CN117923917A

CN117923917A - Multi-element complex-phase carbide for additive manufacturing and preparation process thereof

Info

Publication number: CN117923917A
Application number: CN202410333495.3A
Authority: CN
Inventors: 耿占吉
Original assignee: Changsha Huaxi New Material Co ltd
Current assignee: Changsha Huaxi New Material Co ltd
Priority date: 2024-03-22
Filing date: 2024-03-22
Publication date: 2024-04-26
Anticipated expiration: 2044-03-22
Also published as: CN117923917B

Abstract

The invention discloses a preparation process of multi-element complex phase carbide for additive manufacturing, which relates to the technical field of ceramic materials and comprises the following steps: s1, mixing and grinding carbon black and Ti-containing powder, ta-containing powder and W-containing powder; s2, pressing the mixed powder, carrying out a solid-solid reaction, and then carrying out first carbonization to obtain a sintered product; s3, wet grinding and sieving are carried out on the sinter, and broken materials are obtained; s4, adding TiO ₂, carbon black and nickel powder into the crushed materials, mixing, carbonizing for the second time, hammering and screening to obtain the multi-element complex-phase carbide. The multi-element complex phase carbide comprises, by mass, 10-58% of W, 15-45% of Ti, 9-40% of Ta, 0-13% of Nb, 0-11% of Cr and 9-14% of C. The process is simple and low in cost, and the prepared multi-element complex-phase carbide has large space, large particles and good mechanical properties.

Description

Multi-element complex-phase carbide for additive manufacturing and preparation process thereof

Technical Field

The invention belongs to the technical field of ceramic materials, and particularly relates to a multi-element complex-phase carbide for additive manufacturing and a preparation process thereof.

Background

The multi-element complex-phase carbide material has excellent thermophysical and chemical properties and huge performance regulation space, is widely applied to hard alloy cutters, is a research hot spot in the current ceramic field, and is regarded as a key material capable of solving the performance bottleneck problem of the traditional ceramic material.

The higher hardness and modulus of multi-element carbides, as well as the excellent oxidation resistance and wear resistance, compared to single-element carbides, make them very promising in extreme environments. The multiphase carbide for additive manufacturing is required to have good fluidity. The spherical powder is prepared by adopting a micron-sized fine powder granulating and sintering mode at present, and the problems of long process flow, high cost, small granularity and the like are solved.

In the prior art, CN113620712B discloses a high-entropy carbide ceramic nano powder, a preparation method and application thereof, wherein the high-entropy carbide ceramic nano powder is prepared by pre-pressing metal oxide powder, carbon black, magnesium powder and NaF into sheets, and then sintering, washing and pickling, but the obtained high-entropy carbide ceramic nano powder still has the problem of small particle size. CN115286389B disclosed in the invention is a high-entropy carbide ceramic powder, and its preparation method and application, the obtained high-entropy carbide ceramic powder has the advantages of large component space, high purity, uniform metal element distribution, extremely low oxygen impurity content, etc., but it needs to react in graphite heating element, and the conditions of specific graphite plate element, limited heating element size, fixed power and current, etc. are not suitable for industrial production. CN117164361a provides a high entropy carbide ceramic material, its preparation method and application, when the method is pressed, the upper and lower surfaces are covered with graphite paper coated with hexagonal boron nitride, then the graphite paper is embedded into graphite felt, then the graphite felt is placed in protective atmosphere, and the green body is electrified to produce carbothermic reduction reaction, and the current, time and the like are limited, so that the method is not suitable for industrial production.

Therefore, the development of a rapid and low-cost preparation method of the multi-carbide ceramic powder has very important significance in preparing the multi-carbide ceramic powder with the advantages of huge component space, high purity, uniform metal element distribution, low oxygen impurity content and the like.

Disclosure of Invention

In order to overcome the defects of complex preparation process and high production cost in the prior art and the apparent defects of fine granularity, insufficient space and uneven element distribution of the product; the invention aims to provide a preparation process of a multi-element complex-phase carbide for additive manufacturing, which is simple and convenient, low in cost, and the prepared multi-element complex-phase carbide has high hardness, huge space and uniform element distribution.

The invention discloses a multi-element complex phase carbide for additive manufacturing and a preparation process thereof, which comprises the following steps: s1, mixing and grinding carbon black and raw materials; the raw materials comprise Ti-containing powder, ta-containing powder and W-containing powder; the powder is oxide or carbide corresponding to elements;

S2, pressing the mixed powder, carrying out a solid-solid reaction, and then carrying out first carbonization to obtain a sintered product;

S3, wet grinding and sieving are carried out on the sinter, and broken materials are obtained;

s4, adding TiO2, carbon black and nickel powder into the crushed materials, mixing, carbonizing for the second time, hammering and screening to obtain the multi-element complex-phase carbide.

The raw materials may further include Cr-containing powder and Ti-containing powder.

In S1, the particle size of the crushed material is 1-6 mu m.

In S1, the grain diameter of the multi-element complex phase carbide is less than or equal to 2.0 mu m.

In S1, the particle size of the raw material powder is 1-10 mu m.

In S1, the purity of the carbon black is more than or equal to 99.95 percent; the purity of the raw materials is more than or equal to 99.5 percent.

In S1, the grinding time is 8-10 h.

And S2, the pressing operation is to press the mixed powder into a cake-shaped body with the diameter of 60-100 mm and the thickness of 20-30 mm or a columnar blank with the diameter of 50-80 mm and the length of 200-300 mm by using a press with the weight of 80-100 tons, and the density of the pressed mixed powder is 1.5-4 g/cm ³.

S2 and S4, performing the first carbonization and the second carbonization in an argon atmosphere of a carbon tube furnace or in a vacuum carbonization furnace; further, the flow rate of the argon is 0.1-0.5L/min.

In S2 and S4, the temperature of the first carbonization and the second carbonization is 1800-2300 ℃, preferably 2200-2300 ℃.

In S2 and S4, the time of the first carbonization and the second carbonization is 120-180 min.

Wherein the sinter obtained by the first carbonization is 1-6 mu m multi-carbide.

In the invention, two times of carbonization are carried out in the carbon tube furnace, and the carbon tube furnace can be heated in an open mode, so that continuous production can be realized.

In S3, the wet milling is performed under argon protection.

S3, the mass ratio of the wet-milled added hard alloy balls to the sintered body is (2-3) 1;

and S3, the wet milling time is 8-10 hours.

S4, the mass proportion of the nickel powder to the crushed material is 1-2%; the purity of the nickel powder is more than 99.5%; the particle size of the nickel powder is in the micron order; wherein, the nickel powder plays a role of adhesion, and the nickel powder volatilizes in the carbonization process.

S4, the mass of the additional oxide is 10-30% of the total mass of the oxide; among them, titanium carbide is formed by adding titanium oxide and carbon black, and is more likely to form solid solution with other carbides, so titanium carbide is more likely to form multi-carbide with other carbides.

And S4, the mass of the added carbon black is 10-30% of the total mass of the carbon black.

And S4, mixing for 6-10 hours by using a mixer.

S4, performing secondary carbonization to obtain a block; wherein the second carbonization, i.e. diffusion process, produces coarser and larger multi-carbide, i.e. coarsening process.

In S4, the hammer crushing is operated to crush the bulk carbide to 200 μm or less using a jaw crusher.

In S4, the screening is to screen the interval multi-element multi-phase carbide with different granularity sections to obtain the multi-element multi-phase carbide with the granularity less than or equal to 2.0 mu m, and the large granularity of the product of the invention provides better wear resistance.

The invention also provides a multi-component complex phase carbide for additive manufacturing, which comprises, by mass, 10-58% of W, 15-45% of Ti, 9-40% of Ta, 0-13% of Nb, 0-11% of Cr and 9-14% of C.

The microhardness of the multi-element complex-phase carbide is 30-50 Gpa, and the elastic modulus is 95-108 Gpa.

In the invention, the total mass of the carbide, the oxide and the carbon black which are required to be added in the raw material powder is obtained according to the mass conversion of various elements required in the multi-element complex-phase carbide.

In the invention, the microhardness of the multi-element complex phase carbide is 30-50 Gpa, and the elastic modulus is 95-108 Gpa.

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

1. The preparation process has low cost, simple method and continuous production.

2. The multi-element complex phase carbide prepared by the method has large space and large particles, so the multi-element complex phase carbide has better mechanical properties, and in some preferred schemes, the micro-hardness of the multi-element complex phase carbide is 30-50 Gpa, and the elastic modulus is 95-108 Gpa.

3. The pressing process of the invention has solid-solid reaction, so that the pressing density is high, and the compact and fine-grained sintered product can be obtained through first carbonization; and (3) carrying out secondary carbonization, namely coarsening, on the basis to obtain the multi-element complex-phase carbide with huge space and large particles.

Drawings

Fig. 1 is an SEM morphology of the multi-phase carbide of example 1.

Fig. 2 is an XRD pattern of the multi-phase carbide of example 1.

Fig. 3 is a nanoindentation pattern of the multi-phase carbide of example 3.

Detailed Description

The invention will be described more fully hereinafter with reference to the preferred embodiments for the purpose of facilitating an understanding of the invention, but the scope of the invention is not limited to the specific embodiments described below.

Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.

Example 1

S1, adding WC, tiO ₂ (80% of the total amount of added TiO ₂), ta ₂O₅、Nb₂O₅ and carbon black (80% of the total amount of added carbon black) according to the content of each element of the multi-element complex-phase carbide, mixing, grinding for 8 hours, and obtaining mixed powder, wherein the single processing scale is not more than 500g.

S2, pressing mixed powder, carrying out a solid-solid reaction, wherein the density of the pressed mixed powder is 1.5-4 g/cm ³, placing the pressed compact into a graphite boat, and carrying out primary carbonization at 2200-2300 ℃ at the boat pushing speed of 60 min/boat to obtain a sintered product; the carbon tube furnace can be heated in an open mode, and continuous production can be achieved.

S3, adding the hard alloy balls, and carrying out wet grinding on the sintered product for 8 hours under the protection of argon to obtain 1-6 mu m crushed materials.

S4, adding nickel powder accounting for 2% of the weight of the crushed material into the crushed material, and adding TiO ₂ (20% of the total amount of added TiO ₂) and carbon black (20% of the total amount of added carbon black); mixing materials for 8 hours by a mixer, carbonizing for 120 minutes at 2200-2300 ℃, hammering to below 200 mu m, and screening the multi-component multi-phase carbide with different particle size sections to obtain the multi-component multi-phase carbide with the mass fractions of 55.3% W, 19.2% Ti, 9.3% Ta, 6.2% Nb, 9.7% C and 0.3% as unavoidable impurities.

The grain diameter of the multi-element complex phase carbide is less than or equal to 2.0 mu m, the microhardness is 50Gpa, and the elastic modulus is 108Gpa. The invention has low material cost and processing cost, thus the production cost is low.

Fig. 1 is an SEM morphology diagram of the present embodiment, and it can be seen from fig. 1 that the composition space is huge and the elements are uniformly distributed. Fig. 2 is an XRD pattern of the present example, and it can be seen that the multi-component complex carbide is a multi-component carbide.

Example 2

In this example S1, WC, tiO ₂、Ta₂O₅、Nb₂O₅ and carbon black were added according to the content of each element of the multi-element complex carbide. The multi-phase carbide of this example contained 35.2% w, 20.2% ti, 23.4% ta, 11.1% nb, 9.8% c,0.3% as an unavoidable impurity by mass. The other steps are the same as in example 1.

The grain diameter of the multi-element complex phase carbide is less than or equal to 2.0 mu m, the microhardness is 48Gpa, and the elastic modulus is 99Gpa.

Example 3

In this example S1, WC, tiO ₂、Ta₂O₅、Nb₂O₅ and carbon black were added according to the content of each element of the multi-element complex carbide. The multi-phase carbide of this example contains 10.5% w, 41% ti, 23.4% ta, 11.1% nb, 13.6% c, and 0.4% by mass as unavoidable impurities. The other steps are the same as in example 1.

The particle size of the multi-component complex phase carbide is less than or equal to 2.0 mu m, the microhardness is 30Gpa, and the elastic modulus is 95Gpa, as shown in FIG. 3, which is a nanoindentation chart of the embodiment.

Example 4

In this example S1, WC, tiO ₂、Ta₂O₅、Cr₂O₃ and carbon black were added according to the content of each element of the multi-element complex carbide. The multi-phase carbide of this example contains 21.6% w, 20.1% ti, 37.2% ta, 7.8% cr, 13.2% c, 0.1% unavoidable impurities by mass. The other steps are the same as in example 1.

The grain diameter of the multi-element complex phase carbide is less than or equal to 2.0 mu m, the microhardness is 37Gpa, and the elastic modulus is 98Gpa.

Comparative example 1

In this example, step S1, step S2, and step S4 are the same as in example 1, except that S3 is not included. The particle size of the multi-component complex phase carbide obtained in the embodiment is less than or equal to 500nm, the microhardness is 37Gpa, and the elastic modulus is 70Gpa.

While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.

Claims

1. The preparation process of the multi-element complex-phase carbide for additive manufacturing is characterized by comprising the following steps of:

s1, mixing and grinding carbon black and raw materials; the raw materials comprise Ti-containing powder, ta-containing powder and W-containing powder; the powder is oxide or carbide corresponding to elements;

S4, adding TiO ₂, carbon black and nickel powder into the crushed materials, mixing, carbonizing for the second time, hammering and screening to obtain the multi-element complex-phase carbide.

2. The process for preparing a complex multi-phase carbide for additive manufacturing according to claim 1, wherein the raw materials further comprise Cr-containing powder and Nb-containing powder.

3. The process for producing a multi-component complex carbide for additive manufacturing according to claim 1 or 2, wherein the crushed material has a particle size of 1 to 6 μm;

the grain diameter of the multi-element complex phase carbide is less than or equal to 2.0 mu m;

the particle size of the raw material powder is 1-10 mu m.

4. The process for preparing a multi-component complex carbide for additive manufacturing according to claim 1 or 2, wherein the purity of the carbon black is not less than 99.95%;

The purity of the raw materials is more than or equal to 99.5 percent.

5. The process for preparing a multi-component complex phase carbide for additive manufacturing according to claim 1 or 2, wherein the density of the pressed mixed powder is 1.5-4 g/cm ³.

6. The process for preparing a multi-component complex phase carbide for additive manufacturing according to claim 1 or 2, wherein the first carbonization and the second carbonization are performed in an argon atmosphere of a carbon tube furnace or in a vacuum carbonization furnace;

the temperature of the first carbonization and the second carbonization is 1800-2300 ℃;

the time of the first carbonization and the second carbonization is 120-180 min.

7. The process for preparing multi-component complex phase carbide for additive manufacturing according to claim 6, wherein the first carbonization and the second carbonization are performed in an argon atmosphere of a carbon tube furnace, and the flow rate of the argon is 0.1-0.5L/min.

8. The process for preparing a multi-component complex phase carbide for additive manufacturing according to claim 1 or 2, wherein the wet milling is performed under the protection of argon gas;

the mass ratio of the wet-milled added hard alloy balls to the sintered body is (2-3) 1;

The wet milling time is 8-10 h.

9. The process for producing a multi-component complex phase carbide for additive manufacturing according to claim 1 or 2, wherein the nickel powder accounts for 1 to 2% by mass of the crushed material;

The mass of the additional oxide is 10-30% of the total mass of the additional oxide;

The mass of the additional carbon black is 10-30% of the total mass of the additional carbon black.

10. The multi-element complex-phase carbide for additive manufacturing is characterized by comprising, by mass, 10-58% of W, 15-45% of Ti, 9-40% of Ta, 0-13% of Nb, 0-11% of Cr and 9-14% of C;