Damping type high-impact-resistance titanium-based composite material and manufacturing method thereof

Abstract

The invention discloses a damping type high-impact-resistance titanium-based composite material and a manufacturing method thereof, and relates to the technical field of powder metallurgy, and the manufacturing method comprises the following steps: S1, pretreatment of raw materials; s2, three-layer gradient laying is carried out; s3, performing cold isostatic pressing; s4, laying a porous titanium layer; and S5, sintering and molding. According to the method, gradient layered material construction design, a cold isostatic pressing method and powder metallurgy are combined, the problems that titanium alloy strength improvement is limited, and porous titanium is difficult to directly prepare on the surface of a sample piece are solved, and synchronous manufacturing of the porous titanium layer, the high-strength titanium alloy layer, the transition layer and the high-toughness titanium alloy layer is achieved; the prepared damping type high-impact-resistance titanium-based composite material is high in strength and excellent in impact resistance and damping performance.

Description

Technical Field

[0001] The present invention relates to the technical field of powder metallurgy, and in particular to a shock-absorbing and high-impact-resistant titanium-based composite material and a manufacturing method thereof. Background Art

[0002] Titanium alloys have the advantages of low density, high specific strength, good heat resistance and corrosion resistance, excellent biocompatibility, etc., and have broad application prospects in the national defense industry and civilian industry. They are mainly used in military aircraft, civilian aircraft, aerospace engines, spacecraft, satellite hull connecting seats, etc. However, existing titanium alloys are prone to problems such as crack propagation, shock waves and noise under the impact of external forces, which have an adverse impact on the service life of the product itself and the surrounding environment, and it is difficult to meet the product requirements of aircraft structural parts, armor plates and engine bases working in high-impact environments. It is in this situation that titanium-based composite materials came into being, and their appearance has attracted wide attention in the industry.

[0003] Titanium-based composite materials have the characteristics of high strength and light weight, and are ideal shock-absorbing materials. Components such as shock absorbers and springs made of titanium-based composite materials can effectively reduce the vibration and noise generated during the operation of equipment. However, for extreme impact scenarios such as armor plate bulletproof, ship hull anti-collision and train anti-collision, existing titanium-based composite materials are still difficult to achieve the matching of strength and plasticity (toughness) to achieve a high anti-impact effect, and relying solely on high-strength materials cannot meet the shock-absorbing requirements.

[0004] In order to further improve the shock-absorbing and anti-impact characteristics, there are mainly two methods at present. The first method is to improve the strength by adding reinforcing phases such as ceramic particles to titanium alloys, but it will sacrifice a certain amount of toughness. In order to maintain the necessary plasticity (toughness) of titanium alloys, the addition amount of the reinforcing phase must be controlled, which directly limits the strength improvement range of titanium alloys. The second method is to further improve the shock-absorbing characteristics by adding a layer of porous material on the impact surface of the main material. Porous materials show significant advantages in the shock-absorbing field due to their unique pore structure and deformation ability. Their shock-absorbing mechanism is mainly reflected in that the pore structure can effectively absorb vibration stress and relieve the impact force, and at the same time, the air compressibility in the pores also provides a stable buffering effect; and the deformation of the material after being impacted can further reduce the propagation of the impact force. At present, there are ceramic porous materials, organic porous materials and metal porous materials, etc. Due to the particularity of the vacuum condition and easy chemical reaction during the forming process of titanium alloys, existing technologies need to be connected to the titanium alloy substrate by a later installation form, which has problems such as low connection strength and easy detachment, and cannot realize the synchronous manufacturing and high-strength connection of a high-strength titanium alloy matrix and a porous titanium surface.

[0005] In view of this, the present invention provides a shock-absorbing and high-impact-resistant gradient titanium-based composite material. Summary of the Invention

[0006] The object of the present invention is to provide a shock-absorbing and highly impact-resistant titanium-based composite material to overcome the deficiencies of the prior art; by using gradient laminated material construction design, cold isostatic pressing method and powder metallurgy method, the problems of the limitation of the strength improvement of titanium alloy and the difficulty of directly preparing porous titanium on the surface of the sample are solved, and the synchronous manufacturing of the porous titanium layer, high-strength titanium alloy layer, transition layer and high-toughness titanium alloy layer is realized.

[0007] To achieve the above object, the technical solution adopted by the present invention is: a manufacturing method of a shock-absorbing and highly impact-resistant titanium-based composite material, comprising the following steps:

[0008] Step S1, pretreatment of raw materials: Take three portions of titanium alloy powder, and add TiC particles with a medium particle size of 100-200 nm, TiC particles with a particle size of 15-53 μm and TiB whiskers to them respectively; put the three kinds of mixed powders and zirconia grinding balls into a ball milling tank, and carry out low-energy ball milling and powder mixing at a rotation speed of 80-120 r / min and a total ball milling time of 24 h in an argon atmosphere. The powders after ball milling and mixing are called fine TiC mixed powder, coarse TiC mixed powder and TiB mixed powder in turn;

[0009] Step S2, three-layer gradient laying: Spread the fine TiC mixed powder on the bottom of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom; spread the coarse TiC mixed powder above the fine TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom; spread the TiB mixed powder above the coarse TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom;

[0010] Step S3, cold isostatic pressing: Put the cold isostatic pressing mold after completing the three-layer gradient laying in step S2 into a cold isostatic pressing device, and cold isostatically press it into a dense pre-pressed gradient material;

[0011] Step S4, laying the porous titanium layer: Put the pre-pressed gradient material into a graphite mold with the side containing TiB whiskers facing up; add porous titanium powder above the pre-pressed gradient material in the graphite mold;

[0012] Step S5, sintering and forming: Put the graphite mold into a vacuum sintering device for sintering and forming to obtain a shock-absorbing and highly impact-resistant titanium-based composite material.

[0013] Preferably, the particle size of the titanium alloy powder is 15-45 μm.

[0014] Preferably, the addition amount of the TiC particles with a particle size of 100-200 nm is 2-5% of the total mass of the fine TiC mixed powder.

[0015] Preferably, the addition amount of the TiC particles with a particle size of 15-53 μm is 10-15% of the total mass of the coarse TiC mixed powder.

[0016] Preferably, the whisker diameter of the TiB whiskers is 0.5 - 2.0 μm.

[0017] Preferably, the addition amount of the TiB whiskers is 20 - 30% of the total mass of the TiB mixed powder.

[0018] Preferably, the laying thickness of the fine TiC mixed powder in step S2 is 50 - 60% of the thickness of the material main body.

[0019] Preferably, the laying thickness of the coarse TiC mixed powder in step S2 is 5 - 10% of the thickness of the material main body.

[0020] Preferably, the material of the cold isostatic pressing die in step S3 is thermoplastic elastomer polyurethane or rubber.

[0021] Preferably, the pressure of the cold isostatic pressing in step S3 is 600 - 800 MPa, and the time is 30 - 60 s.

[0022] Preferably, the porous titanium powder in step S4 is sponge titanium debris or a mixture of sponge titanium debris and ceramic hollow spheres.

[0023] Preferably, the diameter of the ceramic hollow spheres is 3 - 10 mm, and the material of the ceramic hollow spheres is one or both of alumina and zirconia.

[0024] Preferably, the porosity of the sponge titanium debris is above 50%, and the particle size is 0.83 - 5 mm.

[0025] Preferably, in the mixture of sponge titanium debris and ceramic hollow spheres, the volume fraction of the ceramic hollow spheres accounts for 10 - 50%.

[0026] Preferably, the thickness of the porous titanium powder is 10 - 20% of the main material.

[0027] Preferably, the process parameters of the sintering and forming in step S5 are as follows: First, heat up at a heating rate of 18 - 22 °C / min to 740 - 760 °C, and keep warm for 9 - 11 min; then heat up at a heating rate of 10 - 15 °C / min to 940 - 960 °C, and keep warm for 9 - 11 min; then heat up at a heating rate of 6 - 10 °C / min to 1040 - 1060 °C, and keep warm for 1 h, and then take out the sample when the furnace is cooled to below 200 °C.

[0028] Another object of the present invention is to provide a shock-absorbing and highly impact-resistant titanium-based composite material manufactured by using the manufacturing method of the above-mentioned shock-absorbing and highly impact-resistant titanium-based composite material. Description of the Drawings

[0029] Figure 1The stress-time curve of porous titanium with a porosity of 50%;

[0030] Figure 2 Schematic diagram of the layering of a shock-absorbing and highly impact-resistant material;

[0031] Figure 3 SEM 500X picture comparison of TC4 and TC4 strengthened by nano-TiC;

[0032] Figure 4 The stress-time curve of porous titanium with a porosity of 90%. Specific implementation method

[0033] A manufacturing method of a shock-absorbing and highly impact-resistant titanium-based composite material, comprising the following steps:

[0034] Step S1, pretreatment of raw materials: Take three portions of titanium alloy powder, and add TiC particles with a medium particle size of 100-200 nm, TiC particles with a particle size of 15-53 μm, and TiB whiskers to them respectively; Put the three kinds of mixed powders and zirconia grinding balls into the ball mill tank respectively, and carry out low-energy ball milling and powder mixing with a rotation speed of 80-120 r / min and a total ball milling time of 24 h in an argon environment. The powders after ball milling and mixing are called fine TiC mixed powder, coarse TiC mixed powder and TiB mixed powder in turn;

[0035] Step S2, three-layer gradient laying: Spread the fine TiC mixed powder on the bottom of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom; Spread the coarse TiC mixed powder on top of the fine TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom; Spread the TiB mixed powder on top of the coarse TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom;

[0036] Step S3, cold isostatic pressing: Put the cold isostatic pressing mold after completing the three-layer gradient laying in step S2 into the cold isostatic pressing equipment, and cold isostatically press it into a dense pre-pressed gradient material;

[0037] Step S4, laying a porous titanium layer: Put the pre-pressed gradient material into the graphite mold with the side containing TiB whiskers facing up; Add porous titanium powder above the pre-pressed gradient material in the graphite mold to form a porous titanium layer;

[0038] Step S5, sintering and forming: Put the graphite mold into the vacuum sintering equipment for sintering and forming to obtain a shock-absorbing and highly impact-resistant titanium-based composite material.

[0039] Preferably, the particle size of the titanium alloy powder is 15-45 μm.

[0040] Preferably, the addition amount of the TiC particles with a particle size of 100-200 nm is 2-5% of the total mass of the fine TiC mixed powder.

[0041] Preferably, the addition amount of the TiC particles with a particle size of 15-53 μm is 10-15% of the total mass of the coarse TiC mixed powder.

[0042] Preferably, the whisker diameter of the TiB whiskers is 0.5-2.0 μm.

[0043] Preferably, the addition amount of the TiB whiskers is 20-30% of the total mass of the TiB mixed powder.

[0044] Preferably, the laying thickness of the fine TiC mixed powder in step S2 is 50-60% of the thickness of the material body.

[0045] Preferably, the laying thickness of the coarse TiC mixed powder in step S2 is 5-10% of the thickness of the material body.

[0046] Preferably, the material of the cold isostatic pressing mold in step S3 is thermoplastic elastomer polyurethane or rubber.

[0047] Preferably, the pressure of the cold isostatic pressing in step S3 is 600-800 MPa, and the time is 30-60 s.

[0048] Preferably, the porous titanium powder in step S4 is sponge titanium chips or a mixture of sponge titanium chips and ceramic hollow spheres.

[0049] Preferably, the diameter of the ceramic hollow spheres is 3-10 mm, and the material of the ceramic hollow spheres is one or both of alumina and zirconia.

[0050] Preferably, the porosity of the sponge titanium chips is above 50%, and the particle size is 0.83-5 mm.

[0051] Preferably, in the mixture of sponge titanium chips and ceramic hollow spheres, the volume fraction of the ceramic hollow spheres accounts for 10-50%.

[0052] Preferably, the thickness of the porous titanium layer is 10-20% of the main material.

[0053] Preferably, the process parameters of the sintering and forming in step S5 are as follows: first, heat up to 740-760 °C at a heating rate of 18-22 °C / min and hold for 9-11 min; then heat up to 940-960 °C at a heating rate of 10-15 °C / min and hold for 9-11 min; then heat up to 1040-1060 °C at a heating rate of 6-10 °C / min and hold for 1 h, and then take out the sample when the furnace is cooled to below 200 °C.

[0054] Another object of the present invention is to provide a shock-absorbing and highly impact-resistant titanium-based composite material manufactured by the manufacturing method of the above-mentioned shock-absorbing and highly impact-resistant titanium-based composite material.

[0055] Due to the application of the above technical solution, the present invention has the following beneficial effects:

[0056] (1) The shock-absorbing and highly impact-resistant titanium-based composite material disclosed by the present invention has a gradient material with a strong and tough layer gradient distribution as the main body of the composite material, which has high hardness and anti-penetration performance, and the defense function can be adjusted by the thickness of different layers;

[0057] (2) The shock-absorbing and highly impact-resistant titanium-based composite material disclosed by the present invention has a porous structure on the surface layer of the composite material, which has the functions of shock absorption and energy absorption. The porosity of the porous titanium on the surface layer can be adjusted by the porosity of titanium sponge, the size of ceramic hollow balls and the addition ratio of the two, so as to obtain products with different shock absorption grades.

[0058] (3) The shock-absorbing and highly impact-resistant titanium-based composite material disclosed by the present invention combines high strength, high impact resistance and excellent shock absorption performance by reasonably selecting the component formula and manufacturing process parameters of each gradient layer material, and can meet the material performance requirements for manufacturing protective shells in fields such as deep sea, weapons and aviation, such as armor plates.

[0059] In order to enable those skilled in the art to better understand the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art under the premise of equivalent changes and modifications based on the embodiments of the present invention shall fall within the protection scope of the present invention.

[0060] Example 1

[0061] A manufacturing method of a shock-absorbing and highly impact-resistant titanium-based composite material includes the following steps:

[0062] Step S1, pretreatment of raw materials: Take three portions of titanium alloy powder, and add TiC particles with a medium particle size of 100 nm, TiC particles with a particle size of 15 μm and TiB whiskers to them respectively; put the three kinds of mixed powders and zirconia grinding balls (ball-to-material ratio 4:1) into a ball milling tank, and carry out low-energy ball milling and powder mixing with a rotation speed of 80 r / min and a total ball milling time of 24 h in an argon environment. The powders after ball milling and mixing are called fine TiC mixed powder, coarse TiC mixed powder and TiB mixed powder in turn;

[0063] Step S2, three-layer gradient laying: Spread the fine TiC mixed powder at the bottom of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom; spread the coarse TiC mixed powder above the fine TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom; spread the TiB mixed powder above the coarse TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom;

[0064] Step S3, cold isostatic pressing: Put the cold isostatic pressing mold after completing the three-layer gradient laying in step S2 into the cold isostatic pressing equipment, and cold isostatically press it into a dense pre-pressed gradient material;

[0065] Step S4, laying the porous titanium layer: Put the pre-pressed gradient material into the graphite mold with the side containing TiB whiskers facing up; add porous titanium powder above the pre-pressed gradient material in the graphite mold to form a porous titanium layer;

[0066] Step S5, sintering and forming: Put the graphite mold into the vacuum sintering equipment for sintering and forming to obtain a shock-absorbing high-impact-resistant titanium-based composite material.

[0067] The particle size of the titanium alloy powder is 15 μm; the addition amount of the TiC particles with a particle size of 100 nm is 2% of the total mass of the fine TiC mixed powder; the addition amount of the TiC particles with a particle size of 15 μm is 10% of the total mass of the coarse TiC mixed powder; the whisker diameter of the TiB whiskers is 0.5 μm; the addition amount of the TiB whiskers is 20% of the total mass of the TiB mixed powder.

[0068] The laying thickness of the fine TiC mixed powder in step S2 is 50% of the thickness of the material main body; the laying thickness of the coarse TiC mixed powder in step S2 is 5% of the thickness of the material main body; the material of the cold isostatic pressing mold in step S3 is thermoplastic elastomer polyurethane; the pressure of the cold isostatic pressing in step S3 is 600 MPa and the time is 30 s; the porous titanium powder in step S4 is sponge titanium debris; the porosity of the sponge titanium debris is 50% and the particle size is 0.83 mm; the thickness of the porous titanium layer is 10% of the main body material.

[0069] The process parameters of the sintering and forming in step S5 are: First, heat up to 740 °C at a heating rate of 18 °C / min and hold for 9 min; then heat up to 940 °C at a heating rate of 10 °C / min and hold for 9 min; then heat up to 1040 °C at a heating rate of 6 °C / min and hold for 1 h, and then take out the sample when it cools down to below 200 °C with the furnace.

[0070] A shock-absorbing high-impact-resistant titanium-based composite material manufactured by using the manufacturing method of the above-mentioned shock-absorbing high-impact-resistant titanium-based composite material.

[0071] Example 2

[0072] A manufacturing method of a shock-absorbing and highly impact-resistant titanium-based composite material, comprising the following steps:

[0073] Step S1, pretreatment of raw materials: Take three portions of titanium alloy powder, and add TiC particles with a medium particle size of 120 nm, TiC particles with a particle size of 25 μm, and TiB whiskers to them respectively; put the three kinds of mixed powders and zirconia grinding balls (ball-to-material ratio 4:1) into a ball milling tank, and carry out low-energy ball milling and powder mixing with a rotation speed of 90 r / min and a total ball milling time of 24 h in an argon atmosphere. The powders after ball milling and mixing are called fine TiC mixed powder, coarse TiC mixed powder, and TiB mixed powder in sequence;

[0074] Step S2, three-layer gradient laying: Lay the fine TiC mixed powder on the bottom of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom; lay the coarse TiC mixed powder above the fine TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom; lay the TiB mixed powder above the coarse TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom;

[0075] Step S3, cold isostatic pressing: Put the cold isostatic pressing mold after completing the three-layer gradient laying in step S2 into a cold isostatic pressing device, and cold isostatically press it into a dense pre-pressed gradient material;

[0076] Step S4, laying a porous titanium layer: Put the pre-pressed gradient material into a graphite mold with the side containing TiB whiskers facing up; add porous titanium powder above the pre-pressed gradient material in the graphite mold to form a porous titanium layer;

[0077] Step S5, sintering and forming: Put the graphite mold into a vacuum sintering device for sintering and forming to obtain a shock-absorbing and highly impact-resistant titanium-based composite material.

[0078] The particle size of the titanium alloy powder is 25 μm; the addition amount of TiC particles with a particle size of 120 nm is 3% of the total mass of the fine TiC mixed powder; the addition amount of TiC particles with a particle size of 25 μm is 11% of the total mass of the coarse TiC mixed powder; the whisker diameter of the TiB whiskers is 0.8 μm; the addition amount of the TiB whiskers is 22% of the total mass of the TiB mixed powder; the laying thickness of the fine TiC mixed powder in step S2 is 53% of the thickness of the material main body; the laying thickness of the coarse TiC mixed powder in step S2 is 6% of the thickness of the material main body; the material of the cold isostatic pressing die in step S3 is rubber; the pressure of the cold isostatic pressing in step S3 is 650 MPa, and the time is 40 s; the porous titanium powder in step S4 is a mixture of titanium sponge debris and ceramic hollow spheres; the sphere diameter of the ceramic hollow spheres is 3 mm, and the material of the ceramic hollow spheres is alumina; the porosity of the titanium sponge debris is 60%, and the particle size is 2 mm; in the mixture of the titanium sponge debris and the ceramic hollow spheres, the volume fraction of the ceramic hollow spheres accounts for 10%; the thickness of the porous titanium layer is 13% of the main material.

[0079] The process parameters of the sintering and forming in step S5 are as follows: First, heat up to 745 °C at a heating rate of 19 °C / min and hold for 10 min; then heat up to 945 °C at a heating rate of 12 °C / min and hold for 10 min; then heat up to 1045 °C at a heating rate of 7 °C / min and hold for 1 h, and then take out the sample when it is cooled in the furnace to below 200 °C.

[0080] A shock-absorbing and highly impact-resistant titanium-based composite material manufactured by using the manufacturing method of the above-mentioned shock-absorbing and highly impact-resistant titanium-based composite material.

[0081] Example 3

[0082] A manufacturing method of a shock-absorbing and highly impact-resistant titanium-based composite material, comprising the following steps:

[0083] Step S1, pretreatment of raw materials: Take three portions of titanium alloy powder, and add TiC particles with a medium particle size of 150 nm, TiC particles with a particle size of 33 μm, and TiB whiskers to them respectively; load the three kinds of mixed powders and zirconia grinding balls (ball-to-material ratio of 4:1) into a ball mill tank, and carry out low-energy ball milling and powder mixing with a rotation speed of 100 r / min and a total ball milling time of 24 h in an argon atmosphere. The powders after ball milling and mixing are called fine TiC mixed powder, coarse TiC mixed powder, and TiB mixed powder in sequence;

[0084] Step S2, three-layer gradient laying: Spread the fine TiC mixed powder on the bottom of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom; Spread the coarse TiC mixed powder on top of the fine TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom; Spread the TiB mixed powder on top of the coarse TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom;

[0085] Step S3, cold isostatic pressing: Place the cold isostatic pressing mold after completing the three-layer gradient laying in step S2 into the cold isostatic pressing equipment, and cold isostatically press it into a dense pre-pressed gradient material;

[0086] Step S4, laying the porous titanium layer: Place the pre-pressed gradient material into the graphite mold with the side containing TiB whiskers facing up; Add porous titanium powder above the pre-pressed gradient material in the graphite mold to form a porous titanium layer;

[0087] Step S5, sintering and forming: Place the graphite mold into a vacuum sintering equipment for sintering and forming to obtain a shock-absorbing high-impact-resistant titanium-based composite material.

[0088] The particle size of the titanium alloy powder is 30 μm; the addition amount of TiC particles with a particle size of 150 nm is 3.5% of the total mass of the fine TiC mixed powder; the addition amount of TiC particles with a particle size of 33 μm is 13% of the total mass of the coarse TiC mixed powder; the whisker diameter of the TiB whiskers is 1.3 μm; the addition amount of the TiB whiskers is 25% of the total mass of the TiB mixed powder; the laying thickness of the fine TiC mixed powder in step S2 is 55% of the thickness of the material main body; the laying thickness of the coarse TiC mixed powder in step S2 is 7% of the thickness of the material main body; the material of the cold isostatic pressing mold in step S3 is thermoplastic elastomer polyurethane; the pressure of the cold isostatic pressing in step S3 is 700 MPa and the time is 45 s; the porous titanium powder in step S4 is sponge titanium debris; the porosity of the sponge titanium debris is 80% and the particle size is 3 mm; the thickness of the porous titanium layer is 15% of the main body material.

[0089] The process parameters of the sintering and forming in step S5 are: First, heat up to 750 °C at a heating rate of 20 °C / min and hold for 10 min; then heat up to 950 °C at a heating rate of 13 °C / min and hold for 10 min; then heat up to 1050 °C at a heating rate of 8 °C / min and hold for 1 h, and then cool the sample in the furnace to below 200 °C and take out the sample.

[0090] A shock-absorbing high-impact-resistant titanium-based composite material manufactured by using the manufacturing method of the above-mentioned shock-absorbing high-impact-resistant titanium-based composite material.

[0091] Example 4

[0092] A manufacturing method of a shock-absorbing and highly impact-resistant titanium-based composite material, comprising the following steps:

[0093] Step S1, pretreatment of raw materials: Take three portions of titanium alloy powder, and add TiC particles with a medium particle size of 180 nm, TiC particles with a particle size of 45 μm, and TiB whiskers thereto respectively; put the three kinds of mixed powders and zirconia grinding balls (ball-to-material ratio of 4:1) into a ball milling tank, and perform low-energy ball milling and powder mixing with a rotation speed of 110 r / min and a total ball milling time of 24 h in an argon atmosphere. The powders after ball milling and mixing are successively called fine TiC mixed powder, coarse TiC mixed powder, and TiB mixed powder;

[0094] Step S2, three-layer gradient laying: Lay the fine TiC mixed powder at the bottom of a cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom; lay the coarse TiC mixed powder above the fine TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom; lay the TiB mixed powder above the coarse TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom;

[0095] Step S3, cold isostatic pressing: Put the cold isostatic pressing mold after completing the three-layer gradient laying in step S2 into a cold isostatic pressing device, and cold isostatically press it into a dense pre-pressed gradient material;

[0096] Step S4, laying a porous titanium layer: Put the pre-pressed gradient material into a graphite mold with the side containing TiB whiskers facing upward; add porous titanium powder above the pre-pressed gradient material in the graphite mold to form a porous titanium layer;

[0097] Step S5, sintering and forming: Put the graphite mold into a vacuum sintering device for sintering and forming to obtain a shock-absorbing and highly impact-resistant titanium-based composite material.

[0098] The particle size of the titanium alloy powder is 40 μm; the addition amount of the TiC particles with a particle size of 180 nm is 4.5% of the total mass of the fine TiC mixed powder; the addition amount of the TiC particles with a particle size of 45 μm is 14% of the total mass of the coarse TiC mixed powder; the whisker diameter of the TiB whiskers is 1.7 μm; the addition amount of the TiB whiskers is 28% of the total mass of the TiB mixed powder; the laying thickness of the fine TiC mixed powder in step S2 is 58% of the thickness of the material main body; the laying thickness of the coarse TiC mixed powder in step S2 is 9% of the thickness of the material main body; the material of the cold isostatic pressing die in step S3 is rubber; the pressure of the cold isostatic pressing in step S3 is 750 MPa and the time is 55 s; the porous titanium powder in step S4 is a mixture of titanium sponge debris and ceramic hollow spheres; the sphere diameter of the ceramic hollow spheres is 8 mm, and the material of the ceramic hollow spheres is zirconia; the porosity of the titanium sponge debris is 85% and the particle size is 4.5 mm; in the mixture of the titanium sponge debris and the ceramic hollow spheres, the volume fraction of the ceramic hollow spheres accounts for 40%; the thickness of the porous titanium layer is 18% of the main material.

[0099] The process parameters of the sintering and forming in step S5 are as follows: First, heat up to 755 °C at a heating rate of 21 °C / min and hold for 10.5 min; then heat up to 955 °C at a heating rate of 14 °C / min and hold for 10.5 min; then heat up to 1055 °C at a heating rate of 9.5 °C / min and hold for 1 h, and then take out the sample when it is cooled in the furnace to below 200 °C.

[0100] A shock-absorbing and highly impact-resistant titanium-based composite material manufactured by using the manufacturing method of the above-mentioned shock-absorbing and highly impact-resistant titanium-based composite material.

[0101] Example 5

[0102] A manufacturing method of a shock-absorbing and highly impact-resistant titanium-based composite material, comprising the following steps:

[0103] Step S1, pretreatment of raw materials: Take three portions of titanium alloy powder, and add TiC particles with a medium particle size of 200 nm, TiC particles with a particle size of 53 μm, and TiB whiskers to them respectively; put the three kinds of mixed powders and zirconia grinding balls (ball-to-material ratio of 4:1) into a ball mill tank, and carry out low-energy ball milling and powder mixing with a rotation speed of 120 r / min and a total ball milling time of 24 h in an argon atmosphere. The powders after ball milling and mixing are called fine TiC mixed powder, coarse TiC mixed powder, and TiB mixed powder in turn;

[0104] Step S2. Three - layer gradient laying: Spread the fine TiC mixed powder at the bottom of the cold isostatic pressing mold, and flatten it with a high - purity graphite block with a flat bottom; Spread the coarse TiC mixed powder above the fine TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high - purity graphite block with a flat bottom; Spread the TiB mixed powder above the coarse TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high - purity graphite block with a flat bottom;

[0105] Step S3. Cold isostatic pressing: Put the cold isostatic pressing mold after completing the three - layer gradient laying in step S2 into the cold isostatic pressing equipment, and cold isostatically press it into a dense pre - pressed gradient material;

[0106] Step S4. Laying the porous titanium layer: Put the pre - pressed gradient material into the graphite mold with the side containing TiB whiskers facing up; Add porous titanium powder above the pre - pressed gradient material in the graphite mold to form a porous titanium layer;

[0107] Step S5. Sintering and forming: Put the graphite mold into the vacuum sintering equipment for sintering and forming to obtain a shock - absorbing and high - impact - resistant titanium - based composite material.

[0108] The particle size of the titanium alloy powder is 45μm; The addition amount of TiC particles with a particle size of 200nm is 5% of the total mass of the fine TiC mixed powder; The addition amount of TiC particles with a particle size of 53μm is 15% of the total mass of the coarse TiC mixed powder; The whisker diameter of the TiB whiskers is 2.0μm; The addition amount of the TiB whiskers is 30% of the total mass of the TiB mixed powder; The laying thickness of the fine TiC mixed powder in step S2 is 60% of the thickness of the material main body; The laying thickness of the coarse TiC mixed powder in step S2 is 10% of the thickness of the material main body; The material of the cold isostatic pressing mold in step S3 is thermoplastic elastomer polyurethane; The pressure of the cold isostatic pressing in step S3 is 800MPa, and the time is 60s; The porous titanium powder in step S4 is sponge titanium debris; The porosity of the sponge titanium debris is 90%, and the particle size is 5mm; The thickness of the porous titanium layer is 20% of the main body material.

[0109] The process parameters of the sintering and forming in step S5 are: First, heat up to 760℃ at a heating rate of 22℃ / min and hold for 11min; Then, heat up to 960℃ at a heating rate of 15℃ / min and hold for 11min; Next, heat up to 1060℃ at a heating rate of 10℃ / min and hold for 1h, and then cool the sample in the furnace. When the temperature drops below 200℃, take out the sample.

[0110] A shock - absorbing and high - impact - resistant titanium - based composite material manufactured by the manufacturing method of the above - mentioned shock - absorbing and high - impact - resistant titanium - based composite material.

[0111] Figure 1The stress-time curve of porous titanium with 50% porosity was obtained by using a universal testing machine to simulate the impact force of the warhead. The size of the test sample was φ60mm×10mm, the simulated pressure was 60MPa, and the corresponding applied force was 168kN. If a titanium alloy of non-porous material was used for the experiment, the test force would rapidly rise to 168kN. It can be seen from the stress-time curve of 50% porous titanium that before reaching a nearly dense state, porous titanium can maintain an energy absorption process of 45kN and form an obvious step because it will undergo a process of over-collapse deformation with continuous backward movement. Compared with the direct force of 168kN, the energy absorption process of porous titanium will inevitably play a more significant shock-absorbing role and absorb a very large amount of energy.

[0112] Figure 2 It is a schematic diagram of the layering of shock-absorbing and high anti-impact materials. The gradient material is divided into three layers: high-strength titanium, transition titanium, and high-toughness titanium. After adding TiB whiskers to the high-strength titanium layer, the toughness decreases, while the hardness and strength are greatly improved, enabling it to resist the huge impacts of entities such as shells and seabed rocks. High-toughness titanium can enhance the strength and toughness of the titanium alloy through the grain refinement effect of nanoparticles and the dispersion strengthening effect of the second phase, and maintain the integrity of the overall material after being subjected to extremely large impacts. The transition titanium plays a transitional role between high-strength titanium and high-toughness titanium, avoiding excessive stress and crack defects between two materials with large performance differences. The TiC and TiB hard phases added to the three-layer material, as well as the differences in the microstructure and phase of different layers, also have the effect of absorbing shock waves more effectively compared with homogeneous titanium alloys.

[0113] Figure 3 It is a comparison of SEM 500X pictures of TC4 titanium alloy and nano-TiC reinforced TC4 titanium alloy. It can be seen that after adding nano-TiC particles, the grains of TC4 are refined, and the TiC particles are dispersed in the matrix, which can play a dispersion strengthening role.

[0114] Figure 4 It is obtained by using a universal testing machine to simulate the action of a large impact force ( Figure 1 the same test force), and the stress-time curve of porous titanium with 90% porosity. The size of the test sample was φ60mm×10mm, the simulated pressure was 60MPa, and the corresponding applied force was 168kN. If a titanium alloy of non-porous material was used for the experiment, the test force would rapidly rise to 168kN. It can be seen from the stress-time curve of 90% porous titanium that before reaching a nearly dense state, porous titanium can maintain an energy absorption process of 30kN and form an obvious step because it will undergo a process of over-collapse deformation with continuous backward movement. Compared with the direct force of 168kN, the energy absorption process of porous titanium will inevitably play a very significant shock-absorbing role and absorb a large amount of energy.

[0115] The above embodiments are only used to illustrate the technical concept and features of the present invention, and the purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly. It is not intended to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit and essence of the present invention should be covered within the protection scope of the present invention.

Claims

1. A method for manufacturing a shock-absorbing high-impact titanium-based composite material, characterized in that: The steps include: Step S1, pretreatment of raw materials: take three portions of titanium alloy powder, add TiC particles with a medium particle size of 100-200 nm, TiC particles with a particle size of 15-53 μm and TiB whiskers respectively thereto; put the three mixed powders and zirconium oxide grinding balls into a ball mill respectively, and perform low-energy ball milling mixing at a speed of 80-120 r / min and a total ball milling time of 24 h in an argon environment, and the powders after ball milling are respectively called fine TiC mixed powder, coarse TiC mixed powder and TiB mixed powder; Step S2, three-layer gradient paving: spread the fine TiC mixed powder to the bottom of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom; spread the coarse TiC mixed powder above the fine TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom; spread the TiB mixed powder above the coarse TiC mixed powder in the cavity of the cold isostatic pressing mold, and flatten it with a high-purity graphite block with a flat bottom; Step S3, cold isostatic pressing: placing the cold isostatic pressing mold after the three-layer gradient laying in step S2 into a cold isostatic pressing device, and cold isostatic pressing to form a dense pre-pressed gradient material; Step S4, laying a porous titanium layer: placing the pre-pressed gradient material into a graphite mold with the side containing the TiB whiskers facing upward; adding porous titanium powder above the pre-pressed gradient material in the graphite mold to form a porous titanium layer; Step S5, sintering: placing the graphite mold in a vacuum sintering device for sintering to obtain a shock-absorbing and highly impact-resistant titanium-based composite material.

2. The method for manufacturing a shock-absorbing high-impact titanium-based composite material according to claim 1, characterized in that: The particle size of the titanium alloy powder is 15-45 μm.

3. The method for manufacturing a shock-absorbing high-impact titanium-based composite material according to claim 1, characterized in that: The added amount of the TiC particles with a particle size of 100-200 nm is 2-5% of the total mass of the fine TiC mixed powder; the added amount of the TiC particles with a particle size of 15-53 μm is 10-15% of the total mass of the coarse TiC mixed powder.

4. The method for manufacturing a shock-absorbing high-impact titanium-based composite material according to claim 1, characterized in that: The diameter of the TiB whisker is 0.5-2.0 μm; the added amount of the TiB whisker is 20-30% of the total mass of the TiB mixed powder.

5. The method for manufacturing a shock-absorbing high-impact titanium-based composite material according to claim 1, characterized in that: The laying thickness of the fine TiC mixed powder in step S2 is 50-60% of the thickness of the main body of the material; the laying thickness of the coarse TiC mixed powder in step S2 is 5-10% of the thickness of the main body of the material.

6. The method for manufacturing a shock-absorbing high-impact titanium-based composite material according to claim 1, characterized in that: The material of the cold isostatic pressing mold in step S3 is thermoplastic elastomer polyurethane or rubber; the pressure of the cold isostatic pressing in step S3 is 600-800 MPa, and the time is 30-60 seconds.

7. The method for manufacturing a shock-absorbing high impact-resistant titanium-based composite material according to claim 1, characterized in that: The porous titanium powder in step S4 is sponge titanium debris or a mixture of sponge titanium debris and ceramic hollow balls; the diameter of the ceramic hollow balls is 3-10 mm, and the material of the ceramic hollow balls is one or two of alumina and zirconia; the porosity of the sponge titanium debris is above 50%, and the particle size is 0.83-5 mm; in the mixture of sponge titanium debris and ceramic hollow balls, the volume fraction of ceramic hollow balls accounts for 10-50%.

8. The method for manufacturing a shock-absorbing high impact-resistant titanium-based composite material according to claim 1, characterized in that: The thickness of the porous titanium layer is 10-20% of the main material.

9. The method for manufacturing a shock-absorbing high impact-resistant titanium-based composite material according to claim 1, characterized in that: The process parameters of the sintering molding in step S5 are: first, heat up to 740-760°C at a heating rate of 18-22°C / min, and keep warm for 9-11 minutes; then heat up to 940-960°C at a heating rate of 10-15°C / min, and keep warm for 9-11 minutes; then heat up to 1040-1060°C at a heating rate of 6-10°C / min, and keep warm for 1 hour, and then take out the sample when it cools to below 200°C in the furnace.

10. A shock-absorbing and high-impact-resistant titanium-based composite material manufactured by the method for manufacturing a shock-absorbing and high-impact-resistant titanium-based composite material according to any one of claims 1 to 9.

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