CN115005683A - Method for preparing amorphous alloy for non-stick cookware - Google Patents

Method for preparing amorphous alloy for non-stick cookware Download PDF

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CN115005683A
CN115005683A CN202111106849.3A CN202111106849A CN115005683A CN 115005683 A CN115005683 A CN 115005683A CN 202111106849 A CN202111106849 A CN 202111106849A CN 115005683 A CN115005683 A CN 115005683A
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amorphous alloy
alloy
stick
main elements
particles
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袁华庭
李超
瞿义生
张明
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Wuhan Supor Cookware Co Ltd
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Wuhan Supor Cookware Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • 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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  • Chemical & Material Sciences (AREA)
  • Food Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention discloses a method for preparing amorphous alloy for non-stick cookers. The method comprises the following steps: melting one of two main elements of the amorphous alloy to serve as a solvent; adding the other of the two main elements and optional impurity elements as solutes into a solvent to obtain an alloy liquid; atomizing the alloy liquid to obtain amorphous alloy particles; and dehydrating and drying the amorphous alloy particles under the protection of inert gas to obtain the amorphous alloy. The amorphous alloy prepared by the method has higher amorphization degree. In addition, the amorphous alloy is sprayed on the non-stick cookware, so that the surface of the non-stick cookware not only has a micro concave-convex structure, but also has a macro porous structure.

Description

Method for preparing amorphous alloy for non-stick cookware
Technical Field
The invention relates to the field of non-stick cookers, in particular to a method for preparing an amorphous alloy for the non-stick cookers.
Background
The non-stick technology of the non-stick cooker is mainly realized from the following three directions: 1) low surface energy of itself; 2) the microcosmic concave-convex structure forms a hydrophobic and oleophobic surface similar to a lotus leaf; 3) the porous oil storage forms a stable oil film, and the oil is used as a mediator to realize non-sticking.
The current nonstick materials for cookers mainly comprise fluorine paint, ceramic paint and organic silicon resin. The three are mainly sprayed on the inner surface of the pan to prepare the non-stick coating so as to achieve the purpose of non-sticking when heating food. The fluorine paint mainly comprises PTFE (polytetrafluoroethylene), PFOA (perfluorooctanoic acid ammonium), PFA (copolymer of perfluoropropyl perfluorovinyl ether and polytetrafluoroethylene), FEP (fluorinated ethylene propylene copolymer), ETFE (ethylene-tetrafluoroethylene copolymer) and the like, and the non-stick principle of the fluorine paint is that the fluorine-containing polymer has extremely low surface free energy. The ceramic coating mainly comprises silicon-oxygen bonds, is a coating with inorganic silicon as a main component, and mainly forms a nano structure on the surface of the pot body so as to achieve the non-sticky effect. The organic silicon resin achieves the effect of non-stick mainly by utilizing the characteristic of low surface energy. The three coatings have non-stick effects, but all have obvious defects, specifically, the fluorine coating non-stick coating is not wear-resistant, dishes can not be fried by an iron shovel, and can not be cleaned by a steel wire ball and scouring pad, harmful substances can be generated by decomposition at high temperature, and the non-stick property is reduced after abrasion; the ceramic coating has a poor non-stick effect compared with a fluorine coating, is mainly non-stick by using silicone oil in a coating system, has poor lasting non-stick property, and is easy to fall off after being generally used for 3 to 6 months; the non-stick 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 gray after the coating is contacted with high temperature or open fire, the hardness is reduced at the high temperature, and the phenomenon of 'back sticking' is easy to generate. Therefore, the phenomenon of poor permanent non-stick property is common in the current non-stick materials.
Therefore, the above-mentioned coating material falls into a bottleneck in terms of non-stick life, and it is difficult to make a major breakthrough.
Therefore, there is a strong need for improvement of the material of the non-stick coating.
Disclosure of Invention
The invention aims at providing a method for preparing an amorphous alloy for non-stick cookers, which can prepare an amorphous alloy with high amorphization degree.
According to an aspect of the present invention, there is provided a method of amorphous alloy for non-stick cookware, the amorphous alloy comprising two main elements 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, and optionally an impurity element 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, and the two main elements and the impurity element being different from each other, the method comprising: melting one of the two main elements to act as a solvent; adding the other of the two main elements and optional impurity elements as solutes into a solvent to obtain an alloy liquid; atomizing the alloy liquid to obtain amorphous alloy particles; and carrying out dehydration and drying treatment on the amorphous alloy particles under the protection of inert gas to obtain the amorphous alloy. The method can be used for preparing the amorphous alloy with high amorphization degree.
In an embodiment of the present invention, the amorphous alloy may include two main elements having a total content of 90 atomic% and a balance of impurity elements, and a content of any one of the two main elements is 10 atomic% or more, based on an atomic percentage of the amorphous alloy. The amorphous alloy can not only enable the surface of the non-stick cooker to have a micro concave-convex structure, but also enable the surface of the non-stick cooker to have a macro porous structure, so that the non-stick cooker achieves a non-stick effect and is long in service life.
In embodiments of the present invention, the difference between the atomic radii of the two major elements may be greater than or equal to 0.0037 nm. The difference between the atomic radii of the two main elements is controlled to be greater than or equal to 0.0037nm, so that the amorphous alloy has severe lattice distortion, high degree of amorphization and low surface energy.
In the embodiment of the present invention, the impurity element 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 amount of the impurity elements 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.
In the embodiment of the present invention, one of the two main elements having a higher melting point may be used as a solvent, and the one of the two main elements having a higher melting point may be melted under conditions of a temperature of 1000 ℃ or more and a melting time of 1 hour or more. Under these conditions, the respective components can be more sufficiently melted.
In an embodiment of the present invention, the step of atomizing the alloy liquid may include: spraying the alloy liquid to an atomizer; and spraying water with the water pressure of 45-75 MPa and the flow rate of 15-30L/min to the alloy liquid flow in the atomizer under the protection of inert gas, so that the alloy liquid flow is crushed, and the amorphous alloy particles are obtained. By preparing the amorphous alloy under such conditions, an amorphous alloy having a higher degree of amorphization can be obtained.
In an embodiment of the present invention, the inert gas may be argon gas, and the pressure of supplying the argon gas may be 0.4 to 0.6MPa, and the flow rate may be 30 to 50L/min. Supplying argon under such conditions can improve production efficiency.
In an embodiment of the present invention, the step of subjecting the amorphous alloy particles to dehydration and drying treatment may be performed at a temperature of 150 ℃ to 200 ℃ under an argon atmosphere. Under the condition, the moisture in the amorphous alloy particles can be sufficiently removed.
In an embodiment of the present invention, the amorphous alloy may be present in the form of particles, and the grain size of the amorphous alloy in the form of particles may be in a range of 200 mesh to 1000 mesh. Controlling the grain size of the amorphous alloy within the range can ensure that the surface of the non-stick cooker forms a micro concave-convex structure and a macro porous structure.
In the embodiments of the present inventionIn the amorphous alloy D in granular form 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 in the range can further ensure that the surface of the non-stick cooker forms a micro concave-convex structure and a macro porous structure.
The amorphous alloy prepared by the method has higher amorphization degree. In addition, the amorphous alloy is sprayed on the non-stick cookware, so that the surface of the non-stick cookware not only has a microscopic concave-convex structure, but also has a macroscopic porous structure, the non-stick cookware realizes a non-stick effect and has long service life, and can be cleaned by using an iron shovel, scouring cloth, a steel wire ball or the like.
Drawings
The above and/or other features and aspects of the present invention will become apparent and appreciated from the following 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 diagram showing a non-stick cookware according to an embodiment of the present invention.
FIG. 3 is a flow chart illustrating a method of manufacturing a non-stick cookware according to an embodiment of the present invention.
Figure 4 is the XRD pattern of example 1.
Detailed Description
The embodiments are described below in order 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 the 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 invention provides an amorphous alloy for non-stick cookware, which is represented by formula 1:
formula 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 present 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, may be selected from 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, Ti, Co, Ni, for example, Mg, Ti, Fe, or Cu.
The other of X and Y may be selected from one of Mg, Al, Ca, Se, Y, Zr, Nb, In, Sn, Sb, Hf, Ge and Ta, for example, may be selected from one of Mg, Al, Ca, Y, Zr, In, Sn, Sb, Ge and Hf. Specifically, the other of X and Y may be Al, Ca, Y, Zr, 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 0.0037 nm. Typically, the radius R of the hydrogen atom is 0.037nm, that is, 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 0.0045 nm. 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 severe, 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 element represented by Z is added as an impurity element to assist in making the crystal lattice of the amorphous alloy more disordered, that is, the number of elements represented by Z is controlled to two or more, so that 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, a + b is more 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 increase; moreover, the amorphous alloy obtained by taking the binary alloy as the main component can meet the application in the field of non-stick cookers.
In formula 1, X, Y and Z are different from each other.
Further, 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 60 Ge 32 Ga 3 Nb 3 Hf 1 O 1 And so on.
In the embodiment of the present invention, the amorphous alloy for the non-stick cooker may include two main elements and optionally impurity elements, and specifically, the amorphous alloy may include two main elements as main components and impurity elements as auxiliary components, or may be composed of two main elements as main components and impurity elements as auxiliary components. Specifically, the amorphous alloy may include two main elements in a total amount of 90 atomic% or more and the balance of impurity elements, based on the atomic percentage of the amorphous alloy. Further, the content of either of the two main elements is 10 atomic% or more. Here, the two main elements correspond to elements denoted by X and Y, respectively, and the impurity element corresponds to an element denoted by Z, and therefore, the main element and the impurity element will not be described in detail.
In the amorphous alloy of the invention, a larger amount of impurity elements are added on the basis of 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 difference in atomic radius between the main elements, the lattice distortion of the amorphous alloy is severe, 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 a binary element and is mixed with a small amount of various other elements, and therefore, 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, that is, because the atomic radii of all the constituent elements are different, all the element atoms occupy all the lattice positions with equal opportunity in the smelting process, so that the lattice of the material is distorted, the large atomic size difference can cause the lattice distortion of the material to be too high, the crystal lattice configuration cannot be maintained, and the lattice of the material collapses to form an amorphous structure. Therefore, the amorphous alloy according to the present invention can obtain a surface energy much lower than that of the conventional material.
Further, in the amorphous alloy existing in the solid solution phase, one of the element represented by X and the 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, 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 gaps between atoms of the element represented by X.
In an embodiment of the present invention, the amorphous alloy may be present in the form of particles, and the grain size of the amorphous alloy in the form of particles may be in a 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 amorphous alloy cannot be subjected to plasma spraying due to too small size, so that the cost is wasted; if the grain size of the amorphous alloy is less than 200 meshes, the powder is difficult to melt in the plasma spraying process, cannot be attached to the surface of a non-stick cooker, and the surface of the final coating is rough, so that the post-treatment is difficult to perform and the texture is poor.
Further, D of the amorphous alloy in the form of particles 50 The particle size distribution may be in the range of 325 mesh to 500 mesh. Here, D 50 The grain diameter corresponding to the cumulative grain size distribution percentage of the amorphous alloy reaching 50 percent is referred to. Amorphous alloy in granular form D 50 The particle size distribution is between 325 meshes and 500 meshes, so that the surface of the non-stick cooker has a micro concave-convex structure (fine powder higher than 500 meshes) and a macro oil-storage micropore (coarse powder lower than 325 meshes).
A method of manufacturing 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 optionally an impurity element as a solute to a 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 higher melting point may be used as a solvent, and the one of the two main elements having a higher melting point may be melted under conditions of a temperature of 1000 ℃ (for example, 1500 ℃) or more and a melting time of 1 hour or more. Specifically, an element having a relatively high melting point (e.g., a metal block) may be placed in a high-temperature crucible in an inert (e.g., argon) atmosphere and then heated to a completely molten state using an induction furnace.
In step S120, an element having a relatively low melting point (e.g., a metal block) and optionally an impurity element are added as solutes to a solvent. Specifically, elements with relatively low melting points (e.g., metal lumps) and optional impurity elements can be slowly added as solutes into the solvent formed in step S110, and the mixture is stirred sufficiently during the melting process, and the melting is repeated for a plurality of times to melt the components uniformly.
In step S130, the alloy liquid is granulated by a water atomization method. Preferably, the alloy liquid is sprayed to an atomizer, and water with the water pressure of 45MPa to 75MPa and the 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, and amorphous alloy particles are obtained. Specifically, the alloy liquid in the step S120 is poured into a tundish of an atomizing device, and then the alloy liquid in the tundish enters an atomizer through a discharge spout at the bottom of the tundish after passing through a beam; then, introducing an inert protective gas (for example, argon) into the atomizer, wherein the pressure of the inert protective 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 crushed into fine liquid drops, and the fine liquid drops are rapidly solidified into amorphous alloy particles by the high-pressure water, the high-pressure water is purified water after oxygen removal, the water pressure is 45MPa to 75MPa, and the flow rate is 15L/min to 30L/min.
In step S140, a 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 also comprise a step of sieving the prepared amorphous alloy, thereby obtaining the amorphous alloy with the granularity of 200 meshes to 1000 meshes.
In the embodiment of the invention, high-pressure water atomization technology is adopted for preparing powder, high-temperature molten alloy liquid is rapidly dispersed and condensed into alloy particles under the impact of high-pressure water flow or water mist, powder with proper granularity can be obtained by controlling proper water flow pressure, and the alloy cannot form a complete crystal structure in time due to high water cooling speed and tends to be in an amorphous state.
The non-stick cookware comprising amorphous alloys according to the present invention will be described in detail below with reference to fig. 2.
Non-stick cookware 100 according to embodiments of the present invention includes a body 110 and a non-stick coating 120.
FIG. 2 is a schematic diagram showing a non-stick cookware according to an embodiment of the present invention.
Referring to FIG. 2, a non-stick cookware 100 according to the present invention includes a body 110 and a non-stick coating 120 disposed on the body 110.
The body 110 (or also referred to as a pan body) may be particularly 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; however, embodiments of the present invention are not limited thereto.
A non-stick coating 120 is disposed on the inner surface of the body 110. 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 in detail herein.
The method of manufacturing the non-stick cookware according to the present invention will be described in detail below with reference to fig. 3.
The method of manufacturing a non-stick cookware according to the invention comprises: preparing a body of the non-stick cookware (step S210); supersonic plasma spraying amorphous alloy onto the 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 non-stick cookware body is prepared, the body including an inner surface for carrying items and an outer surface facing away from the inner surface. The body here 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 an environment of carbon dioxide gas. Such a 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 through a supersonic plasma spraying process. In the embodiment of the present invention, the step of performing supersonic plasma 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 at which hydrogen is supplied is 0.2MPa to 0.4MPa, and the flow rate is 3L/min to 8L/min; argon is supplied at a pressure of 1.2MPa to 2.0MPa and at a flow rate of 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 the amorphous alloy with wider particle size range and controlling the spraying conditions (such as the relative combination of powder feeding speed, pressure and flow of working gas and spraying distance), the inside of the alloy powder can be ensured not to be melted, and the powder can be rapidly cooled from high temperature to low temperature to be deposited on the surface of a pan body to form an amorphous phase, so that the surface of the non-stick cooker can have a microscopic concave-convex structure (fine powder with more than 500 meshes) and macroscopic oil storage micropores (coarse powder with less than 325 meshes). For example, the powder feeding speed and the working gas flow rate are increased, so that the phenomenon that the powder is over-melted to cause the amorphous phase of the solid solution to be transformed into crystals due to precipitation can be avoided; the spraying distance is shortened, the spraying speed is increased, and the outer surface of the pot body is cooled by low-temperature gas, so that the powder is rapidly cooled from high temperature to low temperature and deposited on the surface of the pot body to form an amorphous phase.
In the spraying process, powder with fine granularity (more than 500 meshes) is completely melted to form spherical metal liquid drops, the spherical surface is stressed unevenly to form irregular sharp bulges under the impact of high-speed argon gas, and finally the irregular sharp bulges are deposited on the surface of a pot body with low temperature. The powder with coarser granularity (less than 325 meshes) is only slightly melted on the surface and is not greatly deformed, finally the particles are stacked on the surface of the pot body, gaps can be left among the particles due to different sizes and shapes, and pores with certain depth are formed along with the increase of the film thickness, so that a macroscopic porous structure on the surface of the coating is formed.
According to the embodiment of the invention, the amorphous alloy is sprayed on the surface of the non-stick cooker by the supersonic plasma spraying process, so that the surface of the non-stick cooker not only has a micro concave-convex structure, but also has a macro porous structure, the non-stick cooker achieves a non-stick effect and has long service life, and the non-stick cooker can be cleaned by using an iron shovel, scouring cloth, a steel wire ball or the like.
The amorphous alloy of the present invention will be described in detail with reference to examples and embodiments.
Example 1
Fe is put into a crucible and melted at a temperature of 1600 c, and then Y, In, B, S and P are added thereto, and melting is repeated several times until melting is uniform. Pouring the alloy liquid into a tundish of an atomizing device, and starting a high-pressure water pump before the alloy liquid is injected to enable the high-pressure water atomizing device to work; argon gas is flushed into the high-pressure water atomization device under the conditions that the pressure is 0.4MPa and the flow rate is 30L/min, the alloy liquid flows into the atomizer through a leakage nozzle beam at the bottom of the tundish, and under the action of high-pressure water (the water pressure is 55MPa and the flow rate is 18L/min) from the atomizer, the alloy liquid is continuously crushed 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, thereby obtaining an amorphous alloy having a particle size of 200 mesh to 1000 mesh. Wherein, the contents of each component 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 random, 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 7
An amorphous alloy was prepared in the same manner as in example 1, except that the components in table 1 and the parameters in table 2 were used.
Comparative example 1
Amorphous alloys were prepared in the same manner as in example 1, except that each component (substantially pure titanium powder) in table 1 and the parameters in table 2 were used.
Comparative example 2
Amorphous alloys were prepared in the same manner as in example 1, except that the components in table 1 (the components thereof were the same as those of example 1) and the parameters in table 2 were used.
And (3) testing the degree of amorphization: and (4) performing analysis calculation by using an XRD test and a conventional full spectrum fitting method to obtain the amorphization degree of the sample. The steps of the conventional full-spectrum fitting method are as follows: firstly, finding a crystalline phase with the same chemical structure as the 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 the peak position and the intensity of the amorphous phase; secondly, fitting a pure amorphous phase spectral line to determine the grain size and the microscopic strain; finally, the grain size and the microscopic strain are fixed, and the phase is included in the traditional Rietveld quantitative calculation, so that the content of the amorphous state (namely the amorphization degree) can be obtained. The test results are shown in table 2.
TABLE 1
Figure BDA0003272764600000101
TABLE 2
Figure BDA0003272764600000102
Figure BDA0003272764600000111
As can be seen from table 2, comparative example 1 having single element titanium as a main component is significantly less amorphized than examples 1 to 7 having two elements of the present invention as main components; comparing example 1 with comparative example 2, it can be seen that the water supply condition during the atomization granulation process has a significant effect on the degree of amorphization of the amorphous alloy, and the degree of amorphization of example 1 is significantly higher than that of comparative example 2.
In summary, the amorphous alloy prepared by the method has a higher degree of amorphization, which is about 81% or more. It is known in the art that the degree of amorphization is related to surface energy and non-tackiness, with high degree of amorphization, low surface energy and good non-tackiness.
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 detailed description of the invention but by the appended claims, and all differences within the scope will be construed as being included in the present invention.

Claims (10)

1. A method of making an amorphous alloy for non-stick cookware comprising two major elements 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, and optionally an impurity element 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, and the two major elements and the impurity element being different from each other,
the method comprises the following steps:
melting one of the two main elements to act as a solvent;
adding the other of the two main elements and the optional impurity element as solutes into the solvent to obtain an alloy liquid;
atomizing the alloy liquid to obtain amorphous alloy particles; and
and dehydrating and drying the amorphous alloy particles under the protection of inert gas to obtain the amorphous alloy.
2. The method according to claim 1, wherein the amorphous alloy includes the two main elements in a total content of 90 atomic% and a balance of impurity elements, and a content of any one of the two main elements is 10 atomic% or more, based on an atomic percentage of the amorphous alloy.
3. The method of claim 1, wherein the difference between the atomic radii of the two primary elements is greater than or equal to 0.0037 nm.
4. The method according to claim 1, wherein the impurity element 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.
5. The method according to claim 1, wherein one of the two main elements whose melting point is higher is used as a solvent, and the one of the two main elements whose melting point is higher is melted under conditions in which a temperature is 1000 ℃ or more and a melting time is 1 hour or more.
6. The method according to claim 1, wherein the atomizing the alloy liquid comprises:
spraying the alloy liquid to an atomizer; and
and spraying water with the water pressure of 45-75 MPa and the flow rate of 15-30L/min to the alloy liquid flow in the atomizer under the protection of inert gas, so that the alloy liquid flow is crushed, and the amorphous alloy particles are obtained.
7. The method of claim 6, wherein the inert gas is argon, and the argon is supplied at a pressure of 0.4 to 0.6MPa and at a flow rate of 30 to 50L/min.
8. The method of claim 1, wherein the step of subjecting the amorphous alloy particles to a dehydration and drying process is performed at a temperature of 150 ℃ to 200 ℃ under an argon atmosphere.
9. The method according to claim 1, wherein the amorphous alloy is present in the form of particles, and the grain size of the amorphous alloy in the form of particles is in a range of 200 mesh to 1000 mesh.
10. The method of claim 9, wherein D is amorphous alloy in particulate form 50 The particle size distribution is in the range of 325 mesh to 500 mesh.
CN202111106849.3A 2021-09-22 2021-09-22 Method for preparing amorphous alloy for non-stick cookware Pending CN115005683A (en)

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