阅读说明：本技术 改性纳米粒子弥散强化铜合金及其制备方法和应用、电子元件、机械元件 (Modified nano particle dispersion strengthened copper alloy, preparation method and application thereof, electronic component and mechanical component ) 是由 杨树峰 王田田 李京社 郭皓 刘威 袁航 于 2020-08-07 设计创作，主要内容包括：本发明提供了一种改性纳米粒子弥散强化铜合金及其制备方法和应用、电子元件、机械元件。该改性纳米粒子弥散强化铜合金包括铜和分散在铜内的改性纳米粒子,所述改性纳米粒子包括纳米粒子和包覆在纳米粒子表面的聚多巴胺。该铜合金的制备方法包括以下步骤：(a)将纳米粒子和盐酸多巴胺在碱性条件下反应,得到改性纳米粒子；(b)将改性纳米粒子加入到铜液中,混合均匀,然后浇铸,得到所述改性纳米粒子弥散强化铜合金。上述制备方法工艺科学、简单,无需使用特殊的机械设备,易于实现,生产成本低,能大大缩短生产工艺流程,应用范围广,满足使用要求,实用性强,得到的效果明显且稳定,适合工业化大规模生产。(The invention provides a modified nano particle dispersion strengthened copper alloy, a preparation method and application thereof, an electronic component and a mechanical component. The modified nanoparticle dispersion strengthened copper alloy comprises copper and modified nanoparticles dispersed in the copper, wherein the modified nanoparticles comprise nanoparticles and polydopamine coated on the surfaces of the nanoparticles. The preparation method of the copper alloy comprises the following steps: (a) reacting the nanoparticles with dopamine hydrochloride under an alkaline condition to obtain modified nanoparticles; (b) adding the modified nanoparticles into the copper liquid, uniformly mixing, and then casting to obtain the modified nanoparticle dispersion strengthened copper alloy. The preparation method has the advantages of scientific and simple process, no need of special mechanical equipment, easy realization, low production cost, capability of greatly shortening the production process flow, wide application range, capability of meeting the use requirement, strong practicability, obvious and stable obtained effect and suitability for industrial large-scale production.)

1. The modified nanoparticle dispersion strengthened copper alloy is characterized by comprising copper and modified nanoparticles dispersed in the copper, wherein the modified nanoparticles comprise nanoparticles and polydopamine coated on the surfaces of the nanoparticles.

2. The modified nanoparticle dispersion strengthened copper alloy of claim 1, wherein the nanoparticles comprise inorganic nanoparticles;

preferably, the inorganic nanoparticles include MgO, Al₂O₃、Y₂O₃TiN or SiO₂At least one of (1).

3. The modified nanoparticle dispersion strengthened copper alloy according to claim 1, wherein the nanoparticles have an average particle size of less than 30nm, preferably 10-30 nm;

preferably, the thickness of the polydopamine coated on the surface of the nanoparticle is 5-15 nm.

4. The modified nanoparticle dispersion strengthened copper alloy according to any one of claims 1 to 3, wherein the content of the modified nanoparticles is 0.01 to 0.08 wt%, preferably 0.01 to 0.05 wt%.

5. The method of preparing the modified nanoparticle dispersion-strengthened copper alloy of any one of claims 1 to 4, comprising the steps of: (a) reacting the nanoparticles with dopamine hydrochloride under an alkaline condition to obtain modified nanoparticles; (b) adding the modified nanoparticles into the copper liquid, uniformly mixing, and then casting to obtain the modified nanoparticle dispersion strengthened copper alloy.

6. The method according to claim 5, wherein in the step (a), the reaction conditions include at least one of the following conditions: the reaction time is 15-20h, or the pH is 7.5-9;

preferably, in the step (a), the mass ratio of the nanoparticles to the dopamine hydrochloride is (4-6): (5-10), preferably (4-5): (8-10).

7. The method of claim 5, wherein step (a) comprises: mixing the nano particles, dopamine hydrochloride and an alkaline solution, and then reacting to obtain modified nano particles;

preferably, the alkaline solution comprises tris buffer;

preferably, the concentration of the tris buffer solution is 0.02-0.08 mol/L;

preferably, in step (a), the reaction is carried out under magnetic stirring, preferably at a stirring speed of 150 and 250 rpm.

8. The preparation method according to any one of claims 5 to 7, wherein the step (b) further comprises the steps of encapsulating the modified nanoparticles in a copper tube, and adding the copper tube to the copper solution;

preferably, in the step (b), the molten copper is obtained by melting in a vacuum induction melting furnace;

preferably, step (b) comprises: packaging the modified nanoparticles in a copper pipe, then placing the copper pipe in a charging hopper of a vacuum induction smelting furnace, vacuumizing, heating and melting a copper block, adding the modified nanoparticles into copper liquid after the copper block in the vacuum induction smelting furnace is completely melted, electromagnetically stirring, and then sequentially preserving heat, cooling and casting to obtain the copper alloy.

9. Use of the modified nanoparticle dispersion strengthened copper alloy of any one of claims 1 to 4 or obtained by the method of any one of claims 5 to 8 for the manufacture of an electronic component;

or, use of the modified nanoparticle dispersion strengthened copper alloy of any one of claims 1 to 4 or obtained by the method of any one of claims 5 to 8 for the manufacture of a mechanical component.

10. An electronic component comprising the modified nanoparticle dispersion-strengthened copper alloy according to any one of claims 1 to 4 or the modified nanoparticle dispersion-strengthened copper alloy obtained by the method according to any one of claims 5 to 8;

or, a mechanical component comprising a modified nanoparticle dispersion strengthened copper alloy according to any one of claims 1 to 4 or a modified nanoparticle dispersion strengthened copper alloy obtainable by a method according to any one of claims 5 to 8.

Technical Field

The invention relates to the field of nonferrous metals, in particular to a modified nanoparticle dispersion strengthened copper alloy, a preparation method and application thereof, an electronic component and a mechanical component.

Background

Copper and copper alloys have excellent thermal and electrical conductivity, ductility, corrosion resistance and the like, and are widely applied to the fields of electronics, electrical and mechanical manufacturing, aerospace, transportation and the like. In recent years, with the rapid development of science and technology, higher requirements are put forward on the comprehensive performance of copper and copper alloy in various fields. The method has the advantages that the second-phase reinforced particles are introduced into the matrix to block dislocation movement, so that the method becomes one of effective methods for improving material performance, and is widely applied to the preparation of dispersion-reinforced copper alloy, wherein the size, distribution, high-temperature stability, interface bonding with the matrix and the like of the reinforced phase play a key role in the performance of the material.

The preparation methods of the dispersion strengthened copper alloy are various, such as an internal oxidation method, a carbothermic method, a reaction jet deposition method, a mechanical alloying method and the like, wherein the internal oxidation method and the mechanical alloying method are widely applied, the production process is mature, but some defects still exist. For example, patent CN 107557609 a discloses a single-phase nano-alumina particle dispersion strengthened copper alloy and a preparation method thereof. The method takes water atomized or nitrogen atomized Cu-Al alloy powder as a raw material, and obtains the single-phase nano-alumina particle dispersion strengthened copper alloy with excellent comprehensive performance through the working procedures of liquid phase reaction synthesis, hydrogen drying, pressing, densification, finish machining and the like. However, the processes of water atomization or nitrogen atomization powder preparation, ball milling, hot isostatic pressing densification treatment and the like involved in the method greatly increase the workload and complexity, the production period is long, the cost is high, the raw materials are easy to be polluted, and the industrial production is difficult to realize. Patent CN 107675012A discloses a method for dispersion strengthening copper by titanium nitride. The method adopts an atomization method to prepare copper-titanium alloy powder, then carries out nitridation treatment on the copper-titanium alloy powder, utilizes high-temperature diffusion to generate titanium nitride in situ in the copper-titanium alloy powder, and finally obtains the nano titanium nitride dispersion strengthened copper through cold isostatic pressing, sintering-hot extrusion and the like. However, the nitriding process involved in this method is difficult to control, and sintering-hot extrusion is difficult to obtain a fully dense material, and is difficult to use in industrial production due to low productivity and high cost. Patent CN 110029246 a discloses a preparation method of a yttrium oxide dispersion strengthened copper alloy. The patent relates to oxidizing a Cu-Y amorphous master alloy in an oxidizing atmosphere, and directly smelting to obtain Y₂O₃And (3) dispersion strengthening the copper alloy. In the method, the oxidation of the Cu-Y amorphous is difficult to determine the oxygen partial pressure, oxidation temperature, oxidation time and oxidation degree, and slight changes may be caused to the Cu-Y amorphous₂O₃The preparation of the catalyst causes great influence, the technological process is difficult to control, and the industrial popularization is difficult to realize.

The method has the problems of complicated production procedures, difficult operation, long production period, extremely high requirements on production process control, difficult control of product quality, high production cost and the like, is difficult to carry out large-scale production, and limits the further development, popularization and application of the dispersion strengthened copper alloy.

In view of the above, the present invention is particularly proposed.

Disclosure of Invention

The first purpose of the invention is to provide a modified nanoparticle dispersion strengthened copper alloy which has good mechanical strength.

The second purpose of the invention is to provide a preparation method of the modified nanoparticle dispersion strengthened copper alloy, which has the advantages of scientific and simple process, no need of special mechanical equipment, easy realization, low production cost, capability of greatly shortening the production process flow, wide application range, capability of meeting the use requirement, strong practicability, obvious and stable obtained effect and suitability for industrial large-scale production.

The third purpose of the invention is to provide an application of the modified nano particle dispersion strengthened copper alloy.

A fourth object of the present invention is to provide an electronic component or a mechanical component.

In order to achieve the above purpose of the present invention, the following technical solutions are adopted:

in a first aspect, the invention provides a modified nanoparticle dispersion strengthened copper alloy, which comprises copper and modified nanoparticles dispersed in the copper, wherein the modified nanoparticles comprise nanoparticles and polydopamine coated on the surfaces of the nanoparticles.

As a further preferred technical solution, the nanoparticles comprise inorganic nanoparticles;

preferably, the inorganic nanoparticles include MgO, Al₂O₃、Y₂O₃TiN or SiO₂At least one of (1).

As a further preferred technical solution, the average particle diameter of the nanoparticles is less than 30nm, preferably 10-30 nm;

preferably, the thickness of the polydopamine coated on the surface of the nanoparticle is 5-15 nm.

As a further preferable technical scheme, the content of the modified nano particles is 0.01-0.08 wt%, and preferably 0.01-0.05 wt%.

In a second aspect, the invention provides a preparation method of the modified nanoparticle dispersion strengthened copper alloy, which comprises the following steps: (a) reacting the nanoparticles with dopamine hydrochloride under an alkaline condition to obtain modified nanoparticles; (b) adding the modified nanoparticles into the copper liquid, uniformly mixing, and then casting to obtain the modified nanoparticle dispersion strengthened copper alloy.

As a further preferred technical solution, in the step (a), the reaction conditions include at least one of the following conditions: the reaction time is 15-20h, or the pH is 7.5-9;

preferably, in the step (a), the mass ratio of the nanoparticles to the dopamine hydrochloride is (4-6): (5-10), more preferably (4-5): (8-10).

As a further preferred embodiment, the step (a) comprises: mixing the nano particles, dopamine hydrochloride and an alkaline solution, and then reacting to obtain modified nano particles;

preferably, the alkaline solution comprises tris buffer;

preferably, the concentration of the tris buffer solution is 0.02-0.08 mol/L;

preferably, in step (a), the reaction is carried out under magnetic stirring, preferably at a stirring speed of 150 and 250 rpm.

As a further preferred technical scheme, the step (b) further comprises the steps of firstly encapsulating the modified nanoparticles in a copper tube and then adding the copper tube into the copper liquid;

preferably, in the step (b), the molten copper is obtained by melting in a vacuum induction melting furnace;

preferably, step (b) comprises: packaging the modified nanoparticles in a copper pipe, then placing the copper pipe in a charging hopper of a vacuum induction smelting furnace, vacuumizing, heating and melting a copper block, adding the modified nanoparticles into copper liquid after the copper block in the vacuum induction smelting furnace is completely melted, electromagnetically stirring, and then sequentially preserving heat, cooling and casting to obtain the copper alloy.

In a third aspect, the invention provides an application of the modified nanoparticle dispersion strengthened copper alloy or the modified nanoparticle dispersion strengthened copper alloy obtained by the method in preparing an electronic element;

or the modified nano particle dispersion strengthened copper alloy obtained by the method is applied to the preparation of mechanical elements.

In a fourth aspect, the invention provides an electronic component, which comprises the modified nanoparticle dispersion strengthened copper alloy or the modified nanoparticle dispersion strengthened copper alloy obtained by the method;

or, a mechanical component comprising the modified nanoparticle dispersion strengthened copper alloy or the modified nanoparticle dispersion strengthened copper alloy obtained by the method.

Compared with the prior art, the invention has the beneficial effects that:

the modified nano particle dispersion strengthened copper alloy provided by the invention utilizes specific modified nano particles to carry out dispersion strengthening on copper, the specific surface area of the nano particles is large, the reaction activity is high, and the nano particles have good dispersion distribution, high-temperature stability and wettability after being coated by polydopamine, so that the copper alloy has good mechanical strength.

The preparation method of the modified nanoparticle dispersion strengthened copper alloy provided by the invention is scientific and simple in process, firstly, dopamine hydrochloride is oxidized to form polydopamine under an alkaline condition by using a surface coating method and is coated on the surface of the nanoparticle, so that the modified nanoparticle has better high-temperature stability, wettability and dispersion distribution, the effect of dispersion strengthening copper alloy can be achieved, and the product quality is easy to control; however, if the nanoparticles are directly used, the nanoparticles are easy to agglomerate and grow at high temperature due to the characteristics of large specific surface area and high reaction activity, so that the nanoparticles cannot be uniformly dispersed, and the effect of dispersion-strengthened copper alloy is poor. In addition, compared with the original nanoparticles, the modified nanoparticles prepared by the method have small particle size change, can be better used as heterogeneous nucleation points in copper liquid, are dispersed and distributed in the copper liquid, and strengthen the copper alloy. In addition, the method utilizes the externally added modified nano particles to disperse and reinforce the copper alloy, overcomes the defects of complicated working procedures, difficult operation, long production period, high cost and the like existing in the traditional methods of internal oxidation, carbothermic reduction, mechanical alloying and the like for preparing the dispersion strengthened copper alloy, is easy to control the adding amount of the modified nano particles, simple to operate, free from using special mechanical equipment, easy to realize, low in production cost, capable of greatly shortening the production process flow, wide in application range, capable of meeting the use requirement, strong in practicability, obvious and stable in obtained effect, and suitable for industrial large-scale production.

Drawings

Fig. 1 is a flow chart of a preparation process of the modified nanoparticle dispersion strengthened copper alloy in example 5.

Detailed Description

Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.

According to one aspect of the invention, there is provided in at least one embodiment a modified nanoparticle dispersion strengthened copper alloy comprising copper and modified nanoparticles dispersed within the copper, the modified nanoparticles comprising nanoparticles and polydopamine coated on the surface of the nanoparticles.

The modified nano particle dispersion strengthened copper alloy utilizes specific modified nano particles to carry out dispersion strengthening on copper, the specific surface area of the nano particles is large, the reaction activity is high, and the modified nano particle dispersion strengthened copper alloy has good dispersion distribution, high-temperature stability and wettability after being coated by polydopamine, so that the copper alloy has good mechanical strength.

It should be noted that:

the "copper interior" means the interior of a copper block, not the interior of copper atoms, and the modified nanoparticles are dispersed in a matrix formed of copper atoms and together constitute a copper alloy.

The above-mentioned "dispersion" means a state in which the modified nanoparticles are uniformly or non-uniformly distributed in copper.

In a preferred embodiment, the nanoparticles comprise inorganic nanoparticles. The inorganic nanoparticles refer to nano-sized inorganic particles.

Preferably, the inorganic nanoparticles include MgO, Al₂O₃、Y₂O₃TiN or SiO₂At least one of (1). The nanoparticles include but are not limited to MgO, Al₂O₃，Y₂O₃，TiN，SiO₂MgO and Al₂O₃Combination of (A) and (B), Y₂O₃And TiN, TiN and SiO₂Combination of (A), MgO, Al₂O₃And Y₂O₃A combination of (A) or (Y)₂O₃TiN and SiO₂Combinations of (a), (b), and the like. The nano particles have high melting point and good high-temperature stability, and are favorable for further improving the mechanical strength of the copper alloy.

Preferably, the nanoparticles have an average particle size of less than 30nm, preferably 10-30 nm. The average particle diameter is, for example, 5, 10, 15, 20, 25 or 30 nm. When the average particle size is less than 30nm, the distribution uniformity of the nanoparticles in the copper is better, and the reinforcing effect on the copper alloy is better. When the average particle diameter is too large, the strength of the particles is lowered, and the strength of the copper alloy is poor.

The average particle size refers to a linear average particle size, and is measured by a laser particle sizer.

Preferably, the thickness of the polydopamine coated on the surface of the nanoparticle is 5-15 nm.

In a preferred embodiment, the modified nanoparticles are present in an amount of 0.01 to 0.08 wt.%, preferably 0.01 to 0.05 wt.%. The content refers to the mass percentage of the modified nanoparticles in the copper alloy. The above amount is typically, but not limited to, 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, or 0.08 wt%. The content of the modified nanoparticles should not be too high or too low, particles are easy to agglomerate when the content of the modified nanoparticles is too high, the reinforcing effect is further poor, and reinforcing phases are too small when the content of the modified nanoparticles is too low, so that the reinforcing effect is also reduced. When the content of the modified nanoparticles is within the above range, the mechanical strength of the resulting copper alloy is the highest and the copper alloy is not contaminated.

According to another aspect of the invention, a preparation method of the modified nanoparticle dispersion strengthened copper alloy is provided, which comprises the following steps: (a) reacting the nanoparticles with dopamine hydrochloride under an alkaline condition to obtain modified nanoparticles; (b) adding the modified nanoparticles into the copper liquid, uniformly mixing, and then casting to obtain the modified nanoparticle dispersion strengthened copper alloy.

The preparation method is scientific and simple in process, firstly, dopamine hydrochloride is oxidized to form polydopamine under the alkaline condition by using a surface coating method and is coated on the surfaces of nanoparticles, so that the modified nanoparticles have good high-temperature stability, wettability and dispersion distribution, the effect of dispersion strengthening of copper alloy can be achieved, and the product quality is easy to control; however, if the nanoparticles are directly used, the nanoparticles are easy to agglomerate and grow at high temperature due to the characteristics of large specific surface area and high reaction activity, so that the nanoparticles cannot be uniformly dispersed, and the effect of dispersion-strengthened copper alloy is poor. In addition, compared with the original nanoparticles, the modified nanoparticles prepared by the method have small particle size change, can be better used as heterogeneous nucleation points in copper liquid, are dispersed and distributed in the copper liquid, and strengthen the copper alloy. In addition, the method utilizes the externally added modified nano particles to disperse and reinforce the copper alloy, overcomes the defects of complicated working procedures, difficult operation, long production period, high cost and the like existing in the traditional methods of internal oxidation, carbothermic reduction, mechanical alloying and the like for preparing the dispersion strengthened copper alloy, is easy to control the adding amount of the modified nano particles, simple to operate, free from using special mechanical equipment, easy to realize, low in production cost, capable of greatly shortening the production process flow, wide in application range, capable of meeting the use requirement, strong in practicability, obvious and stable in obtained effect, and suitable for industrial large-scale production.

It should be noted that: the term "alkaline conditions" as used herein means conditions of pH >7 at 25 ℃.

In a preferred embodiment, in step (a), the reaction conditions comprise at least one of the following conditions: the reaction time is 15-20h, or the pH is 7.5-9. The above reaction time is typically, but not limited to, 15, 16, 17, 18, 19 or 20h and the pH is typically, but not limited to, 7.5, 8, 8.5 or 9. When the reaction condition is at least one of the above conditions, the dopamine hydrochloride can be fully oxidized into polydopamine, and the polydopamine is completely coated on the surface of the nano particle.

Preferably, in the step (a), the mass ratio of the nanoparticles to the dopamine hydrochloride is (4-6): (5-10), more preferably (4-5): (8-10). The above mass ratio is typically, but not limited to, 4:5, 4:7, 4:10, 5:5, 5:7, 5:10, 6:5, 6:7, or 6:10, etc. When the mass ratio of the nano particles to the dopamine hydrochloride is in the range, the content of the polydopamine coated on the surfaces of the obtained modified nano particles is reasonable, and the dispersion performance of the modified nano particles is further improved.

In a preferred embodiment, step (a) comprises: mixing the nano particles, dopamine hydrochloride and an alkaline solution, and then reacting to obtain the modified nano particles.

Alternatively, the pH of the above nanoparticles, dopamine hydrochloride and alkaline solution can be adjusted with hydrochloric acid to bring the pH of the mixed solution to a desired range.

Preferably, the alkaline solution comprises tris buffer solution. The alkaline solution has wide sources, and can reduce the production cost of the copper alloy.

Preferably, the concentration of the tris buffer solution is 0.02 to 0.08 mol/L. The concentration of the above buffer solution is typically, but not limited to, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07 or 0.08 mol/L.

The concentration of the trihydroxymethyl aminomethane buffer solution is scientific and reasonable, so that the formed polydopamine can be uniformly coated on the surfaces of the nano particles, the uniformity and consistency of the modified nano particles are improved, the uniformity of all parts in the copper alloy is improved, and the mechanical strength of the copper alloy is further improved. If the concentration is too low, the reaction time is too long; if the concentration is too high, the reaction process is not easy to control, and the product uniformity is poor.

Preferably, in step (a), the reaction is carried out under magnetic stirring, preferably at a stirring speed of 150 and 250 rpm. The term "magnetic stirring" as used herein means stirring with a magnetic stirrer. The magnetic stirring speed is stable, and the temperature control is accurate. The above stirring speed is typically, but not limited to, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240 or 250 rpm.

It is understood that after the reaction in step (a) is finished, the method further comprises the steps of solid-liquid separation and drying in sequence to obtain the modified nanoparticles. The solid-liquid separation can be by filtration and/or centrifugation.

In a preferred embodiment, step (b) further comprises the steps of encapsulating the modified nanoparticles in a copper tube, and adding the copper tube to the copper solution.

Preferably, in the step (b), the molten copper is obtained by melting in a vacuum induction melting furnace. The vacuum induction melting can avoid the oxidation of metal in the melting process, thereby improving the purity of the alloy and having mature and reliable technology.

Preferably, step (b) comprises: packaging the modified nanoparticles in a copper pipe, then placing the copper pipe in a charging hopper of a vacuum induction smelting furnace, vacuumizing, heating and melting a copper block, adding the modified nanoparticles into copper liquid after the copper block in the vacuum induction smelting furnace is completely melted, electromagnetically stirring, and then sequentially preserving heat, cooling and casting to obtain the copper alloy. The process steps are more scientific, the whole melting, mixing, heat preservation and cooling processes can be completed by adopting one device, and the process is smooth, controllable, complete and good in integrity.

According to another aspect of the invention, there is provided a use of the modified nanoparticle dispersion strengthened copper alloy described above in the manufacture of an electronic or mechanical component. The modified nano particle dispersion strengthened copper alloy is applied to the preparation of electronic elements or mechanical elements, and the mechanical properties of the electronic elements or the mechanical elements can be effectively improved.

According to another aspect of the present invention, there is provided an electronic or mechanical component comprising the modified nanoparticle dispersion-strengthened copper alloy described above. The electronic component or the mechanical component comprises the modified nano particle dispersion strengthened copper alloy, so that the electronic component or the mechanical component at least has the advantages of good mechanical property, simple production and low cost.

The present invention will be described in further detail with reference to examples and comparative examples.