CN113215444B - A kind of nanoparticle reinforced TC4 metal powder material and preparation method thereof - Google Patents

Abstract

The invention discloses a nano-particle reinforced TC4 metal powder and a preparation method thereof, belonging to the field of metal powder material preparation. The preparation method of the present invention adopts the molten salt-ultrasonic dispersion combined step to prepare products, and effectively introduces nano-sized solid ceramic particles into the TC4 metal material. The metal powder material prepared by the method has high hardness, high strength, wear resistance and wear resistance. The characteristics of high performance and high performance provide a guarantee of raw materials for expanding the application of TC4-based composite materials in the industrial field. The ceramic particles have a high utilization rate of nanoparticles; Applications of matrix composites in additive manufacturing, hot isostatic pressing and powder metallurgy. The material preparation method of the invention has simple operation steps, high repeatability, safety and environmental protection, and can realize industrialized small-scale production.

Description

A kind of nanoparticle reinforced TC4 metal powder material and preparation method thereof

technical field

The invention relates to the field of metal powder material preparation, in particular to a nano-particle reinforced TC4 metal powder material and a preparation method thereof.

Background technique

Titanium alloy has excellent properties such as low density, high specific strength, high temperature resistance, corrosion resistance, non-magnetic, etc. Its related products are widely used in aviation, aerospace, navigation, medical equipment, thermal power generation and other fields. Among them, TC4 titanium alloy material, as α+β type titanium alloy, has better comprehensive mechanical properties. However, with the change of the external environment, the traditional TC4 titanium alloy is close to its use limit, and it is difficult to meet the increasingly harsh use conditions. Therefore, improving its mechanical properties or improving its mechanical properties under high temperature conditions is a new direction for future research on TC4 matrix composites. At present, the main forming methods of titanium alloy products are powder metallurgy, hot isostatic pressing and additive manufacturing technology, and the main raw material is titanium alloy powder. Therefore, obtaining titanium alloy raw material powder with excellent properties is the premise of preparing high-performance titanium alloy materials.

Ceramic particle reinforced metal matrix composite material refers to a type of metal matrix composite material formed by adding dispersed and distributed reinforced phase ceramic particles to a metal matrix. The reinforcing phase is mainly selected from ceramic particles with high strength, high hardness and high melting point. Due to the relatively low content of reinforcing phase, relatively uniform distribution and fine particles, the composite material basically maintains the original physical properties of the base metal. In addition, the reinforced ceramic particles are dispersed in the metal matrix, and the pinning effect of the particles can effectively hinder the dislocation movement in the metal matrix, so the mechanical properties of the material can be greatly improved. Traditional reinforcement phase materials are dominated by micron or submicron sized particles. Studies have shown that the strengthening effect of nanoparticles with the same mass or volume fraction in the matrix is more obvious than that of traditional micron or submicron sized particles.

Titanium carbide ceramics have excellent properties such as high temperature resistance, high strength, high hardness, high thermal conductivity, low density, and corrosion resistance. Its products are used in petroleum, chemical, microelectronics, automobile, aerospace, aviation, paper, laser, mining and atomic energy industries field has been widely used. Nano-titanium carbide ceramic particles inherit the advantages of titanium carbide ceramics. If nano-titanium carbide ceramic particles are introduced into TC4 powder to prepare nano-titanium carbide ceramics to enhance TC4 powder, the mechanical properties of TC4 powder can be improved, and the expansion of titanium alloy base can be improved. The application of composite materials in the industrial field has positive significance.

SUMMARY OF THE INVENTION

Based on the defects of the prior art, the purpose of the present invention is to provide a preparation method of nano-particle reinforced TC4 metal powder material, which introduces high-strength nano-ceramic material particle titanium carbide into TC4 powder by the method of molten salt-ultrasonic dispersion Among them, the purpose of enhancing the mechanical properties such as hardness and strength of the product can be achieved, and it can ensure a high utilization rate of nanoparticles. The operation steps of the method are simple and controllable, the large-scale production efficiency is high, and the product quality between batches is guaranteed.

In order to achieve the above object, the technical scheme adopted in the present invention is:

A preparation method of nanoparticle-enhanced TC4 metal powder, comprising the following steps:

(1) Mix TC4 metal powder, nano-titanium carbide and inorganic salt evenly, carry out ball milling treatment, and sieve to obtain precursor powder A; the mass ratio of described TC4 metal powder and nano-titanium carbide is 1:0.07～0.35, so The mass ratio of the sum of the mass of TC4 metal powder and nano-titanium carbide to the inorganic salt is: m (TC4 metal powder + nano-titanium carbide): m (inorganic salt)=3～15:85～97;

(2) vacuum heating the precursor powder A described in step (1), and after the powder is melted, the obtained melt is subjected to ultrasonic dispersion treatment, cooled, and the obtained massive solid is pulverized to a powder particle size of less than 5 mm to obtain a precursor Powder B; the vacuum degree during the vacuum heating is less than or equal to 6×10 ^-2 ;

(3) the precursor powder B obtained in step (2) is placed in deionized water to dissolve and stir, then the dissolved suspension is precipitated, and then the upper layer of the suspension is poured out, leaving the bottom black granular material, And repeat this step three times to get bottom mixed solution C;

(4) After the bottom layer mixed solution C obtained in step (3) is subjected to suction filtration and drying, the obtained black powder is sequentially pulverized and sieved to obtain the nanoparticle-enhanced TC4 metal powder.

The nanoparticle-enhanced TC4 metal powder of the present invention is prepared by the method of molten salt-ultrasonic dispersion combination, and the molten salt is used as a dispersion carrier by utilizing the characteristics that the molten TC4 liquid metal, titanium carbide ceramic particles and the molten salt are incompatible with each other. , effectively introduce nano-sized solid ceramic particles into the TC4 metal material, and uniformly disperse the reinforcing material particles in the liquid metal through ultrasonic dispersion. Because titanium carbide has high strength, high hardness, high temperature resistance and small thermal expansion coefficient and other advantages, the metal powder material reinforced and prepared by the method has the characteristics of high hardness, high strength and high wear resistance, which provides a guarantee of raw materials for expanding the application of TC4-based composite materials in the industrial field; at the same time, the nano-titanium carbide particles Reinforcing TC4 powder materials can also expand the application of titanium matrix composites in the fields of additive manufacturing, hot isostatic pressing and powder metallurgy. The material preparation method of the invention has simple operation steps, high repeatability, safety and environmental protection, and can realize industrialized small-scale production.

Preferably, the mass ratio of the TC4 metal powder and the nano-titanium carbide in step (1) is 1:0.2 to 0.35, and the mass ratio of the sum of the mass of the TC4 metal powder and the nano-titanium carbide to the inorganic salt is: m(TC4 Metal powder + nano-titanium carbide): m (inorganic salt)=5～10:95～90.

After many experiments, the inventor found that if the amount of titanium carbide added is too large, it may cause the nanoparticles to agglomerate on the surface of the liquid metal, resulting in a decrease in the efficiency of ultrasonic dispersion; if the amount of titanium carbide is too small, the expected performance enhancement effect cannot be achieved. Under the above ratio, the dispersion uniformity of the titanium carbide ceramic particles in the melt after ultrasonic dispersion is higher, and the mechanical properties of the obtained product are enhanced more greatly.

In addition, inorganic salts are used as carriers of TC4 titanium alloy and reinforcing particles in molten salt-dispersion, and if the proportion is not appropriate, it will inevitably cause problems in material uniformity and production efficiency.

Preferably, the average particle size of the nano-titanium carbide is 40-60 nm.

Titanium carbide ceramic particles with a specific size can effectively inhibit the dislocation movement of the material after being dispersed in the metal matrix, thereby improving the mechanical properties of the product; if the size is not appropriate, not only the reinforcement effect is not good, but also the melting of the product precursor will be affected. , The uniformity of ultrasonic dispersion. When the particle size of the modified ceramic particles is too small and the particles are too fine, it is easy to cause agglomeration of the particles during the mixing and smelting process, so that the dispersion and enhancement effect cannot be achieved; However, the performance improvement effect is not good, but the added particles are wasted and the cost is significantly increased.

Preferably, the average particle size of the TC4 metal powder is 15-74 μm, and the average particle size of the inorganic salt is 500-650 μm;

More preferably, in step (1) TC4 metal powder, nano-titanium carbide and inorganic salt are used in ball milling and the ball-milling medium is titanium carbide grinding ball, and the titanium carbide grinding ball and TC4 metal powder, nano-titanium carbide and inorganic salt The mass ratio of the three raw materials of the salt to the balls is 3-5:1; the ball-milling treatment time is 12-24h, and the rotating speed is 250-300r/min.

Using grinding balls of the same material as the reinforcing material to perform ball milling, while limiting the size of the ball milling raw material and ball milling parameters, can effectively improve the ball milling efficiency.

Preferably, the inorganic salt includes at least one of calcium chloride and barium chloride.

The properties of the two inorganic salts are similar and can be mixed in any proportion and can be effectively used as molten salts and dispersion carriers.

Preferably, the temperature of the vacuum heating in step (2) is 1675-1695° C., and the time is 5-10 min.

Preferably, the time of the ultrasonic dispersion treatment in step (2) is 2-3 min, and the power is 800-1000 W.

The object of the ultrasonic dispersion treatment is a mixture of molten salt particles, so specific time and power are required to ensure that the ceramic titanium carbide particles in the melt can be effectively dispersed into the powder material.

More preferably, during the ultrasonic dispersion treatment in step (2), the ceramic ultrasonic probe is penetrated into the melt for ultrasonic dispersion, and when the ceramic ultrasonic probe is penetrated into the melt, the probe tip is located three points below the liquid level of the melt. second place.

Preferably, the mass ratio of the deionized water in step (3) to the precursor powder B is >5:1;

Preferably, the time for precipitation of the suspension in step (3) is 1-2 min.

Preferably, the drying temperature in step (4) is 100-150°C.

Another object of the present invention is to provide a nanoparticle-enhanced TC4 metal powder material prepared by the method for preparing the nanoparticle-enhanced TC4 metal powder material.

Compared with the existing titanium alloy material, the nanoparticle-reinforced TC4 metal powder material prepared by the invention has higher high temperature resistance, wear resistance and mechanical strength.

The beneficial effect of the present invention is that the present invention provides a nanoparticle-enhanced TC4 metal powder and a preparation method thereof. The preparation method of the present invention adopts the molten salt-ultrasonic dispersion combined step to prepare the product, and utilizes the characteristics that the molten TC4 liquid metal, the titanium carbide ceramic particles and the molten salt are incompatible with each other, and the molten salt is used as a dispersion carrier to effectively disperse the nanometers. The solid ceramic particles of the size are introduced into the TC4 metal material, and ultrasonic dispersion is used to uniformly disperse the reinforcing material particles in the liquid metal. Because titanium carbide has the advantages of high strength, high hardness, high temperature resistance and small thermal expansion coefficient, the The metal powder material prepared by the method has the characteristics of high hardness, high strength and high wear resistance, which provides a guarantee of raw materials for expanding the application of TC4-based composite materials in the industrial field, and the ceramic particles have high nanoparticle utilization rate. At the same time, nano-titanium carbide particles reinforced TC4 powder material can also expand the application of titanium matrix composites in the fields of additive manufacturing, hot isostatic pressing and powder metallurgy. The material preparation method of the invention has simple operation steps, high repeatability, safety and environmental protection, and can realize industrialized small-scale production.

Description of drawings

Fig. 1 is the SEM image of the nanoparticle-enhanced TC4 metal powder material prepared by the present invention.

Detailed ways

In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments and comparative examples, the purpose of which is to understand the content of the present invention in detail, rather than limiting the present invention. All other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention. Unless otherwise specified, the experimental reagents and instruments designed for the implementation of the present invention are commonly used common reagents and instruments.

Example 1

An embodiment of a method for preparing a nanoparticle-enhanced TC4 metal powder according to the present invention includes the following steps:

(1) Put TC4 metal powder, nano-titanium carbide and calcium chloride into a mixing bottle in an argon-protected glove box, add titanium carbide grinding balls, seal and place them on a mixer for ball milling, sieve, The precursor powder A is obtained; the mass ratio of the TC4 metal powder, nano-titanium carbide and calcium chloride is: m (TC4 metal powder): m (nano-titanium carbide): m (inorganic salt)=8:2:90; The average particle size of the nano-titanium carbide is 50 nm; the average particle size of the TC4 metal powder is 15 μm, and the average particle size of the inorganic salt is 500 μm; the titanium carbide grinding ball and the TC4 metal powder, nano-titanium carbide and inorganic salt are The mass ratio of the balls of these three kinds of raw materials is 4:1; the time of the ball milling treatment is 24h, and the rotating speed is 300r/min;

(2) vacuum heating the precursor powder A described in step (1) for 10min, insert the obtained melt into the ceramic ultrasonic probe after the powder is melted, the probe tip is located at two-thirds below the melt level, and the power is 800W. Ultrasonic dispersion treatment for 3min, poured into a ceramic boat for cooling, and the obtained massive solid was pulverized to powder particle size <5mm to obtain precursor powder B; the vacuum degree during the described vacuum heating≤6×10 ⁻² ; the heating temperature is 1695℃;

(3) The precursor powder B obtained in step (2) is placed in deionized water to dissolve and stir, then the dissolved suspension is precipitated for 2 min, and then the upper layer of the suspension is poured out, leaving the bottom black granular material , and repeat this step three times to obtain the bottom layer mixed solution C; the mass ratio of the deionized water to the precursor powder B>5:1;

(4) After the bottom layer mixed solution C obtained in step (3) is subjected to suction filtration and drying at 120° C., the obtained black powder is sequentially pulverized and sieved to obtain the nanoparticle-enhanced TC4 metal powder.

The obtained product was observed under a scanning electron microscope. The results are shown in Figure 1. The titanium carbide particles are uniformly dispersed in the powder material without obvious agglomeration.

Example 2

The only difference between this embodiment and Embodiment 1 is that the step (1) is:

Put TC4 metal powder, nano-titanium carbide and calcium chloride into a mixing bottle in an argon-protected glove box, add titanium carbide grinding balls, seal them, and place them on a mixer for ball-milling treatment, sieve, and obtain precursor powder. Body A; the mass ratio of the TC4 metal powder, nano-titanium carbide and calcium chloride is: m (TC4 metal powder): m (nano-titanium carbide): m (inorganic salt) = 7.5:2.5:90; the nanometer The average particle size of titanium carbide is 40nm; the average particle size of the TC4 metal powder is 53 μm, and the average particle size of the inorganic salt is 550 μm; The mass ratio of the raw materials to the balls is 4:1; the time of the ball milling treatment is 24h, and the rotating speed is 300r/min;

Example 3

The only difference between this embodiment and Embodiment 1 is that the step (1) is:

Put TC4 metal powder, nano-titanium carbide and calcium chloride into a mixing bottle in an argon-protected glove box, add titanium carbide grinding balls, seal them, and place them on a mixer for ball-milling treatment, sieve, and obtain precursor powder. Body A; the mass ratio of the TC4 metal powder, nano-titanium carbide and calcium chloride is: m (TC4 metal powder): m (nano-titanium carbide): m (inorganic salt) = 7.5:2.5:90; the nanometer The average particle size of titanium carbide is 60 nm; the average particle size of the TC4 metal powder is 74 μm, and the average particle size of the inorganic salt is 650 μm; The mass ratio of the raw materials to the balls is 4:1; the time of the ball milling treatment is 24h, and the rotating speed is 300r/min;

Example 4

The only difference between this embodiment and Embodiment 1 is that the step (1) is:

Put TC4 metal powder, nano-titanium carbide, calcium chloride and barium chloride into a mixing bottle in an argon-protected glove box, add titanium carbide grinding balls, seal them, and place them on a mixing machine for ball milling, and sieve them. , to obtain the precursor powder A; the mass ratio of the TC4 metal powder, nano-titanium carbide, calcium chloride and barium chloride is: m (TC4 metal powder): m (nano-titanium carbide): m (calcium chloride): m (barium chloride)=7.5:2.5:10:80; the average particle size of the nano-titanium carbide is 50 nm; the average particle size of the TC4 metal powder is 15 μm, and the average particle size of calcium chloride is 500 μm; chlorine The average particle size of barium oxide is 650 μm; the mass ratio of the titanium carbide grinding ball to the three raw materials of TC4 metal powder, nano-titanium carbide and inorganic salt is 4:1; the time of the ball milling treatment is 24h, and the rotating speed is 300r/min;

Example 5

The only difference between this embodiment and Embodiment 1 is that the step (1) is:

Put TC4 metal powder, nano-titanium carbide and calcium chloride into a mixing bottle in an argon-protected glove box, add titanium carbide grinding balls, seal them, and place them on a mixer for ball-milling treatment, sieve, and obtain precursor powder. Body A; the mass ratio of the TC4 metal powder, nano-titanium carbide and calcium chloride is: m (TC4 metal powder): m (nano-titanium carbide): m (inorganic salt) = 3.75:1.25:95; the nanometer The average particle size of titanium carbide is 50 nm; the average particle size of the TC4 metal powder is 15 μm, and the average particle size of the inorganic salt is 500 μm; the titanium carbide grinding ball and the three types of TC4 metal powder, nano-titanium carbide and inorganic salt The mass ratio of the raw materials to the balls is 4:1; the time of the ball milling treatment is 24h, and the rotating speed is 300r/min;

Example 6

The only difference between this embodiment and Embodiment 1 is that the step (1) is:

Put TC4 metal powder, nano-titanium carbide and calcium chloride into a mixing bottle in an argon-protected glove box, add titanium carbide grinding balls, seal them, and place them on a mixer for ball-milling treatment, sieve, and obtain precursor powder. Body A; the mass ratio of the TC4 metal powder, nano-titanium carbide and calcium chloride is: m (TC4 metal powder): m (nano-titanium carbide): m (inorganic salt) = 2.3:0.7:97; the nanometer The average particle size of titanium carbide is 50 nm; the average particle size of the TC4 metal powder is 15 μm, and the average particle size of the inorganic salt is 500 μm; the titanium carbide grinding ball and the three types of TC4 metal powder, nano-titanium carbide and inorganic salt The mass ratio of the raw materials to the balls is 4:1; the time of the ball milling treatment is 24h, and the rotating speed is 300r/min;

Example 7

The only difference between this embodiment and Embodiment 1 is that the steps (1) and (2) are:

(1) Put TC4 metal powder, nano-titanium carbide and calcium chloride into a mixing bottle in an argon-protected glove box, add titanium carbide grinding balls, seal and place them on a mixer for ball milling, sieve, The precursor powder A is obtained; the mass ratio of the TC4 metal powder, nano-titanium carbide and calcium chloride is: m (TC4 metal powder): m (nano-titanium carbide): m (inorganic salt)=10:0.7:89.3; The average particle size of the nano-titanium carbide is 50 nm; the average particle size of the TC4 metal powder is 15 μm, and the average particle size of the inorganic salt is 500 μm; the titanium carbide grinding ball and the TC4 metal powder, nano-titanium carbide and inorganic salt are The mass ratio of the balls of these three kinds of raw materials is 4:1; the time of the ball milling treatment is 24h, and the rotating speed is 300r/min;

(2) vacuum heating the precursor powder A described in step (1) for 10 minutes, insert the obtained melt into a ceramic ultrasonic probe after the powder is melted, ultrasonically disperse it with a power of 1000W for 2 minutes, pour it into a ceramic boat for cooling, and the obtained block The solid is pulverized until the particle size of the powder is less than 5 mm to obtain the precursor powder B; the vacuum degree during the vacuum heating is less than or equal to 6×10 ^-2 ; the heating temperature is 1675 ° C;

Example 8

The only difference between this embodiment and Embodiment 1 is that the steps are:

(1) Put TC4 metal powder, nano-titanium carbide, barium chloride and calcium chloride into a mixing bottle in an argon-protected glove box, add titanium carbide grinding balls, seal and place them on a mixer for ball milling treatment , sieved to obtain precursor powder A; the mass ratio of the TC4 metal powder, nano-titanium carbide, calcium chloride and barium chloride is: m (TC4 metal powder): m (nano-titanium carbide): m (chlorination calcium): m (barium chloride)=10:2:80:8; the average particle size of the nano-titanium carbide is 50 nm; the average particle size of the TC4 metal powder is 15 μm, and the average particle size of the calcium chloride is 500 μm; the average particle size of barium chloride is 600 μm; the mass ratio of the titanium carbide grinding ball to the three raw materials of TC4 metal powder, nano-titanium carbide and inorganic salt is 4:1; the time of the ball milling treatment is 24h, the speed is 300r/min;

(2) vacuum heating the precursor powder A described in step (1) for 10 min, insert the obtained melt into a ceramic ultrasonic probe after the powder is melted, ultrasonically disperse it with 800W power for 3 min, pour it into a ceramic boat for cooling, and the obtained bulk The solid is pulverized until the particle size of the powder is less than 5 mm to obtain the precursor powder B; the vacuum degree during the vacuum heating is less than or equal to 6×10 ^-2 ; the heating temperature is 1695 ° C;

(3) The precursor powder B obtained in step (2) is placed in deionized water to dissolve and stir, then the dissolved suspension is precipitated for 3 minutes, and then the upper layer of the suspension is poured out, leaving the bottom black granular material , and repeat this step three times to obtain the bottom layer mixed solution C; the mass ratio of the deionized water to the precursor powder B>5:1;

(4) After the bottom layer mixed solution C obtained in step (3) is subjected to suction filtration and drying at 150° C., the obtained black powder is sequentially pulverized and sieved to obtain the nanoparticle-enhanced TC4 metal powder.

Comparative Example 1

The only difference between this comparative example and Example 1 is that the step (1) is:

Put TC4 metal powder, nano-titanium carbide and calcium chloride into a mixing bottle in an argon-protected glove box, add titanium carbide grinding balls, seal them, and place them on a mixer for ball-milling treatment, sieve, and obtain precursor powder. Body A; the mass ratio of the TC4 metal powder, nano-titanium carbide and calcium chloride is: m (TC4 metal powder): m (nano titanium carbide): m (inorganic salt) = 9:6:85; the nanometer The average particle size of titanium carbide is 50 nm; the average particle size of the TC4 metal powder is 15 μm, and the average particle size of the inorganic salt is 500 μm; the titanium carbide grinding ball and the three types of TC4 metal powder, nano-titanium carbide and inorganic salt The mass ratio of the raw materials to the balls is 3:1; the time of the ball milling treatment is 24h, and the rotating speed is 300r/min;

Comparative Example 2

The only difference between this comparative example and Example 1 is that the step (1) is:

Put TC4 metal powder, nano-titanium carbide and calcium chloride into a mixing bottle in an argon-protected glove box, add titanium carbide grinding balls, seal them, and place them on a mixer for ball-milling treatment, sieve, and obtain precursor powder. Body A; the mass ratio of the TC4 metal powder, nano-titanium carbide and calcium chloride is: m (TC4 metal powder): m (nano-titanium carbide): m (inorganic salt) = 9.99:0.01:90; the nanometer The average particle size of titanium carbide is 50 nm; the average particle size of the TC4 metal powder is 15 μm, and the average particle size of the inorganic salt is 500 μm; the titanium carbide grinding ball and the three types of TC4 metal powder, nano-titanium carbide and inorganic salt The mass ratio of the raw materials to the balls is 4:1; the time of the ball milling treatment is 24h, and the rotating speed is 300r/min;

Comparative Example 3

The only difference between this comparative example and Example 1 is that the steps are:

(1) Put TC4 metal powder, nano-titanium carbide and calcium chloride into a mixing bottle in an argon-protected glove box, add titanium carbide grinding balls, seal and place them on a mixer for ball milling, sieve, The precursor powder A is obtained; the mass ratio of the TC4 metal powder, nano-titanium carbide and calcium chloride is: m (TC4 metal powder): m (nano-titanium carbide): m (inorganic salt)=8:2:90; The average particle size of the nano-titanium carbide is 50 nm; the average particle size of the TC4 metal powder is 15 μm, and the average particle size of the inorganic salt is 500 μm; the titanium carbide grinding ball and the TC4 metal powder, nano-titanium carbide and inorganic salt are The mass ratio of the balls of these three kinds of raw materials is 4:1; the time of the ball milling treatment is 24h, and the rotating speed is 300r/min;

(2) The precursor powder A described in step (1) is heated in vacuum for 10 minutes, and after the powder is melted, it is conventionally stirred for 3 minutes, poured into a ceramic boat for cooling, and the obtained massive solid is pulverized to a powder particle size of less than 5 mm to obtain a precursor Powder B; the vacuum degree during the vacuum heating is less than or equal to 6×10 ^-2 ; the heating temperature is 1695°C;

(3) The precursor powder B obtained in step (2) is placed in deionized water to dissolve and stir, then the dissolved suspension is precipitated for 2 min, and then the upper layer of the suspension is poured out, leaving the bottom black granular material , and repeat this step three times to obtain the bottom layer mixed solution C; the mass ratio of the deionized water to the precursor powder B>5:1;

(4) After the bottom layer mixed solution C obtained in step (3) is subjected to suction filtration and drying at 120° C., the obtained black powder is sequentially pulverized and sieved to obtain the TC4 metal powder.

Effect example 1

In order to verify the enhancement effect of the nanoparticle-enhanced TC4 metal powder material of the present invention, the powder materials and pure TC4 powder prepared in Examples 2, 6 and 8 and Comparative Examples 1 to 3 were treated at room temperature (25 °C) and 100 °C, respectively. , 200 ℃, 300 ℃ and 400 ℃ for hardness test, the results are shown in Table 1; at the same time, the nanoparticle utilization rate of each product was sampled at multiple points and the range value was counted, and the results were shown in Table 2 (nanoparticle utilization rate is defined as: the ratio of the mass fraction of nanoparticles in the composite metal powder per unit mass to the ratio of the mass of nanoparticles (nano-titanium carbide) added in the theoretical raw material to the ratio of TC4 powder).

Table 1

product HV/25℃ HV/100℃ HV/200℃ HV/300℃ HV/400℃ TC4 306 280 271.2 256 238 Example 2 591.7 570.5 563.6 551.4 535.1 Example 6 586.3 567.9 560.2 548.8 533.4 Example 8 563.4 541.9 534.5 524.2 510.7 Comparative Example 1 583.1 561.8 552.7 540.5 527.0 Comparative Example 2 331.2 309.0 300.8 287.7 271.4 Comparative Example 3 478.6 455.7 447.2 434.6 419.2

Table 2

product Nanoparticle utilization (%) Example 2 65～71 Example 6 67～73 Example 8 69～76 Comparative Example 1 52～57 Comparative Example 2 78～83 Comparative Example 3 55～62

It can be seen from the above results that, compared with pure TC4 powder, the nano-titanium carbide particles reinforced spherical TC4 powder obtained by the method of molten salt-ultrasonic dispersion of the present invention has higher mechanical properties at room temperature and high temperature, and the modified ceramics in each product. The particles all have high nanoparticle utilization. Although the product obtained in Comparative Example 1 is comparable in performance to the embodiment, the particle utilization rate is relatively low, while in the product obtained in Comparative Example 2, although the utilization rate of ceramic particles is high, its mechanical properties are equivalent to those of pure TC4 powder, indicating that in the precursor powder. The addition ratio of TC4 metal powder, nano-titanium carbide and inorganic salt needs to be optimized at the same time in order to take into account the raw material utilization efficiency and mechanical properties of the product; the product obtained in Comparative Example 3 uses a non-optimized preparation process, and its mechanical properties and nanoparticle utilization rate are not good. ideal.

For those skilled in the art, according to the above-described technical solutions and ideas, various other corresponding compositions can be made, that is, the generated phase is mainly TC4 material reinforced by nano-titanium carbide particles (TiC _np /TC4) In this process, the particle size of the raw material, the ratio of the raw material, the dispersion process, the ultrasonic power, the change and deformation of the drying process, and all these changes and deformations should belong to the protection scope of the claims of the present invention.

In addition, the patent of the present invention is also applicable to other titanium alloy powders, such as TC11 and TA15 metal powders, and the changes of all these raw material powders should fall within the protection scope of the claims of the present invention.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the protection scope of the present invention. Although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that, The technical solutions of the present invention may be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention.

Claims (9)

1. a preparation method of nano-particles reinforced TC4 metal powder, is characterized in that, comprises the following steps: (1) Mix TC4 metal powder, nano-titanium carbide and inorganic salt evenly, carry out ball milling treatment, and sieve to obtain precursor powder A; the mass ratio of the TC4 metal powder and nano-titanium carbide is 1:0.07~0.35, so The mass ratio of the sum of the mass of TC4 metal powder and nano-titanium carbide to the inorganic salt is: m (TC4 metal powder + nano-titanium carbide): m (inorganic salt) = 3~15:85~97; the nano-titanium carbide The average particle size is 40~60nm; (2) The precursor powder A described in step (1) is heated in vacuum, and after the powder is melted, the obtained melt is subjected to ultrasonic dispersion treatment, cooled, and the obtained massive solid is pulverized to a powder particle size of less than 5 mm to obtain a precursor Powder B; the vacuum degree during the vacuum heating is less than or equal to 6×10 ^-2 ; (3) Dissolving and stirring the precursor powder B obtained in step (2) in deionized water, then precipitating the dissolved suspension, and pouring out the upper suspension, leaving the bottom black granular material, And repeat this step three times to get bottom mixed solution C; (4) After the bottom layer mixed solution C obtained in step (3) is subjected to suction filtration and drying, the obtained black powder is sequentially pulverized and sieved to obtain the nanoparticle-enhanced TC4 metal powder. 2. The preparation method of nanoparticle-enhanced TC4 metal powder according to claim 1, wherein the mass ratio of the TC4 metal powder and nano-titanium carbide in step (1) is 1:0.2~0.35, and the TC4 metal powder The mass ratio of the sum of the mass of nano-titanium carbide and the inorganic salt is: m (TC4 metal powder + nano-titanium carbide): m (inorganic salt) = 5~10:95~90. 3. The preparation method of nanoparticle-enhanced TC4 metal powder according to claim 1, wherein the average particle size of the TC4 metal powder is 15-74 μm, and the average particle size of the inorganic salt is 500-650 μm. 4. The preparation method of nanoparticle-enhanced TC4 metal powder according to claim 1, characterized in that, in step (1), the ball milling medium used in the ball milling of the TC4 metal powder, nano-titanium carbide and inorganic salt is titanium carbide grinding balls , the mass ratio of the titanium carbide grinding ball to the three raw materials of TC4 metal powder, nano-titanium carbide and inorganic salt is m (titanium carbide grinding ball): m (TC4 metal powder + nano-titanium carbide + inorganic salt) = 3~5:1; the ball milling treatment time is 12~24h, and the rotating speed is 250~300r/min. 5 . The method for preparing nanoparticle-enhanced TC4 metal powder according to claim 1 , wherein the temperature of the vacuum heating in step (2) is 1675-1695° C., and the time is 5-10 min. 6 . 6 . The method for preparing nanoparticle-enhanced TC4 metal powder according to claim 1 , wherein the ultrasonic dispersion treatment in step (2) takes 2 to 3 minutes and the power is 800 to 1000 W. 7 . 7. The preparation method of nanoparticle-enhanced TC4 metal powder according to claim 6, characterized in that, during the ultrasonic dispersion treatment in step (2), the ceramic ultrasonic probe is penetrated into the melt for ultrasonic dispersion, and the ceramic ultrasonic When the probe penetrates deep into the melt, the probe tip is two-thirds below the melt level. 8 . The method for preparing nanoparticle-enhanced TC4 metal powder according to claim 1 , wherein the time for precipitation of the suspension in step (3) is 1 to 2 minutes; the temperature for drying in step (4) is 100~150℃. 9. The nanoparticle reinforced TC4 metal powder material prepared by the preparation method of the nanoparticle reinforced TC4 metal powder material according to any one of claims 1 to 8.

Images