A preparation method of a Zr56Ti19Cu17Sn8 metallic glass composite with a diamond network as a skeleton

Abstract

The application relates to a preparation method of a Zr56Ti19Cu17Sn8 metallic glass composite material with a diamond network as a skeleton, and relates to a preparation method of a metallic glass composite material. The application aims at solving the problem that existing metallic glasses are difficult to be applied in high-reliability precision devices due to brittleness and poor heat conduction effect. The method comprises the following steps: 1, forming a Cr3C2 layer on the surface of diamond particles by using a diffusion method; 2, sintering to prepare a porous diamond network skeleton; 3, cold isostatic pressing to prepare the diamond network skeleton; 4, preparing Zr56Ti19Cu17Sn8 amorphous powder by using a high-pressure gas mist method; and 5, covering the Zr56Ti19Cu17Sn8 amorphous powder on the upper and lower surfaces of the diamond network skeleton, and then performing discharge plasma sintering. The application is used for preparing the Zr56Ti19Cu17Sn8 metallic glass composite material with the diamond network as the skeleton.

Description

TECHNICAL FIELD

[0001] The present application relates to a preparation method of a metal glass composite material. BACKGROUND

[0002] With the development of aerospace, communication electronics, power transmission and other fields, small size high precision devices are gradually widely used, and the internal gear, bearing and other high speed transmission elements and packaging protection barrier of the devices have higher requirements on the strength and toughness of the materials, the heat conduction and heat distribution, and the wear and corrosion resistance. However, the existing high strength heat conductive materials are difficult to meet the requirements, which hinders the further improvement of the performance and reliability of such devices. Metal glass is an amorphous metal material prepared by modern rapid solidification metallurgy technology, and its unique glassy structure endows it with high strength, corrosion resistance and other excellent properties far exceeding those of traditional metal materials. It is an excellent high-strength and wear-resistant material, but its brittleness and low thermal conductivity limit its wide application in high-reliability precision devices. SUMMARY

[0003] The present application solves the problem that the existing metal glass is difficult to be applied in high-reliability precision devices due to brittleness and poor heat conduction effect, and further provides a preparation method of a Zr56Ti19Cu17Sn8 metal glass composite material with a diamond network as a skeleton.

[0004] A preparation method of a Zr56Ti19Cu17Sn8 metal glass composite material with a diamond network as a skeleton, which is carried out according to the following steps:

[0005] I. Mix diamond particles and chromium powder uniformly, then form a Cr3C2 layer on the surface of the diamond particles by diffusion method to obtain modified diamond particles;

[0006] II. Mix the modified diamond particles with copper powder uniformly to obtain a mixed powder, sinter the mixed powder in a sintering mold, and finally demold after natural cooling to room temperature to obtain a porous diamond network skeleton;

[0007] The porosity of the porous diamond network skeleton is 45% to 75%;

[0008] III. Perform shape-coated cold isostatic pressing on the porous diamond network skeleton, remove the coating after pressure relief to obtain a diamond network skeleton;

[0009] The porosity of the diamond network skeleton is 35% to 60%;

[0010] Four, the Zr56Ti19Cu17Sn8 master alloy ingot is broken and remelted to obtain a molten alloy liquid, the molten alloy liquid is flowed into a ring-shaped gas atomization nozzle through a liquid guide pipe, the molten alloy liquid falling freely from the liquid guide pipe is impacted and broken by high-pressure and high-speed helium gas with a pressure of 4.5 MPa-7.0 MPa and a flow rate of 1.0 kg / min-3.0 kg / min in the nozzle, and the sprayed atomized droplets are rapidly cooled by taking helium gas as a jet medium, and finally sieved to obtain Zr56Ti19Cu17Sn8 amorphous powder;

[0011] Five, the Zr56Ti19Cu17Sn8 amorphous powder is covered on the upper and lower surfaces of the diamond network skeleton, and then discharge plasma sintering is carried out to obtain a Zr56Ti19Cu17Sn8 metallic glass composite material with a diamond network as a skeleton.

[0012] The beneficial effects of the present application are:

[0013] (1) The present application provides a preparation method of a metallic glass composite material with a diamond network as a skeleton, and the diamond network constructed in the present application can be efficiently and uniformly heated in the SPS powder metallurgy process, so that a metallic glass composite material with good internal and external consistency is prepared.

[0014] (2) The diamond / metallic glass composite material prepared by the present application has excellent thermal conductivity due to the diamond network. The thermal conductivity of the Zr56Ti19Cu17Sn8 metallic glass composite material with a diamond network as a skeleton can reach 8.5 W / (m·K)-12.0 W / (m·K) at a room temperature of 15℃.

[0015] (3) The diamond / metallic glass composite material prepared by the present application introduces a diamond network reinforcing phase, which can adjust the behavior of the shear band of the metallic glass matrix in three-dimensional space, further improve the strength of the material, reduce the risk of catastrophic brittle fracture, and improve the reliability. In the compression experiment with a compression rate of 0.050 mm / min, the strength of the Zr56Ti19Cu17Sn8 metallic glass composite material with a diamond network as a skeleton prepared by the method can reach 3.2 GPa-3.8 GPa, the elastic deformation can reach 1.2%-1.7%, and the plastic deformation can reach 0.60%-0.85%.

[0016] Drawings of the specification

[0017] Figure 1 SEM image of the Zr56Ti19Cu17Sn8 amorphous powder prepared in step four of the embodiment;

[0018] Figure 2SEM image of the cross section of the Zr56Ti19Cu17Sn8 metallic glass composite material with diamond network skeleton prepared in Example 1.

[0019] Figure 3 SEM image of the surface of the Zr56Ti19Cu17Sn8 metallic glass composite material with diamond network skeleton prepared in Example 1. DETAILED DESCRIPTION

[0020] Specific embodiment one: a preparation method of the Zr56Ti19Cu17Sn8 metallic glass composite material with diamond network skeleton, which is carried out according to the following steps:

[0021] I. mixing the diamond particles and chromium powder uniformly, then forming a Cr3C2 layer on the surface of the diamond particles by using diffusion method, to obtain modified diamond particles;

[0022] II. mixing the modified diamond particles and copper powder uniformly to obtain mixed powder, sintering the mixed powder in a sintering mold, and finally demolding after natural cooling to room temperature to obtain a porous diamond network skeleton;

[0023] The porosity of the porous diamond network skeleton is 45% to 75%;

[0024] III. cold isostatic pressing the porous diamond network skeleton with a mold, and removing the mold after pressure relief to obtain a diamond network skeleton;

[0025] The porosity of the diamond network skeleton is 35% to 60%;

[0026] IV. crushing and remelting a Zr56Ti19Cu17Sn8 master alloy ingot to obtain a molten alloy liquid, flowing the molten alloy liquid into a ring-shaped gas atomization nozzle through a liquid guide pipe, impacting and breaking the molten alloy liquid falling freely from the liquid guide pipe in the nozzle by using high-pressure high-speed helium gas with a pressure of 4.5 MPa to 7.0 MPa and a flow rate of 1.0 kg / min to 3.0 kg / min, and rapidly cooling the atomized droplets sprayed out by taking helium gas as the jet medium, and finally sieving to obtain Zr56Ti19Cu17Sn8 amorphous powder;

[0027] V. covering the Zr56Ti19Cu17Sn8 amorphous powder on the upper and lower surfaces of the diamond network skeleton, and then carrying out spark plasma sintering to obtain a Zr56Ti19Cu17Sn8 metallic glass composite material with diamond network skeleton.

[0028] The embodiment has the following beneficial effects:

[0029] (1) The embodiment provides a metal glass composite material with a diamond network as a framework, and the diamond network constructed in the embodiment can be uniformly heated in an SPS powder metallurgy process, so that the metal glass composite material with good internal and external consistency is prepared.

[0030] (2) The diamond / metal glass composite material prepared in the embodiment has excellent heat conduction performance due to the diamond network. The thermal conductivity of the Zr56Ti19Cu17Sn8 metal glass composite material with the diamond network as a framework can reach 8.5 W / (m·K) to 12.0 W / (m·K) at a room temperature of 15℃.

[0031] (3) The diamond / metal glass composite material prepared in the embodiment has a diamond network reinforcing phase, can adjust the behavior of a shear band of a metal glass matrix in three-dimensional space, further improve the strength of the material, reduce the risk of catastrophic brittle fracture, and improve the reliability. In a compression experiment with a compression rate of 0.050 mm / min, the strength of the Zr56Ti19Cu17Sn8 metal glass composite material with the diamond network as a framework prepared by the method can reach 3.2 GPa to 3.8 GPa, the elastic deformation can reach 1.2% to 1.7%, and the plastic deformation can reach 0.60% to 0.85%.

[0032] Specific embodiment two: different from the specific embodiment one, the mass ratio of the diamond particles to the chromium powder in step one is 1:(1.5-2.5); the particle size of the diamond particles in step one is 150-600 μm; the purity of the chromium powder in step one is greater than 99.95%, and the particle size is 200-300 mesh; the thickness of the Cr3C2 layer in step one is 25-175 nm. The other steps are the same as those in the specific embodiment one.

[0033] Specific embodiment three: different from the specific embodiment one or two, the Cr3C2 layer on the surface of the diamond particles in step one is formed by a diffusion method, specifically, the Cr3C2 layer is formed by heating the diamond particles in an argon atmosphere with a temperature of 900-950℃ and a pressure of 2.0×10 -1 MPa-5.0×10 -1 MPa for 2-12 h. The other steps are the same as those in the specific embodiment one or two.

[0034] Specific embodiment four: different from the specific embodiment one to three, the mass percentage of the modified diamond particles in the mixed powder in step two is 60%-75%. The other steps are the same as those in the specific embodiment one to three.

[0035] Embodiment five: the difference between this embodiment and one of the embodiments one to four is that the sintering in step two is specifically sintering for 0.5h-2h under the conditions of argon atmosphere, gas pressure of 5Pa-15Pa and temperature of 850℃-950℃. The others are the same as the embodiments one to four.

[0036] Embodiment six: the difference between this embodiment and one of the embodiments one to five is that the cold isostatic pressing in step three is specifically keeping for 3min-5min under the conditions of cold isostatic pressing pressure of 285MPa-315MPa. The others are the same as the embodiments one to five.

[0037] Embodiment seven: the difference between this embodiment and one of the embodiments one to six is that the Zr56Ti19Cu17Sn8 master alloy ingot in step four is specifically prepared by the following steps: taking the elemental metal raw materials of zirconium of 56%, titanium of 19%, copper of 17% and tin of 8% by mass percentage, mixing and then mechanically polishing to remove the surface oxide layer, and then placing in a titanium gettering melting furnace, arc melting for 5-7 times under the conditions of argon atmosphere, pressure of 0.8Pa-1.5Pa and temperature of 1500℃-1700℃, and each melting time is 60s-90s, to obtain the Zr56Ti19Cu17Sn8 master alloy ingot; the purity of the elemental metal raw materials is greater than 99.9%. The others are the same as the embodiments one to six.

[0038] Embodiment eight: the difference between this embodiment and one of the embodiments one to seven is that the remelting in step four is specifically crushing the Zr56Ti19Cu17Sn8 master alloy ingot and then loading into a quartz tube, and then placing in a vacuum radio frequency furnace, and remelting under the conditions of argon atmosphere, pressure of 0.1Pa-15Pa and temperature of 850K-950K to obtain the molten alloy liquid; the caliber of the annular gas atomizing nozzle in step four is 3mm-5mm; the cooling rate of the sprayed atomized droplets in step four is >150K / s; the particle size of the Zr56Ti19Cu17Sn8 amorphous powder in step four is 10μm-80μm. The others are the same as the embodiments one to seven.

[0039] Embodiment nine: the difference between this embodiment and one of the embodiments one to eight is that the spark plasma sintering in step five is specifically performed by the following steps: heating to 620K-650K at a heating rate of >75K / s, sintering for 40s-80s under the conditions of argon atmosphere, temperature of 620K-650K and pressure of 150MPa-200MPa, and then cooling at a cooling rate of >65K / s. The others are the same as the embodiments one to eight.

[0040] Specific implementation ten: the difference between this implementation and one of the specific implementations one to nine is that the volume percentage of the diamond in the diamond network skeleton Zr56Ti19Cu17Sn8 metal glass composite material prepared in step five is 35% to 45%. The others are the same as specific implementations one to nine.

[0041] The volume percentage of the diamond in the diamond network skeleton Zr56Ti19Cu17Sn8 metal glass composite material prepared in this specific implementation refers to the diamond particles that are not processed in step one.

[0042] The following examples are used to verify the beneficial effects of the present application:

[0043] Example one:

[0044] A preparation method of a diamond network skeleton Zr56Ti19Cu17Sn8 metal glass composite material, which is carried out according to the following steps:

[0045] I. The diamond particles are mixed with chromium powder uniformly, and then a Cr3C2 layer is formed on the surface of the diamond particles by using a diffusion method, to obtain modified diamond particles;

[0046] II. The modified diamond particles are mixed with copper powder uniformly to obtain a mixed powder, and the mixed powder is placed in a sintering mold for sintering, and finally demolded after natural cooling to room temperature to obtain a porous diamond network skeleton;

[0047] The porosity of the porous diamond network skeleton is 50%;

[0048] III. The porous diamond network skeleton is cold isostatic pressed with a shaped sleeve, and the sleeve is removed after pressure relief to obtain a diamond network skeleton;

[0049] The porosity of the diamond network skeleton is 45%;

[0050] IV. The Zr56Ti19Cu17Sn8 master alloy ingot is broken and remelted to obtain a molten alloy liquid, the molten alloy liquid is flowed into a 5mm caliber annular gas atomization nozzle through a liquid guide pipe, the molten alloy liquid falling freely from the liquid guide pipe is impacted and broken in the nozzle by using high-pressure and high-speed helium gas with a pressure of 6.5MPa and a flow rate of 1.0kg / min, and the atomized droplets sprayed out are rapidly cooled by using helium gas as a jet medium, and finally sieved to obtain Zr56Ti19Cu17Sn8 amorphous powder;

[0051] V. The Zr56Ti19Cu17Sn8 amorphous powder is covered on the upper and lower surfaces of the diamond network skeleton, and then discharge plasma sintering is carried out to obtain a diamond network skeleton Zr56Ti19Cu17Sn8 metal glass composite material.

[0052] The mass ratio of the diamond particles to the chromium powder in step one is 1:1.5; the particle size of the diamond particles in step one is 150-200 μm; the purity of the chromium powder in step one is greater than 99.95%, and the particle size is 300 mesh; the thickness of the Cr3C2 layer in step one is 120-150 nm.

[0053] In step one, the Cr3C2 layer is formed on the surface of the diamond particles by diffusion method, specifically, under the conditions of a temperature of 900 ℃, a pressure of 2.0×10 -1 MPa, and an argon atmosphere, and heat preservation for 2 h.

[0054] The mass percentage of the modified diamond particles in the mixed powder in step two is 65%.

[0055] The sintering in step two is specifically carried out under the conditions of an argon atmosphere, a gas pressure of 5 Pa, and a temperature of 950 ℃, and sintering for 2 h.

[0056] The cold isostatic pressing in step three is specifically carried out under the conditions of a cold isostatic pressing pressure of 285 MPa, and keeping for 3 min.

[0057] The Zr56Ti19Cu17Sn8 master alloy ingot in step four is specifically prepared as follows: taking the elemental metal raw materials of zirconium, titanium, copper and tin with mass percentages of 56%, 19%, 17% and 8% respectively, mixing and then mechanically polishing to remove the surface oxide layer, and then placing in a titanium gettering melting furnace, arc melting 5 times under the conditions of an argon atmosphere, a pressure of 1.5 Pa, and a temperature of 1700 ℃, and each melting time is 75 s, to obtain the Zr56Ti19Cu17Sn8 master alloy ingot; the purity of the elemental metal raw materials is greater than 99.9%; the titanium gettering melting furnace is a melting furnace for melting Ti ingot 3 times for gettering before melting the Zr56Ti19Cu17Sn8 master alloy.

[0058] The remelting in step four is specifically as follows: crushing the Zr56Ti19Cu17Sn8 master alloy ingot and then placing in a quartz tube, and then placing in a vacuum radio frequency furnace, and remelting under the conditions of an argon atmosphere, a pressure of 1.5 Pa, and a temperature of 950 K, to obtain a molten alloy liquid; the cooling rate of the sprayed atomized droplets in step four is >150 K / s; the particle size of the Zr56Ti19Cu17Sn8 amorphous powder in step four is 60-80 μm.

[0059] The spark plasma sintering in step five is carried out according to the following steps: heating to 620 K at a heating rate of >75 K / s, sintering for 60 s under the conditions of argon atmosphere, temperature of 620 K and pressure of 150 MPa, and then cooling at a cooling rate of >65 K / s.

[0060] The volume percentage of diamond in the Zr56Ti19Cu17Sn8 metallic glass composite material with diamond network as the skeleton prepared in step five is 35%.

[0061] Figure 1 The SEM image of the Zr56Ti19Cu17Sn8 amorphous powder prepared in step four of Example One; it can be seen from the image that the prepared amorphous alloy powder of 60 μm-80 μm has partial pulse patterns generated in the crushing and cooling of the helium stream.

[0062] Figure 2 The SEM image of the section of the Zr56Ti19Cu17Sn8 metallic glass composite material with diamond network as the skeleton prepared in Example One; it can be seen from the image that the amorphous alloy is well filled in the diamond network, and the titanium-containing amorphous alloy forms a good interface bonding with the chromium-modified diamond.

[0063] Figure 3 The SEM image of the surface of the Zr56Ti19Cu17Sn8 metallic glass composite material with diamond network as the skeleton prepared in Example One; it can be seen from the image Figure 2 、 3 that the metallic glass composite material prepared in the diamond network by SPS after cold isostatic pressing has good internal and external consistency.

[0064] The thermal conductivity of the Zr56Ti19Cu17Sn8 amorphous powder prepared in step four of Example One is 5.42 W / (m·K) at a room temperature of 15℃, and the thermal conductivity of the Zr56Ti19Cu17Sn8 metallic glass composite material with diamond network as the skeleton prepared in Example One is 8.74 W / (m·K).

[0065] In the compression experiment at a compression rate of 0.050 mm / min, the compression strength of the Zr56Ti19Cu17Sn8 metallic glass composite material with diamond network as the skeleton prepared in Example One is 3.62 GPa, the elastic deformation is 1.57%, and the plastic deformation is 0.84%.

Claims

1. A method for preparing a Zr56Ti19Cu17Sn8 metallic glass composite with a skeleton of diamond network, characterized in that It is carried out in the following steps: I. The diamond particles are mixed with chromium powder uniformly, then a Cr3C2 layer is formed on the surface of the diamond particles by diffusion method, and modified diamond particles are obtained; II. The modified diamond particles are mixed with copper powder uniformly to obtain mixed powder, the mixed powder is placed in a sintering mold for sintering, and finally, after natural cooling to room temperature, the mold is removed to obtain a porous diamond network skeleton; The porosity of the porous diamond network skeleton is 45% to 75%; III. The porous diamond network skeleton is coated with a cold isostatic press, and the coating is removed after pressure relief to obtain a diamond network skeleton; The porosity of the diamond network skeleton is 35% to 60%; IV. The Zr56Ti19Cu17Sn8 master alloy ingot is crushed and remelted to obtain a molten alloy liquid, the molten alloy liquid is flowed into a ring-shaped gas atomizing nozzle through a liquid guide pipe, the molten alloy liquid falling freely from the liquid guide pipe is impacted and broken by high-pressure high-speed helium gas with a pressure of 4.5 MPa to 7.0 MPa and a flow rate of 1.0 kg / min to 3.0 kg / min in the nozzle, and the atomized droplets sprayed out are rapidly cooled by helium gas as the jet medium, and finally sieved to obtain Zr56Ti19Cu17Sn8 amorphous powder; V. The Zr56Ti19Cu17Sn8 amorphous powder is covered on the upper and lower surfaces of the diamond network skeleton, and then discharge plasma sintering is carried out to obtain a Zr56Ti19Cu17Sn8 metallic glass composite material with a diamond network as the skeleton.

2. The method for preparing a Zr56Ti19Cu17Sn8 metallic glass composite with a diamond network as a skeleton according to claim 1, characterized in that The mass ratio of diamond particles to chromium powder in step I is 1:(1.5 to 2.5); the particle size of the diamond particles in step I is 150 μm to 600 μm; the purity of the chromium powder in step I is greater than 99.95%, and the particle size is 200 to 300 mesh; the thickness of the Cr3C2 layer in step I is 25 nm to 175 nm.

3. The method for preparing a Zr56Ti19Cu17Sn8 metallic glass composite with a diamond network as a skeleton according to claim 1, characterized in that In step one, Cr3C2 layer is formed on the surface of diamond particles by diffusion method. Specifically, the temperature is 900-950℃, the pressure is 2.0×10 -1 MPa-5.0×10 -1 MPa, and the temperature is kept for 2-12 hours.

4. The method for preparing a Zr56Ti19Cu17Sn8 metallic glass composite material with a diamond network as a skeleton according to claim 1, characterized in that The mass percentage of modified diamond particles in the mixed powder in step II is 60% to 75%.

5. The method for preparing a Zr56Ti19Cu17Sn8 metallic glass composite material with a diamond network as a skeleton according to claim 1, characterized in that The sintering in step II is specifically carried out under the conditions of an argon atmosphere, a gas pressure of 5 Pa to 15 Pa, and a temperature of 850°C to 950°C for 0.5 h to 2 h.

6. The method for preparing a Zr56Ti19Cu17Sn8 metallic glass composite material with a diamond network as a skeleton according to claim 1, characterized in that The cold isostatic pressing in step III is specifically carried out under the conditions of a cold isostatic pressing pressure of 285 MPa to 315 MPa for 3 min to 5 min.

7. The method for preparing a Zr56Ti19Cu17Sn8 metallic glass composite material with a diamond network as a skeleton according to claim 1, characterized in that The Zr56Ti19Cu17Sn8 master alloy ingot in step IV is specifically prepared as follows: elemental metal raw materials of zirconium, titanium, copper and tin with a mass percentage of 56%, 19%, 17% and 8% respectively are weighed, mixed and mechanically polished to remove the surface oxide layer, then placed in a titanium gettering melting furnace under the conditions of an argon atmosphere, a pressure of 0.8 Pa to 1.5 Pa and a temperature of 1500°C to 1700°C, and arc melted for 5 to 7 times, each time for 60 s to 90 s, to obtain a Zr56Ti19Cu17Sn8 master alloy ingot; the purity of the elemental metal raw materials is greater than 99.9%.

8. The method for preparing a Zr56Ti19Cu17Sn8 metallic glass composite material with a diamond network as a skeleton according to claim 1, characterized in that The remelting in step four is specifically to crush the Zr56Ti19Cu17Sn8 master alloy ingot and then load it into a quartz tube, and then place it in a vacuum radio frequency furnace, and then remelt it under the conditions of argon atmosphere, pressure of 0.1 Pa to 15 Pa, and temperature of 850 K to 950 K to obtain a molten alloy liquid; the caliber of the annular gas atomization nozzle in step four is 3 mm to 5 mm; the cooling rate of the sprayed atomized droplets in step four is > 150 K / s; the particle size of the Zr56Ti19Cu17Sn8 amorphous powder in step four is 10 μm to 80 μm.

9. The method for preparing a Zr56Ti19Cu17Sn8 metallic glass composite material with a diamond network as a skeleton according to claim 1, characterized in that The spark plasma sintering in step five is specifically performed by the following steps: heating to 620 K to 650 K at a heating rate > 75 K / s, sintering under the conditions of argon atmosphere, temperature of 620 K to 650 K, and pressure of 150 MPa to 200 MPa for 40 s to 80 s, and then cooling at a cooling rate > 65 K / s.

10. The method for preparing a Zr56Ti19Cu17Sn8 metallic glass composite material with a diamond network as a skeleton according to claim 1, characterized in that The volume percentage of the diamond in the Zr56Ti19Cu17Sn8 metallic glass composite with a diamond network as a skeleton prepared in step five is 35% to 45%.

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