Corrosion-resistant multi-element composite non-ferrous metal material and method for manufacturing the same

Abstract

This invention discloses a corrosion-resistant multi-component composite non-ferrous metal material and its preparation method, comprising the following components: Base material: aluminum as the base, containing zinc, magnesium, copper, and manganese by mass percentage; zinc 10%-15%, magnesium 2%-3%, copper 1-1.5%, manganese 0.3%-0.8%; Reinforcing material: a mixture of aluminum oxide and titanium diboride particles; aluminum oxide particle size 30nm-100nm, titanium diboride particle size 0.5-2μm; Passivating material: a composite oxide film of cerium dioxide and molybdenum trioxide, with a thickness of 50nm-200nm. The material of this invention exhibits a two-order-of-magnitude reduction in self-corrosion current density, indicating a significantly enhanced protective passivation film. The critical pitting potential is far higher than the threshold value for industrial applications. The elongation of the metal is significantly improved, resolving the contradiction of low plasticity in high-strength materials. Furthermore, the fatigue limit is improved, making it suitable for dynamic load environments. The low porosity further ensures the material's stability.

Description

Technical Field

[0001] This invention relates to the field of non-ferrous metal materials technology, and in particular to a corrosion-resistant multi-component composite non-ferrous metal material and its preparation method. Background Technology

[0002] Non-ferrous metals, in a narrow sense, also known as non-ferrous metals, refer to all metals other than iron and iron-based alloys. They can be divided into heavy metals, light metals, precious metals, and rare metals. In a broader sense, non-ferrous metals also include non-ferrous alloys, which are alloys composed of one or more other elements added to a non-ferrous metal matrix.

[0003] Traditional single-phase metals containing , Pitting corrosion is prone to occur in the medium; binary alloys sacrifice strength / toughness balance, resulting in high sensitivity to stress corrosion cracking; composite materials have poor interfacial compatibility, which exacerbates galvanic corrosion. Therefore, we propose a corrosion-resistant multi-component composite non-ferrous metal material and its preparation method to solve the above problems. Summary of the Invention

[0004] The purpose of this invention is to provide a corrosion-resistant multi-component composite non-ferrous metal material and its preparation method, so as to solve the problems mentioned in the background art.

[0005] The above-mentioned technical objective of the present invention is achieved through the following technical solution: A corrosion-resistant multi-component composite non-ferrous metal material, characterized in that it comprises the following components: Base material: Based on aluminum, containing zinc, magnesium, copper, and manganese by mass percentage; Reinforcing material: A mixture of aluminum oxide and titanium diboride particles; Passivation material: Cerium dioxide and molybdenum trioxide are combined to form an oxide film with a thickness of 50nm-200nm.

[0006] Furthermore, the reference material contains: zinc 10%-15%, magnesium 2%-3%, copper 1-1.5%, and manganese 0.3%-0.8%.

[0007] Furthermore, in the reinforcing material: aluminum oxide has a particle size of 30nm-100nm, and titanium diboride has a particle size of 0.5-2μm.

[0008] Furthermore, in the passivation material, the ratio of cerium atoms to molybdenum atoms is 1.5-2.5:1.

[0009] Furthermore, the mass ratio of the aluminum oxide to the titanium diboride is 1:0.8-1.2.

[0010] This invention also provides a method for preparing a corrosion-resistant multi-component composite non-ferrous metal material, comprising the following steps: Step 1: Prepare zinc, magnesium, copper and manganese pre-alloyed powders with a particle size of 30μm-40μm by aerosol method; Step 2: Mix the pre-alloyed powder with aluminum oxide, titanium diboride and cerium molybdenum precursors by ball milling. Ball milling parameters: argon protection, ball-to-material ratio 10:1, rotation speed 350rpm-450rpm, time 4h-6h. Step 3: Vacuum hot pressing sintering: 630-670℃, 20-30MPa, holding time 1.5-2.5h; Step 4: Multi-stage aging treatment: Hold at 115-125℃ for 6-10 hours, then water quench at 165-175℃ for 14-18 hours.

[0011] Furthermore, in step 2, the amount of the cerium-molybdenum precursor added is 0.5%-1.5% of the total mass.

[0012] Furthermore: In step 3, the heating program is as follows: heat to 400℃ at 10℃ / min-15℃ / min and hold for 0.5h, then heat to the target temperature at 5℃ / min-8℃ / min.

[0013] Furthermore: In step 4, the water quenching rate is ≤20℃ / s.

[0014] In summary, the present invention has the following beneficial effects: The self-corrosion current density of the material of this invention is reduced by two orders of magnitude, indicating that the protective effect of the passivation film of the material is significantly enhanced. The critical pitting potential is much higher than the threshold value for industrial applications. The elongation of the metal is significantly improved, which solves the contradiction of low plasticity in high-strength materials. Furthermore, the fatigue limit is improved, making it suitable for dynamic load environments. The low porosity further ensures the stability of the material. Attached Figure Description

[0015] Figure 1 This is a schematic diagram of the processing flow of the present invention; Figure 2 This is a schematic diagram of the metallographic structure of the cross-section of the material of the present invention; Figure 3 This is a schematic diagram illustrating the synergistic protection of the composite oxide film and reinforcing particles on the surface of the material of this invention. Detailed Implementation

[0016] The present invention will be further described in detail below with reference to the accompanying drawings.

[0017] In the description of this invention, it should be understood that the terms "upper", "lower", "left", "right", "front", "rear", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0018] Example 1, referring to Figure 1-3 A corrosion-resistant multi-component composite non-ferrous metal material, comprising the following components: The pre-alloyed powder composition (wt%) is: Zn 12.0%, Mg 2.5%, Cu 1.2%, Mn 0.6%, Al balance, and the purity of the raw materials is preferably not less than 99.9%.

[0019] In the melt alloying stage, aluminum raw materials are heated to molten state and zinc, magnesium, copper and manganese are added sequentially, while the melt temperature is controlled at about 780℃ and the melt superheat is controlled at 120℃-160℃. Subsequently, gas atomization is carried out under inert atmosphere protection, using argon atomization at an atomization pressure of 8.0±0.2MPa, and pre-alloyed powder with a particle size of about 35μm is obtained after sieving.

[0020] In the reinforcing phase, nano-alumina is preferably the γ phase with a particle size of 50±10nm; titanium diboride is hexagonal with a particle size of 0.8±0.2μm, and the mass ratio of alumina to titanium diboride is preferably 1:1.0.

[0021] The cerium-molybdenum precursor can be prepared by Ce(NO3)3·6H2O and (NH4)6Mo7O24·4H2O, with a preferred molar ratio of 2:1. The preferred solvent is anhydrous ethanol, and the concentration can be 150 g / L.

[0022] The ball milling process uses a planetary high-energy ball mill with a ball-to-material ratio of 10:1, a rotation speed of 400±10 rpm, and a time of 5 hours. To prevent excessive temperature rise during mixing, the process can be paused for 10 minutes every 30 minutes while maintaining argon circulation with an oxygen content not exceeding 10 ppm and a flow rate of 15 L / min.

[0023] Vacuum hot pressing sintering is carried out in a vacuum hot press furnace with a sintering pressure of 25 MPa. The heating stage can be divided into stages: 0 MPa-10 MPa corresponds to 400℃ holding, and 10 MPa-25 MPa corresponds to 650℃ densification holding. The material density measured by Archimedes method is 2.89 g / cm3, and the porosity is 0.28%.

[0024] In the multi-stage aging process, the first stage of aging is carried out at 120℃ for 8 hours, followed by deionized water quenching at a cooling rate of 18℃ / s; the second stage of aging is carried out at 170℃ for 16 hours under nitrogen protection, followed by air cooling to room temperature.

[0025] Corrosion performance was tested using salt spray test (GB / T 10125-2021) and electrochemical test. No obvious pitting corrosion was observed after 5000h of salt spray test, and the mass loss was 0.38mg / cm2. In the electrochemical test, the self-corrosion current density was 1.18×10^-8A / cm2, and the pitting potential was +1.22V vs. SCE (0.5M NaCl, 25℃).

[0026] The mechanical properties were tested according to GB / T 228.1-2021 tensile test, with a tensile strength of 502 MPa, an elongation of 19.2%, and a fatigue limit of 212 MPa.

[0027] Example 2 differs from Example 1 in that the pre-alloyed powder composition (wt%) is: Zn 10.0%, Mg 2.0%, Cu 1.0%, Mn 0.3%, Al balance, and the raw material purity is preferably not less than 99.9%. Example 3 differs from Example 1 in that the pre-alloyed powder composition (wt%) is: Zn 15.0%, Mg 3.0%, Cu 1.5%, Mn 0.8%, Al balance, and the purity of the raw materials is preferably not less than 99.9%.

[0028] I. Setting up the experiment Raw material preparation: Pre-alloyed powder: composition (wt%): Zn 12.0%, Mg 2.5%, Cu 1.2%, Mn 0.6%, Al balance, and purity ≥99.9%.

[0029] Preparation process: Argon atomization, with a pressure of 8.0±0.2MPa, melt superheat of 200℃, and sieved particle size of 35μm.

[0030] Diffuse-enhanced phase: Nano-alumina: γ phase, particle size 50±10nm, specific surface area 35m² / g; Submicron titanium diboride: hexagonal crystal system, particle size 0.8±0.2μm. Mixing ratio: mass ratio of aluminum oxide to titanium diboride = 1:1.0; Cerium-molybdenum precursor solution: Ce(NO3)3·6H2O : (NH4)6Mo7O 24 ·4H2O = 2:1; Solvent: Anhydrous ethanol with a purity ≥99.5% and a concentration of 150 g / L.

[0031] Composite powder Ball milling equipment: Planetary high-energy ball mill: Parameters: ball-to-material ratio: 10:1, rotation speed: 400±10 rpm; time: 5h, with a 10-minute pause every 30 minutes to prevent overheating, argon gas circulation, during which the oxygen content is ≤10ppm, and the flow rate is 15L / min; Vacuum hot pressing sintering: The equipment adopts a vacuum hot pressing furnace with a pressure of 25MPa and staged loading: 0MPa to 10MPa at 400℃, and 10MPa to 25MPa at 650℃. Densification effect: The density measured by Archimedes method is 2.89g / cm³, and the porosity is 0.28%.

[0032] Multi-stage aging treatment: First stage aging: 120℃×8h, using a box-type resistance furnace with a temperature control accuracy of ±1℃, followed by water quenching with deionized water at a cooling rate of 18℃ / s; Second stage aging: 170℃×16h, with nitrogen protection and then air cooling to room temperature.

[0033] II. Performance Testing 1. Corrosion resistance: Salt spray test (GB / T 10125-2021): No pitting corrosion after 5000h, mass loss 0.38mg / cm²; Electrochemical testing (PARSTAT 4000): Self-corrosion current density: 1.18 × 10⁻⁶ -8 Pitting potential (A / cm²): +1.22V vs. SCE (0.5M NaCl, 25℃); Mechanical properties: Tensile test (GB / T 228.1-2021): Tensile strength 502MPa, elongation 19.2%, fatigue limit: 212MPa.

[0034] 2. Process parameter boundary verification Variable parameter design: Key Results Comparison: From the above, we can conclude that: the self-corrosion current density of the material of the present invention is reduced by two orders of magnitude, indicating that the protective effect of the passivation film of the material is significantly enhanced, the critical pitting potential is much higher than the threshold value for industrial applications, the elongation of the metal is significantly improved, the contradiction of low plasticity of high-strength materials is resolved, the fatigue limit is improved, it is suitable for dynamic load environments, and the low porosity further ensures the stability of the material.

[0035] This specific embodiment is merely an explanation of the present invention and is not intended to limit the invention. After reading this specification, those skilled in the art can make inventive modifications to this embodiment as needed, but as long as they are within the scope of the claims of the present invention, they are protected by patent law.

Claims

1. A corrosion-resistant multi-component composite non-ferrous metal material, characterized in that, It includes the following components: Base material: Based on aluminum, containing zinc, magnesium, copper, and manganese by mass percentage; Reinforcing material: A mixture of aluminum oxide and titanium diboride particles; Passivation material: Cerium dioxide and molybdenum trioxide are combined to form an oxide film with a thickness of 50nm-200nm.

2. The corrosion-resistant multi-component composite non-ferrous metal material according to claim 1, characterized in that: The reference material contains: zinc 10%-15%, magnesium 2%-3%, copper 1-1.5%, and manganese 0.3%-0.8%.

3. The corrosion-resistant multi-component composite non-ferrous metal material according to claim 1, characterized in that: In the reinforcing material: aluminum oxide has a particle size of 30nm-100nm, and titanium diboride has a particle size of 0.5-2μm.

4. The corrosion-resistant multi-component composite non-ferrous metal material according to claim 1, characterized in that: In the passivation material, the ratio of cerium atoms to molybdenum atoms is 1.5-2.5:

1.

5. The corrosion-resistant multi-component composite non-ferrous metal material according to claim 1, characterized in that: The mass ratio of aluminum oxide to titanium diboride is 1:0.8-1.

2.

6. A method for preparing a corrosion-resistant multi-component composite non-ferrous metal material according to any one of claims 1-5, characterized in that, Includes the following steps: Step 1: Prepare zinc, magnesium, copper and manganese pre-alloyed powders with a particle size of 30μm-40μm by aerosol method; Step 2: Mix the pre-alloyed powder with aluminum oxide, titanium diboride and cerium molybdenum precursors by ball milling. Ball milling parameters: argon protection, ball-to-material ratio 10:1, rotation speed 350rpm-450rpm, time 4h-6h. Step 3: Vacuum hot pressing sintering: 630-670℃, 20-30MPa, holding time 1.5-2.5h; Step 4: Multi-stage aging treatment: Hold at 115-125℃ for 6-10 hours, then water quench at 165-175℃ for 14-18 hours.

7. The method for preparing a corrosion-resistant multi-component composite non-ferrous metal material according to claim 5, characterized in that: In step 2, the amount of the cerium-molybdenum precursor added is 0.5%-1.5% of the total mass.

8. The method for preparing a corrosion-resistant multi-component composite non-ferrous metal material according to claim 5, characterized in that: In step 3, the heating program is as follows: heat to 400℃ at 10℃ / min-15℃ / min and hold for 0.5h, then heat to the target temperature at 5℃ / min-8℃ / min.

9. The method for preparing a corrosion-resistant multi-component composite non-ferrous metal material according to claim 5, characterized in that: In step 4, the water quenching rate is ≤20℃ / s.

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