments, the alloy powder may include at least one of stainless steel powder, zr alloy powder, cu alloy powder, al alloy powder, mg alloy powder, ti alloy powder, and equiatomic ratio high entropy alloy powder.
In some embodiments, the alloy powder may include stainless steel powder and/or zirconium alloy powder. The alloy powder in the embodiment has strong amorphization capability, is favorable for obtaining the non-adhesive layer with high amorphous structure content, further reduces the surface energy of the non-adhesive layer, and ensures that the obtained non-adhesive coating shows excellent non-adhesion.
In some embodiments, the substrate may be a substrate of a pot.
Embodiments of the second aspect of the present application provide a non-stick coating comprising: the transition layer is positioned on the surface of the substrate and has a crystal structure; the non-adhesive layer is positioned on the surface of the transition layer, the non-adhesive layer has an amorphous structure, the thickness of the non-adhesive layer is 30% -60% of the total thickness of the non-adhesive coating, and the transition layer and the non-adhesive layer have the same constituent elements. According to the embodiment, the transition layer is arranged between the non-stick layer and the substrate, and the transition layer buffers the temperature difference between the melt layer and the substrate when the melt layer is cooled to form the non-stick layer, so that deformation between the thermal spraying coating and the substrate caused by overlarge temperature difference is avoided, the bonding force between the thermal spraying coating and the substrate is kept unchanged to a certain extent, and the service life of the prepared non-stick coating is prolonged.
In some embodiments, the thermal spray coating may have a thickness of 100 to 800 μm. The non-stick coating formed by the thermal spraying coating in the range of the embodiment has good wear resistance, and meanwhile, the problem that the substrate and the coating are inconsistent in thermal expansion coefficient and easy to crack due to the fact that the temperature difference is large when the melting layer is cooled and converted into the non-stick layer is avoided, and defects such as cracks caused by thermal stress due to the fact that the coating is too thick and heat is easy to gather are avoided.
Embodiments of the third aspect of the present application provide a non-stick coating comprising a substrate and the above.
Drawings
Fig. 1 shows a schematic diagram of the preparation of a non-stick coating according to the present application.
Reference numerals illustrate:
110-thermal spray coating, 120-liquid nitrogen, 130-substrate.
Detailed Description
The inventive concept will now be described more fully hereinafter.
The principle of realizing nonstick of nonstick pan mainly has three aspects: (1) the surface of the pot itself has low surface energy; (2) The surface of the pot is provided with a microscopic concave-convex structure which forms a surface similar to the water and oil repellent performance of lotus leaves; (3) The surface of the pan is coated with a porous oil storage material to form a stable oil film, and the formed oil film is utilized to realize nonstick pan.
The inventor finds that the amorphous alloy (namely, the liquid metal with an amorphous structure) has lower surface energy and good non-adhesiveness compared with the common material in the research process of different materials; further analysis of the cause of the generation by the inventors found that the amorphous alloy exhibited low surface energy because the amorphous alloy had an amorphous structure having long-range disordered, short-range ordered amorphous structure characteristics.
In this regard, the inventors realized that the cookware was tack-free by attaching a layer of coating having an amorphous structure to the inner surface of the cookware. It has been found through experiments that the non-stick coating containing the amorphous structure can be formed by spraying the alloy powder with the amorphous structure on the inner surface of the pot in a thermal spraying manner, but the non-stick of the formed non-stick coating can be changed along with the thermal spraying conditions, and the non-stick of the non-stick coating can be reduced to a certain extent. Further studies on the reason for the decrease in the non-tackiness of the non-tacky coating formed by thermal spraying have found that, because the amorphous structure in the alloy generally has a tendency to crystallize with an increase in the temperature of thermal spraying and an increase in the time of spraying during thermal spraying, the ratio of amorphous structure in the obtained non-tacky coating is decreased, so that the surface energy of the non-tacky coating is increased, resulting in a decrease in the non-tackiness of the non-tacky coating; therefore, when the alloy powder containing the amorphous structure is sprayed on the surface of the pot base body in a thermal spraying mode to form a non-stick coating, the requirement on the thermal spraying process is high.
The application provides a preparation method of a non-stick coating. The method of preparing the non-stick coating according to the present application will be described in detail below in connection with fig. 1. Fig. 1 shows a schematic diagram of the preparation of a non-stick coating.
According to the present application, a method of preparing a non-stick coating may include the steps of: spraying alloy powder on the surface of a substrate by adopting a thermal spraying process, so as to form a thermal spraying coating on the surface of the substrate; carrying out heat preservation on the formed thermal spraying coating; completely melting the surface layer of the thermal spraying coating after heat preservation by adopting laser remelting to form a melting layer; the melted layer is rapidly cooled to form a non-stick coating having an amorphous structure on the surface of the substrate.
In an embodiment of the present application, the substrate may be a substrate of a pot. The surface of the substrate may be pretreated, for example, cleaned, before performing the thermal spraying to roughen the surface of the substrate, thereby enhancing the bonding force between the substrate and the non-stick layer to be formed.
According to embodiments of the present application, the alloy powder forming the thermal spray coating may be crystalline alloy powder or amorphous alloy powder. According to some embodiments of the present application, the alloy powder may include at least one of stainless steel powder, zr alloy powder, cu alloy powder, al alloy powder, mg alloy powder, ti alloy powder, and equiatomic ratio high entropy alloy powder. According to the present application, the thermal spray coating may be formed on the inner surface of the pot substrate by thermal spraying. Preferably, stainless steel powder and/or Zr alloy powder may be used. The amorphization ability of the alloy powder is strong, and the amorphization cooling speed is low; the stronger the amorphization ability of the alloy powder, the easier it is to obtain an alloy with a high amorphous content. The thermal spray process may include plasma spray, however, the present application is not limited thereto and one skilled in the art may select an appropriate thermal spray process to form the thermal spray coating under the teachings of the present inventive concept.
According to embodiments of the present application, the particle size of the alloy powder may be 300 mesh to 800 mesh. Specifically, if the alloy powder is too coarse, the powder is insufficiently melted by heat in the flight process during thermal spraying, and the deformation is small when reaching the surface of the substrate, so that the thermal spraying coating formed by thermal spraying is not compact, and defects such as poor wear resistance and lasting non-tackiness are easily generated; on the other hand, if the alloy powder is too fine, the alloy powder is liable to be excessively burned and oxidized during the thermal spraying, so that a large amount of oxide impurities may be introduced into the formed thermal spray coating to deteriorate the performance of the thermal spray coating.
According to embodiments of the present application, the thickness of the thermal spray coating formed on the surface (e.g., inner surface) of the substrate (e.g., pot substrate) may be in the range of 100 μm to 800 μm. Because thermal stress usually exists in the coating formed by thermal spraying, if the thermal spraying coating is too thick, the coating is easy to generate heat aggregation in the preparation process and the use process of the pot to generate thermal stress, and the thermal spraying coating is caused to generate defects such as cracks, and therefore, the thickness of the thermal spraying coating cannot exceed 800 mu m. On the other hand, if the thickness of the thermal spray coating is less than 100 μm, chipping is likely to occur due to the fact that the thickness of the coating is too thin and the wear life is poor, and the thermal expansion coefficient of the substrate and the coating is not uniform due to a large temperature difference at the time of the rapid cooling for amorphization transition. Further, in the present embodiment, the thermal spraying process may be a plasma spraying process.
According to embodiments of the present application, after forming a thermal spray coating on a surface on which a substrate is formed and before performing laser reflow, the coating needs to be insulated. In particular, thermal stress is usually present in the coating formed by thermal spraying, and the thermal stress will cause the thermal spraying coating to be unable to expand and contract freely, so that the thermal spraying coating cracks and falls off, and therefore, the thermal stress in the thermal spraying coating is weakened by adopting a heat preservation mode. That is, the thermal spray coating is thermally insulated for a period of time after the thermal spray coating is formed, so that thermal stresses in the thermal spray coating are slowly released during the thermal insulation, thereby eventually completely or substantially releasing or minimizing thermal stresses in the thermal spray coating, and further preventing cracks from being generated in the thermal spray coating when a molten layer formed by laser remelting is subsequently cooled to form a non-stick layer. According to embodiments of the present application, the thermal spray coating may be incubated for at least 20 minutes to release thermal stresses in the thermal spray coating as much as possible.
In some embodiments of the present application, the soak temperature may be controlled between 350 ℃ and 450 ℃. Specifically, according to the application, the temperature of the just-formed thermal spraying coating can be 550-650 ℃, if the heat preservation temperature is lower than 350 ℃, the heat dissipation of the surface of the thermal spraying coating is fast due to the large temperature difference between the heat preservation temperature and the temperature of the thermal spraying coating, the difference of the thermal expansion rate between the surface of the thermal spraying coating and the interior of the thermal spraying coating is large, and finally, the thermal stress in the thermal spraying coating cannot be eliminated; and if the holding temperature is too high (above 650 ℃), the economical efficiency is poor. Thus, the temperature used to insulate the thermal spray coating may be in the range of 350 ℃ to 450 ℃.
According to embodiments of the present application, laser remelting may be performed after the thermal spray coating formed on the surface of the substrate is incubated. Specifically, the laser is mainly used for remelting the surface layer of the thermal spraying coating, so that the remelted surface layer in the coating forms a molten layer, the molten layer is converted into an amorphous tissue layer in a subsequent process, and the bottom layer of the coating is an unmelted area serving as a transition layer. In this embodiment, the original crystalline structure in the surface layer of the thermal spray coating is destroyed by laser remelting, so that the thermal spray coating tends to be amorphous, and the non-adhesive layer containing the amorphous structure can be formed by cooling the molten layer in the amorphous state. The thermal spraying coating with a certain thickness is reserved as the transition layer during laser remelting, and the transition layer can form buffer between the melting layer and the matrix when the melting layer is cooled, so that the problem that the thermal spraying coating and the matrix deform due to large temperature difference is avoided, and therefore, the transition layer at least keeps the bonding force between the thermal spraying coating and the matrix unchanged to a certain extent, and the formed non-stick coating is prevented from falling off in the use process.
In some embodiments according to the present application, the thickness of the melt layer may optionally be controlled to be 30% to 60% of the total thickness of the thermal spray coating. If the thickness of the melt layer is too large, the thickness of the transition layer may be too small, resulting in an insignificant cushioning effect; if the thickness of the melt layer is too small, the thickness of the amorphized layer is too small, resulting in poor wear life of the non-stick coating, and the transition layer of this thickness avoids the problem that too small a thickness of the transition layer results in an insignificant cushioning effect.
According to a preferred embodiment of the present application, the step of laser remelting the surface layer of the thermal spray coating may employ the following parameters: the laser power is 500W-2 KW, the diameter of the light spot is 3 mm-10 mm, the lap joint rate is 40% -50%, the gas protection method is argon protection, and the scanning rate is 10 m/min-15 m/min.
According to the embodiment of the application, after the surface of the thermal spraying coating layer is formed into the molten layer, the molten layer is quenched (i.e., rapidly cooled), and in the process, atoms in the molten layer gradually lose kinetic energy along with the reduction of temperature, so as to prevent the crystallization of the molten layer, and finally, the atoms in the molten layer are frozen down, so that the non-adhesive layer with an amorphous structure is formed. According to some embodiments of the present application, the step of rapidly cooling the melt layer may be performed using liquid nitrogen. According to the preferred embodiment of the invention, the cooling rate of the molten layer can be controlled to be equal to or greater than 10 4 K/s. As shown in FIG. 1, a molten layer formed on the surface of a thermal spray coating 110 on a substrate 130 may be quenched with liquid nitrogen 120. However, the present application is not so limited and one skilled in the art may choose to quench the melt layer with other media under the teachings of the present application. Here, when liquid nitrogen is selected to cool the molten layer, cooling conditions for the molten layer include: the flow rate of the liquid nitrogen is 6-12L/min, and the pressure is 0.1MPa, and the flow rate of the liquid nitrogen refers to the flow rate of the liquid nitrogen sprayed out from a nozzle with the diameter of 10 mm.
The non-stick coating formed on the surface (e.g., inner surface) of the substrate according to the above method includes an alloy coating layer (i.e., a transition layer) which is not remelted on the surface of the substrate and a non-stick layer which is formed by cooling a melt layer and has an amorphous structure on the transition layer, so that the obtained non-stick coating layer has a non-stick effect.
According to the method, the problem of amorphous turning crystallization in the process of forming the non-stick coating containing the amorphous structure by adopting the amorphous alloy powder through thermal spraying can be avoided, so that the non-stick layer prepared by adopting the method has high amorphous content, low surface energy, excellent non-stick property and reduced requirement on a thermal spraying process. In addition, since an amorphous alloy (i.e., a liquid metal having an amorphous structure) does not have structural defects such as grain boundaries, twins, lattice defects, dislocations, and faults, as in a crystalline alloy, and does not have heterogeneous phases, precipitates, segregation, and other component fluctuations, it is a disordered structure having a high degree of uniformity in chemistry, and does not have plastic deformation such as grain boundary sliding when subjected to an external force, and has higher strength. Thus, the obtained non-stick coating exhibits excellent abrasion resistance as well as durable non-stick properties.
The present application provides a non-stick coating that may be formed on the inner surface of a pot. Referring to fig. 1, the non-stick coating may include: a transition layer (not shown) on the surface of the substrate 130, the transition layer having a crystal structure; and a non-stick layer (not shown) on the surface of the transition layer, the non-stick layer having an amorphous structure, the thickness of the non-stick layer being 30% to 60% of the total thickness of the non-stick layer, wherein the transition layer and the non-stick layer have the same constituent elements. According to the application, the transition layer is arranged between the non-stick layer and the substrate, so that buffering can be formed when the non-stick layer is prepared, deformation of the coating formed by thermal spraying and the substrate due to overlarge temperature difference when the melting layer forming the non-stick layer is rapidly cooled is avoided, the bonding force between the thermal spraying coating and the substrate is kept unchanged to a certain extent, and the service life of the prepared non-stick coating is prolonged. In addition, the non-stick layer and the transition layer are formed by the same thermal spraying coating, so the non-stick layer and the transition layer are integrated.
The present application will be described in detail with reference to specific embodiments.
Example 1
The preparation of the non-stick coating comprises the following steps:
step C1, preparation of thermal spraying coating
Firstly, cleaning a substrate by using a surfactant Ackesu 226SA, drying, and then carrying out sand blasting on the surface of the substrate, wherein the roughness Ra of the surface of the substrate after sand blasting is 3 mu m.
And secondly, preheating the matrix subjected to sand blasting by adopting a heating furnace, and preheating the matrix to 260 ℃.
Finally, stainless steel powder (commercially available common 316 stainless steel powder) with the granularity of 300 meshes is sprayed on the inner surface of the matrix by adopting a plasma spraying mode to form a thermal spraying coating with the thickness of 160 mu m, and parameters during plasma spraying are as follows: powder feeding speed is 35g/min; the spraying distance is 148mm; arc current 520A; the hydrogen pressure is 0.5MPa, and the flow is 7.5L/min; argon pressure is 0.8MPa, and flow is 50L/min.
Step C2 preparation of non-stick layer
First, the formed thermal spray coating was incubated at a temperature of 350℃for 20min.
Secondly, carrying out laser remelting on the surface layer of the thermal spraying coating after heat preservation, wherein the thickness of the melting layer is 30% of that of the thermal spraying coating; the conditions of laser remelting are as follows: laser power: 1.1KW; spot size: the diameter of the light spot is 7mm; overlap ratio: 45%, gas protection method: argon protection; scanning rate: 12m/min.
Finally, the melt layer was treated with liquid nitrogen at 2.1X10 4 The cooling rate of K/s is cooled to form a non-stick layer having an amorphous structure, thereby obtaining a non-stick coating layer including a transition layer and a non-stick layer.
Example 2
A non-stick coating was prepared in the same manner as in example 1, except that the following conditions were different: the stainless steel powder used in the step C1 has the granularity of 800 meshes and forms the thermal spraying coatingThe thickness of the layer was 790 μm; the thermal spray coating in step C2 was maintained at 420℃for 75 minutes with a molten layer of 58% of the thickness of the thermal spray coating, and 3.4X10 g with liquid nitrogen 4 The cooling rate of K/s cools the melt layer.
Example 3
A non-stick coating was prepared in the same manner as in example 1, except that the following conditions were different: the granularity of the stainless steel powder in the step C1 is 600 meshes, and the thickness of the formed thermal spraying coating is 500 mu m; the thermal spraying coating in the step C2 has a heat preservation temperature of 400 ℃ and a heat preservation time of 75min, and the thickness of the melting layer is 45% of the thickness of the thermal spraying coating.
Example 4
A non-stick coating was prepared in the same manner as in example 1, except that the following conditions were different: the granularity of the stainless steel powder in the step C1 is 600 meshes, and the thickness of the formed thermal spraying coating is 650 mu m; the thermal spray coating in step C2 was maintained at a temperature of 370℃for 60 minutes, the thickness of the molten layer was 50% of the thickness of the thermal spray coating, and 2.4X10 g by liquid nitrogen 4 The cooling rate of K/s cools the melt layer.
Comparative example 1
A non-stick coating was prepared in the same manner as in example 4, except that the thermal spray coating was not incubated in step C2.
Comparative example 2
Except that liquid nitrogen was used in step C2 to produce a liquid nitrogen concentration of 0.7X10 4 A non-stick coating was prepared in the same manner as in example 4, except that the melt layer was cooled at a cooling rate of K/s.
Comparative example 3
A non-stick coating was prepared in the same manner as in example 4, except that the thermal spray coating was entirely remelted with a laser in step C2.
Comparative example 4
Preparation of the first coating:
firstly, a substrate is washed by an alkaline solvent, and after washing and drying, sand blasting is carried out on the surface of the substrate, and the roughness Ra of the surface of the substrate after sand blasting is 3 mu m.
Secondly, preheating the body substrate after sand blasting by adopting a heating furnace, and preheating the body substrate to 260 ℃.
Finally, stainless steel powder with the granularity of 600 meshes is sprayed on the surface of the substrate by adopting a plasma spraying mode, so that a first coating is formed on the surface of the substrate, the thickness of the formed first coating is 325 mu m, and parameters during plasma spraying are the same as those in the embodiment 1.
Preparation of the second coating:
and after the temperature of the first coating is reduced to 280 ℃, carrying out plasma spraying on Fe40-Zr25-Cr9-B6-Cu15-Y5 amorphous alloy with the granularity of 600 meshes on the surface of the first coating, forming a second coating with an amorphous structure on the surface of the first coating, wherein the thickness of the second coating is 325 mu m, and finally obtaining the non-stick coating comprising the first coating and the second coating.
Performance index test
The properties of the non-stick coatings prepared in examples 1 to 4 and comparative examples 1 to 4 were tested and the test results are described in table 1 below.
(1) Tack-free detection
The non-tackiness of the non-tackiness coating is detected by adopting a non-tackiness test method of the non-tackiness coating in national standard GB/T32095 according to a omelette non-tackiness test therein. The adhesion between the omelette and the coating was checked and the non-tackiness of the coating was rated as follows:
excellent (goodo): the plastic shovel can be used for taking out the eggs without damage and leaving residues.
Good (verygood): the eggs cannot be removed without damage by a plastic spatula, but residues can be removed by a wet sponge.
Difference (x): the residue cannot be removed by gently wiping with a wet sponge.
(2) Permanent tack-free detection
The durable non-tackiness test is carried out by referring to a planar abrasion resistance test method in GB/T32095.2, an egg frying test is carried out once every 1000 times of grinding, the test is finished when the egg frying is subjected to a grade of 'poor (X)' twice successively, and the abrasion resistance times are recorded.
(3) Wear resistance detection
The abrasion resistance times of the non-stick coating through the exposed bottom are recorded by referring to the method for testing the plane abrasion resistance in GB/T32095.2.
(4) Binding strength detection
The bond strength between the non-stick coating prepared in the above examples and comparative examples and the substrate was analyzed by a cold and hot impact method, and the specific test method is as follows: the non-stick coated substrate was first heated to 260 c and incubated for 30 minutes, then immediately placed in cold water at 20 c, wherein heating, incubation and cooling were used as a cycle. The standard of the enterprise cookware is that the heat and cold impact is that no damage exists between the 50-time circulating coating and the matrix and the enterprise cookware is qualified.
TABLE 1 Performance index test results
As can be seen from example 4 and comparative example 1 in table 1, the bonding force between the non-stick coating formed after the thermal spray coating was kept warm and the pot substrate was better. As can be seen from examples 4 and 2 in Table 1, when the cooling rate is too low, the abrasion resistance and the long-lasting non-tackiness of the formed non-tacky coating are significantly reduced, because, when the cooling rate is too low, the disturbed atoms in the molten layer are crystallized, and the content of the crystal structure in the formed non-tacky layer is high, resulting in a reduction in the abrasion resistance and the long-lasting non-tackiness of the prepared non-tacky coating. As can be seen from examples 4 and 3 in table 1, the bonding strength between the non-stick coating layer formed after the thermal spray coating layer was entirely laser remelted and the substrate was small because there was no transition layer as a buffer when the laser remelted coating layer was cooled, deformation occurred between the coating layer and the substrate due to a large temperature difference, and the bonding force between the obtained non-stick coating layer and the substrate was weakened.
As can be seen from example 4 and comparative example 4 in table 1, the non-stick coating prepared by the present application is better in both of the durable non-stick property, the abrasion resistance and the bonding strength with the substrate than the non-stick coating prepared by comparative example 4, for mainly two reasons, on one hand, the transition layer and the non-stick layer in the non-stick coating prepared in the present example are formed of the same thermal spray coating, while the first coating and the second coating in the non-stick coating in the comparative example are formed separately by plasma spraying, resulting in poor bonding force between the non-stick coating and the substrate in comparative example 4; on the other hand, the non-stick layer in the non-stick coating layer in the present application is formed by cooling the melt layer, and has a higher amorphous content, whereas the second coating layer in comparative example 4 is crystallized by using a part of amorphous structure in the alloy powder during the plasma spray forming process, resulting in all reduction of the wear resistance and the durable non-stick property of the formed non-stick coating layer.
From the above table 1, it can be seen that the non-stick coating prepared by the method described herein exhibits superior non-stick, abrasion resistance, durable non-stick properties, and better bond strength to the substrate. The reason is that the bonding force between the non-stick coating provided with the transition layer and the matrix is better, because the transition layer reduces the deformation of the coating and the matrix caused by the larger temperature difference between the coating and the matrix when the non-stick layer is prepared, the bonding force between the thermal spraying coating and the matrix is kept unchanged to a certain extent, and the formed non-stick coating and the matrix show excellent bonding strength. In addition, the thermal stress in the thermal spraying coating is reduced by heat preservation, and the non-stick coating in service is observed, so that the non-stick coating prepared after heat preservation is not easy to crack.
According to the above description, the non-stick coating and the preparation method thereof of the present application have the following advantages:
(1) Remelting the surface layer of the formed thermal spraying coating, cooling the melting layer to form an non-stick layer with an amorphous structure, wherein the formed non-stick layer has higher amorphous content and lower surface energy, produces a good non-stick effect, and simultaneously reduces the requirement of a plasma spraying process. In addition, the preparation of the non-stick coating in the application has the characteristics of simple process and easy realization of mass production.
(2) The non-stick coating further comprises a transition layer, and the transition layer is arranged between the non-stick layer and the substrate, so that the deformation of the thermal spraying coating and the substrate caused by the large temperature difference between the thermal spraying coating and the substrate during the preparation of the non-stick coating is reduced, and the formed non-stick coating is firmly attached to the substrate. In addition, the thermal stress in the thermal spraying coating is reduced by adopting a heat preservation mode in the preparation process of the non-stick coating, so that the thermal spraying coating is prevented from cracking when the melting layer is cooled to form the non-stick layer, and the service time of the non-stick coating is prolonged.
While certain embodiments have been shown and described, it will be appreciated by those skilled in the art that changes and modifications may be made in these embodiments (e.g., different features described in the different embodiments may be combined) without departing from the principles and spirit of the application, the scope of which is defined in the claims and their equivalents.
Claims (8)
1. A method for preparing a non-stick coating, the method comprising the steps of:
forming a thermal spray coating by thermally spraying an alloy powder on a surface of a substrate;
carrying out heat preservation on the thermal spraying coating;
completely melting the surface layer of the thermal spraying coating after heat preservation by adopting laser remelting, so that the thermal spraying coating is formed to comprise a melting layer and a transition layer;
rapidly cooling the melted layer to form a non-stick layer having an amorphous structure on the surface of the substrate,
wherein a rapid cooling step is performed by using liquid nitrogen, and in the rapid cooling step, the cooling rate is not less than 10 4 K/s，
Wherein in the heat preservation step, the heat preservation temperature is 350-450 ℃ and the heat preservation time is at least 20min,
wherein the alloy powder comprises at least one of stainless steel powder, zr alloy powder, cu alloy powder, al alloy powder, mg alloy powder, ti alloy powder and equal atomic ratio high-entropy alloy powder,
wherein the transition layer has a crystal structure,
wherein the laser power is 500W-2 KW and
wherein the thickness of the formed melting layer is 30% -60% of the thickness of the thermal spraying coating.
2. The method of claim 1, wherein the thermal spray coating has a thickness of 100 μm to 800 μm.
3. The method according to claim 1, wherein the alloy powder has a particle size of 300 to 800 mesh.
4. The method of claim 1, wherein the alloy powder comprises stainless steel powder and/or Zr alloy powder.
5. The method of claim 1, wherein the substrate is a pot substrate.
6. A non-stick coating prepared using the preparation method of claim 1, wherein the non-stick coating comprises:
a transition layer on a surface of the substrate, the transition layer having a crystalline structure;
the non-adhesive layer is positioned on the surface of the transition layer, the non-adhesive layer has an amorphous structure, the thickness of the non-adhesive layer is 30 to 60 percent of the total thickness of the non-adhesive coating,
wherein the transition layer and the non-stick layer have the same constituent elements.
7. The non-stick coating of claim 6, wherein the thickness of the non-stick coating is 100 μm to 800 μm.
8. A pan comprising a substrate and the non-stick coating of claim 6.
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