CN114058902A - High-hardness titanium-based composite material and preparation method thereof - Google Patents
High-hardness titanium-based composite material and preparation method thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C14/00—Alloys based on titanium
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- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
- C22C1/1052—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites by mixing and casting metal matrix composites with reaction
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
Abstract
The invention discloses a high-hardness titanium-based composite material which comprises the following components in percentage by mass: 4.5-5.5% of Al, 5-6% of Mo, 3-4% of V, 1-2% of Cr, 1-2% of Fe, 3-5% of TiC, and the balance of Ti and inevitable impurities; through the strengthening effect of the solid solution treatment of Al, Cr, Fe and Mo, TiC particles and a Ti matrix have good stress decomposition and strain coordination, and the effect of hardening is achieved. The invention also provides a preparation method of the high-hardness titanium-based composite material, which comprises the steps of carrying out non-consumable vacuum arc melting on the micron-sized TiC particles and the raw materials, and then carrying out homogenization, hot rolling, solid solution and aging in sequence to obtain the high-hardness titanium-based composite material, wherein the hardness can reach over 50HRC, the preparation method is simple in process, and the high-hardness titanium-based composite material is widely applied to the fields of aerospace, war industry, civil use and the like, and obviously improves the economic benefit.
Description
Technical Field
The invention belongs to the technical field of titanium-based composite materials, and particularly relates to a high-hardness titanium-based composite material and a preparation method thereof.
Background
Titanium alloy is widely applied to the fields of aerospace, weaponry, medical chemical industry and the like due to high specific strength, good mechanical properties, biocompatibility, corrosion resistance and the like. However, with the progress of science and technology, people put forward higher requirements on the performance of titanium alloys, particularly in the fields of aerospace and weaponry, the requirements for weight reduction and light weight are increasingly obvious, and the titanium alloy is used for replacing steel, high-temperature alloy and the like, so that the research and development of the titanium alloy are important. However, titanium alloys have a significant difference in hardness compared to steel and superalloys. The hardness of the existing high-strength titanium alloy is generally lower than 45 HRC, such as TB2, Ti-15333, Ti-55531 and the like, and the hardness of high-strength steel is generally higher than 50 HRC. This also greatly limits the goal of achieving weight reduction with titanium alloys.
The existing research mainly focuses on improving the yield strength and the tensile strength of the titanium alloy, but the research on the high-hardness titanium alloy is less, and the development of the industries such as aerospace, weaponry and the like in China is hindered to a certain extent.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a high hardness titanium-based composite material, aiming at the above-mentioned deficiencies of the prior art. The high-hardness titanium-based composite material is composed of Al, Mo, V, Cr, Fe, TiC and Ti, wherein the Al and the Mo play a role in strengthening the strength and the hardness of a matrix alloy by solution treatment, the Cr and the Fe are beneficial to the diffusion of C atoms, the uniformity of TiC particles is promoted, the TiC particles and a Ti matrix have good stress decomposition and strain coordination, a large amount of geometrical necessary dislocation can be formed on an interface, the hardening effect and the hardening effect are played, and the hardness of the titanium-based composite material can reach more than 50 HRC.
In order to solve the technical problems, the invention adopts the technical scheme that: the high-hardness titanium-based composite material is characterized by comprising the following components in percentage by mass: 4.5-5.5% of Al, 5-6% of Mo, 3-4% of V, 1-2% of Cr, 1-2% of Fe, 3-5% of TiC, and the balance of Ti and inevitable impurities.
The high-hardness titanium-based composite material has the advantages that Al and Mo have larger solid solution treatment degree in Ti, a good solid solution treatment strengthening effect can be achieved, the strength and hardness of a matrix alloy are improved, the addition of Cr and Fe is beneficial to the diffusion of C atoms, the uniformity of TiC particles is promoted, if the difference between the strength of a Ti matrix and the hardness of the TiC particles is large, stress shielding and strain mismatch can be caused, and cracking is easy to occur, so that the characteristic of high hardness is lost.
The high-hardness titanium-based composite material is characterized by comprising the following components in percentage by mass: 4.5-5.0% of Al, 5.6-6% of Mo, 3-3.5% of V, 1.5-2% of Cr, 1.6-2% of Fe, 3.0-4.0% of TiC, and the balance of Ti and inevitable impurities.
In addition, the invention provides a method for preparing the high-hardness titanium-based composite material, which is characterized by comprising the following steps of:
step one, uniformly mixing micron-sized TiC particles and titanium sponge particles, and then sealing and wrapping the mixture by using an aluminum foil to obtain an alloy bag;
step two, placing the alloy bag obtained in the step one at the bottom of a non-consumable vacuum electric arc furnace crucible, then uniformly mixing Al-85V intermediate alloy, Ti-32Mo intermediate alloy, Ti-32Fe intermediate alloy, electrolytic chromium and aluminum beans, placing the mixture on the upper part of the alloy bag, and then carrying out non-consumable vacuum electric arc melting to obtain an ingot;
step three, homogenizing the ingot obtained in the step two, and then carrying out hot rolling treatment to obtain a hot rolled ingot;
step four, carrying out solid solution treatment and aging treatment on the hot-rolled ingot obtained in the step three in sequence to obtain a high-hardness titanium-based composite material; the hardness of the high-hardness titanium-based composite material is more than 50 HRC.
The titanium-based composite material prepared by the invention selects micron-sized TiC particles, and can generate the following in-situ reaction in a high-temperature environment, namely when the smelting temperature is more than 3140 ℃: ti1C→Ti1+C+Ti2→Ti2C+Ti1In which Ti1Is Ti atom in TiC particle, Ti2For Ti atoms in titanium sponge, the first in situ reaction is Ti1Decomposition of C particles, and the smaller radius of C atoms, the easier in Ti2Diffusion in the matrix, improving its uniformity, while during solidification, the C atoms are in the Ti2The solubility of Ti decreases with the decrease of temperature, thereby precipitating Ti in situ2C particles, in this case in situ generated Ti2C particle size smaller than added Ti1C, the particle size is larger, and the distribution is more uniform; the size and the appearance of TiC particles can be refined and improved by the in-situ reaction, the micron-sized TiC particles are refined to be about 100nm in particle size, the uniform distribution of the TiC particles is enhanced, the clustering phenomenon of the micron-sized particles is effectively avoided, and the in-situ reaction of the TiC particles does not change the components of the matrix alloy, so that the structural stability of the matrix alloy is facilitated; the phenomenon that the TiC particles are added only and obviously clustered and distributed unevenly is avoided;
in the invention, TiC particles and titanium sponge need to be wrapped by aluminum foil, because the size of the TiC particles is smaller, the TiC particles are easy to scatter by electric arc in a vacuum non-consumable electric arc furnace and can be absorbed away in the process of vacuumizing, the TiC particles and the titanium sponge are wrapped together to shorten the diffusion distance of the TiC particles and the titanium sponge, and the alloy bag is arranged at the bottom of the crucible because of the density difference of raw materials, in the process of smelting, the intermediate alloy with high density sinks, the TiC particles with low density float up with the titanium sponge, and also for sufficient element diffusion, and magnetic stirring can be carried out in the non-consumable vacuum electric arc smelting; the homogenization treatment has the functions of realizing the interface stress relaxation between the TiC particles generated in situ and the titanium alloy matrix and the homogenization of alloy elements; the hot rolling treatment is to refine crystal grains and improve toughness.
The method is characterized in that the grain size of the micron-sized TiC particles in the first step is 2-5 microns. The invention ensures the particle size of TiC in the final titanium-based composite material by controlling the particle size of TiC particles, and improves the performance of the titanium-based composite material.
The method is characterized in that the homogenization treatment process in the step three is as follows: heating to 1000-1200 ℃, and then preserving heat for 9-12 h. According to the invention, by controlling the parameter of homogenization treatment, the uniform distribution of each component in the titanium-based composite material is ensured, the defect that the oxidation is accelerated due to overhigh homogenization temperature to cause embrittlement of the material is avoided, the defect that the in-situ generated TiC particles and the titanium alloy matrix cannot be subjected to interface stress relaxation due to overhigh temperature and the defect that the homogenization of alloy elements cannot be realized due to overlow homogenization effect are avoided, and the defect that the oxidation occurs due to overlong time and poor homogenization effect is avoided.
The method is characterized in that the temperature of the hot rolling treatment in the third step is 900-1100 ℃, the deformation of each pass is 8-12%, and the accumulated deformation is 80-100%. According to the invention, by controlling the parameters of hot rolling treatment, the crystal grains in the titanium-based composite material are refined, the toughness of the titanium-based composite material is improved, the defects that the material is softened and unstable due to overhigh temperature of the hot rolling treatment and the crystal grains grow up due to high temperature are prevented, the defect that the material is cracked due to overlow temperature is prevented, the deformation of each pass is controlled, the cracking is avoided in the hot rolling treatment process, and the effect of controlling the accumulated deformation to achieve uniform structure is achieved.
The method is characterized in that the solution treatment process in the fourth step is as follows: heating to the temperature of 30-50 ℃ below the beta transformation point of the hot-rolled ingot and then preserving heat for 1-2 h; the aging treatment process comprises the following steps: heating to 500-530 ℃ and then preserving heat for 3-5 h. According to the invention, the titanium-based composite material is enabled to obtain a recrystallized structure through solution treatment and aging treatment, the microstructure of the titanium-based composite material is ensured to be more uniform and fine, the performance of the titanium-based composite material is improved, the optimal solution treatment aging treatment effect of the titanium-based composite material is ensured by respectively controlling the parameters of the solution treatment aging treatment, so that the titanium-based composite material subjected to the solution treatment aging treatment has excellent tensile strength, yield strength, corrosion resistance and impact toughness, the defect that recrystallization cannot be realized due to too low temperature is avoided, the defect that crystal grains grow violently due to the fact that the temperature exceeds the phase transition temperature of the titanium alloy due to too high temperature is avoided, the defect that crystallization is incomplete due to too short heat preservation time is avoided, and the defect that the structure is likely to be coarsened further due to too long heat preservation time is avoided.
Compared with the prior art, the invention has the following advantages:
1. the high-hardness titanium-based composite material is composed of Al, Mo, V, Cr, Fe, TiC and Ti, wherein the Al and the Mo play a role in strengthening the strength and the hardness of a matrix alloy by solution treatment, the Cr and the Fe are beneficial to the diffusion of C atoms, the uniformity of TiC particles is promoted, the TiC particles and a Ti matrix have good stress decomposition and strain coordination, a large amount of geometrical necessary dislocation can be formed on an interface, and the effect of hardening are played, so that the hardness of the titanium-based composite material can reach more than 50 HRC.
2. According to the invention, micron-sized TiC particles are selected from the prepared titanium-based composite material and subjected to in-situ reaction in a high-temperature environment, the size and the shape of the TiC particles can be refined and improved due to the in-situ reaction, the uniform distribution of the TiC particles is enhanced, the clustering phenomenon of the micron-sized particles is effectively avoided, and the in-situ reaction of the TiC particles does not change the components of the matrix alloy, so that the tissue stability of the matrix alloy is facilitated.
3. When micron-sized TiC particles are added to the titanium-based composite material prepared by the invention, the TiC particles and the titanium sponge are mixed and are hermetically wrapped by the aluminum foil, so that short-range diffusion of Ti atoms in the smelting process can be realized, the activity of in-situ reaction is increased, and the dispersion distribution of the TiC particles is facilitated.
4. The titanium-based composite material prepared by the invention is prepared by a traditional metallurgical smelting mode, compared with the preparation methods of most titanium-based composite materials, such as powder metallurgy and the like, the preparation method has the advantages of simple process flow and low cost, and can utilize traditional equipment for titanium alloy smelting preparation, so that the cost is obviously reduced.
The technical solution of the present invention is further described in detail by examples below.
Detailed Description
Example 1
The high-hardness titanium-based composite material of the embodiment comprises the following components in percentage by mass: 4.8% of Al, 6% of Mo, 3% of V, 1.5% of Cr, 1.6% of Fe, 3.3% of TiC and the balance of Ti, namely inevitable impurities.
The embodiment comprises the following steps:
step one, uniformly mixing micron-sized TiC particles and titanium sponge particles, and then sealing and wrapping the mixture by using an aluminum foil to obtain an alloy bag; the particle size of the micron-sized TiC particles is 2-5 mu m;
step two, placing the alloy bag obtained in the step one at the bottom of a non-consumable vacuum electric arc furnace crucible, then uniformly mixing Al-85V intermediate alloy, Ti-32Mo intermediate alloy, Ti-32Fe intermediate alloy, electrolytic chromium and aluminum beans, placing the mixture on the upper part of the alloy bag, and performing non-consumable vacuum electric arc melting for 6 times to obtain an ingot;
step three, homogenizing the ingot obtained in the step two, and then carrying out hot rolling treatment to obtain a hot rolled ingot; the homogenization treatment process comprises the following steps: heating to 1100 deg.C, and maintaining the temperature for 10 h; the temperature of the hot rolling treatment is 1000 ℃, the deformation of each pass is 10 percent, and the accumulated deformation is 90 percent;
step four, carrying out solid solution treatment and aging treatment on the hot-rolled ingot obtained in the step three in sequence to obtain a high-hardness titanium-based composite material; the process of the solution treatment comprises the following steps: heating to 40 ℃ below the beta transformation point temperature of the hot-rolled ingot and then preserving heat for 1.5 h; the aging treatment process comprises the following steps: heating to 520 ℃ and then preserving heat for 4 h.
Through detection, the Rockwell hardness value of the high-hardness titanium-based composite material prepared by the embodiment reaches 52 HRC.
Example 2
The high-hardness titanium-based composite material of the embodiment comprises the following components in percentage by mass: 5.5% of Al, 5% of Mo, 4% of V, 1% of Cr, 2% of Fe, 5% of TiC and the balance of Ti, namely inevitable impurities.
The embodiment comprises the following steps:
step one, uniformly mixing micron-sized TiC particles and titanium sponge particles, and then sealing and wrapping the mixture by using an aluminum foil to obtain an alloy bag; the particle size of the micron-sized TiC particles is 2-5 mu m;
step two, placing the alloy bag obtained in the step one at the bottom of a non-consumable vacuum electric arc furnace crucible, then uniformly mixing Al-85V intermediate alloy, Ti-32Mo intermediate alloy, Ti-32Fe intermediate alloy, electrolytic chromium and aluminum beans, placing the mixture on the upper part of the alloy bag, and then carrying out non-consumable vacuum electric arc melting for 7 times to obtain an ingot;
step three, homogenizing the ingot obtained in the step two, and then carrying out hot rolling treatment to obtain a hot rolled ingot; the homogenization treatment process comprises the following steps: heating to 1000 deg.C, and keeping the temperature for 12 h; the temperature of the hot rolling treatment is 900 ℃, the deformation of each pass is 12 percent, and the accumulated deformation is 100 percent;
step four, carrying out solid solution treatment and aging treatment on the hot-rolled ingot obtained in the step three in sequence to obtain a high-hardness titanium-based composite material; the process of the solution treatment comprises the following steps: heating to 50 ℃ below the beta transformation point temperature of the hot-rolled ingot and then preserving heat for 1 h; the aging treatment process comprises the following steps: heating to 500 deg.C, and keeping the temperature for 5 h.
Through detection, the Rockwell hardness value of the high-hardness titanium-based composite material prepared by the embodiment reaches 52 HRC.
Example 3
The high-hardness titanium-based composite material of the embodiment comprises the following components in percentage by mass: 4.5% of Al, 5.6% of Mo, 3.5% of V, 2% of Cr, 1% of Fe, 4% of TiC and the balance of Ti, namely inevitable impurities.
The embodiment comprises the following steps:
step one, uniformly mixing micron-sized TiC particles and titanium sponge particles, and then sealing and wrapping the mixture by using an aluminum foil to obtain an alloy bag; the particle size of the micron-sized TiC particles is 2-5 mu m;
step two, placing the alloy bag obtained in the step one at the bottom of a non-consumable vacuum electric arc furnace crucible, then uniformly mixing Al-85V intermediate alloy, Ti-32Mo intermediate alloy, Ti-32Fe intermediate alloy, electrolytic chromium and aluminum beans, placing the mixture on the upper part of the alloy bag, and performing non-consumable vacuum electric arc melting for 8 times to obtain an ingot;
step three, homogenizing the ingot obtained in the step two, and then carrying out hot rolling treatment to obtain a hot rolled ingot; the homogenization treatment process comprises the following steps: heating to 1200 ℃, and then preserving heat for 9 h; the temperature of the hot rolling treatment is 1100 ℃, the deformation of each pass is 8 percent, and the accumulated deformation is 80 percent;
step four, carrying out solid solution treatment and aging treatment on the hot-rolled ingot obtained in the step three in sequence to obtain a high-hardness titanium-based composite material; the process of the solution treatment comprises the following steps: heating to the temperature of below 30 ℃ of the beta transformation point of the hot-rolled ingot and then preserving heat for 2 h; the aging treatment process comprises the following steps: heating to 530 ℃ and then preserving heat for 3 h.
Through detection, the Rockwell hardness value of the high-hardness titanium-based composite material prepared by the embodiment reaches 50 HRC.
Example 4
The high-hardness titanium-based composite material of the embodiment comprises the following components in percentage by mass: 5% of Al, 5.8% of Mo, 3.3% of V, 1.8% of Cr, 1.8% of Fe, 3% of TiC and the balance of Ti, namely inevitable impurities.
The embodiment comprises the following steps:
step one, uniformly mixing micron-sized TiC particles and titanium sponge particles, and then sealing and wrapping the mixture by using an aluminum foil to obtain an alloy bag; the particle size of the micron-sized TiC particles is 2-5 mu m;
step two, placing the alloy bag obtained in the step one at the bottom of a non-consumable vacuum electric arc furnace crucible, then uniformly mixing Al-85V intermediate alloy, Ti-32Mo intermediate alloy, Ti-32Fe intermediate alloy, electrolytic chromium and aluminum beans, placing the mixture on the upper part of the alloy bag, and then carrying out non-consumable vacuum electric arc melting for 7 times to obtain an ingot;
step three, homogenizing the ingot obtained in the step two, and then carrying out hot rolling treatment to obtain a hot rolled ingot; the homogenization treatment process comprises the following steps: heating to 1100 deg.C, and maintaining for 11 h; the temperature of the hot rolling treatment is 1000 ℃, the deformation of each pass is 11 percent, and the accumulated deformation is 95 percent;
step four, carrying out solid solution treatment and aging treatment on the hot-rolled ingot obtained in the step three in sequence to obtain a high-hardness titanium-based composite material; the process of the solution treatment comprises the following steps: heating to 45 ℃ below the beta transformation point temperature of the hot-rolled ingot and then preserving heat for 2 h; the aging treatment process comprises the following steps: heating to 510 ℃ and then preserving heat for 4 h.
Through detection, the Rockwell hardness value of the high-hardness titanium-based composite material prepared by the embodiment reaches 51 HRC.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (7)
1. The high-hardness titanium-based composite material is characterized by comprising the following components in percentage by mass: 4.5-5.5% of Al, 5-6% of Mo, 3-4% of V, 1-2% of Cr, 1-2% of Fe, 3-5% of TiC, and the balance of Ti and inevitable impurities.
2. The high-hardness titanium-based composite material according to claim 1, wherein the titanium-based composite material comprises the following components in percentage by mass: 4.5-5.0% of Al, 5.6-6% of Mo, 3-3.5% of V, 1.5-2% of Cr, 1.6-2% of Fe, 3.0-4.0% of TiC, and the balance of Ti and inevitable impurities.
3. A method for preparing a high hardness titanium-based composite material as claimed in claim 1 or claim 2, comprising the steps of:
step one, uniformly mixing micron-sized TiC particles and titanium sponge particles, and then sealing and wrapping the mixture by using an aluminum foil to obtain an alloy bag;
step two, placing the alloy bag obtained in the step one at the bottom of a non-consumable vacuum electric arc furnace crucible, then uniformly mixing Al-85V intermediate alloy, Ti-32Mo intermediate alloy, Ti-32Fe intermediate alloy, electrolytic chromium and aluminum beans, placing the mixture on the upper part of the alloy bag, and then carrying out non-consumable vacuum electric arc melting to obtain an ingot;
step three, homogenizing the ingot obtained in the step two, and then carrying out hot rolling treatment to obtain a hot rolled ingot;
step four, carrying out solid solution treatment and aging treatment on the hot-rolled ingot obtained in the step three in sequence to obtain a high-hardness titanium-based composite material; the hardness of the high-hardness titanium-based composite material is more than 50 HRC.
4. The method of claim 3, wherein the first step comprises a step of obtaining TiC particles with a particle size of 2 μm to 5 μm.
5. The method of claim 3, wherein the homogenization treatment in step three is performed by: heating to 1000-1200 ℃, and then preserving heat for 9-12 h.
6. The method of claim 3, wherein the temperature of the hot rolling process in the third step is 900 ℃ to 1100 ℃, the deformation per pass is 8% to 12%, and the cumulative deformation is 80% to 100%.
7. The method according to claim 3, wherein the solution treatment in step four is performed by: heating to the temperature of 30-50 ℃ below the beta transformation point of the hot-rolled ingot and then preserving heat for 1-2 h; the aging treatment process comprises the following steps: heating to 500-530 ℃ and then preserving heat for 3-5 h.
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|---|---|---|---|---|
| CN115142028A (en) * | 2022-08-25 | 2022-10-04 | 西安稀有金属材料研究院有限公司 | Preparation method of wear-resistant corrosion-resistant Fe-Cr-Al composite coating |
| CN115142028B (en) * | 2022-08-25 | 2023-06-30 | 西安稀有金属材料研究院有限公司 | Preparation method of wear-resistant corrosion-resistant Fe-Cr-Al composite coating |
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