Amorphous alloy, preparation method thereof and amorphous alloy intelligent wearable component

Abstract

The invention belongs to the technical field of alloys, and discloses an amorphous alloy, a preparation method thereof and an amorphous alloy intelligent wearable component. The chemical composition of the amorphous alloy comprises at least one of Ti, Ni, Fe, Al or Mg. According to the amorphous alloy disclosed by the invention, through specific element types and a specific preparation process, particularly treatment of a spark plasma sintering process (specific sintering temperature and pressure can avoid growth of crystal grains, eliminate holes and densify the amorphous alloy), the prepared amorphous alloy is few in internal defects and high in strength. Furthermore, the raw materials for preparing the amorphous alloy can further comprise an iron base, a titanium base, a nickel base, an aluminum base or a magnesium base, the raw materials are rich in source, and the preparation cost can be reduced.

Description

Technical Field

[0001] The present invention belongs to the technical field of alloys, and in particular relates to an amorphous alloy and a preparation method thereof, and an amorphous alloy intelligent wearable component. Background Art

[0002] Amorphous alloys have a wide range of uses, for example, they can be used in electronic products, specifically, they can be used as the middle frame or bracelet in smart wearable bracelets, watches, and mobile phones. However, in the prior art, amorphous alloys are often prepared by casting. The insufficient cooling rate of the casting method can easily lead to a large number of micropores inside the amorphous alloy, affecting the structural strength and surface finish of the amorphous alloy. For example, the amorphous watches currently in mass production have many sand hole defects after polishing, and the cost is very high.

[0003] In addition, the preparation of amorphous alloys in the existing technology is limited by the types of raw materials. The existing amorphous alloys are mainly zirconium-based and iron-based. Due to the requirements of the casting process on the alloy composition, it is difficult to expand to other metal systems, resulting in too single raw materials, which will increase the preparation cost.

[0004] Therefore, there is an urgent need to provide a new amorphous alloy and a preparation method thereof, wherein the prepared amorphous alloy has fewer internal defects and higher strength. Summary of the invention

[0005] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes an amorphous alloy and a preparation method thereof and an amorphous alloy smart wearable component. The amorphous alloy of the present invention has few internal defects and high strength. Furthermore, the raw materials for preparing the amorphous alloy of the present invention may also include iron-based, titanium-based, nickel-based, aluminum-based or magnesium-based, and the raw material sources are abundant, which is conducive to reducing the preparation cost.

[0006] A first aspect of the present invention provides an amorphous alloy.

[0007] An amorphous alloy, whose chemical composition includes at least one of Ti, Ni, Fe, Al or Mg.

[0008] Preferably, the chemical composition of the amorphous alloy also includes at least one of Zr, Cu, P, C, B, Be, Al, and O.

[0009] Preferably, the chemical composition of the amorphous alloy includes at least one of Ti-Zr-Cu-Ni, Fe-Cu-PCBO, Ti-Zr-Cu-Ni-Be, Cu-Zr-Al, and Zr-Ti-Cu-Ni-Be.

[0010] Among them, iron-based Fe-Cu-PCBO (density ≥7.20 g / cm 3, saturation flux density 1.1T), titanium-based Ti-Zr-Cu-Ni-Be (high elastic modulus and corrosion resistance), and copper-based Cu-Zr-Al (high conductivity).

[0011] Preferably, the amorphous alloy has a chemical formula of Ti 50 Zr 25 Cu 15 Ni 10 or Fe 75 Cu 5 P 8 C 6 B 3 O 3 .

[0012] A second aspect of the present invention provides a method for preparing an amorphous alloy.

[0013] A method for preparing an amorphous alloy comprises the following steps: Weighing a powdered alloy or a single element raw material to obtain a mixed powder, then mixing it with a steel ball, and ball milling it under a protective gas atmosphere to obtain an amorphous alloy powder; Or, weighing a powdered alloy or a single element raw material to obtain a mixed powder, then mixing it with steel balls, ball milling it under a protective gas atmosphere, annealing it, and quenching it in a water bath to obtain the amorphous alloy powder; The amorphous alloy powder is subjected to a spark plasma sintering (SPS) process, wherein the spark plasma sintering process comprises the following steps: Sintering the amorphous alloy powder in a vacuum or protective gas atmosphere to obtain the amorphous alloy; The sintering temperature is 400-600° C., and the sintering pressure is 300-500 MPa.

[0014] Preferably, the holding time at 400-600° C. is 3-10 minutes, more preferably 5-8 minutes.

[0015] Preferably, the particle size of the amorphous alloy powder is 10-80 μm, more preferably 10-50 μm. The particle size of the powder can be controlled by ball milling or sieving.

[0016] Preferably, the powdered alloy or single substance raw material is weighed according to the stoichiometric ratio of each element in the amorphous alloy.

[0017] Preferably, the mass purity of the single substance raw material is not less than 99%, for example, 99.5-99.9%.

[0018] Preferably, the protective gas atmosphere includes a rare gas, such as argon or helium.

[0019] Preferably, the mass ratio of the mixed powder to the steel balls is 4:1 to 1:10.

[0020] Preferably, the ball milling time is 8-20 hours, more preferably 10-19 hours.

[0021] Preferably, the annealing is performed under vacuum conditions.

[0022] Preferably, the annealing temperature is 800-950° C., and the annealing time is 0.5-1.5 hours.

[0023] A third aspect of the present invention provides an application of an amorphous alloy.

[0024] Amorphous alloy smart wearable components, including the above-mentioned amorphous alloy.

[0025] Preferably, the amorphous alloy smart wearable component includes at least one of a smart wearable bracelet, a watch, and a mobile phone.

[0026] Further preferably, the amorphous alloy smart wearable component includes at least one of a smart wearable bracelet, a watch, a middle frame or a watch strap in a mobile phone.

[0027] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The amorphous alloy of the present invention is processed by specific element types and specific preparation processes, especially spark plasma sintering (SPS) process (specific sintering temperature and pressure can avoid grain growth and eliminate pores, and densify the amorphous alloy), so that the prepared amorphous alloy has few internal defects and high strength. Furthermore, the raw materials for preparing the amorphous alloy of the present invention may also include iron-based, titanium-based or nickel-based, and the raw material sources are abundant, which is conducive to reducing the preparation cost.

[0028] (2) The present invention solves the hole problem: through SPS high-pressure rapid densification, the block density reaches more than 98% of the theoretical value, significantly reducing internal defects. Expanded material types: support any alloy system that can be made into amorphous powder (such as titanium-based, copper-based, zirconium-based, etc.), breaking through the limitations of traditional casting components; Performance advantages: titanium-based amorphous case, Vickers hardness ≥ 800 HV, corrosion resistance is better than 316L stainless steel; iron-based amorphous bracelet: magnetic permeability > 200 (1kHz), suitable for smart watch wireless charging module integration. DETAILED DESCRIPTION

[0029] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be pointed out that the following embodiments do not limit the protection scope of the present invention.

[0030] Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0031] Example 1 An amorphous alloy with the chemical formula Ti 50 Zr 25 Cu 15 Ni 10 .

[0032] A method for preparing an amorphous alloy comprises the following steps: Ti 50 Zr 25 Cu 15 Ni 10 The preparation method adopts high-energy ball milling, and the following are the specific preparation steps: (1) Raw material preparation: Use high-purity Ti, Zr, Cu and Ni powders (purity ≥ 99.9%) and weigh the raw material powders of each element according to the stoichiometric ratio; (2) Ball milling process: the raw material powder and steel balls are loaded into a steel can at a weight ratio of 4:1, and sealed under argon protection, and ball milled using a high-energy ball mill for 19 hours. The temperature is kept close to room temperature to prevent overheating, thereby obtaining an amorphous alloy powder; (3) The amorphous alloy powder is subjected to a spark plasma sintering (SPS) process, wherein the spark plasma sintering process comprises the following steps: In an argon atmosphere, amorphous alloy powder is filled into a mold and sintered to obtain an amorphous alloy; The sintering temperature was 500° C., the holding time at 500° C. was 6 minutes, and the sintering pressure was 450 MPa.

[0033] Example 2 An amorphous alloy with the chemical formula Fe 75 Cu 5 P 8 C 6 B 3 O 3 .

[0034] A method for preparing an amorphous alloy comprises the following steps: Fe 75 Cu 5 P 8 C 6 B 3 O 3 The preparation includes mechanical alloying and subsequent heat treatment. The specific steps are as follows: (1) Raw material preparation: Select high-purity Fe, Cu, C, B powders (purity ≥ 99.5%) and phosphorus pentoxide powder, and weigh the raw material powders of each element according to the stoichiometric ratio; (2) Mechanical alloying: the raw material powders are loaded into a stainless steel tank, carbide balls are added as grinding media, the ball-to-material ratio is 10:1, high-energy ball milling is performed under the protection of an inert gas (such as argon) for 10 hours, and 1 wt.% of stearic acid is added as a process control agent to reduce cold welding; (3) Heat treatment: The powder obtained by the treatment in step (2) is encapsulated in a quartz tube and annealed under vacuum conditions for 1 hour at a temperature of 950°C. After annealing, it is rapidly quenched in a water bath to fix the amorphous structure, thereby obtaining an amorphous alloy powder; (4) The amorphous alloy powder is subjected to a spark plasma sintering (SPS) process. The spark plasma sintering process comprises the following steps: In an argon atmosphere, amorphous alloy powder is filled into a mold and sintered to obtain an amorphous alloy; The sintering temperature was 580° C., the holding time at 580° C. was 5 minutes, and the sintering pressure was 380 MPa.

[0035] Comparative Example 1 Compared with Example 1, the difference of Comparative Example 1 is that when weighing Cu and Ni powders, the amount used in Comparative Example 1 is halved, and the other processes are the same as those of Example 1.

[0036] Comparative Example 2 Compared with Example 1, the difference of Comparative Example 2 is that the sintering temperature of Comparative Example 2 is 650° C., the holding time at 650° C. is 6 minutes, the sintering pressure is 550 MPa, and the other processes are the same as those of Example 1.

[0037] Product effect testing The amorphous alloys prepared in Example 1-2 and Comparative Example 1-2 were tested for tensile strength (tested in accordance with GB / T 228.1-2021), yield strength (tested in accordance with GB / T 228.1-2021), elongation and hardness (tested in accordance with GB / T4340.1-2009), and the results are shown in Table 1.

[0038] Table 1 It can be seen from Table 1 that the amorphous alloy prepared in the embodiment has better mechanical strength than that in the comparative example.

[0039] Application Example 1 The amorphous alloy of Example 1 is used to prepare a watch case, and the process is as follows: Amorphous alloy → CNC (numerical control machining) rough machining → CNC finishing → surface pretreatment → mechanical + manual polishing → cleaning and drying → PVD (physical vapor deposition) pretreatment → PVD coating → inspection → finished product storage.

[0040] CNC Rough Machining: Equipment: Five-axis CNC milling machine (such as DMG Mori) Tool: coated carbide tool; Feed: F = 0.03 mm / tooth; Speed: S = 8000 rpm; Cooling method: oil mist cooling or dry cutting to avoid crystallization caused by high temperature; CNC finishing: Finishing of critical surfaces (such as shell edges); Surface roughness is controlled at Ra ≤ 0.4 μm; Control the surface to be free of chatter marks, chipping, white spots and cracks; Polishing stage: Pre-polishing process: manual grinding + belt sander; Sandpaper grit: #400 → #800 → #1200; Purpose: Remove CNC lines and chamfer transitions; Fine polishing (mirror) tools: cloth wheel + polishing wax + angle grinder / crane grinder; Polishing media particle size: ① 3μm alumina paste (priming); ② 1μm metal polishing wax (middle); ③ 0.3μm diamond paste (mirror surface); Each step takes 12 minutes to polish; Surface effect: Ra ≤ 0.05 μm, no ripples, black spots, or dead corners; Detection: 100% manual visual inspection + reflection test to ensure there are no defects such as "pitting" and "uneven brightness"; Cleaning before PVD coating, ultrasonic cleaning process: alkaline cleaning agent (10 minutes) → deionized water rinse → anhydrous ethanol rinse; Temperature: normal temperature; Frequency: 40kHz Drying treatment: Dry in a vacuum drying oven for 30 minutes, temperature 60°C, pressure <10 Pa; Plasma cleaning: Ar gas low-pressure discharge cleaning in the vacuum chamber for 5 minutes; Function: Remove surface organic pollutants and enhance PVD film adhesion; Result: Case density 7.4 g / cm 3 , mirror polishing effect.

[0041] Application Example 2 A smart watch bracelet comprises the amorphous alloy prepared in Example 2.

[0042] This invention is the first to adapt SPS technology to watch parts, supporting non-traditional amorphous systems such as titanium-based and copper-based; It can realize one-time molding of complex structures (such as hollow dials), and combined with post-processing technology, it can meet the dual needs of high-end watches for aesthetics and functionality.

[0043] The technical solution of the present invention can be applied to mobile phone frames, smart wearable devices and luxury brand mechanical watches, promoting the popularization of amorphous alloys in the field of precision manufacturing. It is expected that the mass production cost will be reduced by 20% compared with the traditional process, and the material utilization rate will be increased to more than 95%.

Claims

1. An amorphous alloy, characterized in that: Its chemical composition includes at least one of Ti, Ni, Fe, Al or Mg.

2. The amorphous alloy according to claim 1, characterized in that: The chemical composition of the amorphous alloy also includes at least one of Zr, Cu, P, C, B, Be, and O.

3. The amorphous alloy according to claim 2, characterized in that: The chemical composition of the amorphous alloy includes at least one of Ti-Zr-Cu-Ni, Fe-Cu-PCBO, Ti-Zr-Cu-Ni-Be, Cu-Zr-Al, and Zr-Ti-Cu-Ni-Be.

4. The amorphous alloy according to claim 2, characterized in that: The amorphous alloy has a chemical formula of Ti 50 Zr 25 Cu 15 Ni 10 or Fe 75 Cu5P8C6B3O3.

5. The method for preparing an amorphous alloy according to any one of claims 1 to 4, characterized in that: The following steps are involved: Weighing a powdered alloy or a single element raw material to obtain a mixed powder, then mixing it with a steel ball, and ball milling it under a protective gas atmosphere to obtain an amorphous alloy powder; Or, weighing a powdered alloy or a single element raw material to obtain a mixed powder, then mixing it with steel balls, ball milling it under a protective gas atmosphere, annealing it, and quenching it in a water bath to obtain the amorphous alloy powder; The amorphous alloy powder is subjected to a spark plasma sintering process, wherein the spark plasma sintering process comprises the following steps: Sintering the amorphous alloy powder in a vacuum or protective gas atmosphere to obtain the amorphous alloy; The sintering temperature is 400-600° C., and the sintering pressure is 300-500 MPa.

6. The preparation method according to claim 5, characterized in that: The holding time at 400-600°C is 3-10 minutes.

7. The preparation method according to claim 5, characterized in that: The particle size of the amorphous alloy powder is 10-80 μm.

8. The preparation method according to claim 5, characterized in that: The protective gas atmosphere includes a rare gas; and / or the mass ratio of the mixed powder to the steel balls is 4:1 to 1:

10.

9. The preparation method according to claim 5, characterized in that: The ball milling time is 8-20 hours; and / or the annealing temperature is 800-950° C., and the annealing time is 0.5-1.5 hours.

10. Amorphous alloy smart wearable component, characterized in that: The amorphous alloy comprises the amorphous alloy described in any one of claims 1 to 4.

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