CN108130502B - Preparation method and device of composite material containing high-entropy alloy coating - Google Patents

Preparation method and device of composite material containing high-entropy alloy coating Download PDF

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CN108130502B
CN108130502B CN201711433757.XA CN201711433757A CN108130502B CN 108130502 B CN108130502 B CN 108130502B CN 201711433757 A CN201711433757 A CN 201711433757A CN 108130502 B CN108130502 B CN 108130502B
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entropy alloy
thermite
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陈刚
苏斌
沈书成
朱立华
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Hunan University
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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
    • C23C4/123—Spraying molten metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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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Abstract

A preparation method of a composite material containing a high-entropy alloy coating comprises the following steps: (1) mixing an oxide or a simple substance of a main element of the high-entropy alloy with aluminum powder to obtain a thermite; (2) putting the thermite in the step (1) into an aluminothermic reactor, igniting the thermite to excite thermite reaction to obtain an alloy melt, stirring, rolling, flowing, layering, and standing to obtain a bottom-layer high-entropy alloy melt and an upper-layer alumina slag; (3) atomizing the bottom-layer high-entropy alloy melt in the step (2) into high-entropy alloy melt drops through a spray coating device, and spraying and coating the high-entropy alloy melt drops on the surface of a substrate to be coated to obtain the composite material containing the high-entropy alloy coating. The invention also provides a device for the preparation method. The whole process of the invention has ingenious design concept, low energy consumption in the preparation process, simple steps and easy operation.

Description

Preparation method and device of composite material containing high-entropy alloy coating
Technical Field
The invention belongs to the field of alloy materials, and particularly relates to a preparation method and a device of a composite material containing an alloy coating.
Background
High-entropy alloys are broadly defined as solid solution alloys of equal (near) atomic ratios composed of a mixture of five or more elements, and the alloy phases are simple in structure and have excellent properties such as high strength, high hardness, good wear resistance, oxidation resistance, and corrosion resistance, and thus high-entropy alloys are increasingly becoming preferred materials for preparing excellent composite materials.
Because the number of the components of the high-entropy alloy is at least 5, and potential differences exist among the components, the method for preparing the coating with uniform thickness by using electroplating and chemical plating is difficult, the main researches for preparing the high-entropy alloy coating at home and abroad currently comprise laser cladding, magnetron sputtering, thermal spraying and the like, but the methods have certain limitations, such as: the preparation process is complex, the equipment requirement is high, the energy consumption is high, and the like. Particularly, the methods are difficult to prepare large thick coatings, and along with the increasingly wide application of large armor plates, heat-resistant and wear-resistant ship decks, large molds and corrosion-resistant containers, urgent needs are brought to the functional multilayer composite materials with large-area thick coatings.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background technology, provide a preparation method of a composite material containing a high-entropy alloy large-thickness coating, especially a multilayer composite plate, which has simple process steps, simple equipment and low cost, and correspondingly provide a preparation device. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a composite material containing a high-entropy alloy coating comprises the following steps:
(1) mixing an oxide or a simple substance of a high-entropy alloy principal element with aluminum powder to obtain a thermite, wherein the oxide or the simple substance of the principal element at least comprises an oxide of one principal element;
(2) putting the thermite in the step (1) into an aluminothermic reactor, igniting the thermite to excite thermite reaction to obtain an alloy melt, stirring, rolling, flowing, layering, and standing to obtain a bottom-layer high-entropy alloy melt (wherein submicron-level alumina can be remained, but submicron-level dispersion particles are hard phases, so that the strength and wear resistance of the high-entropy alloy can be improved, and the properties of a coating are beneficial) and upper-layer alumina slag;
(3) atomizing the bottom-layer high-entropy alloy melt in the step (2) into high-entropy alloy melt drops through a spray coating device, and spraying and coating the high-entropy alloy melt drops on the surface of a substrate to be coated to obtain the composite material containing the high-entropy alloy coating.
In the preparation method of the composite material containing the high-entropy alloy coating, preferably, pre-alloy powder is further added into the thermite, the pre-alloy powder is alloy powder consisting of at least two principal element elements, and the total amount of the pre-alloy powder and the principal element simple substance added accounts for 10-30% of the mass of the thermite. The addition of prealloyed powder has the following benefits: 1. the prealloying powder makes the alloying process of the high-entropy alloy easier; 2. the melting point of the pre-alloyed powder can be adjusted according to the alloy components, and the temperature of the alloy melt can be adjusted by adding the pre-alloyed powder; 3. the average negative enthalpy value of each reaction in the reaction system needs to be more than 320KJ/mol, in order to achieve the purpose, the amount of the oxide (such as increasing the mole number of a high negative enthalpy reactant and reducing the mole number of a low negative enthalpy reactant) needs to be adjusted, and the pre-alloyed powder can well supplement and compensate the condition of insufficient alloy components caused by adjusting the average reaction enthalpy, so that the alloy achieves the component requirement of the high-entropy alloy; 4. the quantity of the added simple substances and the pre-alloyed powder is more than 10-30% of the reactants, and the quantity of the alumina products of the aluminothermic reaction can be reduced as much as possible, so that the high-entropy alloy melt and the alumina slag can be smoothly separated after the reaction, and the alumina slag can be smoothly discharged. However, the addition amount of the pre-alloyed powder cannot be too much, otherwise, the temperature of the high-entropy alloy melt is too low, subsequent slag discharge and spray coating are not facilitated, and the addition amount of the pre-alloyed powder can be calculated through a heat balance equation of heat release and heat absorption.
In the preparation method of the composite material containing the high-entropy alloy coating, preferably, the aluminum powder is active aluminum powder with the activity of more than 98%, the oxide of the main element is an element oxide required by high-entropy alloy such as ferroferric oxide, ferric oxide, chromium sesquioxide, cobalt sesquioxide, manganese dioxide, vanadium pentoxide and the like, the simple substance of the main element is iron, chromium, cobalt, manganese, vanadium and the like, the pre-alloy powder is alloy powder consisting of at least two main element elements, the main element is characterized in that the metal activity of the main element is positioned behind the aluminum element, and the ratio of the main element to the aluminum powder is matched according to the requirement of the high-entropy alloy.
In the preparation method of the composite material containing the high-entropy alloy coating, preferably, a reaction auxiliary agent is further added into the thermite, and the reaction auxiliary agent is KClO4、K2CrO7And KMnO4One or more of them. The purpose of adding the reaction auxiliary agent is to provide more reaction heat for the reaction system, so as to supplement the situation that the heat of the thermite reaction is possibly insufficient, and the K generated by the side reaction2O, KCl, etc., to stir and tumble the melt. The addition amount of the reaction auxiliary agent is reduced as much as possible on the basis of ensuring the smooth reaction.
In the preparation method of the composite material containing the high-entropy alloy coating, preferably, the thickness of the high-entropy alloy coating is 5-10 mm.
In the preparation method of the composite material containing the high-entropy alloy coating, preferably, a slag discharging additive is further added into the thermite, and the slag discharging additive is SiO2And/or CaO, wherein the addition mass of the slag-discharging additive is 1-5% of the mass of the alumina slag. The slagging and floating speed of the alumina can be increased by adding the slagging additive. The slagging is SiO2And/or CaO and the like with Al2O3Form Al with good fluidity2O3CaO or Al2O3-CaO-SiO2A low-melting-point composite oxide.
In the preparation method of the composite material containing the high-entropy alloy coating, preferably, in the step (2), the thermite is placed in the thermite reactor before being preheated to 300-700 ℃, and the thermite reactor is preheated firstly, so that the temperature of the whole reaction system can be increased, and the calorific value of the reaction system is increased.
In the preparation method of the composite material containing the high-entropy alloy coating, preferably, the standing time in the step (2) is 5-15 s, so that the temperature of the melt after standing is 1800-2000 ℃. The aluminum oxide slag can be ensured to float sufficiently after standing for 5-15 s, the standing time is too short, the floating of the floating slag is not sufficient, the standing time is too long, the temperature of the alloy melt is too low, and the subsequent spray coating is not facilitated. The conditions for eliminating the alumina slag in the preparation method of the composite material containing the high-entropy alloy coating are as follows: the melt temperature is about 2400 + -50 deg.C higher than the melting point 2054 deg.C of alumina to make it float as molten slag, and KClO is added for reaching the above temperature4And K2CrO7And/or KMnO4Producing exothermic side reactions, while optimizing the addition of CaO and/or SiO2Reduction of Al2O3Melting point, i.e. Al forming a low melting point2O3CaO or Al2O3-CaO-SiO2And after standing, starting spraying when the temperature of the melt is 1800-2000 ℃.
In the preparation method of the composite material containing the high-entropy alloy coating, preferably, in the step (3), the surface of the substrate to be coated is preheated to 400-800 ℃ before spray coating, and the thickness of the preheated surface is controlled to be 0.2-0.5 mm. The preheating method can adopt a high-frequency sensing heating device to heat the surface of the substrate to be coated, preheat the surface of the substrate to be coated and control the thickness of the preheated surface, and aims to improve the surface temperature of the substrate to be coated, ensure the remelting of atomized liquid drops on the substrate to be coated to realize metallurgical bonding, and only preheat the surface of the substrate to be coated, so that the deterioration of the structure or performance caused by high-temperature annealing after the whole substrate to be coated is heated can be avoided.
In the preparation method of the composite material containing the high-entropy alloy coating, preferably, when the composite material is sprayed and coated in the step (3), the pressure of the atomizing gas is 0.3-0.8 Mpa, the atomizing angle is 0-30 degrees, the moving speed of the substrate to be coated is 5-30 mm/s, the height between a nozzle (such as a liquid guide pipe) of the spraying and coating device and the surface of the substrate to be coated is 50-200 mm, and the inner diameter of the nozzle (such as the inner diameter of the lower end of the liquid guide pipe) is 3-8 mm. In spray coating, the coating is produced by spray deposition, and thus the thickness of the coating layer is the thickness of the deposited layer during spray deposition. The thickness of the single-pass deposition layer is controlled to be 5-10 mm, and the control mainly depends on the quality of the deposited melt sprayed to the substrate in unit time and unit area. The mass of the melt injected per unit time onto the substrate to be coated is determined by the diameter of the catheter and partly also by the fluidity of the metal melt (temperature and composition of the melt). The mass of the melt sprayed onto the substrate per unit area is determined by the area of the atomizing cone, i.e. the atomizing angle and the atomizing height. The quality of the melt which can be deposited is determined by the atomization effect and the atomization height, the atomization is too sufficient or the atomization height is too high, the liquid drops are cooled quickly and become solid particles which can be sputtered and cannot be deposited, the ideal atomization effect is that the liquid drops are atomized into semi-solid liquid drops, the liquid drops are not ensured to flow and can be deposited, the atomization effect is determined by the parameters such as the atomization air pressure, the atomization gas flow, the atomization gas temperature and the like, and the deposition of the high-entropy alloy melt can be realized only by controlling the parameters in the limited range.
The preparation method of the composite material containing the high-entropy alloy coating is based on the following principle: the metal oxide powder and the active aluminum powder are subjected to reduction reaction under certain conditions to obtain an elemental metal mixture, simultaneously, a large amount of heat energy released by thermite reaction (heat energy provided for a reaction system and heat energy provided for reaction auxiliary agents when the thermite reactor is preheated) is utilized to rapidly heat up, metal mixture in the product obtained by thermite reduction is melted, and then the melt is fully rolled in the thermite exothermic reaction (or the melt is fully stirred by a large amount of gas generated by exothermic side reaction) to enable alumina slag of the reaction product to fully float up, thereby obtaining high-entropy alloy melt with even bottom layer components and upper alumina slag, controlling the lower-layer high-entropy alloy melt to flow out through the liquid guide pipe, and atomizing nitrogen into high-entropy alloy molten drops, spraying the high-entropy alloy molten drops on the surface of a matrix to be coated, realizing metallurgical bonding with the matrix to be coated, and obtaining the composite material containing the high-entropy alloy coating.
As a general technical concept, the invention further provides an aluminothermic reactor-spray coating device for preparing the composite material containing the high-entropy alloy coating, which comprises an aluminothermic reactor and an atomizing and spraying device arranged at the bottom of the aluminothermic reactor and communicated with the aluminothermic reactor, wherein a rod plug used for controlling the melt in the aluminothermic reactor to enter the atomizing and spraying device in a delayed manner is arranged between the aluminothermic reactor and the atomizing and spraying device, a preheating device and a slag discharge pipe used for discharging upper-layer slag are arranged on the outer wall of the aluminothermic reactor, and a feeding window and a dust remover are arranged at the upper end of the outer wall of the aluminothermic reactor. In order to realize continuous spray coating operation, a feeding window and a slag discharge pipe (the slag discharge pipe adopts a high-temperature ceramic pipe to penetrate through a preheating device) are arranged, thermite can be added on line after the previous reaction melt is about to be sprayed through the feeding window, the steps of thermite reaction, standing and spraying are repeated, continuous multiple coating operation can be carried out, and continuously generated slag flows out immediately through the slag discharge pipe.
In the aluminothermic reactor-spray coating device, the aluminothermic reactor can be a ceramic crucible lined with a magnesia layer or other devices which are heat-resistant and do not affect the high-entropy alloy components. The rod plug is inserted into the upper end of the liquid guide pipe, mainly plays a role of delaying, is used for controlling the standing and layering time of the alloy melt, and can be made of graphite rods, tungsten rods or other high-temperature-resistant materials.
In the aluminothermic reactor-spray coating apparatus, preferably, the atomizing and spraying apparatus includes a liquid guide tube and an atomizer for atomizing the alloy melt in the liquid guide tube, the liquid guide tube is communicated with the bottom of the aluminothermic reactor, and the atomizer is connected with the liquid guide tube.
Compared with the prior art, the invention has the advantages that:
1. the invention breaks through the conventional method for preparing the high-entropy alloy coating, adopts thermit reaction to prepare the composite material containing the high-entropy alloy coating, omits the step of firstly synthesizing high-entropy alloy powder in the conventional coating preparation, and can prepare the composite material containing the high-entropy alloy layer by utilizing simple steps.
2. The spray coating device used in the invention has simple structure, convenient operation and wide application range, can greatly reduce the production cost of preparing the composite material containing the high-entropy alloy coating, and can be widely applied to the preparation process of the alloy-containing coating.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic view showing the structure of a spray coating apparatus according to the present invention.
FIG. 2 is a gold phase diagram of the bonding part of the high-entropy alloy coating and the substrate to be coated in example 1 of the invention.
FIG. 3 is an EDS energy spectrum of the high-entropy alloy coating in example 2 of the invention.
FIG. 4 is a gold phase diagram of the bonding part of the high-entropy alloy coating and the substrate to be coated in example 2 of the invention.
FIG. 5 is an EDS energy spectrum of the high-entropy alloy coating in example 3 of the invention.
Illustration of the drawings:
1. a rod plug; 2. a protective cover; 3. a feed window; 4. an aluminothermic reactor; 5. a catheter; 6. an atomizer; 7. an atomizing cone; 8. a high entropy alloy coating; 9. a substrate to be coated; 10. a deposition chamber; 11. a high-frequency induction heater; 12. a baffle plate; 13. high entropy alloy melt; 14. alumina slag; 15. a temperature measuring window; 16. an infrared induction thermometer; 17. a preheating device; 18. a slag discharge pipe; 20. a dust remover.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a composite material containing a high-entropy alloy coating comprises a substrate and the high-entropy alloy coating, wherein the high-entropy alloy coating is coated on the surface of the substrate in one step through thermite reaction, and the preparation method comprises the following steps:
(1) preparing an experimental device: preparing the apparatus shown in FIG. 1, including an aluminothermic reactor 4, a rod stopper 1, a liquid guide tube 5 and an atomizer 6; the inner diameter of an aluminous thermal reactor 4 is 12mm, the upper part is provided with a protective cover 2, the protective cover 2 is provided with a dust remover 20, a rod plug 1 is inserted into a groove above a liquid guide pipe 5, the inner diameter (namely the liquid flow diameter) of the lower end of the liquid guide pipe 5 is 5mm, a preheating device 17 is sleeved around the aluminous thermal reactor 4, a slag discharge pipe 18 is specially provided with holes and fixed through the preheating device, the aluminous thermal reactor 4 is preheated to 650 ℃ through the preheating device 17, a matrix 9 to be coated is placed in a deposition chamber 10 and is positioned below the liquid guide pipe 5, the height (namely the atomization height) between the surface of the matrix 9 to be coated and the lower part of the liquid guide pipe 5 is kept to be 150mm, a temperature measurement window 15 is arranged above the aluminous thermal reactor 4, an infrared induction thermometer 16 is used for measuring the temperature, a high;
(2) oxide, simple substance, aluminum powder and auxiliary agent (KClO) of main element of high-entropy alloy3And CaO) are mixed in a V-20 mixer for 15min to obtain thermite, and the thermite is put into an aluminothermic reactor 4 (such as a ceramic crucible) and kept to be freely stacked; wherein, the main element and the content are shown in the following table 1, and the auxiliary agent is KClO3And CaO, the adding amount of the CaO is 5 percent of the total amount of the thermite;
(3) igniting the thermite by using a high-temperature match to excite thermite reaction to obtain alloy melt, discharging slag from the melt under the conditions of exothermic reaction and stirring of reaction gas (a dust remover 20 can be started to remove redundant gas), and obtaining a bottom-layer high-entropy alloy melt 13 and an upper-layer alumina slag 14 after the alloy melt flows and is layered;
(4) after the reaction is finished, the alloy melt is kept stand for 10s, the temperature of the melt is 1800 ℃, the rod plug 1 is pulled out, and the high-entropy alloy melt is positioned at the bottom layer (the upper layer is rich in Al at this time)2O3Ceramic layer is basically solidified, but not flow out) automatically flows out through the liquid guide tube 5, atomized nitrogen is started, the air pressure of the atomized nitrogen is kept to be 0.4MPa, the atomization angle is 5 degrees, the matrix 9 to be coated is moved simultaneously, the moving speed is kept to be 7mm/s, the nitrogen atomized by the atomizer 6 forms an atomization cone 7 and is automatically coated on the surface of the matrix 9 to be coated, so that a layer of 5mm high-entropy alloy coating 8(FeCrNi high-entropy alloy cladding layer) is formed on the surface of the matrix 9 to be coated, and a composite material containing the high-entropy alloy coating 8 is obtained, and in order to prevent atomized liquid drops from splashing on the high-frequency induction coil, the baffle 12 can be.
The equations of the reactions that occur in this example include, but are not limited to, the following reactions:
Figure BDA0001525404170000061
Figure BDA0001525404170000062
Figure BDA0001525404170000063
table 1: high-entropy alloy raw material components and content
Composition (I) Fe3O4 Cr2O3 Ni More than 98% of active aluminum
Content/g 232 228 177 261
In the present embodiment, the metallographic graph of the bonding portion between the high-entropy alloy coating layer 8 and the substrate 9 to be coated is shown in fig. 2, and it can be seen from the metallographic graph that, in the present embodiment, the metallurgical bonding condition between the high-entropy alloy coating layer 8 and the surface of the substrate 9 to be coated is good, the bonding strength is 85% of that of the substrate material, and the hardness of the high-entropy alloy layer is 39 HRC.
Example 2:
a composite material containing a high-entropy alloy coating comprises a substrate and the high-entropy alloy coating, wherein the high-entropy alloy coating is coated on the surface of the substrate in one step through thermite reaction, and the preparation method comprises the following steps:
(1) preparing an experimental device: preparing the apparatus shown in FIG. 1, including an aluminothermic reactor 4, a rod stopper 1, a liquid guide tube 5 and an atomizer 6; the inner diameter of an aluminous thermal reactor 4 is 12mm, the upper part is provided with a protective cover 2, the protective cover 2 is provided with a dust remover 20, a rod plug 1 is inserted into a groove above a liquid guide pipe 5, the inner diameter (namely the liquid flow diameter) of the lower end of the liquid guide pipe 5 is 5mm, a preheating device 17 is sleeved around the aluminous thermal reactor 4, a slag discharge pipe 18 is specially provided with holes and fixed through the preheating device, the aluminous thermal reactor 4 is preheated to 650 ℃ through the preheating device 17, a matrix 9 to be coated is placed in a deposition chamber 10 and is positioned below the liquid guide pipe 5, the height (namely the atomization height) between the surface of the matrix 9 to be coated and the lower part of the liquid guide pipe 5 is kept to be 150mm, a temperature measurement window 15 is arranged above the aluminous thermal reactor 4, an infrared induction thermometer 16 is used for measuring the temperature, a high;
(2) mixing the oxide of the high-entropy alloy principal element, the aluminum powder and the auxiliary agent in a V-20 mixer for 15min to obtain an thermite, and putting the thermite into an thermite reactor 4 (such as a ceramic crucible), wherein the thermite is kept to be freely stacked; wherein, the main element and the content are shown in the following table 2, the reaction auxiliary agent is KClO3And KMnO4And slag discharging additives CaO and SiO2，CaO、SiO 24% of the total amount of the thermite;
(3) igniting the thermite by using a high-temperature match to excite thermite reaction to obtain alloy melt, discharging slag from the melt under the conditions of exothermic reaction and stirring of reaction gas (a dust remover 20 can be started to remove redundant gas), and obtaining a bottom-layer high-entropy alloy melt 13 and an upper-layer alumina slag 14 after the alloy melt flows and is layered;
(4) after the reaction is finished, the alloy melt is kept stand for 15s, the temperature of the melt is 1850 ℃, the rod plug 1 is pulled out, and the high-entropy alloy melt is positioned at the bottom layer (the upper layer is rich in A at this time)l2O3Ceramic layer is basically solidified, but not flow out) automatically flows out through the liquid guide tube 5, atomized nitrogen is started, the air pressure of the atomized nitrogen is kept to be 0.5MPa, the atomization angle is 5 degrees, the matrix 9 to be coated is moved simultaneously, the moving speed is kept to be 7mm/s, the nitrogen atomized by the atomizer 6 forms an atomization cone 7 and is automatically coated on the surface of the matrix 9 to be coated, so that a layer of 4mm high-entropy alloy coating 8(FeCrNiMn high-entropy alloy cladding layer) is formed on the surface of the matrix 9 to be coated, and the composite material containing the high-entropy alloy coating 8 is obtained, and the baffle 12 can be additionally arranged in order to prevent atomized liquid drops from splashing on the high-frequency induction.
The equations of the reactions that occur in this example include, but are not limited to, the following reactions:
Figure BDA0001525404170000071
Figure BDA0001525404170000072
Figure BDA0001525404170000073
Figure BDA0001525404170000074
table 2: high-entropy alloy raw material components and content
Composition (I) Fe3O4 Cr2O3 MnO2 NiO2 More than 98% of active aluminum
Content/g 290 285 326 341 461
In this embodiment, an EDS energy spectrum of the high-entropy alloy coating 8 is shown in fig. 3, and it can be seen from the graph that the main elements in the high-entropy alloy layer are Fe, Cr, Ni, and Mn, and the atomic percentage content of each main element is between 5% and 30%, which meets the requirements of the high-entropy alloy components. The metallographic graph of the bonding portion between the high-entropy alloy coating layer 8 and the substrate 9 to be coated is shown in fig. 4, and it can be seen from the metallographic graph that the surface metallurgical bonding condition between the high-entropy alloy coating layer 8 and the substrate 9 to be coated is good, the bonding strength is 425MPa, and the hardness is 45HRC in the present embodiment. In 3.5% NaCl solution at a corrosion current density of 2.2. mu.A/cm2Relative to the substrate 42.8 muA/cm2And the corrosion resistance of the high-entropy alloy coating 8 is greatly improved. A ball disc type friction wear test is adopted, and under a certain condition, the wear loss is 6% of that of the matrix (45 steel).
Example 3:
a composite material containing a high-entropy alloy coating comprises a substrate and the high-entropy alloy coating, wherein the high-entropy alloy coating is coated on the surface of the substrate in one step through thermite reaction, and the preparation method comprises the following steps:
(1) preparing an experimental device: preparing the apparatus shown in FIG. 1, including an aluminothermic reactor 4, a rod stopper 1, a liquid guide tube 5 and an atomizer 6; the inner diameter of an aluminous thermal reactor 4 is 12mm, the upper part is provided with a protective cover 2, the protective cover 2 is provided with a dust remover 20, a rod plug 1 is inserted into a groove above a liquid guide pipe 5, the inner diameter (namely the liquid flow diameter) of the lower end of the liquid guide pipe 5 is 5mm, a preheating device 17 is sleeved around the aluminous thermal reactor 4, a slag discharge pipe 18 is specially provided with holes and fixed through the preheating device, the aluminous thermal reactor 4 is preheated to 650 ℃ through the preheating device 17, a matrix 9 to be coated is placed in a deposition chamber 10 and is positioned below the liquid guide pipe 5, the height (namely the atomization height) between the surface of the matrix 9 to be coated and the lower part of the liquid guide pipe 5 is kept to be 150mm, a temperature measurement window 15 is arranged above the aluminous thermal reactor 4, an infrared induction thermometer 16 is used for measuring the temperature, a high;
(2) mixing the oxide of the high-entropy alloy principal element, the aluminum powder and the auxiliary agent in a V-20 mixer for 15min to obtain an thermite, and putting the thermite into an thermite reactor 4 (such as a ceramic crucible), wherein the thermite is kept to be freely stacked; wherein, the main element and the content are shown in the following table 3, and the auxiliary agent is K2CrO7And/or KMnO4、CaO、SiO2，CaO、SiO 24% of the total amount of the thermite;
(3) igniting the thermite by using a high-temperature match to excite thermite reaction to obtain alloy melt, discharging slag from the melt under the conditions of exothermic reaction and stirring of reaction gas (a dust remover 20 can be started to remove redundant gas), and obtaining a bottom-layer high-entropy alloy melt 13 and an upper-layer alumina slag 14 after the alloy melt flows and is layered;
(4) after the reaction is finished, the temperature of the alloy melt reaches 2450 ℃, the alloy melt is kept stand for 15s, the temperature of the melt is 2000 ℃, the rod plug 1 is pulled out, and the high-entropy alloy melt is positioned at the bottom layer (the upper layer is rich in Al at this time)2O3The ceramic layer is basically solidified and does not flow out) automatically flows out through the liquid guide pipe 5, the atomized nitrogen is started, the air pressure of the atomized nitrogen is kept at 0.5MPa, the atomization angle is 5 degrees, and the injection height is 180 mm. And simultaneously moving the substrate 9 to be coated, keeping the moving speed at 7mm/s, forming an atomizing cone 7 through nitrogen atomization of an atomizer 6, automatically coating the atomizing cone on the surface of the substrate 9 to be coated, forming a layer of 6mm high-entropy alloy coating 8(FeCrNiMnCo high-entropy alloy cladding layer) on the surface of the substrate 9 to be coated to obtain the composite material containing the high-entropy alloy coating 8, and additionally arranging a baffle 12 in order to prevent atomized liquid drops from splashing on the high-frequency induction coil.
The equations of the reactions that occur in this example include, but are not limited to, the following reactions:
Figure BDA0001525404170000081
Figure BDA0001525404170000082
Figure BDA0001525404170000083
Figure BDA0001525404170000084
Figure BDA0001525404170000085
table 3: high-entropy alloy raw material components and content
Figure BDA0001525404170000086
In this embodiment, an EDS spectrum of the high-entropy alloy layer is shown in fig. 5, and it can be seen from the graph that the main elements in the high-entropy alloy layer are Fe, Cr, Co, Ni, and Mn, and the atomic percentage content of each main element is between 5% and 30%, which meets the requirements of the high-entropy alloy composition.
Example 4:
compared with the preparation method of the embodiment 2, the composite material containing the high-entropy alloy coating is characterized in that the raw material also contains Fe-50Ni pre-alloy powder, and the content of each substance in the components of the composite material is correspondingly changed according to the composition principle of the high-entropy alloy raw material. In this example, a composite material containing a high-entropy alloy coating layer 8 (6 mm in thickness) was finally prepared.

Claims (4)

1. A preparation method of a composite material containing a high-entropy alloy coating is characterized by comprising the following steps:
(1) mixing an oxide or a simple substance of a high-entropy alloy principal element with aluminum powder to obtain a thermite, wherein the oxide or the simple substance of the principal element at least comprises an oxide of one principal element; prealloying powder is added into the thermit, and the prealloying powder is alloy powder consisting of at least two principal element elements;
(2) putting the thermite in the step (1) into an aluminothermic reactor, igniting the thermite to excite thermite reaction to obtain an alloy melt, stirring, rolling, flowing, layering, and standing to obtain a bottom-layer high-entropy alloy melt and an upper-layer alumina slag;
(3) atomizing the bottom-layer high-entropy alloy melt in the step (2) into high-entropy alloy molten drops through a spray coating device, and spraying and coating the high-entropy alloy molten drops on the surface of a substrate to be coated to obtain a composite material containing a high-entropy alloy coating;
the thickness of the high-entropy alloy coating is 4-10 mm;
the standing time in the step (2) is 5-15 s, so that the temperature of the melt after standing is 1800-2000 ℃;
in the step (3), the surface of the substrate to be coated is preheated to 400-800 ℃ before spray coating, and the thickness of the preheated surface is controlled to be 0.2-0.5 mm;
and (3) during spray coating in the step (3), the air pressure of atomizing gas is 0.3-0.8 Mpa, the atomizing angle is 0-30 degrees, the moving speed of the matrix to be coated is 5-30 mm/s, the height between a nozzle of the spray coating device and the surface of the matrix to be coated is 50-200 mm, and the inner diameter of the nozzle is 3-8 mm.
2. The preparation method of the composite material containing the high-entropy alloy coating layer as claimed in claim 1, wherein the total amount of the pre-alloy powder and the elemental principal elements added accounts for 10-30% of the mass of the thermite.
3. A method for preparing a composite material containing a high entropy alloy coating according to claim 1, wherein a reaction is further added to the thermiteAn assistant and a slag discharge additive, wherein the reaction assistant is KClO4、K2CrO7And KMnO4One or more of the slag-off additives are SiO2And/or CaO, wherein the addition mass of the slag-discharging additive is 1-5% of the mass of the alumina slag.
4. A method for preparing a composite material containing a high-entropy alloy coating layer according to any one of claims 1 to 3, wherein in the step (2), the thermite reactor is preheated to 300 to 700 ℃ before the thermite is placed in the thermite reactor.
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