Amorphous multi-component tungsten-nickel-based alloys, their preparation methods and applications

Abstract

This invention relates to the field of amorphous multi-component tungsten-nickel-based alloy production technology, specifically to amorphous multi-component tungsten-nickel-based alloys, their preparation methods, and applications. The amorphous multi-component tungsten-nickel-based alloy comprises raw materials in 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) This invention achieves breakthroughs in high-frequency electromagnetic shielding, efficient heat dissipation, strong interfacial bonding, and environmental stability of amorphous tungsten-nickel-based alloys through a synergistic design of composition, structure, and process. 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 pore sealing optimize the overall performance.

Description

Technical Field

[0001] This invention relates to the field of amorphous multi-component tungsten-nickel-based alloy production technology, specifically to amorphous multi-component tungsten-nickel-based alloys, their preparation methods, and applications. Background Technology

[0002] Amorphous alloys, also known as metallic glasses, are special alloy materials whose internal atomic arrangement lacks a long-range ordered structure. Amorphous multi-component tungsten-nickel-based alloys, with tungsten and nickel as the main components and other alloying elements added to form a multi-component system, combine the high hardness, wear resistance, and high-temperature oxidation resistance of metallic tungsten with the unique isotropy, high toughness, and excellent corrosion resistance of amorphous alloys. This type of alloy lacks crystal defects such as grain boundaries and dislocations, giving it properties in mechanical, electrical, and magnetic fields that differ from traditional crystalline alloys. For example, it exhibits uniform hardness, excellent fatigue resistance, low magnetic permeability, and good electrical conductivity, making it a promising candidate for applications in numerous fields.

[0003] With the rapid development of 5G communication technology, microwave ceramic substrates have become a core material for 5G base station RF 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 (>5GHz), with tanδ values ​​often exceeding 0.01, leading to severe signal attenuation during transmission and seriously affecting communication quality and efficiency. Simultaneously, with the increase in power density of 5G base stations, heat dissipation requirements have increased dramatically. The thermal conductivity of traditional metal coatings is generally below 30W / m·K, far from matching the approximately 30W / m·K thermal conductivity of Al2O3 ceramic substrates. Heat accumulation can easily cause device performance degradation or even failure.

[0004] Furthermore, the interface bonding between the coating and the ceramic substrate presents a significant problem. Due to the difference in the coefficients of thermal expansion of the materials, the bonding strength between conventional coatings and the substrate is low, with a critical scratch load of less than 20N. Under conditions such as high and low temperature cycling, thermal stress can easily lead to coating cracking and peeling, compromising the shielding function. In terms of environmental adaptability, coatings without pore sealing treatment are prone to oxidation and corrosion of metallic materials in harsh environments such as humidity, heat, and salt spray. After 500 hours of salt spray testing, the corrosion area exceeds 5%, significantly shortening the equipment's service life and increasing maintenance costs. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide an amorphous multi-component tungsten-nickel-based alloy, which greatly improves the amorphous 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 objective of this invention is to provide a method for preparing an amorphous multi-component tungsten-nickel-based alloy, which significantly improves its interfacial bonding strength (critical load > 30 N) and corrosion resistance through a Ni transition layer + amorphous alloy layer + AlN protective layer.

[0007] The third objective of this invention is to provide an application of an amorphous multi-component tungsten-nickel-based alloy for use as an amorphous tungsten-nickel-based electromagnetic shielding coating on microwave ceramic substrates for 5G communication base stations.

[0008] This invention is achieved using the following technical solution:

[0009] The aforementioned amorphous multi-component tungsten-nickel-based alloy comprises the following raw materials in atomic percentage: 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 W, Ni, Fe, Co, and Cr are all added as metal powders with a purity ≥99.9%. The particle size of W is 1-5 μm, and the particle size of Ni, Fe, Co, and Cr is 1-3 μm. B is added in the form of Ni-B pre-alloyed powder with a Ni to B mass ratio of 4:1 and a purity ≥99.5%. P is added in the form of Fe-P pre-alloyed powder with a Fe to P mass ratio of 3:1 and a purity ≥99.5%.

[0011] The preparation method of the amorphous multi-component tungsten-nickel-based alloy includes the following steps:

[0012] (1) Target material preparation: W by atomic percentage (45-50) Ni (30-35) Fe (8-10) Co (5-6) B (3-4) P (2-3) Cr (0.5-1.5) The material is taken, ball-milled, and then hot isostatic pressing sintered at 1200-1250℃ and 35-40MPa for 3-4 hours. After cooling to room temperature, it is cut to obtain the target material.

[0013] (2) Coating deposition:

[0014] ① Using ceramic as a substrate, its surface is sequentially subjected to chemical mechanical polishing, ultrasonic cleaning, ion etching and plasma activation to generate a substrate with a hydroxyl-active surface;

[0015] ② Transition layer deposition: Using Ni as the target material, DC sputtering is used to deposit the substrate obtained in step ①;

[0016] ③ Amorphous alloy layer deposition: The target material obtained in step (1) is radio frequency sputtered 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 material, radio frequency sputtering is used to deposit the product obtained in step ③ to obtain an amorphous multi-component tungsten nickel-based alloy substrate;

[0018] (3) Post-treatment: The amorphous multi-component tungsten nickel-based alloy substrate is annealed at 280-300℃ for 1 hour in N2 atmosphere, and then sealed with SiO2 by sol-gel method to obtain the amorphous multi-component tungsten nickel-based alloy.

[0019] In step (1), the ball milling mixing conditions are: argon protection, ball-to-material ratio of 5:1, rotation speed of 200 rpm, and time of 6 hours; the cooling rate of hot isostatic pressing sintering is ≤10℃ / min, and an alloy target with a 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<0.1μm.

[0020] In step ①, the conditions for chemical mechanical polishing are: using diamond polishing slurry, with a surface roughness Ra < 0.05 μm; the conditions for ultrasonic cleaning are: sequentially cleaning in acetone, ethanol, and deionized water for 10 minutes each; and the conditions for ion etching are: Ar... + Bombardment, energy 200eV, beam current 50mA, 5 minutes; plasma activation conditions: O2 atmosphere, 50W RF power treatment for 30 seconds.

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

[0022] In step ③, the RF sputtering power is 200W, the substrate temperature is 80℃, the Ar flow rate is 25sccm, and the vacuum degree is 5×10⁻⁶. -5 Pa, deposition rate of 1 nm / s, time of 2.5-3.5 hours.

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

[0024] The aforementioned amorphous multi-component tungsten-nickel-based alloy is used as an amorphous tungsten-nickel-based electromagnetic shielding coating for microwave ceramic substrates in 5G communication base stations.

[0025] The ceramic substrate is made of Al2O3 with a CTE of 6.5-7.5 × 10⁻⁶. -6 / K; the dielectric constant of the substrate is 8-10.

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

[0027] The specific method is as follows: In a magnetic stirrer, mix TEOS and ethanol in a certain proportion, stirring at 300 rpm for 10 minutes. Slowly add deionized water and hydrochloric acid (pH=2-3), heat to 60℃, and stir for 2 hours to form a transparent SiO2 sol. Add ammonia water (pH=8-9) and continue stirring for 30 minutes, until the sol gradually transitions to a gel state (viscosity approximately 50-100 mPa·s). Immerse the coating substrate in the sol and apply a vacuum to 10... -2 Hold the solution at 0.5-1 mm / s for 30 minutes to ensure the sol fully penetrates the micropores. Slowly lift the substrate at 0.5-1 mm / s to reduce the surface liquid film thickness and avoid excessive sol accumulation. Immediately after lifting, centrifuge at 2000 rpm for 30 seconds to remove excess sol from the surface. Place the substrate in an environment with 50%-60% humidity and 25°C for 24 hours to allow the sol to completely transform into a wet gel. Gradient drying: Dry in a 40°C oven for 2 hours (to remove free water). Dry at 80°C for 4 hours. Then sinter at 450°C for 2 hours at a heating rate of 5°C / min.

[0028] Tungsten (W), as the main element, provides a high melting point (3422℃), high hardness (7.5GPa), and excellent thermal conductivity (170W / m·K), dominating the coating's heat dissipation performance and mechanical strength. Tungsten (W) forms a solid solution with Ni, inhibiting grain boundary migration and enhancing the stability of the amorphous structure; high W content reduces the coefficient of thermal expansion (CTE), matching the ceramic substrate. Nickel (Ni), as the second main element (30-35%), improves the coating's ductility and corrosion resistance, synergistically promoting amorphous formation with amorphous-forming elements (B, P). Nickel (Ni) forms Ni-B short-range ordered clusters with B, increasing atomic size differences and hindering crystal nucleation; Ni's high electrical conductivity optimizes electromagnetic shielding effectiveness (SE). Iron (Fe) is used to adjust magnetic permeability, enhancing the absorption of high-frequency electromagnetic waves; it forms Fe-P pre-alloys with P, lowering the melting point and promoting amorphization. Cobalt (Co) is used to suppress the crystallization process, improving the coating's thermal stability (crystallization temperature T). x(>500℃); optimizes magnetic properties and reduces eddy current losses. Boron (B), as the core element for amorphous formation, forms covalent bonds with Ni, increasing structural disorder; it lowers the alloy melting point, facilitating rapid solidification. Phosphorus (P) synergistically forms Fe-P clusters with Fe, enhancing amorphous formation capability; it refines the coating microstructure and reduces porosity. Chromium (Cr) forms a passivation film (Cr2O3), improving corrosion resistance; trace amounts of Cr doping optimize the coating surface resistivity (10-50 mΩ·cm), balancing shielding effectiveness and signal reflection.

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

[0030] (1) This invention achieves breakthroughs in high-frequency electromagnetic shielding, efficient heat dissipation, strong interface bonding and environmental stability of amorphous tungsten nickel-based alloys through composition-structure-process synergistic design. W / Ni provides basic performance, B / P promotes amorphization, and Cr / AlN enhances weather resistance. Magnetron sputtering ensures amorphous structure, and gradient design and sealing treatment optimize 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 electromagnetic shielding of high-frequency electronic devices. Detailed Implementation

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

[0033] Example 1

[0034] The amorphous tungsten-nickel-based electromagnetic shielding coating used in microwave ceramic substrates for 5G communication base stations is an amorphous multi-element tungsten-nickel-based alloy comprising the following raw materials in atomic percentage: W 45 Ni 34 Fe 10 Co5B3P2Cr1.

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

[0036] A method for preparing amorphous multi-component tungsten-nickel-based alloys includes the following steps:

[0037] (1) Target material preparation: W by atomic percentage 45 Ni 34 Fe 10Co5B3P2Cr1 material was ball-milled and then hot isostatic pressing sintered at 1200℃ and 35MPa for 3 hours. After cooling to room temperature, it was cut to obtain the target material.

[0038] (2) Coating deposition:

[0039] ① Using ceramic as a substrate, its surface is sequentially subjected to chemical mechanical polishing, ultrasonic cleaning, ion etching and plasma activation to generate a substrate with a hydroxyl-active surface;

[0040] ② Transition layer deposition: Using Ni as the target material, DC sputtering is used to deposit the substrate obtained in step ①;

[0041] ③ Amorphous alloy layer deposition: The target material obtained in step (1) is radio frequency sputtered onto the surface of the product obtained in step ②, with a thickness of 8 μm;

[0042] ④ Protective layer deposition: Using AlN as the target material, radio frequency sputtering is used to deposit the product obtained in step ③ to obtain an amorphous multi-component tungsten nickel-based alloy substrate;

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

[0044] In step (1), the conditions for ball milling are: argon protection, ball-to-material ratio of 5:1, rotation speed of 200 rpm, and time of 6 hours; the cooling rate of hot isostatic pressing sintering is 10℃ / min, and an alloy target with a 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.

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

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

[0047] In step ③, the RF sputtering power is 200W, the substrate temperature is 80℃, the Ar flow rate is 25sccm, and the vacuum degree is 5×10⁻⁶. -5 Pa, deposition rate of 1 nm / s, time of 2.5 hours.

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

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

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

[0051] The specific method is as follows: In a magnetic stirrer, TEOS and ethanol are mixed in a specific ratio at 300 rpm for 10 minutes. Deionized water and hydrochloric acid are slowly added dropwise, the temperature is raised to 60°C, and the mixture is stirred for 2 hours to form a transparent SiO2 sol. Ammonia is added, and stirring continues for 30 minutes, during which the sol gradually transitions to a gel state (viscosity 50 mPa·s). The coating substrate is then immersed in the sol, and a vacuum is applied to 10... -2 Hold at 0.5 mm / s for 30 minutes to ensure the sol fully penetrates the micropores. Slowly lift the substrate at 0.5 mm / s to reduce the surface liquid film thickness and avoid excessive sol accumulation. Immediately after lifting, centrifuge at 2000 rpm for 30 seconds to remove excess sol from the surface. Place the substrate in an environment with 50-60% humidity and 25°C for 24 hours to allow the sol to completely transform into a wet gel. Gradient drying: dry in a 40°C oven for 2 hours. Dry at 80°C for 4 hours. Then sinter at 450°C for 2 hours at a heating rate of 5°C / min.

[0052] Example 2

[0053] The amorphous tungsten-nickel-based electromagnetic shielding coating used in microwave ceramic substrates for 5G communication base stations is an amorphous multi-element tungsten-nickel-based alloy comprising the following raw materials in atomic percentage: W 48 Ni 32 Fe8Co6B3P2Cr1.

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

[0055] A method for preparing amorphous multi-component tungsten-nickel-based alloys includes the following steps:

[0056] (1) Target material preparation: W by atomic percentage 48 Ni 32 Fe8Co6B3P2Cr1 material was ball-milled and then subjected to hot isostatic pressing sintering at 1225℃ and 38MPa for 3.5 hours. After cooling to room temperature, it was cut to obtain the target material.

[0057] (2) Coating deposition:

[0058] ① Using ceramic as a substrate, its surface is sequentially subjected to chemical mechanical polishing, ultrasonic cleaning, ion etching and plasma activation to generate a substrate with a hydroxyl-active surface;

[0059] ② Transition layer deposition: Using Ni as the target material, DC sputtering is used to deposit the substrate obtained in step ①;

[0060] ③ Amorphous alloy layer deposition: The target material obtained in step (1) is radio frequency sputtered 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 material, radio frequency sputtering is used to deposit the product obtained in step ③ to obtain an amorphous multi-component tungsten nickel-based alloy substrate;

[0062] (3) Post-treatment: The amorphous multi-component tungsten nickel-based alloy substrate was annealed at 280°C for 1 hour in N2 atmosphere, and then sealed with SiO2 by sol-gel method to obtain the amorphous multi-component tungsten nickel-based alloy.

[0063] In step (1), the conditions for ball milling are: argon protection, ball-to-material ratio of 5:1, rotation speed of 200 rpm, and time of 6 hours; the cooling rate of hot isostatic pressing sintering is 10℃ / min, and an alloy target with a 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.

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

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

[0066] In step ③, the RF sputtering power is 200W, the substrate temperature is 80℃, the Ar flow rate is 25sccm, and the vacuum degree is 5×10⁻⁶. -5 Pa, deposition rate of 1 nm / s, time of 3 hours.

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

[0068] The ceramic substrate is made of Al2O3 with a CTE of 7.5 × 10⁻⁶. -6 / K; the substrate dielectric constant is 10.

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

[0070] The specific method is as follows: In a magnetic stirrer, TEOS and ethanol are mixed in a specific ratio at 300 rpm for 10 minutes. Deionized water and hydrochloric acid are slowly added dropwise, the temperature is raised to 60°C, and the mixture is stirred for 2 hours to form a transparent SiO2 sol. Ammonia is added, and stirring continues for 30 minutes, during which the sol gradually transitions to a gel state (viscosity 80 mPa·s). The coating substrate is then immersed in the sol, and a vacuum is applied to 10... -2 Hold at 0.8 mm / s for 30 minutes to ensure the sol fully penetrates the micropores. Slowly lift the substrate at 0.8 mm / s to reduce the surface liquid film thickness and avoid excessive sol accumulation. Immediately after lifting, centrifuge at 2000 rpm for 30 seconds to remove excess sol from the surface. Place the substrate in an environment with 50-60% humidity and 25°C for 24 hours to allow the sol to completely transform into a wet gel. Gradient drying: dry in a 40°C oven for 2 hours. Dry at 80°C for 4 hours. Then sinter at 450°C for 2 hours at a heating rate of 5°C / min.

[0071] Example 3

[0072] The amorphous tungsten-nickel-based electromagnetic shielding coating used in microwave ceramic substrates for 5G communication base stations is an amorphous multi-element tungsten-nickel-based alloy comprising the following raw materials in atomic percentage: W 49 Ni 30 Fe8Co5B4P 2.5 Cr 1.5 .

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

[0074] A method for preparing amorphous multi-component tungsten-nickel-based alloys includes the following steps:

[0075] (1) Target material preparation: W by atomic percentage 48.5 Ni 30 Fe8Co5B4P3Cr 1.5 The material is collected, ball-milled, and then hot isostatic pressing sintered at 1250℃ and 40MPa for 4 hours. After cooling to room temperature, it is cut to obtain the target material.

[0076] (2) Coating deposition:

[0077] ① Using ceramic as a substrate, its surface is sequentially subjected to chemical mechanical polishing, ultrasonic cleaning, ion etching and plasma activation to generate a substrate with a hydroxyl-active surface;

[0078] ② Transition layer deposition: Using Ni as the target material, DC sputtering is used to deposit the substrate obtained in step ①;

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

[0080] ④ Protective layer deposition: Using AlN as the target material, radio frequency sputtering is used to deposit the product obtained in step ③ to obtain an amorphous multi-component tungsten nickel-based alloy substrate;

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

[0082] In step (1), the conditions for ball milling are: argon protection, ball-to-material ratio of 5:1, rotation speed of 200 rpm, and time of 6 hours; the cooling rate of hot isostatic pressing sintering is 10℃ / min, and an alloy target with a 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 chemical mechanical polishing conditions are: using diamond polishing slurry, with a surface roughness Ra of 0.04 μm; the ultrasonic cleaning conditions are: sequentially cleaning in acetone, ethanol, and deionized water for 10 minutes each; the ion etching conditions are: Ar... + Bombardment, energy 200eV, beam current 50mA, 5 minutes; plasma activation conditions: O2 atmosphere, 50W RF power treatment for 30 seconds.

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

[0085] In step ③, the RF sputtering power is 200W, the substrate temperature is 80℃, the Ar flow rate is 25sccm, and the vacuum degree is 5×10⁻⁶. -5 Pa, deposition rate of 1 nm / s, time of 3.5 hours.

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

[0087] The ceramic substrate is made of Al2O3 with a CTE of 6.5 × 10⁻⁶. -6 / K; the substrate dielectric constant is 8.

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

[0089] The specific method is as follows: In a magnetic stirrer, TEOS and ethanol are mixed in a specific ratio at 300 rpm for 10 minutes. Deionized water and hydrochloric acid are slowly added dropwise, the temperature is raised to 60°C, and the mixture is stirred for 2 hours to form a transparent SiO2 sol. Ammonia is added, and stirring continues for 30 minutes, during which the sol gradually transitions to a gel state (viscosity 100 mPa·s). The coating substrate is then immersed in the sol, and a vacuum is applied to 10... -2 Hold at 0.8 mm / s for 30 minutes to ensure the sol fully penetrates the micropores. Slowly lift the substrate at 0.8 mm / s to reduce the surface liquid film thickness and avoid excessive sol accumulation. Immediately after lifting, centrifuge at 2000 rpm for 30 seconds to remove excess sol from the surface. Place the substrate in an environment with 60% humidity and 25°C for 24 hours to allow the sol to completely transform into a wet gel. Gradient drying: dry in a 40°C oven for 2 hours. Dry at 80°C for 4 hours. Then sinter at 450°C for 2 hours at a heating rate of 5°C / min.

[0090] Comparative Example 1

[0091] The difference from Example 1 is that it is not doped with B or P, and the alloy composition is W. 49 Ni 35 Fe 10 Co5Cr1.

[0092] Comparative Example 2

[0093] The difference from Example 2 is that the substrate was not polished (Ra = 0.5 μm).

[0094] Comparative Example 3

[0095] The difference from Example 3 is that no protective layer deposition and annealing were performed.

[0096] Comparative Example 4

[0097] The difference from Example 1 is that the amorphous alloy layer is deposited with a thickness of 20 μm.

[0098] Comparative Example 5

[0099] The difference from Example 1 is that the sol-gel method for sealing pores with SiO2 was not used.

[0100] Comparative Example 6

[0101] The difference from Example 1 is that no Cr element was added.

[0102] The test data for 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] The data above show that Example 1 (45% W) has a thermal conductivity of 48 W / m·K and an SE of 68 dB; Example 3 (49% W) has a thermal conductivity of 52 W / m·K and an SE of 70 dB. Increasing the W content improves thermal conductivity, but the dielectric properties need to be balanced (the tanδ of Example 3, at 0.003, is still better than the comparative example). With 48% W and 32% Ni, the thermal conductivity is 55 W / m·K and the SE is 72 dB, exhibiting the best overall performance. The highest density (>98%) and bonding strength of 35 N were obtained at the median hot isostatic pressing sintering temperature / pressure (Example 2: 1225℃ / 38MPa). Extending the sputtering time to 3.5 hours (Example 3) resulted in an increase in thickness (15 μm) and a slight decrease in SE (70 dB vs. 72 dB in Example 2). Comparative Example 1 (without B / P): Amorphous formation failed (XRD showed crystalline peaks), tanδ increased to 0.015, and SE was only 50 dB. Comparative Example 4 (excessively thick coating): A thickness of 20 μm resulted in enhanced signal reflection, and SE decreased to 55 dB. The coating without Cr showed severe corrosion after 500 h, while the examples did not oxidize, indicating that Cr significantly improves corrosion resistance by forming a Cr2O3 passivation film.

Claims

1. An amorphous multi-component tungsten-nickel-based alloy, characterized in that, The raw material is W (atomic percentage). (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, characterized in that, The W, Ni, Fe, Co, and Cr are all added as metal powders with a purity of ≥99.9%. The particle size of W is 1-5 μm, and the particle size of Ni, Fe, Co, and Cr is 1-3 μm. B is added in the form of Ni-B pre-alloyed powder with a Ni to B mass ratio of 4:1 and a purity of ≥99.5%. P is added in the form of Fe-P pre-alloyed powder with a Fe to P mass ratio of 3:1 and a purity of ≥99.5%.

3. A method for preparing the amorphous multi-component tungsten-nickel-based alloy according to claim 1 or 2, characterized in that, Includes the following steps: (1) Target preparation: W by atomic percentage (45-50) Ni (30-35) Fe (8-10) Co (5-6) B (3-4) P (2-3) Cr (0.5-1.5) The material is collected, ball-milled, and then hot isostatic pressing sintered at 1200-1250℃ and 35-40 MPa for 3-4 hours. After cooling to room temperature, it is cut to obtain the target material. (2) Coating deposition: ① Using ceramic as a substrate, its surface is sequentially subjected to chemical mechanical polishing, ultrasonic cleaning, ion etching and plasma activation to generate a substrate with a hydroxyl-active surface; ② Transition layer deposition: Using Ni as the target material, DC sputtering is used to deposit the substrate obtained in step ①; ③ Amorphous alloy layer deposition: The target material obtained in step (1) is radio frequency sputtered 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 material, radio frequency sputtering is used to deposit the product obtained in step ③ to obtain an amorphous multi-component tungsten nickel-based alloy substrate; (3) Post-treatment: The amorphous multi-component tungsten nickel-based alloy substrate is annealed at 280-300℃ for 1 hour in N2 atmosphere, and then sealed with SiO2 by sol-gel method to obtain the amorphous multi-component tungsten nickel-based alloy.

4. The method for preparing the amorphous multi-component tungsten-nickel-based alloy according to claim 3, characterized in that, In step (1), the ball milling mixing conditions are: argon protection, ball-to-material ratio of 5:1, rotation speed of 200 rpm, and time of 6 hours; the cooling rate of hot isostatic pressing sintering is ≤10℃ / min, and an alloy target with a 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<0.1 μm.

5. The method for preparing the amorphous multi-component tungsten-nickel-based alloy according to claim 3, characterized in that, In step ①, the conditions for chemical mechanical polishing are: using diamond polishing slurry, with a surface roughness Ra < 0.05 μm; the conditions for ultrasonic cleaning are: sequentially cleaning in acetone, ethanol, and deionized water for 10 minutes each; and the conditions for ion etching are: Ar... + Bombardment, energy 200 eV, beam current 50 mA, 5 minutes; plasma activation conditions: O2 atmosphere, 50 W RF power treatment for 30 seconds.

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

7. The method for preparing the amorphous multi-component tungsten-nickel-based alloy according to claim 3, characterized in that, In step ③, the RF sputtering power is 200 W, the substrate temperature is 80℃, the Ar flow rate is 25 sccm, and the vacuum degree is 5×10⁻⁶. -5 Pa, deposition rate of 1 nm / s, time of 2.5-3.5 hours.

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

9. An application of the amorphous multi-component tungsten-nickel-based alloy according to claim 1 or 2, characterized in that, Amorphous tungsten-nickel-based electromagnetic shielding coating for microwave ceramic substrates used in 5G communication base stations.

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

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