CN115011888B - Amorphous alloy for non-stick cookware, non-stick cookware and manufacturing method thereof - Google Patents
Amorphous alloy for non-stick cookware, non-stick cookware and manufacturing method thereof Download PDFInfo
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- CN115011888B CN115011888B CN202111107900.2A CN202111107900A CN115011888B CN 115011888 B CN115011888 B CN 115011888B CN 202111107900 A CN202111107900 A CN 202111107900A CN 115011888 B CN115011888 B CN 115011888B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
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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
- A47J36/00—Parts, details or accessories of cooking-vessels
- A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
- A47J36/025—Vessels with non-stick features, e.g. coatings
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/005—Amorphous alloys with Mg as the major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/02—Amorphous alloys with iron as the major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
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- 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
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- 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
- C23C4/08—Metallic material containing only metal elements
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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- Metallurgy (AREA)
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- Food Science & Technology (AREA)
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Abstract
The invention discloses an amorphous alloy for a non-stick cooker, the non-stick cooker and a manufacturing method thereof. The amorphous alloy is represented by formula 1: x is X a Y b Z c Wherein X and Y, Z, a, b and c are the same as defined in the specification. The non-stick cookware having a non-stick coating comprising an amorphous alloy has not only a microscopically concave-convex structure but also a macroscopically porous structure, thereby improving non-stick properties. In addition, the non-stick cooker can be cleaned by using a shovel, a scouring pad, a steel wire ball and the like, and has the advantages of long service life and the like.
Description
Technical Field
The present invention relates to the field of non-stick cookware, and more particularly, to an amorphous alloy for non-stick cookware, a non-stick cookware, and a method of manufacturing the same.
Background
The non-sticking technology of the non-sticking cooker is mainly realized from the following three directions: 1) Self low surface energy;
2) Microscopic concave-convex structure, forming a hydrophobic and oleophobic surface similar to lotus leaf; 3) The porous oil storage forms a stable oil film, and the oil is used as an intermediate to realize non-sticking.
The non-stick materials for the cooker at present mainly comprise fluorine paint, ceramic paint and organic silicon resin. The three are mainly prepared into non-stick coating on the inner surface of the pot in a spray coating mode so as to achieve the purpose of non-stick when heating food. The fluorine paint mainly comprises PTFE (polytetrafluoroethylene), PFOA (ammonium perfluorooctanoate), PFA (copolymer of perfluoropropyl perfluorovinyl ether and polytetrafluoroethylene), FEP (perfluoroethylene propylene copolymer), ETFE (ethylene-tetrafluoroethylene copolymer) and the like, and the non-sticking principle is mainly that the fluorine-containing polymer has extremely low surface free energy. The ceramic coating mainly comprises silicon-oxygen bonds, and is a coating with inorganic silicon as a main component, and the ceramic coating mainly has a nano structure on the surface of a pot body so as to achieve the effect of non-adhesion. The organic silicon resin achieves the effect of non-sticking by mainly utilizing the characteristic of low surface energy. Although the three coatings have non-stick effects, the three coatings have obvious defects, in particular, the fluorine coating has non-stick coating and wear resistance, a shovel cannot be used for stir-frying, a steel wire ball and a scouring pad cannot be used for cleaning, harmful substances can be generated by decomposition at high temperature, and the non-stick performance after wear is reduced; the ceramic paint has a lower non-stick effect than the fluorine paint, and is mainly realized by using silicone oil in a paint system, and has poor lasting non-stick property, and the coating is easy to fall off after being used for 3 to 6 months; the non-sticking effect of the coating formed by the organic silicon resin is poorer than that of the coating formed by the fluorine coating, the color is easy to yellow or ash after contacting with high temperature or open flame, the hardness is reduced at high temperature, and the phenomenon of 'back sticking' is easy to occur. Therefore, the phenomenon that the non-stick material is not sticky enough is common at present.
Therefore, the paint is a bottleneck in terms of non-stick life, and a large breakthrough is difficult to obtain.
Thus, there is an urgent need for improvements in the materials of non-stick coatings.
Disclosure of Invention
The invention aims to provide an amorphous alloy for a non-stick cooker, which not only can enable the surface of the non-stick cooker to have a microscopic concave-convex structure, but also can enable the surface of the non-stick cooker to have a macroscopic porous structure, so that the non-stick cooker can realize a non-stick effect and has long service life, and can be cleaned by using a shovel, a scouring pad or a steel wire ball.
Another object of the present invention is to provide a non-stick cooker including an amorphous alloy and a method of manufacturing the same.
According to an aspect of the present invention, there is provided an amorphous alloy for a non-stick cookware, the amorphous alloy being represented by the following formula 1: x is X a Y b Z c Wherein X and Y are each independently selected from one of Mg, al, ca, se, ti, V, cr, mn, fe, co, ni, cu, zn, ga, ge, Y, zr, nb, mo, tc, in, sn, sb, hf, ta and W, Z is selected from at least one of Mg, al, ca, se, ti, V, cr, mn, fe, co, ni, cu, zn, ga, ge, Y, zr, nb, mo, tc, in, sn, sb, hf, ta, W, C, N, O, B, S and P, X, Y and Z are different from each other, 0.1.ltoreq.a.ltoreq.0.9, 0.1.ltoreq.b.ltoreq.0.9, and 0.9.ltoreq.a+b.ltoreq.1, and 0.ltoreq.c.ltoreq.0.1. The amorphous alloy not only can enable the surface of the non-stick cooker to have a microscopic concave-convex structure, but also can enable the surface of the non-stick cooker to have a macroscopic porous structure, so that the non-stick cooker can realize a non-stick effect and has long service life.
According to an embodiment of the present invention, a difference between an atomic radius of an element represented by X and an atomic radius of an element represented by Y may be greater than or equal to 0.0037nm. The difference between the atomic radii of the element represented by X and the element represented by Y is controlled to be 0.0037nm or more, so that the amorphous alloy has serious lattice distortion, high amorphization degree and low surface energy.
According to an embodiment of the present invention, Z may be selected from at least two of Cu, mo, zn, in, B, P, S, si, mn, ti, al, C, N, O, ga, nb, hf, Y and Sn. The number of elements denoted by Z is controlled to be more than two, so that the crystal lattice of the amorphous alloy is disordered, and the surface energy of the amorphous alloy is low.
According to an embodiment of the present invention, the amorphous alloy may exist in a solid solution phase, and one of an element represented by X and an element represented by Y exists as a solvent, and the other of the element represented by X and the element represented by Y and an element represented by Z exists as a solute. The solid solution has a lattice distortion effect, and each element atom occupies each lattice position with equal opportunity, so that the lattice is distorted, and the configuration of the crystal lattice cannot be maintained, thereby collapsing the lattice to form an amorphous structure.
According to an embodiment of the present invention, the amorphous alloy may exist in the form of particles, and the particle size of the amorphous alloy in the form of particles may be in the range of 200 mesh to 1000 mesh. Controlling the grain size of the amorphous alloy within this range can ensure that the surface of the non-stick cookware is made to have a microscopically concave-convex structure and a macroscopically porous structure.
According to an embodiment of the invention, D is an amorphous alloy in the form of particles 50 The particle size distribution may be in the range of 325 mesh to 500 mesh. D of amorphous alloy 50 The particle size distribution is within this range, and it is further ensured that the surface of the non-sticking cookware is formed into a microscopically concave-convex structure and a macroscopically porous structure.
According to another aspect of the present invention, there is provided a non-stick cooker including: a body including an inner surface carrying the article and an outer surface facing away from the inner surface; and a non-stick coating layer disposed on the inner surface of the body and including the above amorphous alloy. The non-stick cooker comprising the amorphous alloy has the advantages that the non-stick effect is realized, the service life is prolonged, and the non-stick cooker can be cleaned by using a shovel, a scouring pad or a steel wire ball and the like.
According to still another aspect of the present invention, there is provided a method of manufacturing a non-stick cooker, the method comprising the steps of: preparing a body of the non-stick cookware, the body comprising an inner surface carrying an item and an outer surface facing away from the inner surface; thermally spraying the amorphous alloy onto the inner surface of the body; and cooling the amorphous alloy sprayed onto the inner surface of the body at a predetermined cooling rate, thereby forming a non-stick coating on the inner surface of the body. The non-stick coating of the non-stick cooker formed by spraying the amorphous alloy through a thermal spraying process can effectively ensure the formation of a microscopic concave-convex structure and a macroscopic porous structure.
According to an embodiment of the present invention, the step of thermal spraying may be performed under conditions that the speed of feeding the amorphous alloy is 30g/min to 70g/min, the spraying distance is 80mm to 130mm, the arc current is 200A to 350A, and hydrogen and argon are used as working gases. Performing the thermal spraying process under such conditions can improve production efficiency while ensuring formation of the corresponding structures.
According to an embodiment of the present invention, the method may further include surface treating the inner surface of the body before performing the step of thermal spraying, and cooling the inner surface of the body to between-10 ℃ and 5 ℃ in an atmosphere of carbon dioxide gas. Such pretreatment of the inner surface of the body may enhance the bonding force between the body and the non-stick coating.
According to an embodiment of the present invention, the predetermined cooling rate may be 180K/s to 200K/s. Performing cooling in this range can improve production efficiency.
The amorphous alloy according to the present invention is sprayed to the surface of the non-stick cookware through a thermal spray (e.g., supersonic plasma spray) process, not only can the surface of the non-stick cookware have a microscopic concavo-convex structure, but also the surface of the non-stick cookware can have a macroscopic porous structure, thereby enabling the non-stick cookware to achieve a non-stick effect and a long service life, and can be cleaned using a spatula, a scouring pad, a wire ball, or the like.
Drawings
The above and/or other features and aspects of the present invention will become apparent from and be readily appreciated by the description of the embodiments taken in conjunction with the accompanying drawings.
Fig. 1 is a flowchart illustrating a method of preparing an amorphous alloy according to an embodiment of the present invention.
Fig. 2 is a schematic view illustrating a non-stick cooker according to an embodiment of the invention.
Fig. 3 is a flowchart illustrating a method of manufacturing a non-stick cooker according to an embodiment of the invention.
Fig. 4 is an XRD pattern of example 1.
Detailed Description
The embodiments will be described below to explain the present invention by referring to the figures. This invention may, however, be embodied in many different forms and should not be construed as limited to the exemplary embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
According to three directions of the non-stick technology of the current non-stick cookware, the invention uses inorganic materials as non-stick materials for improvement.
The present invention provides an amorphous alloy for a non-stick cookware, the amorphous alloy being represented by formula 1:
1 (1)
X a Y b Z c 。
In formula 1, X and Y are each independently selected from one of Mg, al, ca, se, ti, V, cr, mn, fe, co, ni, cu, zn, ga, ge, Y, zr, nb, mo, tc, in, sn, sb, hf, ta and W.
In an embodiment of the invention, one of X and Y may be selected from one of Mg, al, ti, V, cr, mn, fe, co, ni, cu, zn, mo, tc and W, for example, one of Mg, cr, mn, fe, co, ti, ni, cu, zn, ga and Ge. Specifically, one of X and Y may be Mg, cr, mn, fe, co, ti, ni, cu, for example, mg, ti, fe, or Cu.
The other of X and Y may be selected from one of Mg, al, ca, se, Y, ti, zr, nb, in, zn, sn, sb, hf, ge and Ta, for example, from one of Mg, al, ca, Y, ti, zr, in, zn, sn, sb, ge and Hf. Specifically, the other of X and Y may be Al, ca, Y, ti, zr, zn, ge and In, for example Al, Y, ti, zr, ge or Zn.
In an embodiment of the present invention, a difference between an atomic radius of an element represented by X and an atomic radius of an element represented by Y may be greater than or equal to 0.0037nm. Typically, the radius R of the hydrogen atom is 0.037nm, i.e., the difference between the atomic radius of the element represented by X and the atomic radius of the element represented by Y may be greater than or equal to 0.1R. Preferably, the difference between the atomic radius of the element represented by X and the atomic radius of the element represented by Y may be greater than or equal to 0.0038nm, greater than or equal to 0.0039nm, greater than or equal to 0.004nm, greater than or equal to 0.0041nm, or greater than or equal to 0.0045nm. In the present invention, by controlling the difference between the atomic radii of the element represented by X and the element represented by Y to be 0.0037nm or more, the lattice distortion of the amorphous alloy is serious, the degree of amorphization is high, and the surface energy is low.
In formula 1, Z is selected from at least one of Mg, al, ca, se, ti, V, cr, mn, fe, co, ni, cu, zn, ga, ge, Y, zr, nb, mo, tc, in, sn, sb, hf, ta, W, C, N, O, B, S, si and P. Preferably, Z may be selected from at least two, at least three, or at least four of Cu, mo, zn, in, B, P, S, si, mn, ti, al, C, N, O, ga, nb, hf, Y and Sn. In the present invention, the addition of the element represented by Z corresponds to the addition of the element as an impurity element, and serves as an aid in making the crystal lattice of the amorphous alloy more disordered, that is, by controlling the number of elements represented by Z to two or more, the crystal lattice of the amorphous alloy is disordered, and the surface energy of the amorphous alloy is low.
In the formula 1, a is more than or equal to 0.1 and less than or equal to 0.9, b is more than or equal to 0.1 and less than or equal to 0.9 and less than or equal to 1, and c is more than or equal to 0 and less than or equal to 0.1. In the present invention, if the amount of the element represented by Z is more than 10%, the difficulty and cost of smelting are increased; the amorphous alloy obtained by taking the binary alloy as the main component can be applied to the field of non-stick cookers.
In formula 1, X, Y and Z are different from each other.
Furthermore, in a preferred embodiment of the present invention, the amorphous alloy may be Fe 60 Y 30 In 2 B 3 P 4 S 1 、Fe 45 Ti 50 Si 2 Mn 3 、Fe 20 Zr 70 Ti 1 Al 2 C 4 O 3 、Cu 40 Zn 50 Ga 3 Y 2 Sn 5 、Cu 40 Zn 55 Ga 1 Y 2 Sn 2 、Ti 40 Al 56 Cu 1 Mo 1 Si 1 B 1 、Ti 30 Zr 65 Zn 1 Mn 2 C 1 N 1 Or Mg (Mg) 60 Ge 32 Ga 3 Nb 3 Hf 1 O 1 Etc.
In the embodiment of the present invention, the amorphous alloy for the non-stick cookware may include two main elements and optional impurity elements, and in particular, the amorphous alloy may include or may be composed of two main elements as main components and an impurity element as an auxiliary component. Specifically, the amorphous alloy may include two main elements in total of 90 at% or more and the balance of impurity elements based on the atomic percentage of the amorphous alloy. In addition, the content of any one of the two main elements is 10 at% or more. Here, the two main elements correspond to elements represented by X and Y, respectively, and the impurity element corresponds to an element represented by Z, and therefore, the main elements and the impurity element will not be described in detail.
In the amorphous alloy, a larger amount of impurity elements are added based on main elements, so that the crystal lattice of the amorphous alloy is disordered, and the surface energy of the amorphous alloy is low. In addition, by controlling the atomic radius difference between the main elements, the lattice distortion of the amorphous alloy is serious, and thus the degree of amorphization of the amorphous alloy is high.
In the embodiment of the present invention, the amorphous alloy is mainly composed of binary elements and is mixed with a small amount of various other elements, and thus, the amorphous alloy may exist mainly in a solid solution phase. The solid solution phase is divided into a substitutional solid solution and an interstitial solid solution, and the solid solution has a lattice distortion effect, namely, because the atomic radiuses of all the constituent elements are different, all the element atoms occupy all lattice positions with equal opportunity in the smelting process, so that the lattice of the material is distorted, the lattice distortion of the material can be excessively high due to large atomic size difference, the crystal lattice configuration of the material can not be maintained, and the lattice of the material collapses to form an amorphous structure. Thus, the amorphous alloy according to the present invention can obtain a surface energy far lower than that of conventional materials.
In addition, in an amorphous alloy existing in a solid solution phase, one of an element represented by X and an element represented by Y may exist as a solvent, and the other of the element represented by X and the element represented by Y and the element represented by Z may exist as a solute. That is, for example, taking an element represented by X as a solute and an element represented by Y and an element represented by Z as a solvent as examples, the element represented by Y and the element represented by Z occupy a lattice of atoms of the element represented by X, or the element represented by Y and the element represented by Z occupy a gap between atoms of the element represented by X.
In an embodiment of the present invention, the amorphous alloy may exist in the form of particles, and the particle size of the amorphous alloy in the form of particles may be in the range of 200 mesh to 1000 mesh. If the granularity of the amorphous alloy is higher than 1000 meshes, the powder cost is high, and the size of the amorphous alloy is too small to carry out plasma spraying, so that the cost is wasted; if the granularity of the amorphous alloy is less than 200 meshes, the powder is difficult to melt in the plasma spraying process, cannot adhere to the surface of a non-sticking cooker, and can make the surface of a final coating rough, the post-treatment is difficult to carry out, and the texture is poor.
In addition, D of amorphous alloy in granular form 50 The particle size distribution may be in the range of 325 mesh to 500 mesh. Here, D 50 Refers to the particle size corresponding to the cumulative particle size distribution percentage of the amorphous alloy reaching 50%. D of amorphous alloy in particulate form 50 The particle size distribution is between 325 meshes and 500 meshes, so that the surface of the non-sticking cooker has a microscopic concave-convex structure (fine powder higher than 500 meshes) and macroscopic oil storage micropores (coarse powder lower than 325 meshes).
A method of preparing an amorphous alloy according to an embodiment of the present invention will be described in detail with reference to fig. 1.
Fig. 1 is a flowchart illustrating a method of preparing an amorphous alloy according to an embodiment of the present invention.
Referring to fig. 1, a method of preparing an amorphous alloy according to an embodiment of the present invention includes: melting one of the two main elements as a solvent (step S110); adding the other of the two main elements and the optional impurity element as a solute to the solvent (step S120); atomizing the alloy liquid (step S130); and dehydrating and drying the amorphous alloy particles under the protection of inert gas (step S140).
In step S110, one of the two main elements having a high melting point may be used as a solvent, and the one of the two main elements having a high melting point may be melted under the conditions that the temperature is 1000 ℃ (for example, 1500 ℃) or more and the melting time is 1 hour or more. Specifically, an element (e.g., a metal block) having a relatively high melting point may be placed in a high-temperature crucible under an inert (e.g., argon) atmosphere, and then heated to a completely molten state using an induction furnace.
In step S120, an element (e.g., a metal block) having a relatively low melting point and optionally an impurity element are added as a solute to the solvent. Specifically, elements (e.g., metal blocks) having a relatively low melting point and optional impurity elements may be slowly added as solutes to the solvent formed in step S110, and the melting process is sufficiently stirred, and the melting is repeated a plurality of times to uniformly melt the respective components.
In step S130, the alloy liquid is granulated by a water atomization method. Preferably, the alloy liquid is sprayed to the atomizer, and water having a water pressure of 45MPa to 75MPa and a flow rate of 15L/min to 30L/min is sprayed to the alloy liquid flow in the atomizer under the protection of inert gas, so that the alloy liquid flow is broken, thereby obtaining amorphous alloy particles. Specifically, pouring the alloy liquid in the step S120 into a tundish of an atomization device, and then enabling the alloy liquid in the tundish to enter the atomizer through a discharge spout at the bottom of the tundish through beam current; then, introducing inert shielding gas (such as argon) into the atomizer, wherein the pressure of the inert shielding gas is 0.4MPa to 0.6MPa, and the flow rate is 30L/min to 50L/min; then, under the action of high-pressure water from an atomizer, the alloy liquid is continuously broken into tiny liquid drops, and simultaneously, the tiny liquid drops are quickly solidified into amorphous alloy particles by the high-pressure water, wherein the high-pressure water is purified water after deoxidization, the water pressure is 45MPa to 75MPa, and the flow is 15L/min to 30L/min.
In step S140, the step of dehydrating and drying the amorphous alloy particles is performed at a temperature of 150 to 200 ℃ under an argon atmosphere, thereby obtaining an amorphous alloy.
In addition, the method can further comprise the step of screening the prepared amorphous alloy, so that the amorphous alloy with the granularity of 200 meshes to 1000 meshes is obtained.
In the embodiment of the invention, the high-pressure water atomization technology is adopted for powder preparation, the high-temperature molten alloy liquid is rapidly dispersed and condensed into alloy particles under the impact of high-pressure water flow or water mist, and the powder with proper granularity can be obtained by controlling proper water flow pressure, and the alloy tends to be in an amorphous state due to the fact that the water cooling speed is high, and the alloy does not form a complete crystal structure.
A non-stick cookware comprising an amorphous alloy according to the present invention will be described in detail below with reference to fig. 2.
The non-stick cookware 100 according to an embodiment of the invention includes a body 110 and a non-stick coating 120.
Fig. 2 is a schematic view illustrating a non-stick cooker according to an embodiment of the invention.
Referring to fig. 2, the non-stick cookware 100 according to the present invention includes a body 110 and a non-stick coating 120 provided on the body 110.
The body 110 (or may also be referred to as a pan) may be specifically concave in shape, i.e., the body 110 may have an inner surface for carrying items (e.g., food) or the like and an outer surface facing away from the inner surface. The body 110 may be made of stainless steel or the like; embodiments of the present invention are not limited thereto.
The non-stick coating 120 is disposed on the inner surface of the body 110. The non-stick coating 120 comprises an amorphous alloy as described above. The amorphous alloy herein is the same as the amorphous alloy described above, and thus will not be described here in detail.
A method of manufacturing a non-stick cooker according to the present invention will be described in detail with reference to fig. 3.
The method of manufacturing a non-stick cooker according to the present invention includes: preparing a body of a non-stick cooker (step S210); thermally spraying an amorphous alloy to an inner surface of the body (step S220); and cooling the amorphous alloy sprayed onto the inner surface of the body at a predetermined cooling rate (step S230).
In step S210, a body of a non-stick cookware is prepared, the body comprising an inner surface carrying an item and an outer surface facing away from the inner surface. The body herein may be a body as described above. In an embodiment of the present invention, the inner surface of the body may be surface-treated and cooled to between-10 ℃ and 5 ℃ in the presence of carbon dioxide gas. Such pretreatment of the inner surface of the body may enhance the bonding force between the body and the non-stick coating.
In step S220, the amorphous alloy is sprayed onto the inner surface of the body by a thermal spray (e.g., supersonic plasma spray) process. In the embodiment of the present invention, the step of thermal spraying is performed under the conditions that the speed of feeding the amorphous alloy is 30g/min to 70g/min, the spraying distance is 80mm to 130mm, the arc current is 200A to 350A, and hydrogen and argon are used as working gases. Further, the pressure of supplying hydrogen is 0.2MPa to 0.4MPa, and the flow rate is 3L/min to 8L/min; the pressure of supplying argon is 1.2MPa to 2.0MPa, and the flow rate is 1500L/min to 2500L/min.
In step S230, the amorphous alloy sprayed onto the inner surface of the body may be cooled at a cooling rate of 180K/S to 200K/S, thereby forming a non-stick coating on the inner surface of the body.
In the invention, by selecting amorphous alloy with wider granularity range and controlling spraying conditions (such as relative matching among powder feeding speed, pressure and flow of working gas and spraying distance), the alloy powder can be ensured not to be melted, and the powder can be rapidly cooled from high temperature to low temperature and deposited on the surface of a pot body to form amorphous phase, so that the surface of the non-sticking cooker has microscopic concave-convex structure (fine powder higher than 500 meshes) and macroscopic oil storage micropores (coarse powder lower than 325 meshes). For example, by increasing the powder feeding speed and the flow rate of the working gas, the solid solution amorphous phase can be prevented from becoming crystalline due to precipitation; the spraying distance is shortened, the spraying speed is improved, and the outer surface of the pot body is cooled by adopting low-temperature gas, so that powder can be rapidly cooled from high temperature to low temperature and deposited on the surface of the pot body to form amorphous phase.
In the spraying process, fine powder (more than 500 meshes) is completely melted to form spherical metal liquid drops, irregular spike bulges are formed on the spherical surface under the impact of high-speed argon, and finally the spherical metal liquid drops are deposited on the surface of a pot body with very low temperature, and the liquid drops are retracted into spheres, namely solidified due to the fact that the cooling speed is high, one surface close to the pot body deforms compactly under the effect of impact force, and a microscopic bulge structure is reserved on the surface of the metal liquid drops solidified on the surface far away from the pot body, so that a microscopic concave-convex structure on the surface of the coating is formed. The powder with larger granularity (less than 325 meshes) is only slightly melted on the surface, the deformation is not large, finally, the particles are stacked on the surface of the pot body, gaps are left between the particles due to different sizes and shapes, and a certain depth of pores are formed along with the increase of the film thickness, so that a macroscopic porous structure of the surface of the coating is formed.
According to the embodiment of the present invention, the amorphous alloy according to the present invention is sprayed to the surface of the non-stick cookware by a thermal spraying process, not only can the surface of the non-stick cookware be provided with a microscopic concavo-convex structure, but also the surface of the non-stick cookware can be provided with a macroscopic porous structure (for example, the non-stick coating has an amorphization degree of 83% or more), thereby enabling the non-stick cookware to achieve a non-stick effect and a long service life, and can be cleaned using a spatula, a scouring pad, or a wire ball, etc.
The amorphous alloy of the present invention will be described in detail with reference to examples and embodiments.
Example 1
Fe was placed in a crucible and melted at a temperature of 1600 ℃, then Y, in, B, S and P were added thereto, and melting was repeated a plurality of times until the melting was uniform. Pouring the alloy liquid into a tundish of an atomizing device, starting a high-pressure water pump before the alloy liquid is injected, and enabling the high-pressure water atomizing device to start working; argon is injected into a high-pressure water atomization device under the condition of 0.4MPa and 30L/min flow, alloy liquid flows into an atomizer through a leakage nozzle beam at the bottom of a tundish, and under the action of high-pressure water (water pressure is 55MPa and 18L/min flow) from the atomizer, the alloy liquid is continuously broken into fine liquid drops and is rapidly solidified into particles. The particles were dehydrated and dried at a temperature of 150 ℃ under an argon atmosphere and sieved to obtain an amorphous alloy having a particle size of 200 to 1000 mesh. The contents of the respective components in the amorphous alloy are shown in table 1.
The amorphous alloy of example 1 was tested by XRD. As can be seen from fig. 4, the characteristic peaks are not particularly pronounced, the hetero peaks are numerous and disordered, the crystallinity is poor, and the powder crystal structure shows an amorphous tendency, so the amorphous alloy of example 1 has an amorphous structure.
Examples 2 to 4
Amorphous alloys were prepared in the same manner as in example 1, except that the respective components in table 1 and the parameters in table 2 were used.
TABLE 1
TABLE 2
Example 1
The surface of the pot made of stainless steel was surface-treated, and the surface of the pot was cooled to-10 ℃ under the atmosphere of carbon dioxide gas. Performing supersonic plasma spraying under conditions of a speed of feeding the amorphous alloy prepared by example 1 (i.e., a powder feeding speed) of 50g/min, a spraying distance of 80mm, an arc current of 280A, hydrogen and argon as working gases, wherein a pressure of supplying the hydrogen is 0.3MPa, and a flow rate of 5L/min; the pressure of the supplied argon was 1.8MPa and the flow was 1700L/min. And cooling the amorphous alloy sprayed on the surface of the pot body at a cooling speed of 190K/s, thereby obtaining the pot with the non-stick coating.
Examples 2 to 4
Cookware with a non-stick coating was produced in the same manner as in example 1, except that the parameters in table 3 were used to produce a non-stick coating.
Comparative example 1
Cookware with a non-stick coating was produced in the same manner as in example 1, except that a conventional titanium powder (purity 99.5% or more) was used to produce a non-stick coating.
Comparative example 2
Cookware with a non-stick coating was produced in the same manner as in example 1, except that the parameters in table 3 were used to produce a non-stick coating.
TABLE 3 Table 3
Performance test:
the non-stick cookware was tested for degree of amorphization, initial non-stick and permanent non-stick in the same environment based on the following method:
amorphization degree test: XRD testing was used and analytical calculations were performed using conventional full spectrum fitting methods to obtain the degree of amorphism of the samples. The conventional full spectrum fitting method comprises the following steps: firstly, finding a crystalline phase with the same chemical structure as an amorphous phase, and assuming that the amorphous phase is a tiny crystal grain of the crystalline phase, the crystalline phase can be used for establishing a model of peak position and intensity of the amorphous phase; secondly, firstly fitting the spectral line of the pure amorphous phase to determine the grain size and microscopic strain; finally, the grain size and microscopic strain are fixed, and the amorphous content (i.e., the degree of amorphization) is obtained by including this phase in a conventional Rietveld quantitative calculation.
Initial tack-free and permanent tack-free test: according to the relevant regulations in the national standard GB 32388.
The test results are shown in table 4 below:
TABLE 4 Table 4
| Sample of | Degree of amorphization/% | Initial non-tackiness | Durable non-stick |
| Example 1 | 86 | Ⅰ | 45000 |
| Example 2 | 92 | Ⅱ | 27000 |
| Example 3 | 94 | Ⅰ | 52000 |
| Example 4 | 83 | Ⅰ | 26000 |
| Comparative example 1 | 1 | Ⅲ | 0 |
| Comparative example 2 | 13 | Ⅲ | 0 |
As can be seen from table 4, the non-sticking cookware obtained via the amorphous alloy of the present invention was significantly higher in the durable non-sticking of examples 1 to 4 than comparative examples 1 and 2.
In summary, the non-stick coating obtained by the amorphous alloy of the invention realizes the non-stick effect of the non-stick cooker, prolongs the service life of the non-stick cooker, and can clean the non-stick cooker by using a shovel, a scouring pad or a wire ball.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims and their equivalents. The embodiments should be considered in descriptive sense only and not for purposes of limitation. Therefore, the scope of the invention is defined not by the specific embodiments of the invention but by the claims, and all differences within the scope will be construed as being included in the present invention.
Claims (6)
1. A non-stick cookware, the non-stick cookware comprising:
a body comprising an inner surface carrying an article and an outer surface facing away from the inner surface; and
a non-stick coating layer disposed on the inner surface of the body and including an amorphous alloy represented by the following formula 1,
1 (1)
X a Y b Z c ，
Wherein X and Y are each independently selected from one of Mg, al, ca, se, ti, V, cr, mn, fe, co, ni, cu, zn, ga, ge, Y, zr, nb, mo, tc, in, sn, sb, hf, ta and W,
z is at least one selected from Mg, al, ca, se, ti, V, cr, mn, fe, co, ni, cu, zn, ga, ge, Y, zr, nb, mo, tc, in, sn, sb, hf, ta, W, C, N, O, B, S, si and P,
x, Y and Z are different from each other,
a is more than or equal to 0.1 and less than or equal to 0.9, b is more than or equal to 0.1 and less than or equal to 0.9, and a+b is more than or equal to 0.9 and less than or equal to 1
0<c≤0.1，
Wherein the difference between the atomic radius of the element represented by X and the atomic radius of the element represented by Y is greater than or equal to 0.0037nm,
the non-stick cooker is prepared by the following steps: preparing the body of the non-stick cookware; thermally spraying the amorphous alloy to the inner surface of the body under conditions that a speed of feeding the amorphous alloy is 30g/min to 70g/min, a spraying distance is 80mm to 130mm, an arc current is 200A to 350A, and hydrogen and argon are used as working gases; and cooling the amorphous alloy sprayed onto the inner surface of the body at a cooling rate of 180K/s to 200K/s, thereby forming a non-stick coating on the inner surface of the body.
2. The non-stick cookware of claim 1, wherein Z is selected from at least two of Cu, mo, zn, in, B, P, S, si, mn, ti, al, C, N, O, ga, nb, hf, Y and Sn.
3. The non-stick cookware of claim 1, wherein the amorphous alloy exists in a solid solution phase, and one of an element represented by X and an element represented by Y exists as a solvent, and the other of the element represented by X and the element represented by Y and the element represented by Z exists as a solute.
4. A non-stick cookware as claimed in claim 1 wherein the amorphous alloy is present in particulate form and the particle size of the amorphous alloy in particulate form is in the range of 200 mesh to 1000 mesh.
5. The non-stick cookware of claim 4, wherein D of amorphous alloy in granular form 50 The particle size distribution is in the range of 325 mesh to 500 mesh.
6. The non-stick cookware of claim 1, wherein prior to the step of performing thermal spraying, the inner surface of the body is further surface treated and cooled to between-10 ℃ and 5 ℃ in the presence of carbon dioxide gas.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000160242A (en) * | 1998-11-20 | 2000-06-13 | Alps Electric Co Ltd | PRODUCTION OF Fe BASE SOFT MAGNETIC ALLOY |
| CN108330426A (en) * | 2017-01-17 | 2018-07-27 | 佛山市顺德区美的电热电器制造有限公司 | The preparation method of cooker, cooking apparatus component and cooker |
| CN114631726A (en) * | 2020-12-15 | 2022-06-17 | 武汉苏泊尔炊具有限公司 | Cooking utensil and processing method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000160242A (en) * | 1998-11-20 | 2000-06-13 | Alps Electric Co Ltd | PRODUCTION OF Fe BASE SOFT MAGNETIC ALLOY |
| CN108330426A (en) * | 2017-01-17 | 2018-07-27 | 佛山市顺德区美的电热电器制造有限公司 | The preparation method of cooker, cooking apparatus component and cooker |
| CN114631726A (en) * | 2020-12-15 | 2022-06-17 | 武汉苏泊尔炊具有限公司 | Cooking utensil and processing method thereof |
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