Non-stick cookware and method of making the same

Abstract

Provided are non-stick cookware and a manufacturing method thereof, the non-stick cookware comprising: a substrate; a high entropy ceramic layer disposed on the substrate layer; and a fatty acid modified layer disposed on the surface of the high entropy ceramic layer. Since the fatty acid modified layer is disposed on the high entropy ceramic layer, on the one hand, high-valent metal ions in the high entropy ceramic layer are easily chemically bonded with fatty acids in the subsequent process, on the other hand, the high entropy ceramic layer has high hardness and long service life, and thirdly, the high entropy ceramic layer itself has the characteristic of low surface energy, which can further enhance the non-stick effect.

Description

Technical Field

[0001] The present invention belongs to the field of non-stick technology, and more specifically, relates to a non-stick cooker and a manufacturing method thereof. Background Art

[0002] There are three main directions for the realization of non-stick technology: 1) low surface energy of the surface itself; 2) forming a hydrophobic and oleophobic surface similar to the surface of a lotus leaf through a microscopic concave-convex structure; 3) porous oil storage to form a stable oil film, using oil as a medium to achieve non-stick.

[0003] At present, the main non-stick materials for cookware are fluorine coating, ceramic coating and silicone resin. These three non-stick materials are mainly formed on the inner surface of the cookware by spraying to form a non-stick coating to achieve the purpose of non-stick when heating food. Fluorine coatings mainly include PTFE (polytetrafluoroethylene), PFOA (perfluorooctanoic acid ammonium), PFA (copolymer of perfluoropropyl perfluorovinyl ether and polytetrafluoroethylene), FEP (polyperfluoroethylene propylene copolymer), ETFE (ethylene-tetrafluoroethylene copolymer), etc. The non-stick principle is mainly that fluorine-containing polymers have extremely low surface free energy. Ceramic coatings are mainly coatings with inorganic silicon with a silicon-oxygen bond structure as the main component. It mainly achieves the non-stick effect by forming a nanostructure on the surface of the cookware. Silicone resin mainly uses its low surface energy to achieve the non-stick effect. Although these three types of coatings have non-stick effects, they all have obvious defects: the fluorine coating non-stick coating is not resistant to wear, so you cannot use a shovel when cooking, and you cannot use a steel wool or scouring pad to clean it. Decomposition at high temperatures may produce harmful substances, and the non-stick properties decrease after wear; the non-stick effect of ceramic coatings is worse than that of fluorine coatings. It mainly uses the silicone oil in the coating system to achieve non-stickness, but its long-term non-stickness is not good. Generally, the coating will fall off easily after 3 to 6 months of use; the non-stick effect of silicone coatings is also worse than that of fluorine coatings. After contact with high temperature or open flame, its color tends to turn yellow or gray, and its hardness decreases at high temperature, which easily produces "re-sticking" phenomenon.

[0004] It can be seen from this that non-stick materials generally have the problem of poor long-term non-stick properties and are not resistant to high-temperature stir-frying. Summary of the invention

[0005] In order to solve at least one of the problems in the above-mentioned prior art, the present invention provides a non-stick cookware and a preparation method thereof. Since a high entropy ceramic layer is provided on the base layer and a fatty acid modified layer is provided on the high entropy ceramic layer, on the one hand, the high entropy ceramic layer has high hardness and long service life, and it has the characteristics of low surface energy, which can further enhance the non-stick effect, and on the other hand, the high-valent metal ions in the high entropy ceramic layer are easy to chemically bond with organic acids in the subsequent process, and the formed fatty acid modified layer can improve the non-stick effect of the cookware.

[0006] According to one aspect of the present invention, a non-stick cookware may include: a substrate; a high entropy ceramic layer disposed on the substrate; and a fatty acid modified layer disposed on the high entropy ceramic layer.

[0007] In an embodiment, the high entropy ceramic layer may include oxides of four or more of Mg, Cr, Mn, Fe, Co, Ni, Cu, Al, Sn, and Ti.

[0008] In an embodiment, the fatty acid modified layer may include a fatty acid salt formed of an organic acid and a metal element of a metal oxide included in the high entropy ceramic layer.

[0009] In an embodiment, the organic acid may include at least one of stearic acid, palmitic acid, oleic acid, linoleic acid, lauric acid, and linolenic acid.

[0010] In an embodiment, the surface of the high entropy ceramic layer facing away from the substrate may have micron-scale to nanometer-scale protrusions.

[0011] In an embodiment, the thickness of the high entropy ceramic layer may be in the range of 0.5 μm-1 μm.

[0012] According to another aspect of the present invention, a method for manufacturing non-stick cookware may include: providing a substrate; laying a high entropy ceramic layer on the substrate; and modifying the high entropy ceramic layer using an organic acid to form a fatty acid modified layer.

[0013] In an embodiment, the high entropy ceramic layer may include oxides of four or more of Mg, Cr, Mn, Fe, Co, Ni, Cu, Al, Sn, and Ti.

[0014] In an embodiment, a high entropy ceramic layer may be deposited on a substrate using a high entropy alloy target by using a physical vapor deposition process.

[0015] In an embodiment, before forming the fatty acid modified layer, the surface of the high entropy ceramic layer may be laser etched so that the surface of the high entropy ceramic layer facing away from the substrate has micron- to nanometer-scale protrusions.

[0016] In an embodiment, in the step of modifying the high entropy ceramic layer with an organic acid, the temperature of the organic acid may be controlled within a range of its vaporization temperature minus 600° C. and maintained for 50 min to 120 min.

[0017] According to an embodiment of the inventive concept, a high-entropy ceramic layer whose surface is modified by fatty acids is formed on the substrate of the non-stick cookware. On the one hand, compared with the metal film deposited by PVD, the high-entropy ceramic layer has high hardness, strong wear resistance, and long service life, and it itself has the characteristics of low surface energy, which can further enhance the non-stick effect. On the other hand, the high-valent metal ions in the high-entropy ceramic layer are conducive to chemical bonding with fatty acids, and the formed fatty acid modified layer can improve the non-stick effect of the cookware. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The accompanying drawings are provided to provide a further understanding of the present invention, and the accompanying drawings constitute a part of the specification, and are used together with the following specific embodiments to explain the present invention, but do not constitute a limitation of the present invention. In the accompanying drawings:

[0019] Figure 1 is a cross-sectional view of a non-stick cooker according to an embodiment of the present invention; and

[0020] Figure 2 is a schematic diagram of a scanning electron microscope showing a high entropy ceramic layer formed on the surface of a substrate after being modified by fatty acid. DETAILED DESCRIPTION

[0021] Now, the present invention will be more fully described below in conjunction with the accompanying drawings in which exemplary embodiments are shown, however, the present invention can be implemented in many different forms and should not be construed as limited to the embodiments set forth herein. On the contrary, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the present invention to those skilled in the art.

[0022] It will be understood that when an element is referred to as being “on” another element, the element can be directly on the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.

[0023] Now, exemplary embodiments of the present invention will be described in detail hereinafter.

[0024] When using cookware to cook food, the phenomenon of food sticking to the cookware often occurs. The foods that stick are mainly starch and protein. Specifically, during the cooking process, starch undergoes a series of processes such as water absorption, swelling, gelatinization, and finally carbonization, while protein undergoes a series of processes such as peptide chain dissociation and denaturation, hydrolysis and inactivation, and finally dehydration and carbonization. In this series of processes, starch gel and protein gel will combine with the surface of the cookware, thereby starting to stick to the cookware (stick to the pot), and the bonding force reaches its peak after the food contact surface is carbonized. Based on the above aspects, the bonding mechanism mainly includes the following theories:

[0025] 1) Mechanical bonding theory: The bonding force comes from the mechanical interlocking of the two surfaces, which are connected together by anchoring, hooking, wedging, etc. In fact, this force does not play a major role;

[0026] 2) Adsorption theory: caused by molecular contact and interfacial force between two materials. The main source of adhesion is the intermolecular force including hydrogen bonding force and van der Waals force, which plays a dominant role in the gelation process.

[0027] 3) Chemical bond theory: The atoms between two materials form chemical bonds. The bond energy of chemical bonds is much greater than that between molecules, and the adhesion is stronger. This force plays a dominant role in the process of food burning.

[0028] In the above theory, mechanical bonding can be solved by improving the surface roughness of cookware, and surface adsorption and chemical bonds can be solved by grease. That is to say, by forming a strong oil film on the surface of cookware, the bonding and adhesion between food and metal atoms can be transformed into non-stick contact between food and grease, thereby achieving the purpose of non-stick without coating.

[0029] In addition, since the formation of a firm oil film requires increasing the lipophilic effect of the metal surface, the metal surface can be grafted and modified by using fatty acids to achieve the lipophilicity of the metal surface. Here, fatty acids are the products of normal hydrolysis in natural oils and fats, which are dissolved in oils and fats. They can form fatty acid salts with metal atoms, so that on the one hand, surface fatty acid anhydrides can isolate the microscopic contact between food and pots, and on the other hand, fatty acid anhydrides can firmly lock edible oils as lipophilic groups to form oil films, thereby preventing food from sticking to the pot. Specifically, a metal layer can be deposited on a substrate by a physical vapor deposition (PVD) process, and then the metal layer is modified by fatty acids. However, the wear resistance of the metal layer deposited directly by PVD is insufficient, and the service life is short, and the simultaneous modification of fatty acids will corrode equipment and target materials, and the modification of fatty acids under oxygen atom environmental conditions is easy to oxidize fatty acids.

[0030] Therefore, the non-stick cookware according to the present inventive concept may include a substrate, a high entropy ceramic layer formed on the substrate, and a fatty acid modified layer.

[0031] The inventive concept will be described in detail below in conjunction with exemplary embodiments. Non-stick cookware according to exemplary embodiments of the inventive concept.

[0032] Figure 1 is a cross-sectional view of a non-stick cooker according to an embodiment of the present invention.

[0033] like Figure 1 As shown in , the non-stick cookware according to the embodiment may include: a substrate 1; a high entropy ceramic layer 2 disposed on the substrate layer 1; and a fatty acid modified layer 3 disposed on the high entropy ceramic layer 3.

[0034] The substrate is used to provide a storage space for operations such as cooking of the cooker. Therefore, the substrate can be manufactured into various shapes using metal materials. For example, according to an exemplary embodiment, the substrate may include stainless steel, cast iron, aluminum alloy, titanium alloy, copper alloy, magnesium alloy, or a composite material composed of two or more of them, and may have a single-layer or multi-layer structure, but the inventive concept is not limited thereto. In addition, the substrate may be formed into an angled shape and / or a rounded shape according to the process, aesthetic appearance, and specific needs.

[0035] The high entropy ceramic layer can be conformally formed on at least part or all of the inner surface of the substrate to facilitate the subsequent formation of the fatty acid modified layer. The high entropy ceramic layer may include oxides of four or more of Mg, Cr, Mn, Fe, Co, Ni, Cu, Al, Sn, and Ti. According to an example, a high entropy ceramic layer can be formed on part or all of the inner surface of the substrate by reacting a high entropy alloy target with oxygen by a spraying method. The high entropy oxide has the structural characteristics of a high entropy alloy and a more stable chemical state-high temperature structural stability and potential high strength, good ductility and corrosion resistance, and the high entropy ceramic layer has a low surface energy, which can further enhance the non-stick effect.

[0036] According to an exemplary embodiment, the high entropy ceramic layer may have a thickness of 0.5 μm-1 μm, and its surface facing away from the substrate may have nano- to micro-scale protrusions, thereby being able to cooperate with the fatty acid modified layer to be described below to have excellent non-stick properties.

[0037] The fatty acid modified layer can be arranged on the high entropy ceramic layer to at least partially or completely cover the substrate on which the high entropy ceramic layer is arranged. The high entropy ceramic layer can be formed by reacting an organic acid with a metal element in an oxide in the high entropy ceramic. Specifically, an organic acid can be used to contact the above-mentioned high entropy ceramic layer to react between them. Due to the reaction, the metal ions on the surface of the high entropy ceramic layer easily form fatty acid salts with the organic acid as the fatty acid modified layer. Compared with the reaction of metal atoms in the metal layer with organic acids, the metal ions in the oxide in the high entropy ceramic layer have a high valence state and are more likely to bond with fatty acids.

[0038] According to an exemplary embodiment, the organic acid forming the fatty acid modified layer may include at least one of stearic acid, palmitic acid, oleic acid, linoleic acid, lauric acid and linolenic acid. Fatty acids are the products of normal hydrolysis in natural oils and fats, which are dissolved in oils and fats, and chemically bonded with high-valent metal ions on the surface of the high-entropy ceramic layer to form fatty acid salts. On the one hand, the fatty acid anhydride on the surface can isolate the microscopic contact between food and the pot, and on the other hand, the fatty acid anhydride is a lipophilic group, which can firmly lock the edible oil to form an oil film to prevent food from sticking to the pot, thereby improving the non-stick effect of the cooker.

[0039] Above, the non-stick cookware with a three-layer structure according to the present inventive concept is described in detail in conjunction with exemplary embodiments. Hereinafter, a method for manufacturing the non-stick cookware according to the present inventive concept will be described in detail in conjunction with exemplary embodiments.

[0040] First, a substrate can be provided.

[0041] The base is used to provide a holding space for operations such as cooking of the cooker. Therefore, the base can be manufactured into various shapes using suitable metal materials. The base has been described in detail above, so in order to avoid redundancy, the base is not described in detail here.

[0042] After the substrate is provided, the substrate may be pre-treated.

[0043] The step of pre-treating the substrate may include the steps of ultrasonic cleaning, pickling and rinsing the substrate in sequence. For example, first, a metal cleaning agent prepared according to the use requirements can be placed in the ultrasonic cleaning tank, and ultrasonic degreasing and cleaning can be performed; after the ultrasonic cleaning is completed, the substrate can be pickled with a mixture of sulfuric acid, nitric acid and hydrofluoric acid. After the pickling process, the residual alkali solution during ultrasonic cleaning can be neutralized, and the substrate can also be activated; after the pickling is completed, the substrate can be rinsed with deionized water to completely remove the acid solution. Deionized pure water or distilled water must be used for rinsing; after the above three cleaning processes, the substrate is dried immediately or can be dried by wind and then placed in a drying furnace for drying. Here, the drying temperature can be controlled within the range of 100°C-120°C, and the time can be controlled within the range of 1h-1.5h. After three cleanings, the oil stains and residual cleaning liquid on the surface of the substrate can be removed, so that the subsequent process of forming a high entropy ceramic layer to be described later can be better performed. However, the exemplary embodiment is not limited to this, that is, the pre-treatment step can be omitted.

[0044] Thereafter, the step of laying a high entropy ceramic layer can be performed sequentially. According to an exemplary embodiment, a PVD multi-arc ion plating process can be used as a laying process to form a high entropy ceramic layer on a substrate. However, the exemplary embodiment is not limited thereto, and other processes can be selected according to the inventive concept to form a high entropy ceramic layer. In the following, a method of forming a high entropy ceramic layer of the present invention is described in detail using PVD multi-arc ion plating as a specific example of a process for forming a high entropy ceramic layer.

[0045] Before applying the high entropy ceramic layer, some preparation work can be done, such as cleaning the vacuum coating chamber, checking the arc evaporation source, checking the insulation of the workpiece holder, etc. After completing the above preparation work, the substrate can be placed in the vacuum coating chamber and vacuumed.

[0046] In the process of vacuuming, rough pumping can be performed at the beginning, from the atmosphere to about 5Pa. During the rough pumping, it can be baked and heated to 150℃, and then fine pumping can be performed using an oil diffusion pump. As the temperature of the coating chamber increases, the wall outgassing will reduce the vacuum degree in the vacuum chamber, and then it will rise again. When the vacuum degree rises to about 6.6×10 -3 Pa before coating work can be carried out.

[0047] Before performing the coating process on the substrate, the substrate in the vacuum chamber can be subjected to an argon ion bombardment cleaning process. Specifically, when performing the argon ion bombardment cleaning process: high-purity argon gas (99.999%) is introduced to keep the vacuum degree at 2Pa-3Pa, the bombardment voltage is 800V-1000V, and the bombardment time is 10min-15min. By performing argon ion bombardment cleaning on the substrate, dirt and impurities that may exist on the surface of the target material can be removed, and the target material can be activated, so that the subsequent coating process can be carried out stably.

[0048] Next, a high entropy ceramic layer can be formed on the surface of the substrate after the above steps. The high entropy ceramic layer can be formed on the inner surface of the substrate by using a high entropy alloy target and oxygen through a PVD multi-arc ion plating process. Specifically, a high-purity mixed gas of argon and oxygen with a volume ratio of 5:1 can be introduced into the vacuum coating chamber, and the vacuum degree is maintained at 2×10 -2 Pa, and then ignite all arc sources in sequence, the time is 5min-15min, the arc current is 80A-200A, the arc current of appropriate size can be selected according to the material of the target material, the pulse bias is 50V-150V, the duty cycle is 20%-40%, and the deposition temperature is 200℃-250℃. The high entropy alloy target may include four or more metals selected from Mg, Cr, Mn, Fe, Co, Ni, Cu, Al, Sn, and Ti. However, the embodiment is not limited to this, and the high entropy alloy may also include other metals besides those listed here.

[0049] After the above coating process is completed, a cooling process is performed. Specifically, after the coating process is completed, the arc power supply and the bias power supply are first turned off, and then the gas source and the stop frame are turned off. When the substrate is cooled to 80°C-100°C in the vacuum coating chamber, the vacuum coating chamber is filled with air, and then the substrate is taken out.

[0050] After the coating process, a high-entropy ceramic layer with a thickness of 0.5μm-1μm can be formed on the surface of the substrate. This is because: multi-arc ion plating excites metal atoms through pulsed arcs, and migrates to the surface of the substrate for deposition under the action of the electric field. As the deposition thickness increases, the resistance of the high-entropy ceramic film on the surface of the substrate increases, resulting in a weakening of the electric field strength, making it difficult to continue deposition and increase the film thickness. The high-entropy ceramic layer formed on the surface of the substrate may include four or more oxides of Mg, Cr, Mn, Fe, Co, Ni, Cu, Al, Sn, and Ti.

[0051] Since the deposited high entropy ceramic layer is relatively thin (less than 1 μm), conventional mechanical treatment or chemical treatment activation methods will cause the high entropy ceramic layer to be exposed. Therefore, after the high entropy ceramic layer is formed, the high entropy ceramic layer can be subjected to surface treatment. Since high entropy ceramics have a high entropy effect and are stable in nature, it is difficult to react with fatty acids. Therefore, before the high entropy ceramic layer is modified with fatty acids, laser etching can be used to treat the surface of the high entropy ceramic layer facing away from the substrate. Specifically, the surface of the high entropy ceramic layer facing away from the substrate can be etched in a criss-cross manner by laser, so that some small protrusions (concave-convex structures) of micrometer to nanometer scale can be formed on the surface of the high entropy ceramic layer. On the one hand, such protrusions can achieve the purpose of activating the high entropy ceramic layer and cooperating with fatty acid modification, and on the other hand, they can cooperate with the fatty acid modified layer to form a lotus leaf structure, thereby improving the non-stick effect. According to the example, the laser etching parameters are as follows: the spacing is 0.1 μm, the speed is 100 mm / s-120 mm / s, the depth is 8 nm-10 nm, and the laser power is 0.5 W-3 W.

[0052] After completing the laser etching treatment on the surface of the high entropy ceramic layer, the high entropy ceramic layer can be chemically modified using an organic acid to form a fatty acid modified layer on the high entropy ceramic layer. For example, the substrate treated as above can be placed in an autoclave, and then an organic acid is added. Since some organic acids are solid at room temperature, and solid organic acids are not easy to add to the autoclave, according to an exemplary embodiment, an organic acid solution can be used to achieve the addition of organic acid, however, the inventive concept is not limited to organic acid solutions, and those skilled in the art can select organic acids or organic acid solutions according to specific circumstances. Here, the organic acid solution can be an ethanol solution of an organic acid. And the organic acid can include the types of organic acids described above in conjunction with the exemplary embodiments, and the solvent for the organic acid can also be appropriately selected based on the inventive concept, therefore, the organic acid and its solvent are not described too much here. In addition, when the organic acid solution is added, the mass concentration of the organic acid in the solution can be in the range of 30%-80%, however, the embodiment is not limited thereto. After adding the organic acid solution (e.g., fatty acid ethanol solution) into the autoclave, the autoclave can be heated to a temperature within the range of -600°C, the vaporization temperature of the organic acid, to vaporize the organic acid (e.g., fatty acid), and maintained for 50-120 minutes, and then the substrate is taken out and cooled. The above reaction is carried out under an argon atmosphere, so that the oxidation of fatty acids in an oxygen atom environment can be avoided, thereby affecting the non-stick effect of the cookware. After the above modification treatment, a fatty acid modified layer is formed on the surface of the high entropy ceramic layer, such as Figure 2 As shown in Figure 2 In FIG. 1 , a is a microscopic image of a modified layer according to an exemplary embodiment, and b is a super-hydrophobic effect image of the modified layer according to an exemplary embodiment.

[0053] The non-stick cookware and its manufacturing method conceived according to the present invention are described above in combination with exemplary embodiments. According to an embodiment of the present invention, a high entropy ceramic layer is formed on the surface of the substrate of the cookware, and the high entropy ceramic layer is modified with an organic acid to form a fatty acid modified layer. On the one hand, compared with depositing a metal layer on the substrate, the high entropy ceramic layer has high hardness, strong wear resistance, and long service life, and it itself has the characteristics of low surface energy, which can further enhance the non-stick effect. On the other hand, the high-valent metal ions of the oxide in the high entropy ceramic layer are conducive to chemical bonding with fatty acids, and the formed fatty acid modified layer can improve the non-stick effect of the cookware.

[0054] In the following, the beneficial effects of the present inventive concept will be reflected by describing in detail specific examples of the present inventive concept.

[0055] Example 1

[0056] The cookware according to Example 1 was prepared according to the following method.

[0057] Prepare the stainless steel pot.

[0058] The stainless steel pot embryo is placed in an ultrasonic cleaning tank, and a commercially available metal cleaning agent is added for cleaning. Then, the stainless steel pot embryo is pickled using a mixture of 8% sulfuric acid, 25% nitric acid, and 10% hydrofluoric acid by mass fraction. After the pickling is completed, the stainless steel pot embryo is rinsed with deionized water. After the rinsing is completed, the stainless steel pot embryo is placed in a furnace and dried at 100°C.

[0059] Clean the vacuum coating chamber, check whether the arc evaporation source is normal, check whether the workpiece rack is insulated, and when ready, put the stainless steel pot embryo into the vacuum coating chamber and evacuate it. Start with rough evacuation to about 5Pa, bake and heat to 150℃ during rough evacuation, and then use an oil diffusion pump for fine evacuation. As the temperature of the coating chamber rises, the wall of the vessel releases gas, the vacuum degree in the vacuum chamber decreases, and then rises again until the vacuum degree rises to about 6.6×10 -3 Pa.

[0060] Next, the stainless steel pot embryo was cleaned by argon ion bombardment, high-purity argon gas (99.999%) was introduced, the vacuum degree was maintained at 2.5 Pa, the bombardment voltage was 900 V, and the bombardment time was 12 minutes.

[0061] After that, the coating process was carried out. A mixture of high-purity argon and oxygen with a volume ratio of 5:1 was introduced into the vacuum coating chamber, and the vacuum degree was maintained at 2×10 -2 Pa, and then ignite all arc sources (target: MgCrMnCo high entropy alloy) in sequence, the time is 10min, the arc current is 100A, the pulse bias is 100V, the duty cycle is 30%, and the deposition temperature is 200°C. After that, turn off the arc power supply and bias power supply, and then turn off the gas source and stop the rotating frame. When the stainless steel pot embryo cools to 100°C, fill the vacuum coating chamber with air, and then take out the substrate.

[0062] After the coating process, a high-entropy ceramic layer (MgCrMnCo) with a thickness of 0.8μm is formed on the surface of the stainless steel pot embryo.

[0063] Next, a concave-convex structure is formed on the surface of the high-entropy ceramic layer by laser etching. The laser etching parameters are as follows: spacing of 0.1 μm, speed of 100 mm / s, depth of 10 nm, and laser power of 2 W.

[0064] Afterwards, the laser-etched stainless steel pot embryo was placed in a high-pressure reactor (argon atmosphere), a lauric acid ethanol solution with a mass concentration of 50% was added, and the mixture was heated to 400° C. to vaporize the lauric acid, maintained for 100 minutes, and then the stainless steel pot embryo was taken out and cooled.

[0065] Finally, a fatty acid modified layer is formed on the surface of the high entropy ceramic layer formed on the surface of the stainless steel pot embryo, thus completing the manufacture of the pot according to Example 1.

[0066] Example 2

[0067] The difference from Example 1 is that MnCrNiTi alloy is used instead of MgCrMnCo alloy.

[0068] Example 3

[0069] The difference from Example 1 is that the thickness of the formed high entropy ceramic layer is 1 μm.

[0070] Example 4

[0071] The difference from Example 1 is that the thickness of the formed high entropy ceramic layer is 0.5 μm

[0072] Example 5

[0073] The difference from Example 1 is that oleic acid is used instead of lauric acid.

[0074] Example 6

[0075] The difference from Example 1 is that in the step of modifying the high entropy ceramic layer with fatty acid, the step is maintained for 50 minutes.

[0076] Example 7

[0077] The difference from Example 1 is that in the step of modifying the high entropy ceramic layer with fatty acid, the step is maintained for 120 minutes.

[0078] Example 8

[0079] The difference from Example 1 is that in the step of modifying the high entropy ceramic layer with fatty acid, the lauric acid is vaporized by heating to 600°C.

[0080] Example 9

[0081] The difference from Example 1 is that in the step of modifying the high entropy ceramic layer with fatty acid, the lauric acid is vaporized by heating to 500°C.

[0082] Comparative Example 1

[0083] The difference from Example 1 is that metal nickel (Ni) is used instead of the MgCrMnCo alloy.

[0084] Comparative Example 2

[0085] The difference from Example 1 is that in the fatty acid modification step, the argon atmosphere in the reaction vessel is replaced by air atmosphere.

[0086] Comparison Example 3

[0087] The difference from Example 1 is that the step of modifying the high entropy ceramic layer with fatty acid is not performed.

[0088] The cookware manufactured by the above-mentioned reference examples 1-9 and comparative examples 1-3 was subjected to wear resistance and non-stick tests.

[0089] The non-stickiness test of fried eggs was carried out according to 4.2.1 of the national standard GB / T32095.2-2015. The flat wear resistance test was carried out according to 4.3.1 of the national standard GB / T32095.2-2015. The evaluation results are shown in Table 1. The "-" in Table 1 indicates the same data as the corresponding data in Example 1.

[0090] Table 1

[0091]

[0092]

[0093] As can be seen from Table 1, the non-stickiness test results of the pans manufactured according to Examples 1-9 for frying eggs are all Grade I, while the non-stickiness test results of the pans manufactured according to Comparative Examples 1-2 are Grade II, and the non-stickiness test results of the pans manufactured according to Comparative Example 3 are all Grade III. In other words, the non-stickiness of the pans manufactured according to Examples 1-9 is better than the non-stickiness of the pans manufactured according to Comparative Examples 1-3. From the above results, it can be proved that the high entropy ceramic layer itself has non-stick properties, which can improve the non-stickiness of the cookware; fatty acid modification can improve the non-stickiness of the cookware; fatty acid modification under air conditions will oxidize fatty acids and reduce non-stickiness. The wear resistance test results of the pans manufactured according to Examples 1-9 are all Grade I, and the wear resistance test result of the non-stick pans manufactured according to Comparative Example 1 is Grade II, which can prove that the wear resistance of the high entropy ceramic layer is better than the wear resistance of the metal layer.

[0094] According to the concept of the present invention, a non-stick cookware is provided, which includes a high entropy ceramic layer formed on a substrate and a fatty acid modified layer formed on the high entropy ceramic layer. On the one hand, compared with the metal layer deposited by PVD, the high entropy ceramic layer has high hardness, strong wear resistance, long service life, and has the characteristics of low surface energy, which can further enhance the non-stick effect. On the other hand, the high-valent metal ions on the surface of the high entropy ceramic layer are conducive to chemical bonding with fatty acids, and the fatty acid modified layer formed can improve the non-stick effect of the cookware.

[0095] Although the present invention has been described with reference to the above embodiments, it will be understood by those skilled in the art or those skilled in the art with common sense in the art that various modifications and changes may be made to the present invention without departing from the spirit and technical field of the present invention described in the claims. Therefore, the technical scope of the present invention should not be limited to the contents described in the specific embodiments of the specification, and the invention to be protected should be defined by the claims.

Claims

1. A method for manufacturing non-stick cookware, characterized in that: The method comprises: providing a substrate; Laying a high entropy ceramic layer on the substrate, the high entropy ceramic layer comprising oxides of four or more of Mg, Cr, Mn, Fe, Co, Ni, Cu, Al, Sn, and Ti, the thickness of the high entropy ceramic layer being in the range of 0.5 μm to 1 μm; and Modifying the high entropy ceramic layer with an organic acid to form a fatty acid modified layer, wherein the fatty acid modified layer includes a fatty acid salt formed by a reaction of the organic acid with a metal element of a metal oxide included in the high entropy ceramic layer; The step of modifying the high entropy ceramic layer with an organic acid includes: heating the autoclave until the temperature of the organic acid is within the range of its boiling point - 600°C, and maintaining it for 50min-120min, thereby forming the fatty acid modified layer.

2. The method according to claim 1, characterized in that A high entropy ceramic layer is deposited on a substrate using a high entropy alloy target by a physical vapor deposition process.

3. The method according to claim 1, characterized in that Before forming the fatty acid modified layer, the surface of the high entropy ceramic layer is laser etched so that the surface of the high entropy ceramic layer facing away from the substrate has micron- to nanometer-scale protrusions.

4. A non-stick cookware manufactured by the method according to any one of claims 1 to 3, characterized in that: The non-stick cookware comprises: matrix; A high entropy ceramic layer is disposed on the substrate, wherein the high entropy ceramic layer comprises oxides of four or more of Mg, Cr, Mn, Fe, Co, Ni, Cu, Al, Sn, and Ti, and the thickness of the high entropy ceramic layer is in the range of 0.5 μm to 1 μm; and The fatty acid modified layer is disposed on the high entropy ceramic layer, and the fatty acid modified layer includes a fatty acid salt formed by the reaction of an organic acid with a metal element of a metal oxide included in the high entropy ceramic layer.

5. The non-stick cookware according to claim 4, characterized in that: The organic acid includes at least one of stearic acid, palmitic acid, oleic acid, linoleic acid, lauric acid and linolenic acid.

6. The non-stick cookware according to claim 4, characterized in that: The surface of the high entropy ceramic layer facing away from the substrate has micron-scale to nanometer-scale protrusions.

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