A method for preparing a rare earth modified spray coating and a spray coating thereof

Abstract

The present invention discloses a method for preparing a rare earth modified spray coating and a spray coating thereof, wherein a spray powder of a first shape with a first predetermined size and a rare earth powder of a second shape with a second predetermined size are pressed into a matrix powder by cold welding and extrusion of mechanical ball milling, and then a composite powder is formed by solid solution heat treatment to obtain a spray powder modified by a rare earth element, wherein the spray powder includes metals and alloys thereof, ceramics and ceramic-based composite powders, polymers and polymer-based composite powders, and the rare earth powder includes rare earth elements and rare earth compounds, and the first predetermined size is greater than the second predetermined size; the spray powder modified by the rare earth element is prepared by thermal spraying or cold spraying to obtain a rare earth modified coating, wherein the rare earth element is solid-dissolved in the coating to form a strengthening phase. The rare earth modified coating has a small content of inter-particle oxides and impurities.

Description

Technical Field

[0001] The invention belongs to the technical field of material processing, in particular to a method for preparing a rare earth modified spray coating and the spray coating. Background Art

[0002] Coatings prepared by thermal spraying and cold spraying have the advantages of a wide variety of coating materials, high preparation efficiency and low cost, and are widely used in industrial fields such as machinery, aerospace, and shipbuilding. However, when preparing coatings by thermal spraying or cold spraying, the spraying powder particles will inevitably be drawn into the oxygen and nitrogen in the air during the heating and accelerated flight process, causing the elements in the coating to be oxidized, nitrided and decomposed with the oxygen and nitrogen in the air, generating impurities such as oxides and nitrides, which are further introduced into the coating, thereby affecting the interlayer bonding of the coating particles, the composition and performance of the coating, and to a certain extent limiting the application of the coating material and the performance of its performance.

[0003] Rare earth elements are known as industrial MSG and play an irreplaceable role in improving the performance of thermal spray and cold spray coatings. Rare earth elements can effectively inhibit the oxidation, nitridation and decomposition of spray powders, purify impurities in the coating, and dissolve in the coating to form a strengthening phase, thereby improving the performance of the coating. However, how to effectively and accurately add rare earth elements into the spray coating to prepare rare earth-modified thermal spray and cold spray coatings is a problem that needs to be solved urgently by people in this technical field.

[0004] The above information disclosed in this Background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known in this country to a person of ordinary skill in the art. Summary of the invention

[0005] In view of the problems existing in the prior art, the present invention proposes a method for preparing a rare earth modified spray coating and a spray coating thereof, which effectively solves the problem of adding rare earth elements into the spray coating to prepare rare earth modified thermal spray and cold spray coatings.

[0006] The purpose of the present invention is achieved by the following technical scheme. A method for preparing a rare earth modified spray coating comprises the following steps:

[0007] A spray powder of a first shape having a first predetermined size and a rare earth powder of a second shape having a second predetermined size are pressed into a matrix powder by cold welding and extrusion of mechanical ball milling, and then a composite powder is formed by solid solution heat treatment to obtain a spray powder modified by a rare earth element, wherein the spray powder includes metals and alloys thereof, ceramics and ceramic-based composite powders, polymers and polymer-based composite powders, and the rare earth powder includes rare earth elements and rare earth compounds, and the first predetermined size is greater than the second predetermined size;

[0008] The rare earth element modified spray powder is prepared by thermal spraying or cold spraying to obtain a rare earth modified coating, wherein the rare earth element is solid-dissolved in the coating to form a reinforcement phase.

[0009] In the method, the first predetermined size is 20-200 μm, and the second predetermined size is 0.1 nm-10 μm.

[0010] In the method, the first shape or the second shape includes a spherical shape, a polygonal shape and an irregular shape.

[0011] In the method described above, the rare earth compound includes oxides, chlorides, fluorides, hydrides, nitrides, sulfides, halides, carbides and intermetallic compounds of cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.

[0012] In the method, mechanical ball milling includes ball milling using a mixer, a planetary ball mill, a high-energy ball mill, a stirring ball mill or a vibrating ball mill.

[0013] In the method, the mechanical ball mill is subjected to the conditions of a rotation speed of 0.1-2000 r / min, a ball milling time of 0.1-2000 hours, and a ratio of the total powder of the grinding balls and the spray powder to the rare earth powder of 0.1:1-200:1, and the rare earth element-modified spray powder is obtained by cold welding and extrusion.

[0014] In the method, the solution heat treatment includes vacuum solution heat treatment, atmosphere protection solution heat treatment or solution heat treatment in a conventional atmospheric environment.

[0015] In the method, the temperature of the solution heat treatment is 100-3000° C., and the time of the solution heat treatment is 0.1-100 hours.

[0016] In the method, thermal spraying includes flame spraying, arc spraying, plasma spraying, explosion spraying and laser cladding spraying.

[0017] A spray coating is prepared via the method described.

[0018] Beneficial Effects

[0019] The method for preparing the rare earth modified spray coating provided by the present invention is highly practical. The rare earth modified spray powder is used to prepare the coating by thermal spraying or cold spraying. The rare earth elements can effectively purify the impurities in the coating and inhibit the oxidation, nitridation and decomposition of the matrix elements. The problem of the deviation between the composition of the traditional rare earth modified coating and the designed composition, the increase of oxides in the coating, and the poor bonding between the particles of the coating are avoided. At the same time, the rare earth elements can be dissolved in the coating to improve the performance of the spray coating. The present invention provides an effective solution for the preparation of the rare earth modified spray coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] By reading the detailed description of the preferred specific embodiments below, various advantages and benefits of the present invention will become clear to those of ordinary skill in the art. The drawings in the specification are only used for the purpose of illustrating the preferred embodiments and are not considered to be limitations of the present invention. Obviously, the drawings described below are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings without creative work. Moreover, the same reference numerals are used to represent the same components throughout the drawings.

[0021] In the attached picture:

[0022] Figure 1 The morphology of the iron-based alloy powder modified by rare earth cerium (Ce) in a preferred embodiment of the present invention;

[0023] Figure 2 This is an energy spectrum diagram of rare earth cerium (Ce) added to the iron-based alloy powder of a preferred embodiment of the present invention;

[0024] Figure 3 The structure of the iron-based alloy coating modified by rare earth cerium (Ce) in a preferred embodiment of the present invention;

[0025] Figure 4 The structure of the iron-based alloy coating containing no rare earth in a preferred embodiment of the present invention;

[0026] Figure 5 The present invention is a preferred embodiment of the iron-based alloy coating and the wear mass loss of the iron-based alloy modified by rare earth cerium (Ce); wherein A is the iron-based alloy coating, and B is the iron-based alloy coating modified by rare earth cerium (Ce).

[0027] The present invention is further explained below in conjunction with the accompanying drawings and embodiments. DETAILED DESCRIPTION

[0028] The following reference Figures 1 to 5 Specific embodiments of the present invention will be described in more detail. Although specific embodiments of the present invention are shown in the accompanying drawings, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided to enable a more thorough understanding of the present invention and to fully convey the scope of the present invention to those skilled in the art.

[0029] It should be noted that certain words are used in the specification and claims to refer to specific components. Those skilled in the art should understand that technicians may use different nouns to refer to the same component. This specification and claims do not use the difference in nouns as a way to distinguish components, but use the difference in the functions of the components as the criterion for distinction. As mentioned throughout the specification and claims, "including" or "comprising" is an open term, so it should be interpreted as "including but not limited to". The subsequent description of the specification is a preferred embodiment of the present invention, but the description is still based on the general principles of the specification and is not used to limit the scope of the present invention. The scope of protection of the present invention shall be determined by the attached claims.

[0030] To facilitate understanding of the embodiments of the present invention, further explanation will be given below by taking specific embodiments as examples in conjunction with the accompanying drawings, and each of the accompanying drawings does not constitute a limitation on the embodiments of the present invention.

[0031] For better understanding, a method for preparing a rare earth modified spray coating comprises the following steps:

[0032] A spray powder of a first shape having a first predetermined size and a rare earth powder of a second shape having a second predetermined size are pressed into a matrix powder by cold welding and extrusion of mechanical ball milling, and then a composite powder is formed by solid solution heat treatment to obtain a spray powder modified by a rare earth element, wherein the spray powder includes metals and alloys thereof, ceramics and ceramic-based composite powders, polymers and polymer-based composite powders, and the rare earth powder includes rare earth elements and rare earth compounds, and the first predetermined size is greater than the second predetermined size;

[0033] The rare earth element modified spray powder is prepared by thermal spraying or cold spraying to obtain a rare earth modified coating, wherein the rare earth element is solid-dissolved in the coating to form a reinforcement phase, and the rare earth modified coating has less inter-particle oxides and impurities.

[0034] In a preferred embodiment of the method, the first predetermined size is 20-200 μm, and the second predetermined size is 0.1 nm-10 μm.

[0035] In a preferred embodiment of the method, the first shape or the second shape includes a spherical shape, a polygonal shape and an irregular shape.

[0036] In a preferred embodiment of the method, the rare earth compound includes oxides, chlorides, fluorides, hydrides, nitrides, sulfides, halides, carbides and intermetallic compounds of cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.

[0037] In a preferred embodiment of the method, the mechanical ball milling includes ball milling using a mixer, a planetary ball mill, a high-energy ball mill, a stirring ball mill or a vibrating ball mill.

[0038] In a preferred embodiment of the method, the rare earth element-modified spray powder is obtained by cold welding and extrusion under the conditions that the mechanical ball milling speed is 0.1-2000r / min, the ball milling time is 0.1-2000 hours, and the ratio of the total powder of the grinding balls and the spray powder to the rare earth powder is 0.1:1-200:1.

[0039] In a preferred embodiment of the method, the solution heat treatment includes vacuum solution heat treatment, atmosphere protection solution heat treatment or solution heat treatment in a conventional atmospheric environment.

[0040] In a preferred embodiment of the method, the temperature of the solution heat treatment is 100-3000° C., and the time of the solution heat treatment is 0.1-100 hours.

[0041] In a preferred embodiment of the method, thermal spraying includes flame spraying, arc spraying, plasma spraying, detonation spraying and laser cladding spraying.

[0042] In one embodiment, the method includes preparing a rare earth modified coating by thermal spraying or cold spraying of a spray powder modified by a rare earth element. The rare earth elements include rare earth elements and rare earth compounds; the spray powder includes metals and their alloys, ceramics and ceramic-based composite powders, polymers and polymer-based composite powders; the thermal spraying includes flame spraying, arc spraying, plasma spraying, explosion spraying and laser cladding spraying; the rare earth elements can effectively inhibit the oxidation, nitridation and decomposition of the spray powder, purify impurities in the coating, and dissolve in the coating to form a strengthening phase; the rare earth modified coating has a small amount of interlayer oxides and impurities between particles.

[0043] Furthermore, the rare earth elements include single substances, oxides, chlorides, fluorides, hydrides, nitrides, sulfides, halides, carbides and intermetallic compounds of cerium (Ce), lanthanum (La), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).

[0044] Furthermore, the rare earth modified coating is prepared by thermal spraying or cold spraying.

[0045] Furthermore, the thermal spraying includes flame spraying, arc spraying, plasma spraying, explosion spraying and laser cladding spraying.

[0046] Furthermore, the spraying powder includes metals and their alloys, ceramics and ceramic-based composite powders, polymers and polymer-based composite powders.

[0047] Furthermore, the rare earth powder is a powder in a spherical, polygonal, irregular or other shape, and has a size of 0.1 nm-10 μm.

[0048] Furthermore, the spraying powder is a powder in a spherical, polygonal, irregular or other shape, and has a size of 0.1-200 μm.

[0049] Furthermore, the rare earth element is pressed into the matrix powder by cold welding and extrusion of mechanical ball milling, and then a composite powder is formed by solid solution heat treatment to dissolve the rare earth element in the spraying powder.

[0050] Furthermore, the rare earth element can effectively inhibit the oxidation, nitridation and decomposition of the spray powder, purify the impurities in the coating, and be dissolved in the coating to form a strengthening phase.

[0051] Furthermore, the rare earth modified coating has less inter-particle oxides and impurities; the hardness, bonding strength, wear resistance, corrosion resistance, oxidation resistance, electrical, optical, magnetic and biological properties of the rare earth modified coating are significantly improved.

[0052] Example 1

[0053] Polygonal rare earth cerium (Ce) powder with a size of 0.1-2 μm and spherical iron-based alloy powder with a size of 30-80 μm are used for mechanical ball milling in a ball mill, followed by solid solution heat treatment to prepare rare earth cerium (Ce) modified iron-based alloy powder. The morphology of the obtained rare earth cerium (Ce) modified iron-based alloy powder is as follows: Figure 1 shown. Figure 2 The energy spectrum of rare earth cerium (Ce) added to iron-based alloy powder. The microstructure of the iron-based alloy coating modified with rare earth cerium (Ce) prepared by plasma spraying is shown in Figure 2. Figure 3 As shown in Figure 1, rare earth cerium (Ce) has been completely dissolved in the iron-based alloy coating to form a strengthening phase containing rare earth cerium. The microstructure of the iron-based alloy coating without rare earth prepared under the same parameter conditions is shown in Figure 1. Figure 4 As shown in Figure 2, there are fine pores and oxides in the iron-based alloy coating without rare earth. Figure 5 Shown is the mass loss of the wear experiment. Under the same wear conditions, the mass loss of the rare earth cerium (Ce) modified iron-based alloy coating is 2.3 mg, and the mass loss of the traditional iron-based alloy coating is 8.5 mg. The mass loss of the latter is 3.7 times that of the former.

[0054] Example 2

[0055] A rare earth promethium (Pm) powder with a polygonal shape and a size of 0.2-3 μm and a polygonal copper-based alloy powder with a size of 15-60 μm are used to prepare a rare earth promethium (Pm) modified copper-based alloy powder through mechanical ball milling and solid solution treatment. A rare earth promethium (Pm) modified copper-based alloy coating is prepared by cold spraying, and the rare earth promethium (Pm) is completely dissolved in the copper-based alloy coating, and its wear resistance is twice that of the copper-based alloy coating without adding rare earth promethium (Pm).

[0056] Example 3

[0057] Irregular rare earth neodymium (Nd) powder with a size of 0.1-10μm and irregular nickel-based alloy powder with a size of 15-100μm are used to prepare rare earth neodymium (Nd) modified nickel-based alloy powder through mechanical ball milling and solid solution treatment. Rare earth neodymium (Nd) modified nickel-based alloy coating is prepared by laser cladding spraying. Rare earth neodymium (Nd) is completely dissolved in the nickel-based alloy coating, and its corrosion resistance is twice that of the nickel-based alloy coating without rare earth neodymium (Nd) added.

[0058] Example 4

[0059] Irregular rare earth dysprosium (Dy) powder with a size of 0.1nm-3μm and irregular zirconia powder with a size of 30-100μm are used to prepare rare earth dysprosium (Dy) modified zirconia powder through mechanical ball milling and solid solution treatment. Rare earth dysprosium (Dy) modified zirconia coating is prepared by supersonic flame spraying. Rare earth dysprosium (Dy) is completely dissolved in the zirconia coating, and its oxidation resistance is 3 times that of the zirconia coating without rare earth dysprosium (Dy) added.

[0060] Example 5

[0061] Spherical rare earth erbium oxide (Er2O3) powder with a size of 0.2nm-3μm and spherical polyester-epoxy resin powder with a size of 20-75μm are used to prepare rare earth erbium oxide (Er2O3) modified polyester-epoxy resin powder through mechanical ball milling and solid solution treatment. Rare earth erbium oxide (Er2O3) modified polyester-epoxy resin coating is prepared by flame spraying, and rare earth erbium oxide (Er2O3) is completely solid-dissolved in the polyester-epoxy resin coating, and its anti-shielding performance is twice that of the polyester-epoxy resin coating without adding rare earth erbium oxide (Er2O3).

[0062] Example 6

[0063] Spherical rare earth lutetium oxide (Lu2O3) powder with a size of 0.1nm-2μm and irregular nylon powder with a size of 20-100μm are used to prepare rare earth lutetium oxide (Lu2O3) modified nylon powder through mechanical ball milling and solid solution treatment. Rare earth lutetium oxide (Lu2O3) modified nylon coating is prepared by flame spraying. Rare earth lutetium oxide (Lu2O3) is completely dissolved in the nylon coating, and its corrosion resistance is twice that of the nylon coating without rare earth lutetium oxide (Lu2O3).

[0064] A spray coating is prepared by the method. Rare earth elements can effectively inhibit the oxidation, nitridation and decomposition of spray powder, purify impurities in the coating, and solid-dissolve in the coating to form a strengthening phase; the rare earth modified coating has a small amount of interlayer oxides and impurities; the hardness, bonding strength, wear resistance, corrosion resistance, oxidation resistance, electrical, optical, magnetic and biological properties of the rare earth modified coating are significantly improved.

[0065] Although the embodiments of the present invention are described above in conjunction with the accompanying drawings, the present invention is not limited to the above specific embodiments and application fields, and the above specific embodiments are only illustrative and instructive, rather than restrictive. A person of ordinary skill in the art can also make many forms under the guidance of this specification and without departing from the scope of protection of the claims of the present invention, all of which belong to the protection of the present invention.

Claims

1. A method for preparing a rare earth modified spray coating, characterized in that: The method comprises the following steps: A spray powder of a first shape having a first predetermined size and a rare earth powder of a second shape having a second predetermined size are pressed into a matrix powder by cold welding and extrusion of mechanical ball milling, and then a composite powder is formed by solid solution heat treatment to obtain a spray powder modified by a rare earth element, wherein the spray powder includes metals and alloys thereof, ceramics and ceramic-based composite powders, polymers and polymer-based composite powders, and the rare earth powder includes rare earth elements and rare earth compounds, and the first predetermined size is greater than the second predetermined size; The rare earth element modified spray powder is prepared by thermal spraying or cold spraying to obtain a rare earth modified coating, wherein the rare earth element is solid-dissolved in the coating to form a reinforcing phase; the first predetermined size is 20-200µm, the second predetermined size is 0.1nm-10µm, the mechanical ball milling is performed at a speed of 0.1-2000r / min, the ball milling time is 0.1-2000 hours, and the ratio of the total powder of the grinding balls and the spray powder to the rare earth powder is 0.1:1-200:1, and the rare earth element modified spray powder is obtained by cold welding and extrusion, and the rare earth element inhibits the oxidation, nitridation and decomposition of the matrix element.

2. The method according to claim 1, characterized in that The first shape or the second shape includes a spherical shape, a polygonal shape, and an irregular shape.

3. The method according to claim 1, characterized in that Rare earth compounds include oxides, chlorides, fluorides, hydrides, nitrides, sulfides, carbides and intermetallic compounds of cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.

4. The method according to claim 1, characterized in that: Mechanical ball milling includes ball milling using a planetary ball mill, a high-energy ball mill, a stirring ball mill or a vibrating ball mill.

5. The method according to claim 1, characterized in that Solution heat treatment includes vacuum solution heat treatment, atmosphere protection solution heat treatment or solution heat treatment in conventional atmospheric environment.

6. The method according to claim 1, characterized in that The temperature of the solid solution heat treatment is 100-3000° C., and the time of the solid solution heat treatment is 0.1-100 hours.

7. The method according to claim 1, characterized in that Thermal spraying includes flame spraying, arc spraying, plasma spraying, detonation spraying and laser cladding spraying.

8. A spray coating, characterized in that: It is prepared by the method according to any one of claims 1 to 7.

Images