Aluminum-based amorphous alloy powder and preparation method thereof

Abstract

The present invention relates to the field of alloy materials, in particular to an aluminum-based amorphous alloy powder and a preparation method thereof. The aluminum-based amorphous alloy powder is expressed as Al 85 Ni6Si 4.5 Nb3Nd 1.5 +M+RE; wherein, M is metal nitride and / or metal carbide and / or metal boride; RE is a rare earth element; Al 85 Ni6Si 4.5 Nb3Nd 1.5 The mass ratio of M to RE is 100-120:5-15:0.1-1. The aluminum-based amorphous alloy prepared by the present invention exhibits more positive self-corrosion potential and pitting potential. As a coating, it has higher corrosion resistance and pitting resistance, and has extremely high strength and hardness, and has excellent protection for the substrate.

Description

Technical Field

[0001] The present invention relates to the field of alloy materials, in particular to an aluminum-based amorphous alloy powder and a preparation method thereof. Background Art

[0002] Amorphous alloy (also known as metallic glass, Metallic Glass, MG) is an unusual metal material. Its internal atoms have the characteristics of short-range order and long-range disorder in three-dimensional space. This is different from the long-range ordered structure of ordinary metal crystals. Therefore, amorphous alloy is actually a metal material with an amorphous structure.

[0003] In 1960, Duwez team and others prepared Au from liquid metal for the first time. 75 Si 25 Amorphous alloys. Since the discovery of amorphous alloys, they have quickly attracted the keen attention of researchers around the world. Through research, it has been found that amorphous alloys have excellent mechanical, physical and chemical properties, and are considered to be a material with great application potential. Amorphous alloys combine the characteristics of metal materials and amorphous materials, showing excellent properties such as high strength, high elastic modulus, corrosion resistance and wear resistance. At the same time, the metal elements contained in the amorphous alloys themselves are more likely to form a good interface bond with the metal matrix to improve wettability, and the thermal expansion coefficients between the amorphous alloys and the metal matrix are not much different. Therefore, it is also a relatively ideal reinforcement phase for metal-based composite materials. At present, although some research on amorphous alloys has been done at home and abroad, and good results have been achieved, the performance shown has not yet met people's expectations. Summary of the Invention

[0004] Purpose of the invention: In order to solve the above technical problems, the present invention proposes an aluminum-based amorphous alloy powder and a preparation method thereof.

[0005] The technical solutions adopted are as follows:

[0006] An aluminum-based amorphous alloy powder, wherein the expression of the aluminum-based amorphous alloy powder is Al 85 Ni6Si 4.5 Nb3Nd 1.5 +M+RE;

[0007] Wherein, M is a metal nitride and / or a metal carbide and / or a metal boride;

[0008] RE is a rare earth element;

[0009] Al 85 Ni6Si 4.5 Nb3Nd 1.5 The mass ratio of M and RE is 100-120:5-15:0.1-1.

[0010] Furthermore, the metal nitride is any one or more combinations of TiN, AlN, and Si3N4, the metal carbide is TiC or SiC, and the metal boride is any one or more combinations of MgB2, TiB2, CaB6, and ZrB2.

[0011] Furthermore, the M is TiN and ZrB2.

[0012] Furthermore, the RE is any one or more combinations of La, Gd, and Ce.

[0013] Furthermore, the RE is La and Gd.

[0014] Furthermore, Al 85 Ni6Si 4.5 Nb3Nd 1.5 The mass ratio of M and RE is 120:10:0.5.

[0015] The present invention also provides a method for preparing aluminum-based amorphous alloy powder:

[0016] According to the expression, Al, Ni, Si, Nb, Nd, and RE are weighed, and repeatedly smelted 3-5 times under vacuum conditions to obtain an alloy ingot, which is atomized to obtain a powder. The powder is mixed with M, ball-milled, and sieved to obtain the aluminum-based amorphous alloy powder.

[0017] Furthermore, atomization is performed using a tightly coupled atomizing device, the atomizing gas is argon, the atomizing gas pressure is 8-12 MPa, the superheat is 150-200° C., and the diameter of the draft tube is 3-5 mm.

[0018] Furthermore, the ball milling is carried out under argon protection, with a ball-to-material ratio of 10-15:1, the ball mill is paused for 15-30 minutes after working for 15-30 minutes, and operates alternately in forward and reverse directions. The total ball milling time is 4-6 hours, and the ball mill speed is 200-400 r / min.

[0019] Furthermore, the particle size of the aluminum-based amorphous alloy powder is 10-50 μm.

[0020] Beneficial effects of the present invention:

[0021] The present application provides an aluminum-based amorphous alloy powder. The amorphous alloy powder has a reasonable composition, high glass-forming ability and thermal stability, does not sublimate in a high-temperature flame flow, and is particularly suitable for plasma spraying. By adding metal nitride and / or metal carbide and / or metal boride particles, deformation caused by stress release during the spraying process can be reduced, dimensional stability can be improved, and the mechanical strength of the resulting coating can be enhanced. The addition of rare earth elements can purify the melt and improve the structure, so that the amorphous alloy exhibits a more positive self-corrosion potential and pitting corrosion potential. Moreover, rare earth elements have active chemical properties and can form chemically stable compounds with almost all non-metallic elements (oxygen, sulfur, halogen elements, etc.). In a neutral salt solution, rare earth elements can quickly form a stable passivation film with the halogen ions in the solution, thereby improving the corrosion resistance of the amorphous alloy. The aluminum-based amorphous alloy prepared by the present invention exhibits a more positive self-corrosion potential and pitting corrosion potential, has higher corrosion resistance and pitting corrosion resistance as a coating, and has extremely high strength and hardness, and has an excellent protective effect on the substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The XRD diffraction patterns of the aluminum-based amorphous alloy powders prepared in Examples 1-3 and Comparative Example 1 of the present invention are as follows: Figure 1 It can be seen that the aluminum-based amorphous alloys prepared in Examples 1-3 all present a good amorphous morphology;

[0023] Figure 2 This is a SEM image of the surface morphology of the aluminum-based amorphous alloy powder prepared in Example 1 of the present invention;

[0024] Figure 3 This is a SEM image of the surface morphology of the aluminum-based amorphous alloy powder prepared in Comparative Example 6 of the present invention;

[0025] Figure 4 This is a SEM image of the surface morphology of the aluminum-based amorphous alloy powder prepared in Comparative Example 7 of the present invention;

[0026] Depend on Figure 2-4 By comparison, it can be seen that the addition of La and Gd helps to improve the sphericity of aluminum-based amorphous alloy powders and improve the surface morphology. DETAILED DESCRIPTION

[0027] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or those recommended by the manufacturer. All reagents or instruments used, if the manufacturer is not specified, are commercially available conventional products.

[0028] Example 1:

[0029] An aluminum-based amorphous alloy powder, the expression of which is Al 85 Ni6Si 4.5 Nb3Nd 1.5+M+RE;

[0030] Wherein, M is TiN and ZrB2 with a mass ratio of 1:1;

[0031] RE is La and Gd with a mass ratio of 1:1;

[0032] Al 85 Ni6Si 4.5 Nb3Nd 1.5 The mass ratio of M and RE is 120:10:0.5.

[0033] A method for preparing aluminum-based amorphous alloy powder:

[0034] The raw materials were weighed according to the expression, and Al, Ni, Si, Nb, Nd, and RE were repeatedly melted four times in a high vacuum arc melting system under vacuum conditions to obtain alloy ingots, which were atomized using a tightly coupled atomizing device. The atomizing gas was argon, the atomizing pressure was 10 MPa, the superheat was 160°C, and the diameter of the draft tube was 5 mm. The powder obtained by atomization was mixed with M and ball milled. The ball milling was carried out under argon protection, with a ball-to-material ratio of 15:1. The ball mill was paused for 30 minutes after every 30 minutes of operation, and operated alternately in forward and reverse directions. The total ball milling time was 6 hours, and the ball mill speed was 350 r / min. After screening, aluminum-based amorphous alloy powder with a particle size of 10-50 μm was obtained.

[0035] Example 2:

[0036] An aluminum-based amorphous alloy powder, the expression of which is Al 85 Ni6Si 4.5 Nb3Nd 1.5 +M+RE;

[0037] Wherein, M is TiN and ZrB2 with a mass ratio of 2:1;

[0038] RE is La and Gd with a mass ratio of 1:1;

[0039] Al 85 Ni6Si 4.5 Nb3Nd 1.5 The mass ratio of M and RE is 120:10:0.5.

[0040] A method for preparing aluminum-based amorphous alloy powder:

[0041] The raw materials were weighed according to the expression, and Al, Ni, Si, Nb, Nd, and RE were repeatedly melted 5 times in a high vacuum arc melting system under vacuum conditions to obtain alloy ingots, which were atomized using a tightly coupled atomizing device. The atomizing gas was argon, the atomizing pressure was 12 MPa, the superheat was 200°C, and the diameter of the draft tube was 5 mm. The powder obtained by atomization was mixed with M and ball milled. The ball milling was carried out under argon protection, with a ball-to-material ratio of 15:1. The ball mill was paused for 30 minutes after every 30 minutes of operation, and operated alternately in forward and reverse directions. The total ball milling time was 6 hours, and the ball mill speed was 400 r / min. After screening, aluminum-based amorphous alloy powder with a particle size of 10-50 μm could be obtained.

[0042] Example 3:

[0043] An aluminum-based amorphous alloy powder, the expression of which is Al 85 Ni6Si 4.5 Nb3Nd 1.5 +M+RE;

[0044] Wherein, M is TiN and ZrB2 with a mass ratio of 3:1;

[0045] RE is La and Gd with a mass ratio of 1:1;

[0046] Al 85 Ni6Si 4.5 Nb3Nd 1.5 The mass ratio of M and RE is 120:10:0.5.

[0047] A method for preparing aluminum-based amorphous alloy powder:

[0048] The raw materials were weighed according to the expression, and Al, Ni, Si, Nb, Nd, and RE were repeatedly melted three times in a high vacuum arc melting system under vacuum conditions to obtain alloy ingots, which were atomized using a tightly coupled atomizing device. The atomizing gas was argon, the atomizing pressure was 8 MPa, the superheat was 150°C, and the diameter of the draft tube was 3 mm. The powder obtained by atomization was mixed with M and ball milled. The ball milling was carried out under argon protection, with a ball-to-material ratio of 10:1. The ball mill was paused for 15 minutes after every 15 minutes of operation, and operated alternately in forward and reverse directions. The total ball milling time was 4 hours, and the ball mill speed was 200 r / min. After screening, aluminum-based amorphous alloy powder with a particle size of 10-50 μm could be obtained.

[0049] Example 4:

[0050] An aluminum-based amorphous alloy powder, the expression of which is Al 85 Ni6Si 4.5 Nb3Nd 1.5 +M+RE;

[0051] Wherein, M is TiN and ZrB2 with a mass ratio of 1:1;

[0052] RE is La and Gd with a mass ratio of 1:1;

[0053] Al 85 Ni6Si 4.5 Nb3Nd 1.5 The mass ratio of M and RE is 120:10:0.5.

[0054] A method for preparing aluminum-based amorphous alloy powder:

[0055] The raw materials were weighed according to the expression, and Al, Ni, Si, Nb, Nd, and RE were repeatedly melted three times in a high vacuum arc melting system under vacuum conditions to obtain alloy ingots, which were atomized using a tightly coupled atomizing device. The atomizing gas was argon, the atomizing pressure was 12 MPa, the superheat was 150°C, and the diameter of the draft tube was 5 mm. The powder obtained by atomization was mixed with M and ball milled. The ball milling was carried out under argon protection, with a ball-to-material ratio of 10:1. The ball mill was paused for 15 minutes after every 30 minutes of operation, and operated alternately in forward and reverse directions. The total ball milling time was 6 hours, and the ball mill speed was 200 r / min. After screening, aluminum-based amorphous alloy powder with a particle size of 10-50 μm could be obtained.

[0056] Example 5:

[0057] An aluminum-based amorphous alloy powder, the expression of which is Al 85 Ni6Si 4.5 Nb3Nd 1.5 +M+RE;

[0058] Wherein, M is TiN and ZrB2 with a mass ratio of 1:1;

[0059] RE is La and Gd with a mass ratio of 1:1;

[0060] Al 85 Ni6Si 4.5 Nb3Nd 1.5 The mass ratio of M and RE is 120:10:0.5.

[0061] A method for preparing aluminum-based amorphous alloy powder:

[0062] The raw materials were weighed according to the expression, and Al, Ni, Si, Nb, Nd, and RE were repeatedly melted 5 times in a high vacuum arc melting system under vacuum conditions to obtain alloy ingots, which were atomized using a tightly coupled atomizing device. The atomizing gas was argon, the atomizing pressure was 8 MPa, the superheat was 200°C, and the diameter of the draft tube was 3 mm. The powder obtained by atomization was mixed with M and ball milled. The ball milling was carried out under argon protection, with a ball-to-material ratio of 15:1. The ball mill was paused for 30 minutes after every 15 minutes of operation, and operated alternately in forward and reverse directions. The total ball milling time was 4 hours, and the ball mill speed was 400 r / min. After screening, aluminum-based amorphous alloy powder with a particle size of 10-50 μm could be obtained.

[0063] Example 6:

[0064] An aluminum-based amorphous alloy powder, the expression of which is Al 85 Ni6Si 4.5 Nb3Nd 1.5 +M+RE;

[0065] Wherein, M is TiN and ZrB2 with a mass ratio of 1:1;

[0066] RE is La and Gd with a mass ratio of 1:1;

[0067] Al 85 Ni6Si 4.5 Nb3Nd 1.5 The mass ratio of M and RE is 120:10:0.5.

[0068] A method for preparing aluminum-based amorphous alloy powder:

[0069] The raw materials were weighed according to the expression, and Al, Ni, Si, Nb, Nd, and RE were repeatedly melted four times in a high vacuum arc melting system under vacuum conditions to obtain alloy ingots, which were atomized using a tightly coupled atomizing device. The atomizing gas was argon, the atomizing pressure was 12 MPa, the superheat was 180°C, and the diameter of the draft tube was 3 mm. The powder obtained by atomization was mixed with M and ball milled. The ball milling was carried out under argon protection, with a ball-to-material ratio of 10:1. The ball mill was paused for 20 minutes after every 20 minutes of operation, and operated alternately in forward and reverse directions. The total ball milling time was 6 hours, and the ball mill speed was 300 r / min. After screening, aluminum-based amorphous alloy powder with a particle size of 10-50 μm could be obtained.

[0070] Comparative Example 1:

[0071] It is basically the same as Example 1, except that TiN, ZrB2, La and Gd are not added.

[0072] Comparative Example 2:

[0073] It is basically the same as Example 1, except that TiN and ZrB2 are not added.

[0074] Comparative Example 3:

[0075] It is basically the same as Example 1, except that only TiN is added.

[0076] Comparative Example 4:

[0077] It is basically the same as Example 1, except that only ZrB2 is added.

[0078] Comparative Example 5:

[0079] The method is basically the same as Example 1, except that La and Gd are not added.

[0080] Comparative Example 6:

[0081] The process is basically the same as Example 1, except that only La is added.

[0082] Comparative Example 7:

[0083] It is basically the same as Example 1, except that only Gd is added.

[0084] Performance testing:

[0085] A 316L stainless steel sample was used as the spraying substrate, and the surface of the substrate was pickled, alkali washed, and rinsed with deionized water, and then polished until the roughness Ra was 3.2-12.5 μm. The aluminum-based amorphous alloy powders prepared in Examples 1-6 of the present invention and Comparative Examples 1-7 were respectively used as spraying raw materials, and the substrate surface was vacuum plasma sprayed (the spraying equipment was the A-2000 system of Sulzer Metco AG). During spraying, the instantaneous temperature of the substrate surface was controlled at 2200-2500°C, and the plasma flame flow speed was 1600 m / s. After spraying, linseed oil was applied to the coating surface, and then baked at 90°C for 2 hours and naturally cooled, and then polished until the surface roughness Ra was less than 1 μm. The spraying thickness was 0.1 mm to obtain the sample.

[0086] The corrosion behavior of the samples was tested using a Princeton 2273 electrochemical testing workstation. The polarization curves and AC impedance spectra of the samples in 0.6 mol / L NaCl solution were measured at room temperature and open circuit potential. The parts of the samples other than the test surface were sealed with epoxy resin. The test area was 10 mm × 10 mm. A standard three-electrode system was used, with a saturated calomel electrode (SCE) as the reference electrode and a Pt electrode as the counter electrode.

[0087] The test results are shown in Table 1 below:

[0088] Table 1:

[0089]

[0090]

[0091] As can be seen from Table 1 above, compared with the 316L stainless steel sample, the aluminum-based amorphous alloy prepared in the present invention exhibits more positive self-corrosion potential and pitting potential in 0.6 mol / L NaCl solution, indicating that the aluminum-based amorphous alloy has higher corrosion resistance and pitting resistance than the 316L stainless steel sample, and has an excellent protective effect on the substrate as a coating.

[0092] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. An aluminum-based amorphous alloy powder, characterized in that: The expression of the aluminum-based amorphous alloy powder is Al 85 Ni6Si 4.5 Nb3Nd 1.5 +M+RE; Wherein, M is a metal nitride and / or a metal carbide and / or a metal boride; RE is a rare earth element; Al 85 Ni6Si 4.5 Nb3Nd 1.5 The mass ratio of M and RE is 100-120:5-15:0.1-1; The metal nitride is any one or more combinations of TiN, AlN, and Si3N4, the metal carbide is TiC or SiC, and the metal boride is any one or more combinations of MgB2, TiB2, CaB6, and ZrB2; The RE is any one or more combinations of La, Gd, and Ce.

2. The aluminum-based amorphous alloy powder according to claim 1, characterized in that The M is TiN and ZrB2.

3. The aluminum-based amorphous alloy powder according to claim 1, characterized in that The RE is La and Gd.

4. The aluminum-based amorphous alloy powder according to claim 1, wherein Al 85 Ni6Si 4.5 Nb3Nd 1.5 The mass ratio of M and RE is 120:10:0.

5.

5. A method for preparing aluminum-based amorphous alloy powder as claimed in claim 1, characterized in that: According to the formula, Al, Ni, Si, Nb, Nd, and RE are weighed, and repeatedly smelted 3-5 times under vacuum conditions to obtain an alloy ingot, which is atomized to obtain a powder, and the powder is mixed with M and ball-milled and sieved to obtain the aluminum-based amorphous alloy powder; Atomization is performed using a tightly coupled atomizing device, with argon as the atomizing gas, atomizing pressure of 8-12 MPa, superheat of 150-200°C, and a draft tube diameter of 3-5 mm; The ball milling is carried out under argon protection, with a ball-to-material ratio of 10-15:

1. The ball mill is paused for 15-30 minutes after every 15-30 minutes of operation, and the forward and reverse rotations are alternately operated. The total ball milling time is 4-6 hours, and the ball mill speed is 200-400 r / min. The particle size of the aluminum-based amorphous alloy powder is 10-50 μm.

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