WO2020019716A1 - Récipient de cuisson et son procédé de fabrication, système de fabrication de récipient de cuisson et ustensile de cuisine - Google Patents

Récipient de cuisson et son procédé de fabrication, système de fabrication de récipient de cuisson et ustensile de cuisine Download PDF

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Publication number
WO2020019716A1
WO2020019716A1 PCT/CN2019/076732 CN2019076732W WO2020019716A1 WO 2020019716 A1 WO2020019716 A1 WO 2020019716A1 CN 2019076732 W CN2019076732 W CN 2019076732W WO 2020019716 A1 WO2020019716 A1 WO 2020019716A1
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Prior art keywords
quasicrystal
layer
cookware
powder
present
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PCT/CN2019/076732
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English (en)
Chinese (zh)
Inventor
万鹏
陈永君
曹达华
陈炜杰
解志文
董闯
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佛山市顺德区美的电热电器制造有限公司
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Priority claimed from CN201811299619.1A external-priority patent/CN110757915A/zh
Priority claimed from CN201811299219.0A external-priority patent/CN110754914B/zh
Priority claimed from CN201811299230.7A external-priority patent/CN110756811B/zh
Application filed by 佛山市顺德区美的电热电器制造有限公司 filed Critical 佛山市顺德区美的电热电器制造有限公司
Publication of WO2020019716A1 publication Critical patent/WO2020019716A1/fr

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    • 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
    • A47J37/00—Baking; Roasting; Grilling; Frying
    • A47J37/10—Frying pans, e.g. frying pans with integrated lids or basting devices
    • 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

Definitions

  • the present invention relates to the field of cooking utensils, and in particular, the present invention relates to a cooking utensil and a preparation method thereof, a system for preparing a cooking utensil, and a cooking utensil.
  • non-stick coatings are prepared on the inside of the pot body.
  • the most commonly used are organic fluorine resin coating and ceramic coating, followed by iron pots and stainless steel pots with special surface treatment.
  • These coatings have some shortcomings, such as the low hardness of the organic fluorine resin coating, poor wear resistance, resistance to shovel and scratch, and prone to corrosion and peeling when cooking acidic food for a long time; ceramic non-stick coating
  • the non-stick effect is mainly achieved by a layer of silicone oil on the surface, so the weather resistance is poor, the non-stick is reduced for long-term use, and the oily ceramic coating will cause pollution to the environment during construction. Now more and more consumers are pursuing healthy uncoated metal pans, but the non-stick properties of surface-treated iron pans and stainless steel pans are still not ideal.
  • an object of the present invention is to provide a cooker having the advantages of good hardness, good abrasion resistance, long service life, or good non-stickiness.
  • the ceramic coating is easy to hydrolyze, and the non-stick performance of the coating tends to decrease as the number of uses increases.
  • Quasicrystal material is a material with low surface energy characteristics, but also has high hardness, low friction coefficient, wear resistance and corrosion resistance, which makes quasicrystal materials have the potential to replace the existing non-stick coating.
  • Al-Cu-Fe series quasicrystalline alloy whose surface energy is between stainless steel and polytetrafluoroethylene, is about 25% larger than polytetrafluoroethylene, and has excellent surface properties.
  • the present invention provides a cooker.
  • the cookware includes a body; and at least one quasicrystal layer, and at least one quasicrystal layer is sequentially stacked on the surface of the body. Therefore, by forming a quasicrystal layer on the surface of the main body of the cookware, the surface properties such as hardness, abrasion resistance, corrosion resistance, and non-stick performance can be significantly improved, and the combination of the quasicrystal layer and the base material of the cookware body Strong force and good abrasion resistance and corrosion resistance. It is not easy to be scratched or hydrolyzed during use. It can effectively prevent food sticks and the main body of the pot from corrosion due to the exposure of the pot body and damage to the user. A series of issues such as health.
  • the body includes a mouth portion, an upper side portion, a lower side portion, and a bottom portion; a thickness of the quasicrystal layer at the bottom portion and the lower side portion is greater than that of the quasicrystal layer located at the upper side portion and the mouth portion. Thickness of the quasicrystalline layer.
  • the body is a single-layer or multi-layer structure containing at least one material of ceramic, aluminum alloy, aluminum, titanium, stainless steel, carbon steel, and iron.
  • the quasicrystal layer contains at least one of aluminum, copper, iron, and chromium.
  • the quasicrystal layer contains 50 to 70% aluminum, 15 to 25% copper, and 5 to 15% iron; or the quasicrystal layer contains 60. -70% aluminum, 15-25% copper, 5-15% iron, 5-15% chromium.
  • the thickness of the quasicrystal layer is 10-500 microns.
  • the thickness of the quasicrystal layer at the mouth is not greater than 40 microns.
  • the thickness of the quasicrystal layer at the mouth is not less than 10 microns.
  • the thickness of the quasicrystal layer on the lower side and the bottom is 100-200 microns.
  • the thickness of the quasicrystal layer on the upper side is 50-100 micrometers.
  • the thickness of the quasicrystal layer gradually increases in a direction from the upper side portion to the bottom portion.
  • the middle portion of the inner peripheral surface of the cookware projects outward from both ends of the inner peripheral surface of the cookware.
  • the upper side portion and the lower side portion are within a spherical surface.
  • the quasicrystal layer contains quasicrystal particles, the at least one quasicrystal layer is sequentially stacked on the inner surface of the body, and the quasicrystal is in contact with the inner surface. At least a part of the quasicrystal particles in the crystal layer is embedded in the body.
  • an area embedded on the outer surface of the body by the quasicrystal particles accounts for 50% to 95% of an area of the outer surface of the body.
  • the particle size of the quasicrystal particles is 20 ⁇ m to 150 ⁇ m.
  • two to three quasicrystal layers are included.
  • the particle size of the quasicrystal particles in the quasicrystal layer from the inside to the outside gradually decreases.
  • the quasicrystal layer is formed by cold spraying.
  • the quasicrystal layer meets at least one of the following conditions: the surface roughness is not greater than 2 microns; the thermal conductivity is 0.1 W / mK to 3W / mK; the porosity is 0.1% or more and less than or equal to 20%; the content of the quasicrystal material in the quasicrystal layer is 20wt% to 90wt%.
  • the invention provides a cooking appliance.
  • the cooking appliance includes the aforementioned cooker. Therefore, by using the cookware of the above embodiment, the cooking appliance can effectively and effectively prevent food from sticking to the pan during cooking, and effectively improve the heating condition of the food.
  • the cooking appliance further includes: a coil plate, a heating zone is defined in the coil plate, and a lower side portion and a bottom portion of the pot are located in the heating zone.
  • the present invention provides a method for preparing the aforementioned cookware.
  • the method includes: spraying at least one time on the inner surface of the body to sequentially form at least one quasicrystal layer containing quasicrystal particles on the inner surface of the body.
  • the preparation process is mature, easy to operate, and easy to industrialize production, and a quasicrystal layer is formed on the inner surface of the main body of the preparation pot, which can significantly improve its surface such as hardness, wear resistance, corrosion resistance, non-stick performance Performance, strong bonding between the quasicrystal layer and the base body of the cookware, and good wear resistance and corrosion resistance, it is not easy to be scratched or hydrolyzed during use, which can effectively prevent the base body of the cookware from being exposed As a result, a series of problems such as corrosion of the food stick pan and the main body of the cookware and damage to the user's health are caused.
  • the spraying method is cold spraying, wherein at least a part of the quasicrystal particles in the quasicrystal layer in contact with the outer surface of the body is embedded in the body.
  • the cold spraying is completed under at least one of the following conditions: spraying power is 20 to 40KW, powder feeding amount is 5 to 80g / min, spraying pressure is 1 to 10MPa, and spraying gas heating temperature 700 to 800 ° C.
  • the quasicrystal particles are obtained by the following steps: smelting a raw material mixture to form an alloy ingot, wherein the raw material mixture contains an atomic ratio of (60-70): (15-25 ): (5-15) of aluminum, copper, and iron, or the raw material mixture contains an atomic ratio of (60-70): (15-25): (5-15): (5-15) Aluminum, copper, iron, and chromium; subjecting the alloy ingot to atomization and pulverization in a vacuum or a protective atmosphere to obtain a first quasicrystal powder; and spheroidizing the first quasicrystal powder so that The quasicrystal particles are obtained.
  • the method further includes a step of polishing an outer surface of the quasicrystal layer.
  • the present invention provides a system for preparing the aforementioned cookware.
  • the system includes: a mixing device, the mixing device is adapted to mix the second quasicrystal powder with an additive so as to obtain a mixed material; a pressing device, the pressing device and the mixing device
  • the sintering device is connected to the inner surface of the body so as to form a primary quasicrystal layer on the inner surface of the body; the sintering device is connected to the pressing device and is suitable for A sintering process is performed on the body formed with the primary quasicrystal layer to obtain the cooking utensil.
  • the second quasicrystal powder is mixed with an additive by using a mixing device.
  • the addition of the additive can make the second quasicrystal powder have better fluidity, and it will be more effective in the subsequent process. It is easy to press and release, and can further improve the flow performance of the second quasicrystal powder.
  • the body of the cooker is pressed by a pressing device, and a mixture material including a second quasicrystal powder and an additive is applied to the inner surface of the main body to form a primary quasicrystal layer on the surface of the body.
  • the sintering device is used to sinter the body formed with the quasicrystal layer.
  • the second quasicrystal powder particles in the primary quasicrystal layer are bonded by atomic diffusion to enhance the bonding between the particles and further increase the Strength and density, thereby further improving the surface properties of the inner surface of the cookware (such as high hardness, low friction coefficient, wear resistance, corrosion resistance, etc.). Therefore, according to the system for preparing a cooker according to the embodiment of the present invention, a quasicrystal layer is formed on the inner surface of the cooker body through a powder metallurgy process, which can significantly improve the surface performance of the cooker.
  • the system further comprises: a pre-firing device, the pre-firing device is disposed between the pressing device and the sintering device, and is suitable for forming the The body with the quasicrystal layer is pre-fired.
  • the system further includes: a polishing device connected to the sintering device and adapted to perform polishing processing on the cooking utensil.
  • the system further includes: a smelting device, the smelting device is adapted to perform a smelting process on a mixture containing at least one of an aluminum material, a copper material, an iron material, and a chromium material to obtain a quasicrystal Alloy ingot; pulverizing device, said pulverizing device is connected to said melting device and said mixing device, and is suitable for pulverizing said quasicrystal alloy ingot to obtain said second quasicrystal powder .
  • a smelting device the smelting device is adapted to perform a smelting process on a mixture containing at least one of an aluminum material, a copper material, an iron material, and a chromium material to obtain a quasicrystal Alloy ingot
  • pulverizing device said pulverizing device is connected to said melting device and said mixing device, and is suitable for pulverizing said quasicrystal alloy ingot to obtain said second quasicrystal powder .
  • the system further comprises: a sieving device, the sieving device is connected to the pulverizing device and the mixing device, and is suitable for sieving the pulverized product Processing to obtain the second quasicrystal powder.
  • the present invention provides a method for preparing a pan using the system described above.
  • the method includes: (1) supplying a second quasicrystal powder and an additive to a mixing device for mixing, so as to obtain a mixed material; (2) pressing the body with a pressing device, and The mixed material is applied to the inner surface of the pot to form a primary quasicrystal layer on the inner surface of the body; (3) the body having the primary quasicrystal layer formed is sintered to obtain the pot With. Therefore, in the method for preparing a pan, the second quasicrystal powder is mixed with an additive by using a mixing device.
  • the addition of the additive can make the second quasicrystal powder have better fluidity, and it will be more effective in the subsequent process. It is easy to press and release, and can further improve the flow performance of the second quasicrystal powder.
  • the body of the cooker is pressed by a pressing device, and a mixture material including a second quasicrystal powder and an additive is applied to an inner surface of the body to form a quasicrystal layer on the surface of the body.
  • the sintering device is used to sinter the body formed with the primary quasicrystal layer.
  • the quasicrystal powder particles in the primary quasicrystal layer are bonded by atomic diffusion to enhance the bonding between the particles and further increase the strength of the sintered body of the quasicrystal layer.
  • a quasicrystal layer is formed on the inner surface of the cooker body through a powder metallurgy process, which can significantly improve the surface performance of the cooker.
  • the second quasicrystal powder is prepared from a quasicrystal alloy ingot through a powdering treatment.
  • the quasi-crystalline alloy ingot is formed by smelting a mixture containing at least one of an aluminum material, a copper material, an iron material, and a chromium material, wherein the aluminum material is pure aluminum and the copper
  • the material is pure copper
  • the iron material is pure iron
  • the chromium material is pure chromium or a chromium-titanium alloy.
  • the additive includes a lubricant and a binder, and the lubricant and the binder are each independently selected from the group consisting of zinc stearate, lithium stearate, stearic acid, paraffin, and ethyl acetate. At least one of bis-stearic acid amides.
  • the added amount of the binder is 0.2 to 1.0% by weight of the second quasicrystal powder.
  • the pressing temperature is 90 to 150 ° C, and the pressing force is 400 to 850 MPa.
  • the method before step (3), further includes: supplying the body having the quasicrystal layer formed therein to a pre-baking device, and the pre-baking conditions include: heating in a hydrogen atmosphere to 400 ⁇ 450 °C, heat preservation for 20min; heat up to 600 ⁇ 650 °C, heat preservation for 10-60min, among which, the temperature increase rate is 5 °C / min.
  • the sintering process is performed in an inert atmosphere or a vacuum, and the temperature of the sintering process is 700-1000 ° C.
  • the conditions of the sintering treatment include: heating up to 150-250 ° C, holding for 20 minutes; heating up to 350-450 ° C, holding for 10 minutes; heating up to 700-1000 ° C, holding for 30 minutes.
  • a particle size of at least 90% of the particles in the second quasicrystal powder is not more than 180 ⁇ m.
  • FIG. 1 is a schematic structural diagram of a cooker in an embodiment of the present invention.
  • FIG. 2 is a schematic structural diagram of a cooker in still another embodiment of the present invention.
  • FIG. 3 is a schematic structural view of a portion of a cooker according to still another embodiment of the present invention.
  • FIG. 4 is a schematic structural view of a portion of a cooker according to still another embodiment of the present invention.
  • FIG. 5 is a schematic structural diagram of a portion of a cooker according to still another embodiment of the present invention.
  • FIG. 6 is a schematic structural diagram of a cooking appliance in an embodiment of the present invention.
  • FIG. 7 is a schematic structural diagram of a cooking appliance in still another embodiment of the present invention.
  • FIG. 8 is a flowchart of a method for preparing quasicrystal particles according to an embodiment of the present invention.
  • FIG. 9 is a schematic structural diagram of a system for preparing a pan in an embodiment of the present invention.
  • FIG. 10 is a schematic structural diagram of a system for preparing a pan in another embodiment of the present invention.
  • FIG. 11 is a schematic structural diagram of a system for preparing a pan in another embodiment of the present invention.
  • FIG. 12 is a schematic structural diagram of a system for preparing a pan in another embodiment of the present invention.
  • FIG. 13 is a schematic structural diagram of a system for preparing a pan in another embodiment of the present invention.
  • FIG. 14 is a schematic flowchart of a method for preparing a pan in an embodiment of the present invention.
  • 15 is a schematic flowchart of a method for preparing a pan in another embodiment of the present invention.
  • 16 is a schematic flowchart of a method for preparing a pan in another embodiment of the present invention.
  • FIG. 17 is a schematic flowchart of a method for preparing a pan in another embodiment of the present invention.
  • FIG. 18 is a schematic flowchart of a method for preparing a pan in another embodiment of the present invention.
  • Example 19 is a sintering treatment temperature curve diagram in Example 4 of the present invention.
  • FIG. 20 is a surface morphology diagram of the quasicrystal layer on the surface of the body in Embodiment 4 of the present invention.
  • first and second are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as “first” and “second” may explicitly or implicitly include one or more of the features. Further, in the description of the present invention, unless otherwise stated, the meaning of "plurality" is two or more.
  • the invention provides a cooker.
  • the cookware includes a body and a quasicrystal layer formed on the body. Therefore, by forming a quasicrystal layer on the inner surface of the cookware, the surface properties such as hardness, abrasion resistance, corrosion resistance and non-stick performance can be significantly improved, and the service life of the cookware can be extended.
  • the layer has a strong binding force with the base body of the cookware, and has good abrasion resistance and corrosion resistance. It is not easy to be scratched or hydrolyzed during use, and can effectively avoid food stickiness caused by the base material of the cookware body being exposed. A series of problems such as corrosion of the base material of the pot and the pot body and damage to the user's health.
  • the cooker includes a main body 100 and a quasicrystal layer 200 formed on the main body 100;
  • the main body 100 includes a mouth portion 110, an upper side portion 120, a lower side portion 130, and a bottom portion 140;
  • the thickness of the quasicrystal layer 200 of the lower side portion 130 and the bottom portion 140 is greater than the thickness of the quasicrystal layer 200 located on the upper side portion 120 and the mouth portion 110.
  • the cookware according to the embodiment of the present invention by forming a quasicrystal layer on the body, the surface properties such as hardness, abrasion resistance, corrosion resistance, and non-stick performance can be significantly improved, and the quasicrystal layer and the cookware body substrate It has a strong binding force and has good abrasion resistance and corrosion resistance. It is not easy to be scratched or hydrolyzed during use. It can effectively prevent food from sticking to the pot and the base of the pot. A series of problems such as corrosion and damage to users' health.
  • the thickness of the quasicrystal layer in the directly heated part (lower side and bottom) of the cooker is larger than other parts (upper side and mouth), so that the temperature difference between the upper and lower sides of the cooker is reduced, and the heat transfer uniformity of the cooker is improved. , Improve the boiling effect, thereby improving the cooking effect of food.
  • the mouth portion 110 is a portion indicated by H3
  • the upper portion is a portion indicated by H2
  • the lower portion 130 is a portion indicated by H1.
  • the material used to form the body is not particularly limited, and those skilled in the art can select according to actual needs.
  • the material of the body may be a single-layer or multi-layer material containing at least one of ceramic, aluminum alloy, aluminum, titanium, stainless steel, carbon steel, and iron; that is, the body of the cookware It is a single-layer or multilayer structure containing at least one of ceramic, aluminum alloy, aluminum, titanium, stainless steel, carbon steel, and iron. Therefore, the source of the pot material is wide and rich in variety, and the body formed of a variety of different materials is suitable for forming a quasicrystal layer and has strong adaptability.
  • the quasicrystal layer contains at least one of aluminum, copper, iron, and chromium.
  • the inventors have found that when a quasicrystal layer formed using the above elements is used, the surface properties of the quasicrystal layer (eg, high hardness, low friction coefficient, wear resistance, corrosion resistance, etc.) can be further improved.
  • the quasicrystal layer 200 may include aluminum, copper, and iron.
  • the inventors have found that when a quasicrystal layer formed using the above elements is used, the surface properties of the quasicrystal layer (eg, high hardness, low friction coefficient, wear resistance, corrosion resistance, etc.) can be further improved.
  • the quasicrystal layer may further include other elements that can form quasicrystals that are well known to those skilled in the art.
  • the quasicrystal layer may further include Cr and Ti, and thus, the quasicrystal layer has stronger corrosion resistance.
  • the quasicrystal layer contains 50 to 70% aluminum, 15 to 25% copper, and 5 to 15% iron.
  • the quasicrystal layer 200 contains The atomic percentage of aluminum, copper and iron is 50 to 70% of aluminum, 15 to 25% of copper and 5 to 15% of iron; or the quasicrystal layer contains 60 to 70% of aluminum, 15 to 25% Copper, 5-15% iron, 5-15% chromium.
  • the quasicrystal layer meets at least one of the following conditions: the porosity is 0.1% or more and 20% or less; the thickness of the quasicrystal layer is 10 to 500 microns; and the thermal conductivity is 0.1 to 3W / mK.
  • the surface properties such as the hardness, abrasion resistance, corrosion resistance, and non-stick performance of the quasicrystal layer. If the porosity is too high, it will easily cause local overheating and make the heat transfer uneven; if the porosity is too low, it will reduce the heat transfer performance and make the boiling effect poor.
  • the thickness of the quasicrystal layer is too small, the thermal conductivity is reduced and the thermal uniformity is deteriorated; if the thickness is too large, the thermal conductivity is also reduced, and the surface roughness of the quasicrystal layer is increased, and the hardness, wear resistance and non-stickiness of the coating are increased. relatively low.
  • the thickness of the quasicrystal layer at the mouth portion 110 is not greater than 40 microns, and preferably, the thickness of the quasicrystal layer at the mouth portion is not smaller than 10 microns.
  • the inventors have found that quasicrystal materials do not have high thermal conductivity, and when the cookware is applied to a cooking device (also known as a cooking appliance), its mouth is usually located at the mouth of the cooking device. Therefore, in order to ensure the overall thermal conductivity of the cookware, the thickness of the quasicrystal layer at the mouth of the cookware should not be too large.
  • the cooking device is a rice cooker
  • the condensed water on the lid of the rice cooker will flow to the mouth of the cookware at the mouth of the pot. If the thickness of the quasicrystal layer on the mouth is too large, it will cause The condensed water cannot be dried and flows into the rice in the rice cooker, making the rice taste worse.
  • the thickness of the quasicrystal layer on the lower portion 130 and the bottom 140 is 100-200 microns, for example, 100 microns, 120 microns, 140 microns, 160 microns, 180 microns, or 200 microns; the upper portion 120
  • the thickness of the quasicrystal layer is 50-100 micrometers, such as 50 micrometers, 60 micrometers, 70 micrometers, 80 micrometers, 90 micrometers, or 100 micrometers.
  • the inventors have found that when a cooker is applied to a cooking device, its lower side and bottom are generally located in a directly heated place, and the heat is concentrated.
  • the heat transfer during cooking can be effectively improved, and the uniform heating of the food is further facilitated 3.
  • the thickness of the quasicrystal layer 200 gradually increases along the upper side portion 120 to the lower side portion 130, in other words, the thickness of the quasicrystal layer 200 along the upper side
  • the direction from the portion 120 to the bottom portion 140 gradually increases.
  • the middle portion of the inner peripheral surface of the cookware projects outward from both ends of the inner peripheral surface of the cookware.
  • the inventors have found that by adopting the above-mentioned settings, the diameter of the mouth and bottom of the cookware is smaller than the middle of the cookware, that is, D1 ⁇ D, D2 ⁇ D, so that the heat can be effectively concentrated to the middle of the cookware and the heat dissipation can be reduced.
  • the heat is locked into the cookware to make up for the deficiency of insufficient heating of the food in the middle area of the cookware during the cooking process, which can further improve the utilization of heat and the effect of uniform temperature heating.
  • the upper side portion 120 and the lower side portion 130 of the cookware may be within a spherical surface.
  • the heat can form a spherical reflection in the cookware, thereby further compensating the deficiency of insufficient heating in the middle of the cookware, especially the central position, during cooking, so that the food is evenly heated, thereby achieving better energy saving and uniform temperature heating effects.
  • the cookware includes: a body 100; at least one quasicrystal layer 200, the quasicrystal layer contains quasicrystal particles 21, and at least one quasicrystal layer 200 is sequentially stacked on the body At least a part of the quasicrystal particles 21 in the quasicrystal layer 200 on the inner surface 11 of the 100 and in contact with the inner surface 11 of the body is embedded in the body 100 (wherein "at least a part” means that each At least a portion of the quasicrystal particles in contact with the inner surface).
  • quasicrystals have good properties such as good non-stickiness, high hardness, high corrosion resistance, and low coefficient of friction
  • embedding at least a part of the quasicrystal particles in the body can increase the binding force with the body.
  • the quasicrystal particles can withstand first Scratches from the outside world, and because the quasicrystal particles can be firmly combined with the body, the quasicrystal layer is prevented from being scraped off, further protecting the body from being damaged, thereby greatly improving the hardness and wear resistance of the surface of the pot, and the quasicrystal
  • the layer setting also makes the cookware non-sticky, and because the quasicrystal particles have a low surface energy, a thin air layer can be formed between the quasicrystal particles, which will further increase the nonstickness of the cookware.
  • the “sequentially stacked arrangement” specifically refers to the sequentially stacked arrangement from the inner surface 11 of the main body in a direction away from the main body 100.
  • the material forming the body there is no limitation on the material forming the body, as long as it has sufficient strength to spray the quasicrystal particles on its surface.
  • the body is selected from at least one of ceramic, aluminum alloy, stainless steel, carbon steel, and iron. As a result, the body has sufficient strength to withstand the pressure during spraying. In this way, the cooker can be used to form the body or liner of a cooking device, where the quasicrystal layer is in direct contact with food, thereby improving the body or the interior. Bile non-stick nature.
  • the body When metals such as aluminum alloy, stainless steel, carbon steel, and iron are used as the body, the density, structure, and thermal expansion coefficient of the quasicrystal and the body are close, which can better improve the high bonding strength of the quasicrystal and the body.
  • the gallbladder is not prone to generate thermal stress, thereby increasing the service life of the pot.
  • the gaps between the quasicrystal particles can be formed.
  • the thin air layer further forms a hydrophobic structure on the outer surface of the quasicrystal layer, which improves the hydrophobicity of the outer surface of the cookware and further improves the non-stickiness of the cookware.
  • the specific size of the gap may be designed by those skilled in the art according to the particle size of the quasicrystal particles, as long as a continuous hydrophobic structure can be formed on the outer surface of the body.
  • the particle size of the quasicrystal particles in the quasicrystal layer of the same layer may be the same or different, and those skilled in the art may flexibly set according to actual requirements, and there is no restriction requirement here.
  • the area embedded by the quasicrystal particles on the inner surface of the body accounts for 50% to 95% of the area of the inner surface of the body. For example, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%. Therefore, it is possible to ensure that a continuous layer of hydrophobic structure is formed on the inner surface of the body, and to ensure that the pot has good non-stickiness; if the area embedded by the quasicrystal particles on the inner surface of the body accounts for less than 50 of the inner surface of the body %, The inner surface of the body cannot form a continuous hydrophobic structure.
  • the non-stick properties of the pot are improved, but the improvement is not obvious; and due to the limitation of the preparation process, the inner surface of the body is quasicrystalline particles
  • the embedded area occupies an area of the inner surface of the body which is difficult to be higher than 95%, and the manufacturing cost will be greatly increased.
  • the particle size of the quasicrystal particles is 20 micrometers to 150 micrometers, such as 20 micrometers, 25 micrometers, 30 micrometers, 35 micrometers, 40 micrometers, 50 micrometers, 60 micrometers.
  • the quasicrystal particles can be perfectly embedded in the body; if the particle size is less than 20 microns, some quasicrystal particles may be completely embedded in the body when the quasicrystal layer is formed, resulting in the outer body of the body A layer of continuous hydrophobic structure cannot be formed on the surface.
  • the non-stick properties of the cookware are improved, but the improvement is not obvious, and the preparation cost is higher. If the particle size is greater than 150 microns, compared with the body, The non-stick improvement of the cookware is not obvious.
  • the gap between adjacent quasicrystal particles must be designed to be less than 20 microns to prevent the The quasicrystal particles in the quasicrystal layer (the quasicrystal layer far from the body) fall into the quasicrystal layer (the quasicrystal layer near the body) in the inner layer.
  • the cookware in order to form a quasicrystal layer with an appropriate thickness, referring to FIG. 4 (two layers are taken as an example in the figure), the cookware includes 2 to 3 quasicrystal layers.
  • a quasicrystal layer with a suitable thickness can be obtained, which ensures that the pot has high strength, strong corrosion resistance, and better non-stickiness.
  • the quasicrystal layer of the pot has only one layer, if it is in the preparation process, When the step of polishing the outer surface of the crystal layer is included, the thickness of the polished quasicrystal layer will be reduced, which will affect the strength, corrosion resistance and non-stickiness of the cookware. If the number of layers is too large, the thickness of the quasicrystal layer will be thicker, which will cause the non-stickiness of the pot to be improved compared to the body.
  • a quasicrystal layer (which may include different particle diameters) formed by large-size quasicrystal particles may be used.
  • the multi-layer quasicrystal layer formed by quasicrystal particles) is disposed on the inner layer (the inner layer refers to the side near the surface of the body), and the quasicrystal layer formed by small-sized quasicrystal particles is disposed on the outermost layer (most The outer layer refers to the side that is in direct contact with external objects during use). Therefore, the utilization rate of the quasicrystal particles can be greatly improved, and the quasicrystal layer can be guaranteed to have good non-stickiness.
  • the particle size of the quasicrystal particles in the quasicrystal layer from the inside to the outside gradually decreases (from inside to outside means from the inner surface of the body, To the outermost layer of the quasicrystal layer). Therefore, the quasicrystal layer formed by the large-size quasicrystal particles can be arranged on the surface of the body, which can improve the utilization rate of the quasicrystal particles, and make the quasicrystal layer formed by the large-size quasicrystal particles have a certain porosity. A certain porosity can further reduce the thermal conductivity of the quasicrystal layer, make the surface temperature of the entire quasicrystal layer more uniform, which can improve the non-stickiness of the coating.
  • the cost of preparing large-sized quasicrystal particles is low.
  • the consumption cost of the entire process is reduced; however, the porosity has a large impact on the corrosion resistance, so a layer of denser particles is placed on the surface of the quasicrystal layer formed by large-size quasicrystal particles away from the body.
  • the quasicrystal layer formed by quasicrystal particles is used to improve the corrosion resistance and compactness of the quasicrystal layer finally obtained.
  • the quasicrystal layer formed by quasicrystal particles with small particle diameter is more non-sticky, which can improve the quasicrystal layer. Non-sticky cookware.
  • the quasicrystal layer is formed by cold spraying.
  • the preparation process is mature, easy to operate, and easy to control. Pots with different performance parameters can be produced according to different use needs, and it is easy to industrialize production.
  • the quasicrystal layer satisfies at least one of the following conditions:
  • the surface roughness (or surface finish) of the quasicrystal layer is not greater than 2 microns, which helps to further improve the non-stickiness and abrasion resistance of the quasicrystal layer, that is, to further improve the non-stickiness and abrasion resistance of the cookware. ;
  • the thermal conductivity of the quasicrystal layer is from 0.1 W / mK to 3 W / mK, such as 0.1 W / mK, 0.5 W / mK, 1 W / mK, 1.5 W / mK, 2 W / mK, or 3 W / mK. Due to the high thermal conductivity of the body, for example, the thermal conductivity of low-carbon steel exceeds 50 W / mK, when applied to cookware, a temperature difference occurs between the pot body and the bottom of the pot, resulting in paste bottom and sticky pot. The thermal conductivity is low, 0.1 ⁇ 3W / mK, so the quasicrystal layer is set on the body is equivalent to a protective layer on the surface of the pot. The low thermal conductivity of the quasicrystal layer makes the heat uniform on the surface of the pot. Distribution, solve the problem of paste bottom and sticky pot, that is, improve the non-stickiness of the pot;
  • the porosity of the quasicrystal layer is 0.1% or more and 20% or less, such as 0.1%, 0.5%, 1%, 1.5%, 2.0%, 2.5%, 3%, 3.5%, 4%, 5%, 5.5%, 6%, 7%, 8%, 8.5%, 9%, 9.5%, 10%, 11%, 13%, 15%, 17%, 18%, 20%.
  • reasonable pores in the quasicrystal layer can reduce stress concentration and avoid coating cracks, but when the porosity in the quasicrystal layer is greater than 20%, the hardness and wear resistance of the coating will be greatly reduced, resulting in the durability of the quasicrystal layer Sex reduction
  • the content of the quasicrystal material in the quasicrystal layer is 20 to 90% by weight, such as 20% by weight, 30% by weight, 40% by weight, 50% by weight, 60% by weight, 70% by weight, 80% by weight, or 90% by weight. Therefore, it can be ensured that the quasicrystal layer has better non-stickiness, higher strength, and strong corrosion resistance, that is, the cookware has better non-stickiness, higher strength, and stronger corrosion resistance.
  • the invention proposes a cooking appliance.
  • the cooking appliance includes the cookware of the above embodiment.
  • the cooking utensils according to the embodiments of the present invention can effectively prevent food from sticking to the pan during cooking and effectively improve the heating condition of the food by using the cooking utensils of the above embodiments.
  • the cooking appliance of the present invention further includes: a coil plate 400.
  • a heating zone 410 is defined in the coil plate 400, and the lower side portion 130 and the bottom 140 of the cookware are located in the heating zone 410. Therefore, during the cooking process, the lower side portion 130 and the bottom portion 140 of the cookware are directly heated, and the heat is concentrated. Furthermore, by setting the thickness of the quasicrystal layer 200 located on the lower side portion 130 and the bottom portion 140 to be greater than the thickness of the quasicrystal layer 200 located on the upper side portion 120 and the mouth portion 110, the heat transfer during cooking can be effectively improved, which is further beneficial to the food Heat evenly to improve the cooking effect of food.
  • the cooking appliance may be a rice cooker, an electric pressure cooker, a soup pot, an electric cooker, a wok, a frying pan, a saucepan, or a milk pan. Accordingly, the cooking appliance of the present invention has a wide range of applications and is highly applicable.
  • the cooking appliance also includes structures or components necessary for conventional cooking appliances.
  • the cooking appliance also includes structures or components necessary for conventional cooking appliances.
  • the rice cooker in addition to the quasicrystal layer and the The cooker body also includes a handle and the like; taking the rice cooker as an example, in addition to the inner liner described above, the rice cooker also includes structures or components such as a cooker body, a base, a steam valve, a lid, an electric heating plate, an operation interface, and the like.
  • the present invention provides a method for preparing the aforementioned cookware.
  • the method includes: spraying at least one time on the inner surface of the body to sequentially form at least one quasicrystal layer containing quasicrystal particles on the inner surface of the body, wherein At least a part of the quasicrystal particles in the quasicrystal layer in contact with the inner surface of the body is embedded in the body.
  • the binding force with the body can be increased, and the quasicrystal particles can first withstand scraping from the outside And because the quasicrystal particles can be firmly combined with the body to prevent the quasicrystal layer from being scraped off, further protecting the body from being damaged, thereby greatly improving the hardness and wear resistance of the surface of the pot, and extending the service life of the pot, Moreover, the setting of the quasicrystal layer also makes the cookware have good non-stickiness, and due to the low surface energy of the quasicrystal particles, and a thin air layer can be formed between the quasicrystal particles, which will further improve the cookware's non-stickiness. viscosity.
  • the quasicrystal layer is formed by cold spraying.
  • the preparation process is mature, easy to operate, and easy to control. Pots with different performance parameters can be produced according to different use needs, and it is easy to industrialize production.
  • the spraying power is 20 to 40kw, such as 20kw, 25kw, 30kw, 35kw, or 50kw.
  • the amount is 5 ⁇ 80g / min, such as 5g / min, 10g / min, 20g / min, 30g / min, 40g / min, 50g / min, 60g / min, 70g / min or 80g / min, and the injection pressure is 1 ⁇ 10MPa , Such as 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, or 10MPa, the heating temperature of spraying gas is 700 ⁇ 800 °C, such as 700 °C, 720 °C, 740 °C, 750 °C, 760 ° C, 780 ° C or 800 ° C.
  • the performance of the prepared quasicrystal layer is the best, and the non-stickiness, abrasion resistance and corrosion resistance of the cookware are the best.
  • the spray power is too large or too small, and the performance of the prepared cookware is compared with the body.
  • the improvement is not obvious; due to the higher room temperature brittleness of the quasicrystal, the shaping and ductility of the quasicrystal above 600 ° C are greatly improved. Therefore, in order to obtain a quasicrystal layer with better performance, the cold spray temperature of this application is 700-800 ° C.
  • the performance of the quasicrystal layer obtained in this temperature range is better than that obtained in other temperature ranges.
  • the powder feed amount is more than 80g / min, the fastness of the quasicrystal particles and the body is poor, and the adhesion is not good. Compared with the main body, the effect of improving the non-stickiness, strength and corrosion resistance of the pot is not obvious; if the powder feeding amount is less than 30g / min, although a quasicrystal layer with better performance can be formed, the spraying efficiency is lower and the cost is increased ; If the injection pressure is greater than 10MPa, it is possible to completely embed the quasicrystal particles in the body if the injection pressure is less than 1MPa. If the injection pressure is less than 1MPa, the quasicrystal particles are too small in the body, and the quasicrystal particles and the body are too small. Binding force Strong, so it will affect the life of the cookware.
  • the quasicrystal particles are obtained through the following steps:
  • the first quasicrystal powder is an aluminum reference crystal powder
  • the step of forming the aluminum reference crystal powder in order to obtain a quasicrystal layer with a high quasicrystal content, aluminum, copper, and iron
  • the atomic number ratio with chromium is (60-70): (15-25): (5-15): (5-15).
  • the quasicrystal content in the quasicrystal layer finally obtained can be relatively high, which can reach 20-90%, so that the quasicrystal layer has better non-stickiness.
  • the quasicrystal obtained by the above method has five-times rotation symmetry or ten-times rotation symmetry feature.
  • quasicrystals have the above-mentioned special quasi-periodic arrangement characteristics.
  • the quasicrystals cannot fill the entire space.
  • the coating surface formed by the quasicrystals has micron- or micro-nanoscale gaps composed of crystal grains. Concave-convex structure, this structure can play an excellent hydrophobic effect, better non-stick effect.
  • the crystal shape of the quasicrystal is a polyhedron structure. Therefore, the grains formed by the polyhedron structure cannot fill the entire space, and the surface of the quasicrystal layer contains an uneven structure, so as to achieve a non-stick effect.
  • the crystal shape of the quasicrystal is icosahedron or rhombohedral (tenth quasicrystal). Therefore, when the quasicrystal contains icosahedron or rhombohedral (ten-time quasicrystal) grains, it has a denser structure, which makes the quasicrystal have higher hardness, wear resistance, scratch resistance, and corrosion resistance. , Longer service life, and better non-stick performance, thereby making the use of coatings containing the above quasicrystals better.
  • the alloy ingot is subjected to atomizing powder treatment in a vacuum or a protective atmosphere, so as to obtain a first quasicrystal powder.
  • the alloy ingot in the atomizing and pulverizing treatment, is melted into a liquid at 1000 to 1200 ° C., and then the rapid-moving fluid (atomizing medium) is impacted or otherwise melted.
  • the liquid is broken up into fine droplets, and then condensed into a solid powder, that is, a first quasicrystal powder.
  • the process is mature, easy to operate, and easy to industrialize.
  • S300 Spheroidize the first quasicrystal powder to obtain quasicrystal particles.
  • quasicrystal particles with a desired particle size can be obtained, and quasicrystal particles with a particle diameter of 20 ⁇ m to 150 ⁇ m can be obtained through screening, for example, 20 ⁇ m, 50 ⁇ m, 70 ⁇ m, 90 ⁇ m, 100 ⁇ m, 130 Micron or 150 micron.
  • the quasicrystal particles can be perfectly embedded in the body; if the particle diameter is less than 20 micrometers, some quasicrystal particles may be completely embedded in the body when the quasicrystal layer is formed, resulting in the interior of the body.
  • a layer of continuous hydrophobic structure cannot be formed on the surface.
  • the non-stick properties of the cookware are improved, but the improvement is not obvious, and the preparation cost is higher. If the particle size is greater than 150 microns, compared with the body, The non-stick improvement of the cookware is not obvious, and the powder output rate is not good when spraying. It should be noted that when the quasicrystal particles have a particle size of 20 to 150 microns and the cookware includes multiple quasicrystal layers, the gap between adjacent quasicrystal particles must be designed to be less than 20 microns to prevent the The quasicrystal particles in the quasicrystal layer (the quasicrystal layer far from the body) fall into the quasicrystal layer (the quasicrystal layer near the body) in the inner layer.
  • the method further includes a step of aligning and polishing the outer surface of the crystal layer.
  • the surface roughness of the quasicrystal layer can be reduced, a quasicrystal layer having a more suitable surface roughness can be obtained, and the non-stickiness of the quasicrystal layer can be improved.
  • the surface roughness of the quasicrystal layer is less than 2 microns. This helps to further improve the non-stickiness of the quasicrystal layer.
  • the non-stickiness of the cookware means that when the cookware is used in cooking equipment, the body of the cookware is used as the cookware body or the liner body, and the quasicrystal layer of the cookware is disposed on the cookware body or the liner body. When it is on the inner surface, that is, the quasicrystal layer is directly contacted with the food, and the food does not stick to the pot during the cooking process.
  • the invention proposes a system for preparing a pan.
  • the system includes: a mixing device 1000, a pressing device 2000, and a sintering device 3000.
  • the mixing device 100 is suitable for mixing the second quasicrystal powder with the additive to obtain a mixed material
  • the pressing device 2000 is connected to the mixing device 1000 and is suitable for applying the mixed material to the inner surface of the body so as to A primary quasicrystal layer is formed on the inner surface of the substrate
  • the sintering device 3000 is connected to the pressing device 2000, and is suitable for sintering the body formed with the primary quasicrystal layer to obtain a cooker.
  • the mixing device 100 is suitable for mixing the second quasicrystal powder with the additive to obtain a mixed material
  • the pressing device 2000 is connected to the mixing device 1000 and is suitable for applying the mixed material to the inner surface of the body so as to A quasicrystal layer is formed on the inner surface of the body
  • the sintering device 3000 is connected to the pressing device 2000, and is suitable for sintering the body with the crystal layer formed to obtain a cooker.
  • a second quasicrystal powder is mixed with an additive by using a mixing device, and the addition of the additive can make the second quasicrystal powder have better fluidity. It is easier to press and demold, and can further improve the flow performance of the second quasicrystal powder. Further, the body of the cooker is pressed by a pressing device, and a mixture material including a second quasicrystal powder and an additive is applied to the inner surface of the body to form a primary quasicrystal layer (or a quasicrystal layer) on the surface of the body. .
  • the second quasicrystal powder particles in the quasicrystal layer can be bonded through atomic diffusion to enhance the bonding between the particles and further improve the quasicrystal layer sintered body.
  • Strength and density thereby further improving the surface properties of the inner surface of the cookware (such as high hardness, low friction coefficient, wear resistance, corrosion resistance, etc.). Therefore, according to the system for preparing a cooker according to the embodiment of the present invention, a quasicrystal layer is formed on the inner surface of the cooker body through a powder metallurgy process, which can significantly improve the surface performance of the cooker.
  • the mixing device 1000 is adapted to mix the second quasicrystal powder with the additive so as to obtain a mixed material.
  • the addition of a lubricant can make the second quasicrystal powder have better fluidity, and it is easier to press and demould in the subsequent process; and the binder can further improve the flow performance of the second quasicrystal powder.
  • the additives may include a lubricant and a binder.
  • the types of the above-mentioned lubricants and binders are not particularly limited, and lubricants and binders of powder metallurgy processes that are well known to those skilled in the art may be used.
  • the above-mentioned lubricant and binder may be independently selected from the group consisting of zinc stearate (ZnSt), lithium stearate, stearic acid, paraffin, and ethylene distearate (EBS). At least one of them.
  • the fluidity of the mixed material can be further improved, so that it can be more easily pressed and demoulded in the subsequent process.
  • at least one of zinc stearate, lithium stearate, stearic acid, paraffin, and ethylenebisstearic acid amide has the functions of a lubricant and a binder. Actually need to choose.
  • the added amount of the binder is 0.2 to 1.0% by weight of the second quasicrystal powder, for example, 0.2% by weight, 0.4% by weight, 0.6% by weight, 0.8% by weight, or 1.0% by weight, It is thoroughly mixed with the second quasicrystal powder by stirring.
  • the pressing device 2000 is connected to the mixing device 1000 and is adapted to apply the mixed material to the inner surface of the body so as to form a primary quasicrystal layer (or, form a quasicrystal layer) on the inner surface of the body. .
  • the body can be pressed under a suitable heating condition, and the pressing temperature can be 90-150 ° C, such as 90 ° C, 100 ° C, 110 ° C, 120 ° C, 130 ° C, 140 ° C or 150 ° C.
  • the pressing force may be 400 to 850 MPa, for example, 400 MPa, 450 MPa, 500 MPa, 550 MPa, 600 MPa, 650 MPa, 700 MPa, 750 MPa, 800 MPa, or 850 MPa. Therefore, it can be further beneficial to form a primary quasicrystal layer (or, in other words, form a quasicrystal layer) on the inner surface of the body by using the mixed material.
  • the sintering device 3000 is connected to the pressing device 2000, and is suitable for sintering the body formed with the primary quasicrystal layer, so as to obtain a pot with an quasicrystal layer formed on the inner surface.
  • the second mechanically mixed second quasicrystal powder particles can be bonded by atomic diffusion at the sintering temperature, and the bonding between the particles can be enhanced to achieve the purpose of improving the strength and density of the sintered body.
  • the sintering treatment may be performed in an inert atmosphere (such as a nitrogen atmosphere, an argon atmosphere) or a vacuum.
  • the temperature of the sintering treatment is 700 to 1000 ° C, such as 700 ° C, 750 ° C, 800 ° C, 850 ° C. , 900 ° C, 950 ° C or 1000 ° C. Therefore, the bonding between the second quasicrystal powder particles can be further facilitated, thereby further improving the surface performance of the quasicrystal layer.
  • the conditions of the sintering treatment may include: heating up to 150-250 ° C, for example, 150 ° C, 170 ° C, 190 ° C, 210 ° C, 230 ° C or 250 ° C, and holding for 20 minutes; heating up to 350-450 ° C, For example, 350 ° C, 370 ° C, 390 ° C, 410 ° C, 430 ° C, or 450 ° C, and hold for 10 minutes; heat up to 700 ⁇ 1000 ° C, such as 700 ° C, 750 ° C, 800 ° C, 850 ° C, 900 ° C, 950 ° C, or 1000 ° C , Keep for 30min. Therefore, the bonding between the second quasicrystal powder particles can be further facilitated, thereby further improving the surface performance of the quasicrystal layer.
  • the system for preparing a pan according to the present invention further includes a pre-burning device 4000.
  • the burn-in device 4000 is provided between the pressing device 2000 and the sintering device 3000, and is suitable for pre-burning the body formed with the primary quasicrystal layer before the sintering process.
  • pre-firing the body on which the primary quasicrystal layer is formed at least a part of the lubricant and / or the binder in the compact (primary quasicrystal layer) can be effectively eliminated.
  • the pre-firing conditions include: heating to 400-450 ° C. at a heating rate of 5 ° C./min in a hydrogen atmosphere, for example, 400 ° C., 410 ° C., 420 ° C., 430 ° C., and 440 ° C.
  • the foregoing calcination may be performed by placing the compact in an aluminum wire resistance furnace.
  • the system for preparing a pan according to the present invention further includes a polishing device 5000.
  • the polishing device 5000 is connected to a 4000 sintering device and is suitable for polishing the cookware, or polishing the quasicrystal layer on the inner surface of the cookware.
  • the system for preparing a pan according to the present invention further includes: a melting device 7000 and a pulverizing device 8000.
  • the melting device 7000 is adapted to subject a mixture containing at least one of aluminum, copper, iron, and chromium to a smelting alloy ingot;
  • a pulverizing device 8000 is connected to the melting device 7000 and a mixing device 1000, and It is suitable for quasicrystal alloy ingot to be pulverized so as to obtain a second quasicrystal powder.
  • the melting device 7000 may be an intermediate frequency induction furnace
  • the powder making device 8000 may be an atomizing powder making device.
  • the quasi-crystalline alloy ingot is formed by performing a melting treatment on a mixture containing at least one of an aluminum material, a copper material, an iron material, and a chromium material. Therefore, the obtained quasicrystal alloy ingot is more suitable for subsequent formation of a quasicrystal layer.
  • the atomic percentages of aluminum, copper, iron, and chromium in the mixture are: 60 to 70% aluminum, 10 to 25% copper, 5 to 15% iron, and 5 to 15% chromium.
  • the quasicrystal content in the obtained quasicrystal layer can be made high.
  • the above-mentioned mixture contains aluminum, copper, and iron having an atomic ratio of (60-70): (15-25): (5-15); in some other implementations of the present invention, In the example, the above mixture contains aluminum, copper, iron, and chromium having a ratio of atomic numbers of (60-70): (15-25): (5-15): (5-15).
  • the aluminum material is pure aluminum
  • the copper material is pure copper
  • the iron material is pure iron
  • the chromium material is pure chromium or chrome-titanium alloy.
  • the inventors have discovered that by using a chrome-titanium alloy as a chromium material for preparing a quasi-crystalline alloy ingot, that is, by adding an appropriate amount of titanium element to the quasi-crystal, the intercrystalline corrosion tendency of the quasi-crystalline alloy can be further reduced, thereby making it Corrosion resistance is further improved.
  • the above-mentioned aluminum material, copper material, iron material, and chrome material can be all conventional products obtained through commercial purchase.
  • the system for preparing a pan according to the present invention further includes: a screening device 6000.
  • the sieving device 6000 is connected to the mixing device 1000 and is suitable for sieving the quasicrystal alloy powder to obtain a second quasicrystal powder.
  • the sieving device 6000 is connected to the pulverizing device 8000 (not shown in the figure) and the mixing device 1000, and is suitable for sieving the pulverized product to obtain a second quasicrystalline powder. .
  • the second quasicrystal powder obtained by sieving at least 90% of the particles have a particle size of not more than 180 ⁇ m. Therefore, using the second quasicrystal powder with the above-mentioned particle size to form a quasicrystal layer can effectively reduce the surface roughness of the obtained quasicrystal layer and improve the surface performance of the quasicrystal layer. If the particle size of the second quasicrystal powder is too large, the surface roughness of the quasicrystal layer will be increased, resulting in too large porosity and high roughness of the quasicrystal layer. Due to the capillary effect of the pores, the water droplets will spread on the surface. The surface of the coating reduces the hydrophobic angle, which results in a decrease in the non-stick properties of the quasicrystal layer.
  • the present invention provides a method for preparing a cooker by using the system for preparing a cooker according to the foregoing embodiment.
  • the method includes: (1) supplying a second quasicrystal powder and an additive to a mixing device for mixing, so as to obtain a mixed material; (2) pressing the body with a pressing device, and mixing the mixture The material is applied to the inner surface of the body so as to form a primary quasicrystal layer on the inner surface of the body; (3) the body on which the primary quasicrystal layer is formed is subjected to a sintering treatment to obtain a pan.
  • the method includes: (1) supplying the second quasicrystal powder and the additive to a mixing device for mixing to obtain a mixed material; (2) using a pressing device to press the body and applying the mixed material to a pot The inner surface of the body, so as to form a quasicrystal layer on the inner surface of the pot body; (3) sintering the pot body formed with the quasicrystal layer to obtain a pot.
  • a second quasicrystal powder is mixed with an additive by using a mixing device, and the addition of the additive can make the second quasicrystal powder have better fluidity.
  • the body of the cooker is pressed by a pressing device, and a mixture material including a second quasicrystal powder and an additive is applied to an inner surface of the body to form a quasicrystal layer on the surface of the body.
  • the sintering process is performed on the pre-fired body formed with the primary quasicrystal layer (or, in other words, the quasicrystal layer) by using a sintering device, so that the primary quasicrystal can be formed.
  • the second quasicrystal powder particles in the layer are bonded by atomic diffusion to enhance the bonding between the particles, and further improve the strength and density of the sintered body of the quasicrystal layer, thereby further improving the surface properties of the body surface. Therefore, according to the method for preparing a cooker according to the embodiment of the present invention, a quasicrystal layer is formed on the inner surface of the cooker by a powder metallurgy process, which can significantly improve the surface performance of the cooker.
  • the method includes:
  • the second quasicrystal powder and the additive are supplied to a mixing device and mixed to obtain a mixed material.
  • the addition of a lubricant can make the second quasicrystal powder have better fluidity, and it is easier to press and demould in the subsequent process; and the binder can further improve the flow performance of the second quasicrystal powder.
  • the additives may include a lubricant and a binder.
  • the types of the above-mentioned lubricants and binders are not particularly limited, and lubricants and binders of powder metallurgy processes that are well known to those skilled in the art may be used.
  • the above-mentioned lubricant and binder may be independently selected from the group consisting of zinc stearate (ZnSt), lithium stearate, stearic acid, paraffin, and ethylene distearate (EBS). At least one of them.
  • the fluidity of the mixed material can be further improved, so that it can be more easily pressed and demoulded in the subsequent process.
  • at least one of zinc stearate, lithium stearate, stearic acid, paraffin, and ethylenebisstearic acid amide has the functions of a lubricant and a binder. Actually need to choose.
  • the added amount of the binder is 0.2 to 1.0% by weight of the second quasicrystal powder, for example, 0.2% by weight, 0.4% by weight, 0.6% by weight, 0.8% by weight, or 1.0% by weight, It is thoroughly mixed with the second quasicrystal powder by stirring.
  • the body is pressed by a pressing device, and the mixture is applied to the inner surface of the body so as to form a quasicrystal layer on the inner surface of the body.
  • the body can be pressed under a suitable heating condition, and the pressing temperature can be 90-150 ° C, such as 90 ° C, 100 ° C, 110 ° C, 120 ° C, 130 ° C, 140 ° C or 150 ° C.
  • the pressing force may be 400 to 850 MPa, for example, 400 MPa, 450 MPa, 500 MPa, 550 MPa, 600 MPa, 650 MPa, 700 MPa, 750 MPa, 800 MPa, or 850 MPa. Therefore, it is further advantageous to form a primary quasicrystal layer (or, in other words, form a quasicrystal layer) on the inner surface of the body by using the mixed material.
  • the body on which the primary quasicrystal layer is formed is subjected to a sintering process to obtain a cooker.
  • the second mechanically mixed second quasicrystal powder particles can be bonded by atomic diffusion at the sintering temperature, and the bonding between the particles can be enhanced to achieve the purpose of improving the strength and density of the sintered body.
  • the sintering treatment may be performed in an inert atmosphere (such as a nitrogen atmosphere, an argon atmosphere) or a vacuum.
  • the temperature of the sintering treatment is 700 to 1000 ° C, such as 700 ° C, 750 ° C, 800 ° C, 850 ° C , 900 ° C, 950 ° C or 1000 ° C. Therefore, the bonding between the second quasicrystal powder particles can be further facilitated, thereby further improving the surface performance of the quasicrystal layer.
  • the conditions of the sintering treatment may include: heating up to 150-250 ° C, for example, 150 ° C, 170 ° C, 190 ° C, 210 ° C, 230 ° C or 250 ° C, and holding for 20 minutes; heating up to 350-450 ° C, For example, 350 ° C, 370 ° C, 390 ° C, 410 ° C, 430 ° C, or 450 ° C, and hold for 10 minutes; heat up to 700 ⁇ 1000 ° C, such as 700 ° C, 750 ° C, 800 ° C, 850 ° C, 900 ° C, 950 ° C, or 1000 ° C , Keep for 30min. Therefore, the bonding between the second quasicrystal powder particles can be further facilitated, thereby further improving the surface performance of the quasicrystal layer.
  • the method for preparing a pan according to the present invention before S3000 further includes:
  • the body on which the quasicrystal layer is formed is supplied to a burn-in device for burn-in.
  • a burn-in device for burn-in.
  • the pre-firing conditions include: heating to 400-450 ° C. at a heating rate of 5 ° C./min in a hydrogen atmosphere, such as 400 ° C., 410 ° C., 420 ° C., 430 ° C., and 440 ° C.
  • the foregoing calcination may be performed by placing the compact in an aluminum wire resistance furnace.
  • the method for preparing a pan according to the present invention further includes: S5000: a pulverizing process and S6000: a smelting process.
  • the second quasicrystal powder is prepared from a quasicrystal alloy ingot through a powder treatment S5000.
  • the quasicrystal alloy ingot is prepared by melting a mixture containing at least one of aluminum, copper, iron, and chromium. Processed by S6000.
  • the atomic percentages of aluminum, copper, iron, and chromium in the mixture are: 60 to 70% aluminum, 10 to 25% copper, 5 to 15% iron, and 5 to 15% chromium .
  • the quasicrystal content in the obtained quasicrystal layer can be made high.
  • the above-mentioned mixture contains aluminum, copper, and iron having an atomic ratio of (60-70): (15-25): (5-15); in some other implementations of the present invention, In the example, the above mixture contains aluminum, copper, iron, and chromium having a ratio of atomic numbers of (60-70): (15-25): (5-15): (5-15).
  • the aluminum material is pure aluminum
  • the copper material is pure copper
  • the iron material is pure iron
  • the chromium material is pure chromium or chrome-titanium alloy.
  • the inventors have discovered that by using a chrome-titanium alloy as a chromium material for preparing a quasi-crystalline alloy ingot, that is, by adding an appropriate amount of titanium element to the quasi-crystal, the intercrystalline corrosion tendency of the quasi-crystalline alloy can be further reduced, thereby making it Corrosion resistance is further improved.
  • the above-mentioned aluminum material, copper material, iron material, and chrome material can be all conventional products obtained through commercial purchase.
  • the method for preparing a pan according to the present invention after S3000 further includes:
  • the cookware obtained from S300 is polished.
  • the method for preparing a pan according to the present invention before S1000 further includes:
  • the crystalline alloy powder is sieved to obtain a second quasi-crystalline powder for performing S1000.
  • the pulverized product is sieved to obtain a second quasi-crystalline powder.
  • the second quasicrystal powder obtained by sieving at least 90% of the particles have a particle size of not more than 180 ⁇ m. Therefore, using the second quasicrystal powder with the above-mentioned particle size to form a quasicrystal layer can effectively reduce the surface roughness of the obtained quasicrystal layer and improve the surface performance of the quasicrystal layer. If the particle size of the second quasicrystal powder is too large, the surface roughness of the quasicrystal layer will be increased, resulting in too large porosity and high roughness of the quasicrystal layer. Due to the capillary effect of the pores, the water droplets will spread on the surface. The surface of the coating reduces the hydrophobic angle, which results in a decrease in the non-stick properties of the quasicrystal layer.
  • the present invention also provides a system for preparing a pan.
  • the system includes: a mixing device, a pressing device, a calcining device, and a sintering device.
  • the mixing device is suitable for mixing the second quasicrystal powder with a lubricant and a binder to obtain a mixed material;
  • the pressing device is connected to the mixing device and is suitable for applying the mixed material to the inner surface of the body so that A primary quasicrystal layer is formed on the inner surface of the body;
  • the pre-firing device is connected to the pressing device and is suitable for pre-firing the body on which the primary quasi-crystal layer is formed;
  • the sintering device is connected to the pre-firing device and is suitable for pre-firing
  • the body formed with the primary quasicrystal layer is subjected to a sintering treatment to obtain a cooker.
  • a quasicrystal powder is first mixed with a lubricant and a binder using a mixing device.
  • the addition of a lubricant can make the quasicrystal powder have better fluidity.
  • the subsequent process is easier to press and demold; and the binder can further improve the flow properties of the second quasicrystal powder.
  • the body of the cooker is pressed by a pressing device, and a mixed material including a second quasicrystal powder, a lubricant, and a binder is applied to an inner surface of the main body to form a primary quasicrystal layer on the surface of the body.
  • the sintering device After firing and removing at least a part of the lubricant and / or the binder, the sintering device is used to sinter the pre-fired body formed with the primary quasicrystal layer, so that the second quasicrystal powder particles in the primary quasicrystal layer can be sintered.
  • Atomic diffusion produces bonding, which strengthens the bonding between particles, further increasing the strength and density of the sintered body of the quasicrystal layer, thereby further improving the surface properties of the inner surface of the cookware (such as high hardness, low friction coefficient, wear resistance, Corrosion, etc.). Therefore, according to the system for preparing a cooker according to the embodiment of the present invention, a quasicrystal layer is formed on the inner surface of the cooker body through a powder metallurgy process, which can significantly improve the surface performance of the cooker.
  • the mixing device is adapted to mix the quasicrystal powder with a lubricant and a binder so as to obtain a mixed material.
  • a lubricant can make the quasicrystal powder have better fluidity, and it is easier to press and demould in the subsequent process; and the binder can further improve the flow performance of the quasicrystal powder.
  • the types of the above-mentioned lubricants and binders are not particularly limited, and lubricants and binders of powder metallurgy processes that are well known to those skilled in the art may be used.
  • the above-mentioned lubricant and binder may be independently selected from the group consisting of zinc stearate (ZnSt), lithium stearate, stearic acid, paraffin, and ethylene distearate (EBS). At least one of them. Therefore, the fluidity of the mixed material can be further improved, so that it can be more easily pressed and demoulded in the subsequent process. It should be noted that at least one of zinc stearate, lithium stearate, stearic acid, paraffin, and ethylenebisstearic acid amide has the functions of a lubricant and a binder. Actually need to choose.
  • the added amount of the binder is 0.2 to 1.0% by weight of the second quasicrystal powder, for example, 0.2% by weight, 0.4% by weight, 0.6% by weight, 0.8% by weight, or 1.0% by weight, It is thoroughly mixed with the second quasicrystal powder by stirring.
  • the pressing device is connected to the mixing device and is adapted to apply the mixed material to the inner surface of the body so as to form a quasicrystal layer on the inner surface of the body.
  • the body can be pressed under a suitable heating condition, and the pressing temperature can be 90-150 ° C, such as 90 ° C, 100 ° C, 110 ° C, 120 ° C, 130 ° C, 140 ° C or 150 ° C.
  • the pressing force may be 400 to 850 MPa, for example, 400 MPa, 450 MPa, 500 MPa, 550 MPa, 600 MPa, 650 MPa, 700 MPa, 750 MPa, 800 MPa, or 850 MPa. Therefore, it can be further beneficial to form a primary quasicrystal layer (or, in other words, form a quasicrystal layer) on the inner surface of the body by using the mixed material.
  • the pre-burning device is connected to the pressing device and is suitable for pre-burning the body on which the primary quasicrystal layer is formed.
  • pre-firing the body on which the primary quasicrystal layer is formed at least a part of the lubricant and / or the binder in the compact can be effectively eliminated.
  • the pre-firing conditions include: heating to 400-450 ° C. at a heating rate of 5 ° C./min in a hydrogen atmosphere, for example, 400 ° C., 410 ° C., 420 ° C., 430 ° C., and 440 ° C.
  • the calcining may be performed by placing the compact (primary quasicrystal layer) in an aluminum wire resistance furnace.
  • the sintering device is connected to the pre-sintering device, and is suitable for pre-sintering the body formed with the primary quasicrystal layer to perform the sintering treatment so as to obtain a cooker.
  • the second mechanically mixed second quasicrystal powder particles can be bonded by atomic diffusion at the sintering temperature, and the bonding between the particles can be enhanced to achieve the purpose of improving the strength and density of the sintered body.
  • the sintering treatment may be performed in an inert atmosphere (such as a nitrogen atmosphere, an argon atmosphere) or a vacuum.
  • the temperature of the sintering treatment is 700 to 1000 ° C, such as 700 ° C, 750 ° C, 800 ° C, 850 ° C. , 900 ° C, 950 ° C or 1000 ° C. Therefore, the bonding between the second quasicrystal powder particles can be further facilitated, thereby further improving the surface performance of the quasicrystal layer.
  • the conditions of the sintering treatment may include: heating up to 150-250 ° C, for example, 150 ° C, 170 ° C, 190 ° C, 210 ° C, 230 ° C or 250 ° C, and holding for 20 minutes; heating up to 350-450 ° C, For example, 350 ° C, 370 ° C, 390 ° C, 410 ° C, 430 ° C, or 450 ° C, and hold for 10 minutes; heat up to 700 ⁇ 1000 ° C, such as 700 ° C, 750 ° C, 800 ° C, 850 ° C, 900 ° C, 950 ° C, or 1000 ° C , Keep for 30min. Therefore, the bonding between the second quasicrystal powder particles can be further facilitated, thereby further improving the surface performance of the quasicrystal layer.
  • the system for preparing a cookware may further include: a polishing device.
  • the polishing device is connected to the sintering device and is suitable for polishing the cookware, or polishing the quasicrystal layer on the inner surface of the cookware.
  • the system for preparing a cooker may further include: a melting device and a powder making device.
  • the melting device is suitable for smelting a mixture containing at least one of aluminum, copper, iron, and chromium to obtain a quasicrystalline alloy ingot;
  • the pulverizing device is connected to the smelting device and the mixing device, and is suitable for The crystalline alloy ingot is pulverized to obtain a second quasicrystalline powder.
  • the melting device may be an intermediate frequency induction furnace
  • the powder making device may be an atomizing powder making device
  • the quasi-crystalline alloy ingot is formed by performing a melting treatment on a mixture containing at least one of an aluminum material, a copper material, an iron material, and a chromium material. Therefore, the obtained quasicrystal alloy ingot is more suitable for subsequent formation of a quasicrystal layer.
  • the atomic percentages of aluminum, copper, iron, and chromium in the mixture are: 60 to 70% aluminum, 10 to 25% copper, 5 to 15% iron, and 5 to 15% chromium.
  • the quasicrystal content in the obtained quasicrystal layer can be made high.
  • the above-mentioned mixture contains aluminum, copper, and iron having an atomic ratio of (60-70): (15-25): (5-15); in some other implementations of the present invention, In the example, the above mixture contains aluminum, copper, iron, and chromium having a ratio of atomic numbers of (60-70): (15-25): (5-15): (5-15).
  • the aluminum material is pure aluminum
  • the copper material is pure copper
  • the iron material is pure iron
  • the chromium material is pure chromium or chrome-titanium alloy.
  • the inventors have discovered that by using a chrome-titanium alloy as a chromium material for preparing a quasi-crystalline alloy ingot, that is, adding an appropriate amount of titanium element to the quasi-crystal, the intercrystalline corrosion tendency of the quasi-crystalline alloy can be further reduced, thereby Corrosion resistance is further improved.
  • the above-mentioned aluminum material, copper material, iron material, and chrome material can be all conventional products obtained through commercial purchase.
  • the system for preparing a cookware may further include: a screening device.
  • the sieving device is connected to the mixing device and is suitable for sieving the second quasicrystal alloy powder to obtain a quasicrystal powder.
  • the pulverized product is sieved to obtain a second quasi-crystalline powder.
  • the quasicrystal powder obtained by sieving at least 90% of the particles have a particle size of not more than 180 ⁇ m. Therefore, using the quasicrystal powder having the above-mentioned particle size to form a quasicrystal layer can effectively reduce the surface roughness of the obtained quasicrystal layer and improve the surface performance of the quasicrystal layer. If the particle size of the quasicrystal powder is too large, the resulting quasicrystal layer may have excessive porosity, high roughness, and reduced surface properties.
  • the steps for preparing the quasicrystal layer are:
  • the first quasicrystal powder is made by using powder making equipment under vacuum or in a protective atmosphere environment.
  • Spheroidization Spheroidizing and sieving the first quasicrystal powder to obtain quasicrystal particles with a particle diameter of 20 ⁇ m-150 ⁇ m.
  • Cleaning the surface of the body Use alcohol, trichloroethylene or pure water and ultrasonic to clean and dry the surface of the body, so that the surface of the body is free of rust before plasma spraying, and then sandblasted to make the surface of the body rough.
  • Cold spraying The cold spraying process using gas heating sprays on the surface of the above body to form a quasicrystal layer with a power of 30kw, a powder feed rate of 75g / min, a spray pressure of 2MPa, and a spraying gas heating temperature of 700 ° C.
  • Polishing Polish the outer surface of the quasicrystal layer to a surface roughness Ra ⁇ 2 microns.
  • the steps for preparing the quasicrystal layer are:
  • the first quasicrystal powder is made by using powder making equipment under vacuum or in a protective atmosphere environment.
  • Spheroidization Spheroidizing and sieving the first quasicrystal powder to obtain quasicrystal particles with a particle diameter of 20 ⁇ m-150 ⁇ m.
  • Cleaning the surface of the body Use alcohol, trichloroethylene or pure water and ultrasonic to clean and dry the surface of the body, so that the surface of the body is free of rust before plasma spraying, and then sandblasted to make the surface of the body rough.
  • Cold spraying The cold spraying process using gas heating sprays on the surface of the above body to form a quasicrystal layer with a power of 30kw, a powder feed rate of 35g / min, a spray pressure of 1.5MPa, and a spraying gas heating temperature of 700 ° C.
  • Polishing Polish the outer surface of the quasicrystal layer to a surface roughness Ra ⁇ 2 microns.
  • the steps for preparing the quasicrystal layer are:
  • the first quasicrystal powder is made by using powder making equipment under vacuum or in a protective atmosphere environment.
  • Spheroidization Spheroidizing and sieving the first quasicrystal powder to obtain quasicrystal particles with a particle diameter of 20 ⁇ m-150 ⁇ m.
  • Cleaning the surface of the body Use alcohol, trichloroethylene or pure water and ultrasonic to clean and dry the surface of the body, so that the surface of the body is free of rust before plasma spraying, and then sandblasted to make the surface of the body rough.
  • Cold spraying The cold spraying process using gas heating sprays on the surface of the above body to form a quasicrystal layer with a power of 30kw, a powder feed rate of 10g / min, a spray pressure of 5MPa, and a spraying gas heating temperature of 700 ° C.
  • Polishing Polish the outer surface of the quasicrystal layer to a surface roughness Ra ⁇ 2 microns.
  • the body of the above examples 1-3 is made of aluminum alloy, and the quasicrystal content in the aluminum alloy and the quasicrystal layer is measured by X-ray diffraction spectroscopy.
  • the hardness is measured by a Vickers hardness tester.
  • the hydrophobic angle is measured by a hydrophobic angle tester. Table 1. The larger the hydrophobic angle, the better the non-stickiness.
  • the non-stickiness is the test method for the non-stickiness of fried eggs. The test methods and standards are tested according to the national standard GB / T 32095-2015.
  • the quasi-crystalline alloy ingot is supplied to the atomizing and powder-making device, and atomization and pulverization is performed, and the whole process is protected by inert gas or vacuum is applied to the system to obtain the quasi-crystalline alloy powder.
  • the quasicrystalline alloy powder is supplied to a sieving device, and sieving yields at least 90% of a second quasicrystalline powder having a particle diameter of not more than 180 ⁇ m.
  • the second quasicrystal powder is mixed with zinc stearate (added amount is 0.2 to 1.0% by weight, and used as a lubricant and a binder at the same time) to obtain a mixed material.
  • the pressing device is used to press the main body at a temperature of 90 to 150 ° C. and a pressing force of 400 to 850 MPa, and the mixed material is applied to the inner surface of the main body so as to form a quasicrystal layer on the inner surface of the main body.
  • the body formed with the quasicrystal layer is supplied to a calcination device for calcination.
  • the calcination conditions include: heating in a hydrogen atmosphere to 400-450 ° C and holding for 20 minutes; heating to 600-650 ° C, holding 10 to 60 minutes, in which the heating rate is 5 ° C / min.
  • the surface morphology of the quasicrystal layer of the product was detected by a scanning electron microscope, and the results are shown in FIG. 20.
  • the scale is 1 mm (magnified 100 times); It was 100 ⁇ m (1000 times magnification).
  • the test results show that the quasicrystal layer formed on the surface of the body by powder metallurgy has fewer defects.

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  • Physics & Mathematics (AREA)
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Abstract

L'invention concerne un récipient de cuisson et son procédé de fabrication, un système de fabrication d'un récipient de cuisson, et un ustensile de cuisine. Le récipient de cuisson comprend un corps principal (100) et un revêtement quasi cristallin (200) formé au niveau du corps principal (100). Au moins une opération de pulvérisation est effectuée sur une surface interne (11) du corps principal (100) pour former le revêtement quasi cristallin (200). Le système de fabrication d'un récipient de cuisson comprend un dispositif de mélange de matériau (1000), un dispositif de pressage (2000) et un dispositif de frittage (3000) pour mélanger et appliquer des matériaux et pour effectuer un frittage sur ceux-ci. Le revêtement quasi cristallin peut améliorer significativement la rigidité, la résistance à l'abrasion, la résistance à la corrosion et les performances antiadhésives d'un récipient de cuisson.
PCT/CN2019/076732 2018-07-27 2019-03-01 Récipient de cuisson et son procédé de fabrication, système de fabrication de récipient de cuisson et ustensile de cuisine WO2020019716A1 (fr)

Applications Claiming Priority (18)

Application Number Priority Date Filing Date Title
CN201810845000 2018-07-27
CN201810845000.X 2018-07-27
CN201810847209.X 2018-07-27
CN201810847209 2018-07-27
CN201810848225 2018-07-27
CN201810848225.0 2018-07-27
CN201811299619.1A CN110757915A (zh) 2018-07-27 2018-11-02 复合材料及其制备方法、烹饪设备和家用电器
CN201821806207.8 2018-11-02
CN201811299619.1 2018-11-02
CN201811299219.0A CN110754914B (zh) 2018-07-27 2018-11-02 锅具和具有该锅具的烹饪器具
CN201811299230.7A CN110756811B (zh) 2018-07-27 2018-11-02 制备锅具的系统和方法以及锅具
CN201821806829.0U CN209300845U (zh) 2018-07-27 2018-11-02 锅具和烹饪器具
CN201811299219.0 2018-11-02
CN201821806198.2 2018-11-02
CN201821806198.2U CN209550608U (zh) 2018-07-27 2018-11-02 制备锅具的系统以及锅具
CN201821806207.8U CN209883845U (zh) 2018-07-27 2018-11-02 锅具和具有该锅具的烹饪器具
CN201811299230.7 2018-11-02
CN201821806829.0 2018-11-02

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