ALUMINUM-BASED METALLIC GLASS CLADDING LAYER AND PREPARATION METHOD THEREOF

Abstract

The present invention discloses an aluminum-based metallic glass cladding layer and a preparation method thereof. The aluminum-based metallic glass cladding layer takes aluminum-based amorphous alloy powder as a raw material and is prepared by a magnetic field stirring laser cladding molding technology; the aluminum-based amorphous alloy powder consists of the following elements: 5 wt %-8 wt % of Ni, 3 wt %-6 wt % of Y, 1 wt %-5 wt % of Co, 0.5 wt %-3 wt % of La and Al as balance; the particle size range of the aluminum-based amorphous alloy powder is 25-71 mum; and the oxygen content of the aluminum-based amorphous alloy powder is below 1,000 ppm. The aluminum-based amorphous alloy powder adopted by the present invention has high degree of sphericity, good flowability and moderate particle size; the added alloy elements have the characteristics of strong amorphous forming capability and stable structure; and meanwhile, the aluminum-based metallic glass cladding layer has excellent mechanical property, wear resistance property and corrosion resistance property.

Claims

1. An aluminum-based metallic glass cladding layer, characterized in that: the aluminum-based metallic glass cladding layer takes aluminum-based amorphous alloy powder as a raw material and is prepared by a magnetic field stirring laser cladding molding technology, wherein the aluminum-based amorphous alloy powder consists of the following elements: 5 wt %-8 wt % of Ni, 3 wt %-6 wt % of Y, 1 wt %-5 wt % of Co, 0.5 wt %-3 wt % of La and Al as balance.

2. The aluminum-based metallic glass cladding layer according to claim 1, characterized in that: the particle size range of the aluminum-based amorphous alloy powder is 25-71 mum.

3. The aluminum-based metallic glass cladding layer according to claim 1, characterized in that: the oxygen content of the aluminum-based amorphous alloy powder is below 1,000 ppm.

4. The aluminum-based metallic glass cladding layer according to claim 1, characterized in that: the aluminum-based amorphous alloy powder consists of the following elements: 6 wt %-7 wt % of Ni, 4 wt %-5 wt % of Y, 2 wt %-3 wt % of Co, 1 wt %-2 wt % of La and Al as balance.

5. A preparation method of an aluminum-based metallic glass cladding layer, characterized in that: according to the preparation method, the aluminum-based amorphous alloy powder is cladded on a matrix by the magnetic field stirring laser cladding molding technology; and the specific methods are described as follows: the matrix to be cladded is placed in an annular stirring magnetic field, so that the matrix generates a rotating magnetic field on the horizontal plane of a molten pool under the lasting stirring action of magnetic field force in a cladding forming process, so as to be capable of exerting the lasting stirring action of the magnetic field force on the molten pool, a coaxial powder-feed YG: Nd solid laser is vertical to the surface of the matrix, and a robot controls reciprocating motion for multi-path multi-layer cladding forming.

6. The preparation method of the aluminum-based metallic glass cladding layer according to claim 5, characterized in that: the specific process parameters of the magnetic field stirring laser cladding molding technology are as follows: laser power: 1,700-2,400 W, scanning speed:

3. 5-7 mm/s, spot diameter: 3 mm, powder feeding rate: 6-8 g/min, frequency of the magnetic field: 15-35 Hz, exciting current: 10-50 A, cladding time at every time: 10-15 s and cladding interval: 120-180 s.

7. The preparation method of the aluminum-based metallic glass cladding layer according to claim 5, characterized in that: the magnetic field stirring laser cladding molding technology also includes setting a cladding forming path: first, carrying out longitudinal single-path cladding, then choosing an appropriate amount of overlap for horizontal cladding, setting the length and overlap times of every single-path cladding according to the length and the width of the designed cladding layer, doing repeating motion and accumulating layer by layer, so as to form the cladding layer with a certain thickness finally.

8. The preparation method of the aluminum-based metallic glass cladding layer according to claim 7, characterized in that: in the setting of the cladding forming path, the amount of overlap is 30%-50%; the length of the cladding layer is 50-70 mm, the width of the cladding layer is 15-25 mm, and the thickness of the cladding layer is 0.5-5 mm; and the single-path cladding length is 50-70 mm, the number of overlap times is 8-12, and the number of layers in accumulating layer by layer is 6-10.

9. The preparation method of the aluminum-based metallic glass cladding layer according to claim 5, characterized in that: the preparation method further includes powder pretreatment and matrix pretreatment before the magnetic field stirring laser cladding molding technology: the powder pretreatment includes the following steps: drying the aluminum-based amorphous alloy powder with a vacuum drying chamber with vacuum degree of 0.05-0.1 standard atmospheric pressure at the temperature of 100-120 DEG C through 1-1.5 h of thermal insulation; and the matrix pretreatment includes the following steps: ultrasonic cleaning the surface of the matrix with acetone and alcohol respectively for 15-20 min and preheating to the temperature of 100-150 DEG C before cladding.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0025] FIG. 1 is an SEM (Scanning Electron Microscope) photograph of aluminum-based amorphous alloy powder adopted by an embodiment 1.

[0026] FIG. 2a is a back scattering photograph of a structure of the top of a cladding layer prepared by the embodiment 1.

[0027] FIG. 2b is a back scattering photograph of a structure of the top of a cladding layer prepared by a reference example 1.

[0028] FIG. 3a is a metallograph of a multi-path overlap position of the cladding layer prepared by the embodiment 1.

[0029] FIG. 3b is a partial enlarged drawing of the overlap position in FIG. 3a.

[0030] FIG. 3c is a metallograph of a multi-path overlap position of the cladding layer prepared by the reference example 1.

[0031] FIG. 3d is a partial enlarged drawing of the overlap position in FIG. 3c.

[0032] FIG. 4 is x-ray diffraction (XRD) spectrograms of the cladding layers and a complete amorphous ribbon that are prepared by the embodiment 1 and the reference example 1; in FIG. 4, 1 corresponds to the cladding layer of the embodiment 1, and 2 corresponds to the cladding layer of the reference example 1.

[0033] FIG. 5a is a DSC (Differential Scanning calorimetry) curve of the complete amorphous ribbon.

[0034] FIG. 5b is a DSC curve of the cladding layers prepared by the embodiment 1 and the reference example 1.

[0035] FIG. 6 are curves of friction coefficients along with time of the cladding layers and 5083 aluminum alloy matrixes that are prepared by the embodiment 1 and the reference example 1 under the condition of a test example 4.

[0036] FIG. 7 are potentiodynamic polarization curves of the cladding layers and the 5083 aluminum alloy matrixes that are prepared by the embodiment 1 and the reference example 1 in 3.5% NaCl solution.

DETAILED DESCRIPTION

Embodiment 1

[0037] Aluminum-based amorphous alloy powder adopted by an aluminum-based metallic glass cladding layer of the present embodiment consists of the following elements: 6 wt % of Ni, 4.5 wt % of Y, 2 wt % of Co, 1.5 wt % of La and Al as balance, i.e. Al.sub.86Ni.sub.6Y.sub.4.5Co.sub.2La.sub.1.5.

[0038] The particle size range of the aluminum-based amorphous alloy powder is 25-71 mum, and the oxygen content is less than 1,000 ppm.

[0039] A Quanta 200 type environmental SEM configured with an EDS (Energy Dispersive Spectrometer) accessory is adopted for microstructure and morphology observation for the aluminum-based amorphous alloy powder; and an SEM photograph of the aluminum-based amorphous alloy powder is shown in FIG. 1.

[0040] It can be seen from FIG. 1 that: the aluminum-based amorphous alloy powder is spherical and has good flowability, and the surfaces of a part of large particles are bonded with a small amount of steel balls, which are beneficial for improving loading density of the powder and are suitable for an automatic powder feeding type cladding process.

[0041] A preparation method of the aluminum-based metallic glass cladding layer includes the following steps:

[0042] (1) powder pretreatment and matrix pretreatment:

[0043] drying the aluminum-based amorphous alloy powder with a vacuum drying chamber with vacuum degree of 0.08 standard atmospheric pressure at the temperature of 110 DEG C through 1.2 h of thermal insulation; and ultrasonic cleaning the surface of a 5083 aluminum alloy matrix with acetone and alcohol respectively for 18 min and preheating to the temperature of 120 DEG C before cladding.

[0044] (2) setting a cladding forming path: first, carrying out longitudinal single-path cladding, then choosing an appropriate amount of overlap for horizontal cladding, setting the length and overlap times of every single-path cladding according to the length and the width of the designed cladding layer, doing repeating motion and accumulating layer by layer, so as to form the cladding layer with a certain thickness finally,

[0045] wherein the amount of overlap is 30%, the dimension of the cladding layer is 60 mm*20 mm*1.2 mm, the length of the single-path cladding is 60 mm, the number of overlap times is 10, and the number of layers of accumulating is 8.

[0046] (3) the 5083 aluminum alloy matrix to be cladded is placed in an annular stirring magnetic field, so that the matrix generates a rotating magnetic field on the horizontal plane of a molten pool under the lasting stirring action of magnetic field force in a cladding forming process, so as to be capable of exerting the lasting stirring action of the magnetic field force on the molten pool, a coaxial powder-feed YG: Nd solid laser is vertical to the surface of the matrix, and a robot controls reciprocating motion for multi-path multi-layer cladding forming.

[0047] The specific process parameters are as follows: laser power: 2,000 W, scanning speed: 5.5 mm/s, spot diameter: 3 mm, powder feeding rate: 7 g/min, frequency of the magnetic field: 25 Hz and exciting current: 30 A.

Reference Example 1

[0048] A reference example 1 is basically the same as the embodiment 1, and the different between the reference example 1 and the embodiment 1 is that: no magnetic field stirring is adopted in the step (3).

Reference Example2

[0049] A reference example 2 is basically the same as the embodiment 1, and the different between the reference example 2 and the embodiment 1 is that: the particle size range of aluminum-based amorphous alloy powder in the reference example 2 is 75-100 mum.

Text Example 1

Micro-Morphologies of the Cladding Layers

[0050] An OLYMPUS-60 metallographic optical microscope (OM) is adopted for metallographic observation for the cross section of the cladding layer.

[0051] FIG. 2a and FIG. 2b are respectively a back scattering photograph of a structure of the top of the cladding layer prepared by the embodiment 1 and a back scattering photograph of a structure of the top of a cladding layer prepared by the reference example 1.

[0052] Through comparison between FIG. 2a and FIG. 2b, it can be found that: metallic compound phases such as AlNiY and the like inside the cladding layer of the reference example 1 constantly precipitates and grows in a melt cooling process to form a thicker and bigger snowflake-shaped dendritic structure, while the structure of the inside of the cladding layer of the embodiment 1 is that: a network structure is distributed on a spheroidized alpha-Al phase as the stirring action of the magnetic field is exerted on the inside of the cladding layer, and it can be known that the network structure is an amorphous phase according to XRD and DSC characterization analysis (with reference to FIG. 4 and FIG. 5b below).

[0053] FIGS. 3a and 3b and FIGS. 3c and 3d are respectively a metallograph of a multi-path overlap position of the cladding layer prepared by the embodiment 1 and a metallograph of a multi-path overlap position of the cladding layer prepared by the reference example 1.

[0054] It can be seen from the figures that: dark blocky crystal grains are formed along the junctions of the network structure in an overlap area of the embodiment 1. It can be seen from a partial enlarged drawing that: the crystal grains the embodiment 1 are smaller in size and do not obviously grow up. While stripe-shaped dendritic crystals are formed in an overlap area of the reference example 1, and it can be seen from a partial enlarged drawing that: relative to an internal structure of the cladding layer, the size of the dendritic crystals is obviously increased. In the solidification process, as the temperature gradient of the junction of the overlap area and the former-path cladding layer is bigger, and crystal grains in the reference example 1 are bigger in size and have a certain degree of segregation, intermetallic compounds are easy to form at the junction based on the existing dendritic crystals and can constantly grow up along an element segregation area to form a thick and big dendritic crystal structure, the thick and big dendritic crystal structure grows up inwards the overlap area along the opposite direction of heat flow, and finally, stripe-shaped structures through the whole overlap area that are connected with each other are formed. As the formed stripe-shaped structures have large brittleness, and the stress is larger at the junctions at different positions and different directions, the stripe-shaped structures are easy to fracture to generate cracks and are easy to expand along the crystal boundary to form bigger cracks, thus seriously affecting the performance of the cladding layer.

[0055] After the stirring action of an added rotating magnetic field, on one hand, the temperature gradient is reduced, and the thermal stress is reduced; on the other hand, the growth of the blocky crystal grains formed at the junctions of the network structure is obviously inhibited, and the stress concentration is reduced, thus effectively inhibiting generation of the cracks and maintaining the stability of the structure of the whole cladding layers.

[0056] In order to measure the defects such as interspaces, black oxide inclusions, the cracks and the like in the cladding layers, ImageJ2 software is applied for processing images of cross sections of the cladding layers, calculating the proportion of the internal defects of the cladding layers and selecting average measured values of a plurality of areas, and the results are shown in Table 1.

Text Example 2

Microstructures of the Cladding Layers

[0057] A Rigaku D/max 2400 diffractometer made in Japan is adopted to test XRD spectrograms of the cladding layers and a complete amorphous ribbon that are prepared by the embodiment 1 and the reference example 1, which are shown in FIG. 4.

[0058] The diffractometer adopts a Cu Kalpha radiation source and is equipped with a monochromator, the power is 12 kW, the tube voltage is 50 kV, the current is 100 mA, and the stepping is 0.02.

[0059] Through comparison with the complete amorphous ribbon, it can be known that: the XRD spectrograms of the cladding layers of the reference example 1 and the embodiment 1 are basically the same (the spectrogram 1 represents the embodiment 1, and the spectrogram 2 represents the reference example 1.), the 2theta angle indicates that typical amorphous peaks exist at 30-50, the strength is different, which indicates that the amorphous phases exist in the cladding layers, while crystallization phases are mainly metallic compound phases such as alpha-Al, Al.sub.4NiY and the like.

Text Example 3

Heat Stability of the Cladding Layers

[0060] A Perkin-Elmer DSC-7 is adopted to characterize glass transition and crystallization behaviors of the cladding layers and the complete amorphous ribbon that are prepared by the embodiment 1 and the reference example 1, and DSC curves measured are respectively shown in FIG. 5a and FIG. 5b.

[0061] The detection conditions are: flowing protective high-purify argon gas with 0.05 L/min flow is pumped in, 20 DEG C/min of heating rate is adopted in a continuous heating mode, and the highest temperature is 1,200 DEG C.

[0062] It can be seen from FIG. 5a that: the complete amorphous ribbon has two obvious crystallization exothermic peaks and has a complete amorphous structure.

[0063] It can be seen from FIG. 5b that: the area of the exothermic peaks of the cladding layer prepared by the embodiment 1 is smaller than that of the complete amorphous ribbon, which indicates that a certain degree of crystallization and transition occurs in the preparation process of the cladding layer; the starting crystallization temperature is about 340 DEG C, which indicates that the cladding layer is stable at the temperature of below 340 DEG C, the crystallization process does not occur, and the cladding layer has good stability. The cladding layer prepared by the reference example 1 is basically the same as that prepared by the embodiment 1, but the area of crystallization exothermic peaks in the reference example 1 is reduced.

[0064] The amorphous contents of the cladding layers that are prepared by the embodiment 1 and the reference example 1 are respectively calculated according to the DSC curves, and the results are shown in Table 1.

Text Example 4

Wear Resistance of the Cladding Layers

[0065] ACETR UMT-3 type reciprocating friction testing machine is adopted, so that a GCr15 ball friction pair with 4mm of diameter and about 770 HV of hardness does reciprocating motion on a friction surface in a ball/surface contact manner, and samples are respectively the cladding layers and the 5083 aluminum alloy matrixes that are prepared by the embodiment 1 and the reference example 1.

[0066] The experimental operating conditions are: the reciprocating frequency is 5 Hz, the set load is 10 N, and the loading time is 20 min.

[0067] Curves of friction coefficients along with time of the cladding layers under a 10 N load at different scanning speeds are shown in FIG. 6, and the average friction coefficients of the cladding layers and the5083 aluminum alloy matrixes that are prepared by the embodiment 1 and the reference example 1 are respectively 0.288, 0.384 and 0.571 through calculation.

[0068] Therefore, it can be seen that: the friction coefficients of the cladding layers prepared by the embodiment 1 and the reference example 1 are less than the friction coefficients of the 5083 aluminum alloy matrixes prepared by the embodiment 1 and the reference example 1, and the embodiment 1 has the minimum friction coefficients, which indicates that the cladding layer prepared by the embodiment 1 has excellent anti-friction property.

[0069] The test results of the wear volumes are shown in Table 1.

Text Example 5

Wear Resistance of the Cladding Layers

[0070] An electrochemical integrated test system Potentiostat/Galvanostat (EG&G Princeton Applied Research Model 2273) is adopted to test the electrochemical properties of the cladding layers and the 5083 aluminum alloy matrixes that are prepared by the embodiment 1 and the reference example 1, and potentiodynamic polarization curves of the cladding layers and the 5083 aluminum alloy matrixes are shown in FIG. 7.

[0071] The testing conditions are as follows: the dimension of a sample is 10*10 mm, electrochemical potentiodynamic scanning is carried out in 3.5% NaCl solution, anodic polarization is carried out at the potential scanning rate of 0.333 mV/s, and the scanning is stopped until 100 mV.sub.SCE or current density reaches 10.sup.2 A/cm.sup.2.

[0072] It can be seen from FIG. 7 that: the cladding layer of the embodiment 1 has an obvious passivation behavior, the passivation current is lower, a passivation film is easy to form, the self-corrosion potential is high than that of the 5083 aluminum alloy matrix, and the self-corrosion current is lower than that of the 5083 aluminum alloy matrix, thus being capable of playing a good role in protecting the 5083 aluminum alloy matrix.

[0073] The cladding layer of the reference example 1 has many defects, thus causing poorer corrosion resistance as the cladding layer of the reference example 1 has bigger self-corrosion current than the aluminum alloy matrix and has no passivation range although the self-corrosion potential thereof is higher than that of the 5083 aluminum alloy matrix.

Text Example 6

Mechanical Property of the Cladding Layers

[0074] The cladding layers and the 5083 aluminum alloy matrixes that are prepared by the embodiment 1 and the reference example 1 are respectively processed into non-proportional drawing pieces according to a GB/T 228.1-2010 standard. According to the actual repair requirement, in order to test repair of the cladding layers for the strength of a structure-damaged part, along the thickness direction of each of drawing samples of the embodiment 1 and the reference example 1, one half is the cladding layer, and the other half is the 5083 aluminum alloy matrix.A drawing test is carried out by a CMT4304 type electronic all-purpose testing machine, the loading rate is 1 mm/min, the average values are obtained after the testing is completed, and the results of the drawing strength are shown in Table 1.

[0075] An HXD-1000 type microhardness tester is adopted to respectively carry out average microhardness tests for the surfaces of the cladding layers and the 5083 aluminum alloy matrixes that are prepared by the reference example 1 and the embodiment 1, the load is 100 g, the holding time is 10s, and the results are shown in Table 1.

TABLE-US-00001 TABLE 1 Embodi- Reference Reference 5083aluminum ment 1 example 1 example 2 alloy matrix Defect proportion 0.3% 10.5% 3.8% Content of 36.1% 17.0% 25.3% amorphous phase Friction coefficient 0.288 0.384 0.321 0.571 Wear volume 2.516 5.027 3.234 45.638 (10.sup.7 mum.sup.3) Drawing strength 289 MPa 260 MPa 275 MPa 275 MPa Microhardness 385 HV 244 HV 288 HV 75 HV

Embodiment 2-Embodiment 3

[0076] The embodiments 2 and 3 are basically the same as the embodiment 1, and the difference between the embodiments 2 and 3 and the embodiment 1 is the element composition of aluminum-based amorphous alloy powder, which is shown in Table 2 and Table 3.

TABLE-US-00002 TABLE 2 Embodiment 1 Embodiment 2 Embodiment 3 Element composition Al.sub.86Ni.sub.6Y.sub.4.5Co.sub.2La.sub.1.5 Al.sub.85Ni.sub.5Y.sub.6Co.sub.3.5La.sub.0.5 Al.sub.84Ni.sub.7Y.sub.4.5Co.sub.1.5La.sub.3 Defect proportion 0.3% 0.8% 0.5% Content of 36.1% 32.4% 33.8% amorphous phase Friction coefficient 0.288 0.302 0.296 Wear volume (10.sup.7 mum.sup.3) 2.516 2.836 2.752 Drawing strength 289 MPa 281 MPa 286 MPa Microhardness 385 HV 325 HV 338 HV

TABLE-US-00003 TABLE 3 Embodiment 4 Embodiment 5 Embodiment 6 Element composition Al.sub.85Ni.sub.8Y.sub.5.5Co.sub.1La.sub.0.5 Al.sub.85Ni.sub.6Y.sub.3Co.sub.5La.sub.1 Al.sub.85Ni.sub.6.5Y.sub.4.5Co.sub.2La.sub.2 Defect proportion 0.7 0.8% 0.5% Content of 33.5% 34.7% 35.8% amorphous phase Friction coefficient 0.315 0.320 0.288 Wear volume (10.sup.7 mum.sup.3) 2.957 2.843 2.520 Drawing strength 280 MPa 279 MPa 288 MPa Microhardness 335 HV 327 HV 355 HV

Embodiment 4-Embodiment 5

[0077] The embodiments 4 and 5 are basically the same as the embodiment 1, and the difference between the embodiments 4 and 5 and the embodiment 1 is the specific process parameters of magnetic field stirring laser cladding molding, which is shown in Table4.

TABLE-US-00004 TABLE 4 Embodi- Embodi- Embodi- Embodi- Embodi- Embodi- ment 1 ment 7 ment 8 ment 9 ment 10 ment 11 Laser power 2000 W 1700 W 1900 W 2200 2300 2400 Scanning speed 5.5 mm/s 3.5 mm/s 5 mm/s 6 mm/s 6.5 mm/s 7 mm/s Spot diameter 3 mm 3 mm 3 mm 3 mm 3 mm 3 mm Powder feeding rate 7 g/min 6 g/min 6.5 g/min 7 g/min 7.5 g/min 8 g/min Frequency of magnetic 25 Hz 15 HZ 35 Hz 20 Hz 25 Hz 25 Hz field Exciting current 30 A 10 A 20 A 40 A 50 A 30 A Defect proportion 0.3% 0.4% 0.6% 0.8% 0.7% 0.9% Content of amorphous 36.1% 34.1% 32.7% 36.5% 31.5% 32.1% phase Friction coefficient 0.288 0.299 0.306 0.285 0.314 0.325 Wear volume 2.516 2.793 2.673 2.420 2.844 3.028 (10.sup.7 mum.sup.3) Drawing strength 289 MPa 285 MPa 283 MPa 298 MPa 278 MPa 269 MPa Microhardness 385 HV 332 HV 350 HV 380 HV 342 HV 335 HV

[0078] The relevant properties of the cladding layers prepared by the reference example 2 and the embodiment 2-embodiment 11 according to the methods of the test examples 1, 3, 4 and 6, and the results are respectively shown in Table 1-Table 4.