1. The preparation method of the high-strength titanium-based composite material is characterized by comprising the following steps:

step 1, weighing Ti powder and CrB₂Powder and zirconia balls, mixing Ti powder and CrB₂Putting the powder and 0.04-0.12 wt% of vacuum pump oil into a mixing bottle of a three-dimensional vibrating powder mixer, mixing for 1-1.5h, adding zirconia balls, and continuously mixing for 2-3h, wherein the vibration frequency of the powder mixer is 30-60Hz during mixing to obtain mixed powder A;

step 2, putting the mixed powder A obtained in the step 1 into a die for pressing, and pressing into a green body B;

step 3, sintering the blank B obtained in the step 2 by adopting a vacuum rapid hot-pressing sintering furnace to obtain a composite material C;

and 4, preserving the heat of the composite material C obtained in the step 3 by using a muffle furnace, upsetting and cooling to obtain the high-strength titanium-based composite material.

2. The method of claim 1, wherein the CrB is selected from the group consisting of CrB and CrB in step 1₂The mass fraction ratio of the powder to the Ti powder is 0.01-0.1:1, and the grains of the Ti powderDiameter of 20-30 μm, CrB₂The particle size of the powder is 0.5-1 μm.

3. The method of claim 1, wherein the CrB is selected from the group consisting of CrB and CrB in step 1₂The mass ratio of the powder to the Ti powder to the zirconia balls is 1-3: 1.

4. the method of claim 1, wherein the zirconia balls in step 1 comprise big balls and small balls, the ratio of the big balls to the small balls is 3-5:1, the diameter of the big balls is 9-11 μm, and the diameter of the small balls is 5-6 μm.

5. The method of claim 1, wherein the graphite mold with a diameter of 40mm is used as the mold in step 2, and the pressing process is performed under a uniform pressure of 4-8MPa for a pressure maintaining time of 1-6 min.

6. The method as claimed in claim 1, wherein the temperature of the sintering process in step 3 is increased by 80-100 ℃/min, the sintering pressure is 30-40MPa, the sintering temperature is 900-1000 ℃, and the sintering time is 1-2 h.

7. The method as claimed in claim 1, wherein the temperature of step 4 is 800-1000 ℃ and the time of the temperature is 10-30 min.

8. The method of claim 1, wherein the upsetting pressure in step 4 is 8-12Mpa, and the cooling is performed in air.

Background

Titanium is an important structural metal developed in the 50 s of the 20 th century, is mainly used for manufacturing parts of an air compressor of an aircraft engine, and is a structural part of rockets, missiles and high-speed airplanes. Many countries have made a lot of research and development on titanium and titanium alloy, so that it has got many applications, but with the rapid development of modern science and technology, people have made higher performance requirements on materials, and the titanium alloy has the disadvantages of high production cost, low rigidity and low hardness, etc., which greatly limits the application range of titanium alloy.

The titanium-based composite material is a composite material with more excellent performance formed by adding one or more reinforcing phases into a pure titanium or titanium alloy matrix; the titanium alloy matrix powder is generally prepared by adopting a gas atomization method, and is relatively expensive, while the pure titanium matrix powder is relatively cheap. The composite material prepared by pure titanium powder is popular, but the use requirement is more rigorous, and the strength and the plasticity cannot be met, so that the composite material needs to be continuously strengthened; while the titanium alloy powder is expected to obtain better strength, the cost for preparing the titanium alloy powder is higher, and the composite material needs to be reinforced by other methods in consideration of economy.

Disclosure of Invention

The invention aims to provide a preparation method of a high-strength titanium-based composite material, which solves the problems of poor strength and poor plasticity of the titanium-based composite material in the prior art.

The technical scheme adopted by the invention is that the preparation method of the high-strength titanium-based composite material is implemented according to the following steps:

step 1, weighing Ti powder and CrB₂Powder and zirconia balls, mixing Ti powder and CrB₂Putting the powder and 0.04-0.12 wt% of vacuum pump oil into a mixing bottle of a three-dimensional vibrating powder mixer, mixing for 1-1.5h, adding zirconia balls, and continuously mixing for 2-3h, wherein the vibration frequency of the powder mixer is 30-60Hz during mixing to obtain mixed powder A;

step 2, putting the mixed powder A obtained in the step 1 into a die for pressing, and pressing into a green body B;

step 3, sintering the blank B obtained in the step 2 by adopting a vacuum rapid hot-pressing sintering furnace to obtain a composite material C;

and 4, preserving the heat of the composite material C obtained in the step 3 by using a muffle furnace, upsetting and cooling to obtain the high-strength titanium-based composite material.

The invention is also characterized in that:

CrB in step 1₂The mass fraction ratio of the powder to the Ti powder is 0.01-0.1:1, the particle diameter of the Ti powder is 20-30 μm, and CrB₂The particle size of the powder is 0.5-1 μm.

CrB in step 1₂The mass ratio of the powder to the Ti powder to the zirconia balls is 1-3: 1.

the zirconia ball in the step 1 comprises a big ball and a small ball, the ratio of the big ball to the small ball is 3-5:1, the diameter of the big ball is 9-11 μm, and the diameter of the small ball is 5-6 μm.

And 2, selecting a graphite die with the diameter of 40mm as the die in the step 2, and uniformly pressurizing in the pressing process, wherein the pressing pressure is 4-8MPa, and the pressure maintaining time is 1-6 min.

The temperature rise speed of the sintering in the step 3 is 80-100 ℃/min, the sintering pressure is 30-40MPa, the sintering temperature is 900-.

In the step 4, the heat preservation temperature is 800-.

And (4) upsetting the steel in the step (4), wherein the pressure is 8-12Mpa, and cooling in air.

The invention has the beneficial effects that: the invention adds CrB into Ti powder₂Powder, preparation of Ti-CrB by powder metallurgy₂The TiB whiskers are formed in the matrix of the composite material, so that the aim of strengthening is fulfilled. In addition, Cr is a beta titanium stabilizing element, so that the content of beta titanium in the titanium matrix can be greatly reserved, and the ductility and toughness of the titanium matrix are improved. Ti-CrB₂The hardness of the composite material of the system reaches 300-500Hv, and the tensile strength reaches 850-1250 MPa; without addition of CrB₂The hardness of the composite material can only reach 200-250Hv and the tensile strength is 650-750 MPa. Obviously, adding CrB₂Systematic Ti-CrB₂The composite material has better hardness and tensile strength and more excellent performance, can be better applied to the fields of aerospace, automobile industry and the like, and is suitable for industries with higher performance requirements.

Drawings

FIG. 1 is a 1000-fold metallographic structure diagram of a high-strength titanium-based composite material obtained in example 1 of the present invention;

FIG. 2 is a 1000-fold metallographic structure diagram of a high-strength titanium-based composite material obtained in example 2 of the present invention;

FIG. 3 is a 1000-fold metallographic structure diagram of a high-strength titanium-based composite material obtained in example 3 of the present invention;

FIG. 4 is a 1000-fold metallographic structure diagram of a high-strength titanium-based composite material obtained in example 4 of the present invention;

FIG. 5 is a metallographic structure diagram showing a structure 1000 times that of a high-strength titanium-based composite material obtained in example 5 of the present invention.

Detailed Description

The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

The invention relates to a preparation method of a high-strength titanium-based composite material, which is implemented according to the following steps:

step 1, weighing Ti powder and CrB₂Powders and zirconia balls, CrB₂The mass fraction ratio of the powder to the Ti powder is 0.01-0.1:1, the particle diameter of the Ti powder is 20-30 μm, and CrB₂The powder has a particle size of 0.5-1 μm and CrB₂The mass ratio of the powder to the Ti powder to the zirconia balls is 1-3: 1, zirconia balls comprise big balls and small balls, the ratio of the big balls to the small balls is 3-5:1, the diameter of the big balls is 9-11 mu m, the diameter of the small balls is 5-6 mu m, Ti powder and CrB are mixed₂Putting the powder and 0.04-0.12 wt% of vacuum pump oil into a mixing bottle of a three-dimensional vibrating powder mixer, mixing for 1-1.5h, adding zirconia balls, and continuously mixing for 2-3h, wherein the vibration frequency of the powder mixer is 30-60Hz during mixing to obtain mixed powder A;

2, putting the mixed powder A obtained in the step 1 into a mold for pressing, wherein the mold is a graphite mold with the diameter of 40mm, and pressing the mixed powder A into a blank B under the pressing pressure of 4-8MPa for 1-6min in a uniform pressing process;

step 3, sintering the blank B obtained in the step 2 by adopting a vacuum rapid hot-pressing sintering furnace, wherein the sintering temperature rise speed is 80-100 ℃/min, the sintering pressure is 30-40MPa, the sintering temperature is 900-;

and 4, preserving the heat of the composite material C obtained in the step 3 by using a muffle furnace at the temperature of 800-.

Example 1

A preparation method of a high-strength titanium-based composite material is implemented according to the following steps:

step 1, mixing the original powder

Preparing the required original powder, Ti powder with the grain diameter of 20 mu m and CrB with the grain diameter of 0.5 mu m₂Powder; 56.57g of Ti powder and 0.36g of CrB powder were weighed out separately₂The powder and the used zirconia balls are put well for standby; the ratio of balls to materials is 1:2, the ratio of big balls to small balls is 3:1, the diameter of the big balls is 9-11mm, and the diameter of the small balls is 5-6 mm; and mixing the powder by adopting a three-dimensional vibration powder mixer, wherein the frequency of the three-dimensional vibration powder mixer is 50 HZ. Firstly, pure Ti powder and CrB₂Adding 0.04-0.12 mass percent of vacuum pump oil into the powder, putting the powder into a plastic bottle, mixing for 1 hour, then putting a zirconia ball, and mixing for 2 hours to obtain mixed powder A;

step 2, press forming

Putting the mixed powder A obtained in the step 1 into a die for pressing to obtain a blank B, uniformly pressurizing in the pressing process, selecting a graphite die with the diameter of 40mm, and keeping the pressing pressure at 2MPa for 2 min;

step 3, sintering the green body

Sintering the blank B obtained in the step 2 by adopting a vacuum rapid hot-pressing sintering furnace to obtain a composite material C, wherein the heating speed is 100 ℃/min, the sintering pressure is 40MPa, the sintering temperature is 1000 ℃, and the sintering time is 1 h; and (3) putting the loaded graphite mold into a furnace chamber of a vacuum rapid hot-pressing sintering furnace, inserting a thermocouple, starting vacuumizing after checking to be correct, starting a heating program when the vacuum degree is less than 10Pa, immediately closing the program when sintering is finished, cooling to room temperature along with the furnace, and taking out the sintered composite material C, wherein the diameter of the composite material C is 40mm, and the height of the composite material C is 10 mm.

Step 4, upsetting the sample

Upsetting the composite material C obtained by sintering in the step 3, and preserving heat of the sample by adopting a muffle furnace before upsetting, wherein the heat preservation temperature is 850 ℃ and the heat preservation time is 20 min. The pressure at the time of upsetting the sample was 10MPa, and then the composite material C was taken out and air-cooled to obtain an upset sample D. To this end, Ti-CrB₂And (5) completing the preparation of the system composite material.

Ti-CrB prepared in inventive example 1₂The microstructure of the system composite material is shown in figure 1, the composition of the system composite material comprises an alpha titanium + intercrystalline beta titanium structure and fibrous TiB, and the interface combination is good; determination of Ti-CrB by Archimedes drainage method₂Calculating the density of the system composite material; the Vickers hardness was measured using an electric Brookfield hardness tester of type HBRV-187.5, the indenter for Vickers hardness being a diamond indenter of a regular quadrangular pyramid shape, the test force being 30 kg.N, and the holding pressure time being 30 s. Tensile strength was measured using a microcomputer controlled electronic universal tester of WDW-20. Ti-CrB prepared in example 1 of the present Process by the above method₂The density, hardness and tensile strength of the system composite material are tested and calculated, and the density is 99.12%, the hardness is 307.84Hv, and the tensile strength is 891 MPa.

Example 2

A preparation method of a high-strength titanium-based composite material is implemented according to the following steps:

step 1, mixing the original powder

Preparing the required original powder, Ti powder with the grain diameter of 20 mu m and CrB with the grain diameter of 0.5 mu m₂Powder; 56.47g Ti powder and 0.72g CrB powder are weighed respectively₂The powder and the used zirconia balls are put well for standby; the ratio of balls to materials is 1:2, the ratio of big balls to small balls is 3:1, the diameter of the big balls is 9-11mm, and the diameter of the small balls is 5-6 mm; and mixing the powder by adopting a three-dimensional vibration powder mixer, wherein the frequency of the three-dimensional vibration powder mixer is 50 HZ. Firstly, pure Ti powder and CrB₂Adding vacuum pump oil 0.04-0.12 wt% into the powder, mixing in a plastic bottle for 1 hr, and adding oxygenZirconium balls are melted and mixed for 2 hours to obtain mixed powder A;

step 2, press forming

Putting the mixed powder A obtained in the step 1 into a die for pressing to obtain a blank B, uniformly pressurizing in the pressing process, selecting a graphite die with the diameter of 40mm, and keeping the pressing pressure at 2MPa for 2 min;

step 3, sintering the green body

Sintering the blank B obtained in the step 2 by adopting a vacuum rapid hot-pressing sintering furnace to obtain a composite material C, wherein the heating speed is 100 ℃/min, the sintering pressure is 40MPa, the sintering temperature is 1000 ℃, and the sintering time is 1 h; and (3) putting the loaded graphite mold into a furnace chamber of a vacuum rapid hot-pressing sintering furnace, inserting a thermocouple, starting vacuumizing after checking to be correct, starting a heating program when the vacuum degree is less than 10Pa, immediately closing the program when sintering is finished, cooling to room temperature along with the furnace, and taking out the sintered composite material C, wherein the diameter of the composite material C is 40mm, and the height of the composite material C is 10 mm.

Step 4, upsetting the sample

Upsetting the composite material C obtained by sintering in the step 3, and preserving heat of the sample by adopting a muffle furnace before upsetting, wherein the heat preservation temperature is 850 ℃ and the heat preservation time is 20 min. The pressure at the time of upsetting the sample was 10MPa, and then the composite material C was taken out and air-cooled to obtain an upset sample D. To this end, Ti-CrB₂And (5) completing the preparation of the system composite material.

Ti-CrB prepared in inventive example 2₂The microstructure of the system composite material is shown in figure 2, the composition of the system composite material comprises an alpha titanium + platelet-intercrystalline beta titanium matrix tissue and fibrous TiB, and the interface combination is good; determination of Ti-CrB by Archimedes drainage method₂Calculating the density of the system composite material; the Vickers hardness was measured using an electric Brookfield hardness tester of type HBRV-187.5, the indenter for Vickers hardness being a diamond indenter of a regular quadrangular pyramid shape, the test force being 30 kg.N, and the holding pressure time being 30 s. Tensile strength was measured using a microcomputer controlled electronic universal tester of WDW-20. Ti-CrB prepared in example 2 of the present Process by the above method₂Density, hardness and resistance of the composite material of the systemThe tensile strength is tested and calculated, and the density is 99.03%, the hardness is 322.29Hv, and the tensile strength is 910 MPa.

Example 3

A preparation method of a high-strength titanium-based composite material is implemented according to the following steps:

step 1, mixing the original powder

Preparing the required original powder, Ti powder with the grain diameter of 20 mu m and CrB with the grain diameter of 0.5 mu m₂Powder; 56.38g Ti powder and 1.08g CrB powder are weighed respectively₂The powder and the used zirconia balls are put well for standby; the ratio of balls to materials is 1:2, the ratio of big balls to small balls is 3:1, the diameter of the big balls is 9-11mm, and the diameter of the small balls is 5-6 mm; and mixing the powder by adopting a three-dimensional vibration powder mixer, wherein the frequency of the three-dimensional vibration powder mixer is 50 HZ. Firstly, pure Ti powder and CrB₂Adding 0.04-0.12 mass percent of vacuum pump oil into the powder, putting the powder into a plastic bottle, mixing for 1 hour, then putting a zirconia ball, and mixing for 2 hours to obtain mixed powder A;

step 2, press forming

Putting the mixed powder A obtained in the step 1 into a die for pressing to obtain a blank B, uniformly pressurizing in the pressing process, selecting a graphite die with the diameter of 40mm, and keeping the pressing pressure at 2MPa for 2 min;

step 3, sintering the green body

Sintering the blank B obtained in the step 2 by adopting a vacuum rapid hot-pressing sintering furnace to obtain a composite material C, wherein the heating speed is 100 ℃/min, the sintering pressure is 40MPa, the sintering temperature is 1000 ℃, and the sintering time is 1 h; and (3) putting the loaded graphite mold into a furnace chamber of a vacuum rapid hot-pressing sintering furnace, inserting a thermocouple, starting vacuumizing after checking to be correct, starting a heating program when the vacuum degree is less than 10Pa, immediately closing the program when sintering is finished, cooling to room temperature along with the furnace, and taking out the sintered composite material C, wherein the diameter of the composite material C is 40mm, and the height of the composite material C is 10 mm.

Step 4, upsetting the sample

Upsetting the composite material C obtained by sintering in the step 3, and adopting a horse before upsettingAnd (4) preserving the heat of the sample by a muffle furnace, wherein the heat preservation temperature is 850 ℃, and the heat preservation time is 20 min. The pressure at the time of upsetting the sample was 10MPa, and then the composite material C was taken out and air-cooled to obtain an upset sample D. To this end, Ti-CrB₂And (5) completing the preparation of the system composite material.

Ti-CrB prepared in inventive example 3₂The microstructure of the system composite material is shown in figure 3, the composition of the system composite material comprises an alpha titanium + intercrystalline beta titanium structure and fibrous TiB, and the interface combination is good; determination of Ti-CrB by Archimedes drainage method₂Calculating the density of the system composite material; the Vickers hardness was measured using an electric Brookfield hardness tester of type HBRV-187.5, the indenter for Vickers hardness being a diamond indenter of a regular quadrangular pyramid shape, the test force being 30 kg.N, and the holding pressure time being 30 s. Tensile strength was measured using a microcomputer controlled electronic universal tester of WDW-20. Ti-CrB prepared in example 2 of the present Process by the above method₂The density, hardness and tensile strength of the system composite material are tested and calculated, and the density is 98.99%, the hardness is 357.52Hv and the tensile strength is 1065 MPa.

Example 4

A preparation method of a high-strength titanium-based composite material is implemented according to the following steps:

step 1, mixing the original powder

Preparing the required original powder, Ti powder with the grain diameter of 20 mu m and CrB with the grain diameter of 0.5 mu m₂Powder; 56.18g of Ti powder and 1.79g of CrB powder were weighed out separately₂The powder and the used zirconia balls are put well for standby; the ratio of balls to materials is 1:2, the ratio of big balls to small balls is 3:1, the diameter of the big balls is 9-11mm, and the diameter of the small balls is 5-6 mm; and mixing the powder by adopting a three-dimensional vibration powder mixer, wherein the frequency of the three-dimensional vibration powder mixer is 50 HZ. Firstly, pure Ti powder and CrB₂Adding 0.04-0.12 mass percent of vacuum pump oil into the powder, putting the powder into a plastic bottle, mixing for 1 hour, then putting a zirconia ball, and mixing for 2 hours to obtain mixed powder A;

step 2, press forming

Putting the mixed powder A obtained in the step 1 into a die for pressing to obtain a blank B, uniformly pressurizing in the pressing process, selecting a graphite die with the diameter of 40mm, and keeping the pressing pressure at 2MPa for 2 min;

step 3, sintering the green body

Sintering the blank B obtained in the step 2 by adopting a vacuum rapid hot-pressing sintering furnace to obtain a composite material C, wherein the heating speed is 100 ℃/min, the sintering pressure is 40MPa, the sintering temperature is 1000 ℃, and the sintering time is 1 h; and (3) putting the loaded graphite mold into a furnace chamber of a vacuum rapid hot-pressing sintering furnace, inserting a thermocouple, starting vacuumizing after checking to be correct, starting a heating program when the vacuum degree is less than 10Pa, immediately closing the program when sintering is finished, cooling to room temperature along with the furnace, and taking out the sintered composite material C, wherein the diameter of the composite material C is 40mm, and the height of the composite material C is 10 mm.

Step 4, upsetting the sample

Upsetting the composite material C obtained by sintering in the step 3, and preserving heat of the sample by adopting a muffle furnace before upsetting, wherein the heat preservation temperature is 850 ℃ and the heat preservation time is 20 min. The pressure at the time of upsetting the sample was 10MPa, and then the composite material C was taken out and air-cooled to obtain an upset sample D. To this end, Ti-CrB₂And (5) completing the preparation of the system composite material.

Ti-CrB prepared in inventive example 4₂The microstructure of the system composite material is shown in figure 4, the composition of the system composite material comprises an alpha titanium + intercrystalline beta titanium structure and fibrous TiB, and the interface combination is good; determination of Ti-CrB by Archimedes drainage method₂Calculating the density of the system composite material; the Vickers hardness was measured using an electric Brookfield hardness tester of type HBRV-187.5, the indenter for Vickers hardness being a diamond indenter of a regular quadrangular pyramid shape, the test force being 30 kg.N, and the holding pressure time being 30 s. Tensile strength was measured using a microcomputer controlled electronic universal tester of WDW-20. Ti-CrB prepared in example 1 of the present Process by the above method₂The density, hardness and tensile strength of the system composite material are tested and calculated, and the density is 98.96%, the hardness is 405.12Hv and the tensile strength is 1118 MPa.

Example 5

A preparation method of a high-strength titanium-based composite material is implemented according to the following steps:

step 1, mixing the original powder

Preparing the required original powder, Ti powder with the grain diameter of 20 mu m and CrB with the grain diameter of 0.5 mu m₂Powder; 55.97g of Ti powder and 2.52g of CrB powder are weighed respectively₂The powder and the used zirconia balls are put well for standby; the ratio of balls to materials is 1:2, the ratio of big balls to small balls is 3:1, the diameter of the big balls is 9-11mm, and the diameter of the small balls is 5-6 mm; and mixing the powder by adopting a three-dimensional vibration powder mixer, wherein the frequency of the three-dimensional vibration powder mixer is 50 HZ. Firstly, pure Ti powder and CrB₂Adding 0.04-0.12 mass percent of vacuum pump oil into the powder, putting the powder into a plastic bottle, mixing for 1 hour, then putting a zirconia ball, and mixing for 2 hours to obtain mixed powder A;

step 2, press forming

Putting the mixed powder A obtained in the step 1 into a die for pressing to obtain a blank B, uniformly pressurizing in the pressing process, selecting a graphite die with the diameter of 40mm, and keeping the pressing pressure at 2MPa for 2 min;

step 3, sintering the green body

Sintering the blank B obtained in the step 2 by adopting a vacuum rapid hot-pressing sintering furnace to obtain a composite material C, wherein the heating speed is 100 ℃/min, the sintering pressure is 40MPa, the sintering temperature is 1000 ℃, and the sintering time is 1 h; and (3) putting the loaded graphite mold into a furnace chamber of a vacuum rapid hot-pressing sintering furnace, inserting a thermocouple, starting vacuumizing after checking to be correct, starting a heating program when the vacuum degree is less than 10Pa, immediately closing the program when sintering is finished, cooling to room temperature along with the furnace, and taking out the sintered composite material C, wherein the diameter of the composite material C is 40mm, and the height of the composite material C is 10 mm.

Step 4, upsetting the sample

Upsetting the composite material C obtained by sintering in the step 3, and preserving heat of the sample by adopting a muffle furnace before upsetting, wherein the heat preservation temperature is 850 ℃ and the heat preservation time is 20 min. The pressure at the time of upsetting the sample was 10MPa, and then the composite material C was taken out and air-cooled to obtain an upset sample D. To this end, Ti-CrB₂System composite materialAnd (5) finishing the material preparation.

Ti-CrB prepared in inventive example 5₂The microstructure of the system composite material is shown in fig. 5, the composition of the system composite material comprises an alpha titanium + intercrystalline beta titanium structure and fibrous TiB, and the interface combination is good; determination of Ti-CrB by Archimedes drainage method₂Calculating the density of the system composite material; the Vickers hardness was measured using an electric Brookfield hardness tester of type HBRV-187.5, the indenter for Vickers hardness being a diamond indenter of a regular quadrangular pyramid shape, the test force being 30 kg.N, and the holding pressure time being 30 s. Tensile strength was measured using a microcomputer controlled electronic universal tester of WDW-20. Ti-CrB prepared in example 1 of the present Process by the above method₂The density, hardness and tensile strength of the system composite material are tested and calculated, and the density is 98.87%, the hardness is 441.30Hv and the tensile strength is 1265 MPa.