Amorphous multi-element tungsten-nickel-based alloy as well as preparation method and application thereof

Abstract

The invention relates to the technical field of amorphous multi-element tungsten-nickel-based alloy production, in particular to an amorphous multi-element tungsten-nickel-based alloy and a preparation method and application thereof. The amorphous multi-element tungsten-nickel-based alloy comprises the following raw materials in atomic percent: 45 to 50 percent of W, 30 to 35 percent of Ni, 8 to 10 percent of Fe, 5 to 6 percent of Co, 3 to 4 percent of B, 2 to 3 percent of P and 0.5 to 1.5 percent of Cr. Through component-structure-process collaborative design, breakthrough of the amorphous tungsten-nickel-based alloy in the aspects of high-frequency electromagnetic shielding, efficient heat dissipation, strong interface bonding and environmental stability is achieved, W / Ni provides basic performance, B / P promotes amorphization, and Cr / AlN enhances weather resistance; the magnetron sputtering ensures the amorphous structure, and the gradient design and the hole sealing treatment optimize the comprehensive performance.

Description

Technical Field

[0001] The present invention relates to the technical field of the production of amorphous multi-component tungsten-nickel-based alloys, and specifically to an amorphous multi-component tungsten-nickel-based alloy, a preparation method thereof, and an application thereof. Background Art

[0002] Amorphous alloys, also known as metallic glasses, are special alloy materials with an internal atomic arrangement that does not have a long-range ordered structure. Amorphous multi-component tungsten-nickel-based alloys mainly consist of tungsten and nickel, and form a multi-component system by adding other alloying elements, combining the high hardness, wear resistance, and high-temperature oxidation resistance of metallic tungsten, as well as the unique isotropy, high toughness, and excellent corrosion resistance of amorphous alloys. Such alloys do not have crystal defects such as grain boundaries and dislocations, enabling them to exhibit characteristics different from those of traditional crystalline alloys in terms of mechanical, electrical, magnetic, and other properties. For example, they have uniform hardness, excellent fatigue resistance, and low magnetic permeability and good electrical conductivity, showing great application potential in many fields.

[0003] With the rapid development of 5G communication technology, microwave ceramic substrates have become the core basic materials for 5G base station radio frequency modules due to their advantages such as high dielectric constant, low dielectric loss, and good thermal stability. However, in practical applications, their dielectric loss increases significantly at high frequencies (>5 GHz), and the tanδ value often exceeds 0.01, resulting in serious signal attenuation during transmission, severely affecting communication quality and efficiency. At the same time, with the increase in the power density of 5G base stations, the heat dissipation demand has increased sharply. The thermal conductivity of traditional metal coatings is generally lower than 30 W / m·K, far from matching the thermal conductivity of Al2O3 ceramic substrates of about 30 W / m·K, and heat accumulation is likely to cause a decline in device performance or even failure.

[0004] In addition, the interface bonding problem between the coating and the ceramic substrate is prominent. Due to the difference in the thermal expansion coefficients of the materials, the bonding strength between the conventional coating and the substrate is low, and the critical load of the scratch is less than 20 N. Under working conditions such as high and low temperature cycling, thermal stress is extremely likely to cause the coating to crack and peel off, damaging the shielding function. In terms of environmental adaptability, for coatings that have not undergone sealing treatment, in harsh environments such as humidity and salt spray, the metal materials are prone to oxidation corrosion, and the corrosion area exceeds 5% after 500 h of salt spray test, significantly shortening the service life of the equipment and increasing the maintenance cost. Summary of the Invention

[0005] In view of the above deficiencies in the prior art, the object of the present invention is to provide an amorphous multi-component tungsten-nickel-based alloy, which greatly improves the glass-forming ability and dielectric properties (tanδ < 0.005) by optimizing the W / Ni ratio (45 - 50% W, 30 - 35% Ni) and introducing B / P / Cr.

[0006] Another object of the present invention is to provide a method for preparing an amorphous multi-component tungsten-nickel-based alloy, which greatly improves its enhanced interfacial bonding force (critical load > 30 N) and corrosion resistance through a Ni transition layer + amorphous alloy layer + AlN protective layer.

[0007] The third object of the present invention is to provide an application of the amorphous multi-component tungsten-nickel-based alloy, which is used for an amorphous tungsten-nickel-based electromagnetic shielding coating on a microwave ceramic substrate of a 5G communication base station.

[0008] The present invention is implemented by the following technical solutions:

[0009] The amorphous multi-component tungsten-nickel-based alloy described above includes raw materials with the following atomic percentages: W (45-50) Ni (30-35) Fe (8-10) Co (5-6) B (3-4) P (2-3) Cr (0.5-1.5) .

[0010] The above-mentioned W, Ni, Fe, Co, and Cr are all added in the form of metal powders, and their purities are all ≥ 99.9%. The particle size of W is 1 - 5 μm, and the particle sizes of Ni, Fe, Co, and Cr are all 1 - 3 μm; B is added in the form of Ni-B pre-alloy powder, and the mass ratio of Ni to B is 4:1, and the mass ratio of Ni to B is 4:1, with a purity ≥ 99.5%; P is added in the form of Fe-P pre-alloy powder, and the mass ratio of Fe to P is 3:1, with a purity ≥ 99.5%.

[0011] The method for preparing the amorphous multi-component tungsten-nickel-based alloy described above includes the following steps:

[0012] (1) Target preparation: According to the atomic percentages, take materials of W (45-50) Ni (30-35) Fe (8-10) Co (5-6) B (3-4) P (2-3) Cr (0.5-1.5) Take the materials, carry out ball milling, and then carry out hot isostatic pressing sintering at 1200 - 1250 °C, a pressure of 35 - 40 MPa, with a holding time of 3 - 4 hours. Take it out and cool it to room temperature, and then cut it to obtain the target;

[0013] (2) Coating deposition:

[0014] ① Using a ceramic as the substrate, chemically mechanically polish its surface, ultrasonically clean it, ion etch it, and plasma activate it in sequence to generate a substrate with a hydroxyl-active surface;

[0015] ② Transition layer deposition: Using Ni as the target, deposit it on the substrate obtained in step ① by DC sputtering;

[0016] ③ Amorphous alloy layer deposition: Sputtering the target obtained in step (1) by radio frequency onto the surface of the product obtained in step ②, with a thickness of 8 - 15 μm;

[0017] ④ Protective layer deposition: Using AlN as the target, depositing on the product obtained in step ③ by radio frequency sputtering to obtain an amorphous multi - element tungsten - nickel - based alloy substrate;

[0018] (3) Post - treatment: Annealing the amorphous multi - element tungsten - nickel - based alloy substrate, in an N2 atmosphere, at 280 - 300 °C for 1 hour, and then performing SiO2 sealing treatment by the sol - gel method to obtain an amorphous multi - element tungsten - nickel - based alloy.

[0019] In the said step (1), the conditions for ball - milling and mixing are: under argon protection, a ball - to - material ratio of 5:1, a rotation speed of 200 rpm, and a time of 6 hours; the cooling rate of hot isostatic pressing sintering is ≤10 °C / min, and after hot isostatic pressing sintering, an alloy target with a relative density ≥98% is obtained; the cutting conditions are: a disc with a diameter of 100 mm and a thickness of 5 mm, and the surface is polished to Ra < 0.1 μm.

[0020] In the said step ①, the conditions for chemical - mechanical polishing are: using diamond polishing fluid, with a surface roughness Ra < 0.05 μm; the conditions for ultrasonic cleaning are: cleaning for 10 minutes each in acetone, ethanol, and deionized water in sequence; the conditions for ion etching are: bombarded with Ar + with an energy of 200 eV, a beam current of 50 mA, for 5 minutes; the conditions for plasma activation are: under an O2 atmosphere, treated with a radio - frequency power of 50 W for 30 seconds.

[0021] In the said step ②, the purity of Ni is above 99.99%, the power of DC sputtering is 100 W, the argon flow rate is 20 sccm, and a 50 - nm Ni layer is deposited.

[0022] In the said step ③, the power of radio - frequency sputtering is 200 W, the substrate temperature is 80 °C, the Ar flow rate is 25 sccm, the vacuum degree is 5×10 -5 Pa, the deposition rate is 1 nm / s, and the time is 2.5 - 3.5 hours.

[0023] In the said step ④, the purity of AlN is greater than 99.9%, the power of radio - frequency sputtering is 150 W, the volume ratio of N2 / Ar mixed gas is 1:3, and a 10 - nm AlN layer is deposited.

[0024] The application of the said amorphous multi - element tungsten - nickel - based alloy is used for the amorphous tungsten - nickel - based electromagnetic shielding coating of a 5G communication base station microwave ceramic substrate.

[0025] The material of the said ceramic substrate is Al2O3, and the CTE is 6.5 - 7.5×10 -6 / K; the substrate dielectric constant is 8 - 10.

[0026] During the sol - gel method SiO2 sealing treatment, the volume ratio of raw materials is: tetraethyl orthosilicate (TEOS): ethanol: deionized water: hydrochloric acid (0.1M): ammonia water = 10:60:20:5:5;

[0027] The specific method is as follows: In a magnetic stirrer, mix TEOS and ethanol in proportion, with a stirring speed of 300 rpm for 10 minutes. Slowly add dropwise deionized water and hydrochloric acid (pH = 2 - 3), heat up to 60 °C, and stir for 2 hours to form a transparent SiO2 sol. Add ammonia water (pH = 8 - 9), continue stirring for 30 minutes, and the sol gradually transforms into a gel state (viscosity about 50 - 100 mPa·s). Immerse the coated substrate into the sol, evacuate to 10 -2 Pa, and maintain for 30 minutes to ensure that the sol fully penetrates the micropores. Slowly lift the substrate at a speed of 0.5 - 1 mm / s to reduce the thickness of the surface liquid film and avoid excessive sol accumulation. After lifting, immediately centrifuge and spin - coat at a speed of 2000 rpm for 30 seconds to remove the excess sol on the surface. Place the substrate in an environment with a humidity of 50% - 60% and a temperature of 25 °C and let it stand for 24 hours, and the sol is completely converted into a wet gel. Gradient heating and drying: Dry in an oven at 40 °C for 2 hours (to remove free water). Dry at 80 °C for 4 hours. Then sinter at 450 °C for 2 hours, with a heating rate of 5 °C / min, and that's it.

[0028] Tungsten (W) is used as the main element, providing a high melting point (3422 °C), high hardness (7.5 GPa), and excellent thermal conductivity (170 W / m·K), and dominating the heat dissipation performance and mechanical strength of the coating. Tungsten (W) forms a solid solution with Ni, inhibits grain boundary migration, and enhances the stability of the amorphous structure; a high W content reduces the coefficient of thermal expansion (CTE) to match the ceramic substrate. Nickel (Ni) is used as the second main element (30 - 35%), improving the ductility and corrosion resistance of the coating, and promoting the formation of the amorphous state synergistically with the amorphous - forming elements (B, P). Nickel (Ni) forms Ni - B short - range ordered clusters with B, increasing the atomic size difference and hindering crystal nucleation; the high electrical conductivity of Ni optimizes the electromagnetic shielding effectiveness (SE). Iron (Fe) is used to adjust the magnetic permeability and enhance the absorption ability of high - frequency electromagnetic waves; it forms a Fe - P pre - alloy with P, reducing the melting point and promoting amorphization. Cobalt (Co) is used to inhibit the crystallization process and improve the thermal stability of the coating (crystallization temperature T x>500 °C); optimize the magnetic properties and reduce the eddy current loss. Boron (B), as a core element for amorphous formation, forms covalent bonds with Ni, increasing the structural disorder; reduces the melting point of the alloy, facilitating rapid solidification. Phosphorus (P) forms Fe-P clusters in cooperation with Fe, enhancing the amorphous formation ability; refines the microstructure of the coating and reduces the porosity. Chromium (Cr) forms a passivation film (Cr2O3), improving the corrosion resistance; trace Cr doping optimizes the surface resistivity of the coating (10 - 50 mΩ·cm), balancing the shielding effectiveness and signal reflection.

[0029] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0030] (1) Through the collaborative design of composition-structure-process, the present invention achieves breakthroughs in high-frequency electromagnetic shielding, efficient heat dissipation, strong interfacial bonding, and environmental stability of amorphous tungsten-nickel-based alloys. W / Ni provides the basic performance, B / P promotes amorphization, and Cr / AlN enhances weather resistance; magnetron sputtering ensures the amorphous structure, and gradient design and sealing treatment optimize the comprehensive performance.

[0031] (2) This solution not only meets the stringent requirements of 5G base stations for signal integrity and reliability but also has the feasibility of industrial implementation, providing an innovative solution for the electromagnetic shielding of high-frequency electronic devices. Detailed implementation manners

[0032] To make the objectives and technical solutions of the present invention clearer and more understandable, the present invention will be further described in detail below.

[0033] Example 1

[0034] An amorphous tungsten-nickel-based electromagnetic shielding coating for a microwave ceramic substrate of a 5G communication base station, the coating being an amorphous multi-component tungsten-nickel-based alloy, comprising raw materials in the following atomic percentages: W 45 Ni 34 Fe 10 Co5B3P2Cr1.

[0035] Among them, W, Ni, Fe, Co, and Cr are all added in the form of metal powders, with a purity of 99.9% for each. The particle size of W is 3 μm, and the particle sizes of Ni, Fe, Co, and Cr are all 2 μm. B is added in the form of Ni-B pre-alloy powder, with a mass ratio of Ni to B of 4:1 and a purity of 99.5%. P is added in the form of Fe-P pre-alloy powder, with a mass ratio of Fe to P of 3:1 and a purity of 99.5%.

[0036] A method for preparing an amorphous multi-component tungsten-nickel-based alloy, comprising the following steps:

[0037] (1) Target preparation: According to the atomic percentages, W 45 Ni 34 Fe 10Take Co5B3P2Cr1, carry out ball milling, and then perform hot isostatic pressing sintering at 1200 °C and a pressure of 35 MPa for 3 hours of holding time. Take it out and cool it to room temperature, and then cut it to obtain a target.

[0038] (2) Coating deposition:

[0039] ① Use ceramics as the substrate, and sequentially perform chemical mechanical polishing, ultrasonic cleaning, ion etching, and plasma activation on its surface to generate a substrate with a hydroxyl-active surface.

[0040] ② Transition layer deposition: Use Ni as the target and perform deposition on the substrate obtained in step ① by DC sputtering.

[0041] ③ Amorphous alloy layer deposition: RF sputter the target obtained in step (1) onto the surface of the product obtained in step ②, with a thickness of 8 μm.

[0042] ④ Protective layer deposition: Use AlN as the target and perform deposition on the product obtained in step ③ by RF sputtering to obtain an amorphous multi-component tungsten-nickel-based alloy substrate.

[0043] (3) Post-treatment: Anneal the amorphous multi-component tungsten-nickel-based alloy substrate at 290 °C for 1 hour in an N2 atmosphere, and then perform SiO2 sealing treatment by the sol-gel method to obtain an amorphous multi-component tungsten-nickel-based alloy.

[0044] In step (1), the conditions for ball milling and mixing are: under argon protection, a ball-to-material ratio of 5:1, a rotation speed of 200 rpm, and a time of 6 hours; the cooling rate of hot isostatic pressing sintering is 10 °C / min, and an alloy target with a relative density of 98% is obtained after hot isostatic pressing sintering; the cutting conditions are: a disk with a diameter of 100 mm and a thickness of 5 mm, and the surface is polished to Ra of 0.09 μm.

[0045] In step ①, the conditions for chemical mechanical polishing are: using diamond polishing fluid, with a surface roughness Ra of 0.04 μm; the conditions for ultrasonic cleaning are: cleaning in acetone, ethanol, and deionized water for 10 minutes each in sequence; the conditions for ion etching are: Ar + bombardment, with an energy of 200 eV, a beam current of 50 mA, for 5 minutes; the conditions for plasma activation are: treatment with a 50 W RF power in an O2 atmosphere for 30 seconds.

[0046] In step ②, the purity of Ni is 99.99%, the power of DC sputtering is 100 W, the argon flow rate is 20 sccm, and a 50 nm Ni layer is deposited.

[0047] In step ③, the power of RF sputtering is 200 W, the substrate temperature is 80 °C, the Ar flow rate is 25 sccm, the vacuum degree is 5×10 -5 Pa, the deposition rate is 1 nm / s, and the time is 2.5 hours.

[0048] In step ④, the purity of AlN is 99.9%, the power of RF sputtering is 150 W, the ratio of N2 / Ar mixed gas is 1:3, and a 10-nm AlN layer is deposited.

[0049] The ceramic substrate is made of Al2O3 with a CTE of 7×10 -6 / K; the dielectric constant of the substrate is 9.

[0050] When performing the sol-gel method SiO2 sealing treatment, the volume ratio of raw materials is: tetraethyl orthosilicate: ethanol: deionized water: hydrochloric acid: ammonia water = 10:60:20:5:5;

[0051] The specific method is as follows: In a magnetic stirrer, mix TEOS and ethanol in proportion, with a stirring speed of 300 rpm for 10 minutes. Slowly add deionized water and hydrochloric acid, heat up to 60 °C, and stir for 2 hours to form a transparent SiO2 sol. Add ammonia water and continue stirring for 30 minutes, and the sol gradually transforms into a gel state (viscosity is 50 mPa·s). Immerse the coated substrate in the sol, evacuate to 10 -2 Pa, and hold for 30 minutes to ensure that the sol fully penetrates the micropores. Slowly lift the substrate at a speed of 0.5 mm / s to reduce the thickness of the surface liquid film and avoid excessive accumulation of the sol. After lifting, immediately centrifuge and spin-coat at a speed of 2000 rpm for 30 seconds to remove the excess sol on the surface. Place the substrate in an environment with a humidity of 50 - 60% and a temperature of 25 °C and let it stand for 24 hours, and the sol is completely converted into a wet gel. Gradient heating and drying: Dry in an oven at 40 °C for 2 hours. Dry at 80 °C for 4 hours. Then sinter at 450 °C for 2 hours with a heating rate of 5 °C / min, and that's it.

[0052] Example 2

[0053] An amorphous tungsten-nickel-based electromagnetic shielding coating for a 5G communication base station microwave ceramic substrate, the coating is an amorphous multi-component tungsten-nickel-based alloy, including raw materials with the following atomic percentages: W 48 Ni 32 Fe8Co6B3P2Cr1.

[0054] Among them, W, Ni, Fe, Co, and Cr are all added in the form of metal powders, with a purity of 99.9% for all. The particle size of W is 2 μm, and the particle sizes of Ni, Fe, Co, and Cr are all 1 μm. B is added in the form of Ni-B pre-alloy powder, and the mass ratio of Ni to B is 4:1, with a purity of 99.5%. P is added in the form of Fe-P pre-alloy powder, and the mass ratio of Fe to P is 3:1, with a purity of 99.5%.

[0055] The preparation method of the amorphous multi-component tungsten-nickel-based alloy includes the following steps:

[0056] (1) Target preparation: Take materials in atomic percentages of W 48 Ni 32 Fe8Co6B3P2Cr1, carry out ball milling, and then perform hot isostatic pressing sintering. At 1225 °C and a pressure of 38 MPa, keep the temperature for 3.5 hours, take it out and cool it to room temperature, and then cut it to obtain the target;

[0057] (2) Coating deposition:

[0058] ① Using ceramics as the substrate, chemically mechanically polish, ultrasonically clean, ion etch, and plasma activate its surface in sequence to generate a substrate with a hydroxyl-active surface;

[0059] ② Transition layer deposition: Using Ni as the target, deposit on the substrate obtained in step ① by DC sputtering;

[0060] ③ Amorphous alloy layer deposition: RF sputter the target obtained in step (1) onto the surface of the product obtained in step ②, with a thickness of 12 μm;

[0061] ④ Protective layer deposition: Using AlN as the target, deposit on the product obtained in step ③ by RF sputtering to obtain an amorphous multi-component tungsten-nickel-based alloy substrate;

[0062] (3) Post-treatment: Anneal the amorphous multi-component tungsten-nickel-based alloy substrate. In an N2 atmosphere, at 280 °C, anneal for 1 hour, and then perform SiO2 sealing treatment by the sol-gel method to obtain the amorphous multi-component tungsten-nickel-based alloy.

[0063] In step (1), the conditions for ball milling and mixing are: argon protection, a ball-to-material ratio of 5:1, a rotation speed of 200 rpm, and a time of 6 hours; the cooling rate of hot isostatic pressing sintering is 10 °C / min, and an alloy target with a density of 98% is obtained after hot isostatic pressing sintering; the cutting conditions are: a disk with a diameter of 100 mm and a thickness of 5 mm, and the surface is polished to Ra of 0.09 μm.

[0064] In step ①, the conditions for chemical mechanical polishing are: using diamond polishing fluid, with a surface roughness Ra of 0.04 μm; the conditions for ultrasonic cleaning are: cleaning in acetone, ethanol, and deionized water for 10 minutes each in sequence; the conditions for ion etching are: Ar + bombardment, with an energy of 200 eV, a beam current of 50 mA, for 5 minutes; the conditions for plasma activation are: treatment with a 50 W RF power in an O2 atmosphere for 30 seconds.

[0065] In step ②, the purity of Ni is above 99.99%, the power of DC sputtering is 100 W, the argon flow rate is 20 sccm, and a 50 nm Ni layer is deposited.

[0066] In step ③, the power of radio frequency sputtering is 200 W, the substrate temperature is 80 °C, the Ar flow rate is 25 sccm, the vacuum degree is 5×10 -5 Pa, the deposition rate is 1 nm / s, and the time is 3 hours.

[0067] In step ④, the purity of AlN is greater than 99.9%, the power of radio frequency sputtering is 150 W, the ratio of N2 / Ar mixed gas is 1:3, and a 10-nm AlN layer is deposited.

[0068] The material of the ceramic substrate is Al2O3, and the CTE is 7.5×10 -6 / K; the substrate dielectric constant is 10.

[0069] When performing the sol-gel method SiO2 sealing treatment, the volume ratio of raw materials is: tetraethyl orthosilicate: ethanol: deionized water: hydrochloric acid: ammonia water = 10:60:20:5:5;

[0070] The specific method is as follows: In a magnetic stirrer, mix TEOS and ethanol in proportion, with a stirring speed of 300 rpm for 10 minutes. Slowly add deionized water and hydrochloric acid dropwise, heat up to 60 °C, and stir for 2 hours to form a transparent SiO2 sol. Add ammonia water and continue stirring for 30 minutes, and the sol gradually transforms into a gel state (viscosity is 80 mPa·s). Immerse the coated substrate in the sol, evacuate to 10 -2 Pa, keep it for 30 minutes to ensure that the sol fully penetrates the micropores. Slowly lift the substrate at a speed of 0.8 mm / s to reduce the surface liquid film thickness and avoid excessive sol accumulation. After lifting, immediately centrifuge and spin-coat at 2000 rpm for 30 seconds to remove the excess sol on the surface. Place the substrate in an environment with a humidity of 50-60% and a temperature of 25 °C and let it stand for 24 hours, and the sol is completely converted into a wet gel. Gradient heating and drying: Dry in an oven at 40 °C for 2 hours. Dry at 80 °C for 4 hours. Then sinter at 450 °C for 2 hours, with a heating rate of 5 °C / min, and that's it.

[0071] Example 3

[0072] An amorphous tungsten-nickel-based electromagnetic shielding coating for a 5G communication base station microwave ceramic substrate, the coating is an amorphous multi-component tungsten-nickel-based alloy, and the raw materials include the following atomic percentages: W 49 Ni 30 Fe8Co5B4P 2.5 Cr 1.5 .

[0073] Among them, W, Ni, Fe, Co, and Cr are all added in the form of metal powders, and their purities are all ≥99.9%. The particle size of W is 4 μm, and the particle sizes of Ni, Fe, Co, and Cr are all 3 μm. B is added in the form of Ni-B pre-alloy powder, and the mass ratio of Ni to B is 4:1, with a purity of 99.5%. P is added in the form of Fe-P pre-alloy powder, and the mass ratio of Fe to P is 3:1, with a purity of 99.5%.

[0074] A preparation method of an amorphous multi-component tungsten-nickel-based alloy, comprising the following steps:

[0075] (1) Target preparation: According to atomic percentages, take materials for W 48.5 Ni 30 Fe8Co5B4P3Cr 1.5 Take materials, perform ball milling, and then perform hot isostatic pressing sintering. At 1250 °C and a pressure of 40 MPa, keep the temperature for 4 hours, take it out and cool it to room temperature, and then cut it to obtain the target;

[0076] (2) Coating deposition:

[0077] ① Use ceramics as the substrate, and sequentially perform chemical mechanical polishing, ultrasonic cleaning, ion etching, and plasma activation on its surface to generate a substrate with a hydroxyl-active surface;

[0078] ② Transition layer deposition: Use Ni as the target and perform deposition on the substrate obtained in step ① by DC sputtering;

[0079] ③ Amorphous alloy layer deposition: Sputter the target obtained in step (1) onto the surface of the product obtained in step ②, with a thickness of 15 μm;

[0080] ④ Protective layer deposition: Use AlN as the target and perform deposition on the product obtained in step ③ by RF sputtering to obtain an amorphous multi-component tungsten-nickel-based alloy substrate;

[0081] (3) Post-treatment: Anneal the amorphous multi-component tungsten-nickel-based alloy substrate in an N2 atmosphere at 300 °C for 1 hour, and then perform SiO2 sealing treatment by the sol-gel method to obtain the amorphous multi-component tungsten-nickel-based alloy.

[0082] In step (1), the conditions for ball milling and mixing are: under argon protection, the ball-to-material ratio is 5:1, the rotation speed is 200 rpm, and the time is 6 hours; the cooling rate of hot isostatic pressing sintering is 10 °C / min, and an alloy target with a relative density of 98% is obtained after hot isostatic pressing sintering; the cutting conditions are: a disc with a diameter of 100 mm and a thickness of 5 mm, and the surface is polished to Ra of 0.09 μm.

[0083] In Step ①, the conditions for chemical mechanical polishing are as follows: diamond polishing fluid is used, and the surface roughness Ra is 0.04 μm; the conditions for ultrasonic cleaning are as follows: cleaning is carried out in acetone, ethanol, and deionized water for 10 minutes each in sequence; the conditions for ion etching are as follows: Ar + bombardment, with an energy of 200 eV, a beam current of 50 mA, for 5 minutes; the conditions for plasma activation are as follows: under an O2 atmosphere, treatment is carried out with a radio frequency power of 50 W for 30 seconds.

[0084] In Step ②, the purity of Ni is above 99.99%, the power of DC sputtering is 100 W, the argon flow rate is 20 sccm, and a 50-nm Ni layer is deposited.

[0085] In Step ③, the power of radio frequency sputtering is 200 W, the substrate temperature is 80 °C, the Ar flow rate is 25 sccm, the vacuum degree is 5×10 -5 Pa, the deposition rate is 1 nm / s, and the time is 3.5 hours.

[0086] In Step ④, the purity of AlN is 99.9%, the power of radio frequency sputtering is 150 W, the ratio of N2 / Ar mixed gas is 1:3, and a 10-nm AlN layer is deposited.

[0087] The material of the ceramic substrate is Al2O3, and the CTE is 6.5×10 -6 / K; the substrate dielectric constant is 8.

[0088] When performing the sol-gel method SiO2 sealing treatment, the raw material volume ratio is: tetraethyl orthosilicate: ethanol: deionized water: hydrochloric acid: ammonia water = 10:60:20:5:5;

[0089] The specific method is as follows: In a magnetic stirrer, mix TEOS and ethanol in proportion, with a stirring speed of 300 rpm for 10 minutes. Slowly add deionized water and hydrochloric acid, heat up to 60 °C, and stir for 2 hours to form a transparent SiO2 sol. Add ammonia water and continue to stir for 30 minutes, and the sol gradually transforms into a gel state (viscosity is 100 mPa·s). Immerse the coated substrate in the sol, evacuate to 10 -2 Pa, and hold for 30 minutes to ensure that the sol fully penetrates the micropores. Slowly lift the substrate at a speed of 0.8 mm / s to reduce the thickness of the surface liquid film and avoid excessive sol accumulation. After lifting, immediately centrifuge and spin coat at a speed of 2000 rpm for 30 seconds to remove the excess sol on the surface. Place the substrate in an environment with a humidity of 60% and a temperature of 25 °C and let it stand for 24 hours, and the sol is completely converted into a wet gel. Gradient heating and drying: dry in an oven at 40 °C for 2 hours. Dry at 80 °C for 4 hours. Then sinter at 450 °C for 2 hours, with a heating rate of 5 °C / min, and that's it.

[0090] Comparative Example 1

[0091] It is different from Example 1 in that B and P are not doped, and the alloy composition is W 49 Ni 35 Fe 10 Co5Cr1

[0092] Comparative Example 2

[0093] It is different from Example 2 in that the substrate is not polished (Ra = 0.5 μm).

[0094] Comparative Example 3

[0095] It is different from Example 3 in that the deposition of the protective layer and annealing are not carried out.

[0096] Comparative Example 4

[0097] It is different from Example 1 in that the deposition thickness of the amorphous alloy layer is 20 μm.

[0098] Comparative Example 5

[0099] It is different from Example 1 in that the sol-gel method SiO2 sealing treatment is not carried out.

[0100] Comparative Example 6

[0101] It is different from Example 1 in that the Cr element is not added.

[0102] The test data of Examples 1-3 and Comparative Examples 1-6 are shown in Table 1.

[0103] Table 1: Test data of Examples 1-3 and Comparative Examples 1-6

[0104]

[0105]

[0106] From the above data, it can be seen that for Example 1 (W 45%), the thermal conductivity is 48 W / m·K and the SE is 68 dB; for Example 3 (W 49%), the thermal conductivity is 52 W / m·K and the SE is 70 dB. The increase in W content improves the thermal conductivity, but the dielectric properties need to be balanced (the tanδ of Example 3 = 0.003 is still better than that of the comparative example). When W is 48% and Ni is 32%, the thermal conductivity is 55 W / m·K and the SE is 72 dB, with the best comprehensive performance. The intermediate value of the hot isostatic pressing sintering temperature / pressure (Example 2: 1225 °C / 38 MPa) obtains the highest relative density (>98%), and the bonding strength reaches 35 N. Extending the sputtering time to 3.5 hours (Example 3) results in an increase in thickness (15 μm) and a slight decrease in SE (70 dB vs. 72 dB of Example 2). Comparative example 1 (without B / P): The formation of the amorphous fails (XRD shows crystalline peaks), the tanδ rises to 0.015, and the SE is only 50 dB. Comparative example 4 (too thick coating): A thickness of 20 μm leads to enhanced signal reflection and the SE drops to 55 dB. The coating without the addition of Cr shows severe corrosion after 500 h, while none of the examples are oxidized, indicating that Cr significantly improves the corrosion resistance by forming a Cr2O3 passivation film.

Claims

1. An amorphous multi-component tungsten-nickel-based alloy, characterized in that, Raw materials including the following atomic percentages: W (45-50) Ni (30-35) Fe (8-10) Co (5-6) B (3-4) P (2-3) Cr (0.5-1.5) .

2. The amorphous multi-component tungsten-nickel-based alloy according to claim 1, wherein The W, Ni, Fe, Co and Cr are all added in the form of metal powders, and their purities are all ≥99.9%. The particle size of W is 1-5 μm, and the particle sizes of Ni, Fe, Co and Cr are all 1-3 μm; B is added in the form of Ni-B pre-alloy powder, and the mass ratio of Ni to B is 4:1, with a purity ≥99.5%; P is added in the form of Fe-P pre-alloy powder, and the mass ratio of Fe to P is 3:1, with a purity ≥99.5%.

3. A method for preparing the amorphous multi-component tungsten-nickel-based alloy according to claim 1 or 2, characterized in that, It includes the following steps: (1) Target preparation: Take materials in the atomic percentages of W (45-50) Ni (30-35) Fe (8-10) Co (5-6) B (3-4) P (2-3) Cr (0.5-1.5) perform ball milling, and then perform hot isostatic pressing sintering at 1200 - 1250 °C and a pressure of 35 - 40 MPa for a holding time of 3 - 4 hours. Take it out and cool it to room temperature, and then cut it to obtain the target; (2) Coating deposition: ① Using ceramics as the substrate, chemically mechanically polish, ultrasonically clean, ion etch and plasma activate its surface in sequence to generate a substrate with a hydroxyl-active surface; ② Transition layer deposition: Using Ni as the target, and adopting DC sputtering to deposit on the substrate obtained in step ①; ③ Amorphous alloy layer deposition: Sputtering the target obtained in step (1) onto the surface of the product obtained in step ②, with a thickness of 8-15 μm; ④ Protective layer deposition: Using AlN as the target, and adopting RF sputtering to deposit on the product obtained in step ③ to obtain an amorphous multi-component tungsten-nickel-based alloy substrate; (3) Post-treatment: Anneal the amorphous multi-component tungsten-nickel-based alloy substrate, at 280-300 °C in an N2 atmosphere for 1 hour, and then perform SiO2 sealing treatment by the sol-gel method to obtain an amorphous multi-component tungsten-nickel-based alloy.

4. The preparation method of the amorphous multi-component tungsten-nickel-based alloy according to claim 3, wherein, In the said step (1), the conditions for ball milling and mixing are: under argon protection, the ball-to-material ratio is 5:1, the rotation speed is 200 rpm, and the time is 6 hours; the cooling rate of hot isostatic pressing sintering is ≤10 °C / min, and after hot isostatic pressing sintering is completed, an alloy target with a relative density ≥98% is obtained; the cutting conditions are: a disk with a diameter of 100 mm and a thickness of 5 mm, and the surface is polished to Ra <0.1 μm.

5. The preparation method of the amorphous multi-component tungsten-nickel-based alloy according to claim 3, wherein, In step ①, the conditions for chemical mechanical polishing are as follows: using diamond polishing liquid, the surface roughness Ra < 0.05 μm; the conditions for ultrasonic cleaning are as follows: cleaning in acetone, ethanol, and deionized water for 10 minutes each in sequence; the conditions for ion etching are as follows: Ar + bombardment, with an energy of 200 eV, a beam current of 50 mA, for 5 minutes; the conditions for plasma activation are as follows: under an O2 atmosphere, treatment with a radio frequency power of 50 W for 30 seconds.

6. The method for preparing an amorphous multi-component tungsten-nickel-based alloy according to claim 3, wherein In the said step ②, the purity of Ni is above 99.99%, the power of DC sputtering is 100 W, the argon flow rate is 20 sccm, and a 50-nm Ni layer is deposited.

7. The preparation method of the amorphous multi-component tungsten-nickel-based alloy according to claim 3, characterized in that, In step ③, the power of radio frequency sputtering is 200 W, the substrate temperature is 80 °C, the Ar flow rate is 25 sccm, the vacuum degree is 5×10 -5 Pa, the deposition rate is 1 nm / s, and the time is 2.5 - 3.5 hours.

8. The method for preparing an amorphous multi-component tungsten-nickel-based alloy according to claim 3, characterized in that, In the said step ④, the purity of AlN is greater than 99.9%, the power of RF sputtering is 150 W, the volume ratio of the N2 / Ar mixed gas is 1:3, and a 10-nm AlN layer is deposited.

9. Use of the amorphous multi-component tungsten-nickel-based alloy according to claim 1 or 2, characterized in that, An amorphous tungsten-nickel-based electromagnetic shielding coating for a microwave ceramic substrate of a 5G communication base station.

10. Use of the amorphous multi-component tungsten-nickel-based alloy according to claim 9, characterized in that, The material of the ceramic substrate is Al2O3, and its CTE is 6.5 - 7.5×10 -6 / K; the dielectric constant of the substrate is 8 - 10.

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