CN110218958B - Method for preparing silicon carbide nanowire reinforced titanium-based composite material at low temperature - Google Patents
Method for preparing silicon carbide nanowire reinforced titanium-based composite material at low temperature Download PDFInfo
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Abstract
The invention discloses a method for preparing a silicon carbide nanowire reinforced titanium-based composite material at low temperature, which comprises the steps of uniformly mixing absolute ethyl alcohol, tetraethoxysilane, distilled water and hydrochloric acid solution, adding graphite powder to obtain silica sol-coated graphite powder, carrying out carbothermic reduction reaction to obtain a silicon carbide nanowire, carrying out ultrasonic dispersion on the silicon carbide nanowire, adding titanium powder, carrying out heat preservation and stirring uniformly, drying to obtain mixed powder of the silicon carbide nanowire and the titanium powder, and carrying out discharge plasma hot-pressing sintering to obtain the silicon carbide nanowire reinforced titanium-based composite material. The invention carries out discharge plasma hot-pressing sintering at low temperature and high pressure, avoids the reaction of the silicon carbide nanowire and titanium to generate carbide and silicide in a high-temperature environment, and ensures the strengthening and toughening effect of the silicon carbide nanowire; meanwhile, the silicon carbide nanowire is tightly combined with the titanium matrix to form a multi-scale toughening structure, so that the toughening effect of the silicon carbide nanowire is improved, and the mechanical property of the silicon carbide nanowire reinforced titanium matrix composite is improved.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a method for preparing a silicon carbide nanowire reinforced titanium-based composite material at a low temperature.
Background
Titanium and titanium alloy are used as lightweight structural materials with excellent performance, have high specific strength and specific stiffness and good processability, corrosion resistance and high temperature resistance, and have wide application prospects in various fields such as aerospace, ships and automobiles, weapon engineering, medical instruments, chemical energy and the like. However, the weak points of poor wear resistance and low hardness of titanium and titanium alloy hinder the application of titanium and titanium alloy in engineering. In order to meet various requirements accompanying rapid development of high and new technologies, research and development of novel titanium alloy composite materials are urgently needed to meet the requirements of aerospace industry development.
The silicon carbide nanowire has excellent performances of high strength, high modulus, heat resistance, wear resistance and the like, is successfully applied to reinforcing and modifying ceramic matrix, metal matrix and resin matrix composite materials, and shows a good toughening effect. In the process of preparing the silicon carbide nanowire reinforced titanium-based composite material by utilizing the hot-pressing sintering process, because the activity ratio of titanium is higher in a high-temperature environment (the temperature of the hot-pressing sintering process is usually 1200-1400 ℃), the silicon carbide nanowire is easy to react with titanium to generate carbide and silicide, and the inherent structural characteristics of the silicon carbide nanowire are lost, so that the toughening effect of the silicon carbide nanowire is weakened.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing a silicon carbide nanowire reinforced titanium-based composite material at a low temperature aiming at the defects of the prior art. According to the method, after the silicon carbide nanowires and titanium powder are mixed uniformly, discharge plasma hot-pressing sintering is carried out under the conditions of low temperature and high pressure to prepare the silicon carbide nanowire reinforced titanium-based composite material, so that the silicon carbide nanowires and titanium are prevented from reacting to generate carbide and silicide in a high-temperature environment in the conventional hot sintering process, and the toughening effect of the silicon carbide nanowires is ensured; meanwhile, the silicon carbide nanowire is tightly combined with the titanium matrix to form a multi-scale toughening structure, so that the toughening effect of the silicon carbide nanowire is improved, and the mechanical property of the silicon carbide nanowire reinforced titanium matrix composite is improved.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for preparing a silicon carbide nanowire reinforced titanium-based composite material at low temperature is characterized by comprising the following steps:
step one, mixing absolute ethyl alcohol and ethyl orthosilicate, uniformly stirring, adding distilled water and a hydrochloric acid solution, and uniformly stirring to obtain a silicon dioxide sol; the molar ratio of the absolute ethyl alcohol to the ethyl orthosilicate to the hydrochloric acid in the distilled water to the hydrochloric acid solution is (3-5): (0.5-2): (3-8): (0.1 to 0.5);
step two, adding graphite powder with the granularity of 60-150 meshes into the silica sol obtained in the step one, uniformly stirring, then placing the mixture into a drying oven, and drying the mixture for 12-24 hours at the temperature of 100 ℃ to obtain graphite powder coated with the silica sol;
step three, placing the graphite powder coated with the silicon dioxide sol obtained in the step two in a high-temperature tube furnace for carbothermic reduction reaction, then carrying out ultrasonic cleaning and centrifugation, and removing supernatant fluid to obtain a precipitate which is a silicon carbide nanowire; the specific process of the carbothermic reduction reaction is as follows: heating to 1400-1700 ℃ at the speed of 5-10 ℃/min under the condition of argon protective atmosphere, and then preserving heat for 1-3 h;
step four, adding the silicon carbide nanowires obtained in the step three into absolute ethyl alcohol, performing ultrasonic treatment for 60-120 min, then adding titanium powder, mechanically stirring uniformly under the condition of heat preservation of a water bath kettle at 60-80 ℃, and drying to obtain mixed powder of the silicon carbide nanowires and the titanium powder;
step five, putting the mixed powder of the silicon carbide nanowires and the titanium powder obtained in the step four into a die, then placing the die into a discharge plasma hot-pressing sintering furnace for discharge plasma hot-pressing sintering, and cooling to obtain the silicon carbide nanowire reinforced titanium-based composite material; the technological parameters of the spark plasma hot-pressing sintering are as follows: vacuum degree of 1.0X 10-3Pa～3.0×10- 3Pa, the temperature is 600-900 ℃, the pressure is 40-180 MPa, and the heat preservation time is 5-10 min.
According to the invention, the silicon carbide nanowire is prepared by adopting a sol-gel carbothermic reaction method, then the silicon carbide nanowire and titanium powder are uniformly mixed and then subjected to discharge plasma hot-pressing sintering, the silicon carbide nanowire reinforced titanium-based composite material is prepared under the conditions of low temperature and high pressure of 600-900 ℃ and 40-180 MPa, the phenomenon that the silicon carbide nanowire and titanium react to generate carbide and silicide in a high-temperature environment in the conventional hot sintering process to lose the inherent structural characteristics of the silicon carbide nanowire is avoided, the toughening effect of the silicon carbide nanowire is weakened, and meanwhile, the silicon carbide nanowire and the titanium base are tightly combined under the conditions of low temperature and high pressure to form a multi-scale toughening structure, the toughening effect of the silicon carbide nanowire is improved, and the mechanical property of the silicon carbide nanowire reinforced titanium-based composite material is improved.
The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at the low temperature is characterized in that the mass concentration of the hydrochloric acid solution in the step one is 37%. The concentration of the hydrochloric acid solution is the common use concentration, and the preparation is convenient.
The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at the low temperature is characterized in that in the second step, the mass ratio of the graphite powder with the granularity of 60-150 meshes to the silica sol is 1:5, and the stirring is carried out uniformly for 20-60 min. The mass ratio of the graphite powder and the silicon dioxide sol and the corresponding stirring time promote the graphite powder to be uniformly wrapped around the silicon dioxide sol, and the silicon carbide nanowires with uniform size can be obtained.
The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at the low temperature is characterized in that the ultrasonic cleaning and the centrifuging are performed twice in the third step, and the rotating speed of the centrifuging is 8000r/min to 10000 r/min. The ultrasonic cleaning and centrifuging times and the centrifugal rotating speed are beneficial to removing impurities in a carbothermic reduction reaction system, so that the silicon carbide nanowire without impurities on the surface is obtained.
The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at the low temperature is characterized in that the diameter of the silicon carbide nanowire obtained in the third step is 50-200 nm. The silicon carbide nanowires with the sizes have large specific surface area and high strength, and can be uniformly dispersed in titanium powder.
The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at the low temperature is characterized in that the granularity of the titanium powder in the fourth step is 15-45 microns. The titanium powder with the granularity is proper in granularity and is beneficial to dispersion.
The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at the low temperature is characterized in that the mechanical stirring is carried out for 6-12 hours in the fourth step. The mechanical stirring time promotes the titanium powder and the silicon carbide nano-wire to be fully and uniformly mixed.
The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at the low temperature is characterized in that the drying temperature in the fourth step is 80-100 ℃, and the drying time is 8-12 hours. The drying parameters can be quickly dried to obtain the mixed powder of the silicon carbide nanowire and the titanium powder.
The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at the low temperature is characterized in that the diameter of the die in the fifth step is 30-60 mm. The mould is beneficial to the rapid passing of current through the mould and heating in the discharge plasma hot-pressing sintering process, so that the rapid temperature rise is realized.
The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at the low temperature is characterized in that in the fifth step, the mass fraction of the silicon carbide nanowires in the silicon carbide nanowire reinforced titanium-based composite material is 0.01-10%. The silicon carbide nanowires with the mass fraction can be uniformly dispersed in the titanium matrix, so that the mechanical property of the titanium matrix composite material is effectively improved.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, after the silicon carbide nanowires and the titanium powder are mixed uniformly, discharge plasma hot-pressing sintering is carried out under the conditions of low temperature and high pressure, so that the silicon carbide nanowire reinforced titanium-based composite material is prepared, the silicon carbide nanowires and titanium are prevented from reacting to generate carbide and silicide in a high-temperature environment in the conventional hot sintering process, the toughening effect of the silicon carbide nanowires is ensured, and the mechanical property of the silicon carbide nanowire reinforced titanium-based composite material is improved.
2. The invention adopts the low-temperature high-pressure discharge plasma hot-pressing sintering condition to tightly combine the silicon carbide nanowire with the titanium matrix to form a multi-scale toughening structure, thereby improving the toughening effect of the silicon carbide nanowire and improving the mechanical property of the silicon carbide nanowire reinforced titanium matrix composite.
3. According to the invention, the silicon carbide nanowires are prepared by adopting a sol-gel carbothermic reduction reaction method, and then the prepared silicon carbide nanowires are rapidly and uniformly dispersed in an ethanol solution by utilizing ultrasonic dispersion equipment, so that the uniform distribution of the silicon carbide nanowires in the composite material is ensured.
4. According to the invention, titanium powder is added into the silicon carbide nanowire dispersion liquid, and the titanium powder and the silicon carbide nanowire dispersion liquid are uniformly mixed in a mechanical stirring manner under a heat preservation condition, so that the damage to the silicon carbide nanowire in the preparation process is reduced, and the strengthening and toughening effects of the silicon carbide nanowire are further ensured.
5. Compared with the non-reinforced titanium-based material, the compressive yield strength of the silicon carbide nanowire reinforced titanium-based composite material prepared by the invention is improved by 107.7-136.8%.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is an SEM image (5000X) of silicon carbide nanowires prepared in example 1 of the present invention.
Fig. 3 is an SEM image (20000 ×) of silicon carbide nanowires prepared in example 1 of the present invention.
FIG. 4 is a FE-SEM image (50000X) of the fracture of the silicon carbide nanowire reinforced titanium matrix composite prepared in example 1 of the present invention.
Fig. 5 is a fracture SEM image (5000 ×) of the titanium-based material prepared by comparative example 1 of the present invention.
FIG. 6 is a SEM image (5000X) of a fracture of the silicon carbide nanowire-reinforced titanium-based composite prepared in comparative example 2 of the present invention.
Detailed Description
As shown in FIG. 1, the specific process for preparing the silicon carbide nanowire reinforced titanium-based composite material comprises the following steps: mixing and stirring the silicon dioxide sol and graphite powder to obtain graphite powder coated with the silicon dioxide sol, then carrying out carbothermic reduction reaction to obtain a silicon carbide nanowire, uniformly mixing the silicon carbide nanowire and titanium powder, and carrying out discharge plasma hot-pressing sintering to obtain the silicon carbide nanowire reinforced titanium-based composite material.
Example 1
The embodiment comprises the following steps:
step one, mixing absolute ethyl alcohol and ethyl orthosilicate, uniformly stirring, adding distilled water and hydrochloric acid solution with the mass concentration of 37%, and uniformly stirring to obtain silicon dioxide sol; the molar ratio of the absolute ethyl alcohol to the ethyl orthosilicate to the hydrochloric acid in the distilled water to the hydrochloric acid solution is 3: 0.5: 3: 0.1;
step two, adding graphite powder with the granularity of 60-150 meshes into the silica sol obtained in the step one, stirring for 20min, then placing the silica sol into a drying oven, and drying for 12h at the temperature of 100 ℃ to obtain graphite powder coated with the silica sol; the mass ratio of the graphite powder with the granularity of 60 meshes to 150 meshes to the silicon dioxide sol is 1: 5;
step three, placing the graphite powder coated with the silica sol obtained in the step two in a high-temperature tube furnace for carbothermic reduction reaction, and then sequentially carrying out primary ultrasonic cleaning, primary centrifugation, secondary ultrasonic cleaning and secondary centrifugation to remove supernatant of the secondary centrifugation, so as to obtain a precipitate which is a silicon carbide nanowire; the rotating speeds adopted by the primary centrifugation and the secondary centrifugation are both 8000 r/min; the specific process of the carbothermic reduction reaction is as follows: heating to 1400 ℃ at the speed of 5 ℃/min under the condition of argon protective atmosphere, and then preserving heat for 1 h; the diameter of the silicon carbide nanowire is 50 nm;
step four, adding 0.01g of the silicon carbide nanowires obtained in the step three into 100g of absolute ethyl alcohol, performing ultrasonic treatment for 60min, then adding 100g of titanium powder with the granularity of 15-45 microns, mechanically stirring the titanium powder uniformly for 6h under the condition of heat preservation of a water bath kettle at the temperature of 60 ℃, and drying the titanium powder for 8h under the condition of the temperature of 80 ℃ to obtain mixed powder of the silicon carbide nanowires and the titanium powder;
step five, putting the mixed powder of the silicon carbide nanowires and the titanium powder obtained in the step four into a die, then placing the die into a discharge plasma hot-pressing sintering furnace for discharge plasma hot-pressing sintering, and cooling to obtain the silicon carbide nanowire reinforced titanium-based composite material; the diameter of the die is 30 mm; the technological parameters of the spark plasma hot-pressing sintering are as follows: vacuum degree of 1.0X 10-3Pa, temperature 600 ℃, pressure 180MPa, and heat preservation time 5 min.
Fig. 2 is an SEM image (5000 ×) of the silicon carbide nanowires prepared in the present example, and fig. 3 is an SEM image (20000 ×) of the silicon carbide nanowires prepared in the present example, and it can be seen from fig. 2 and 3 that the silicon carbide nanowires prepared in the present example did not undergo an agglomeration phenomenon.
Fig. 4 is an FE-SEM image (50000 x) of a fracture of the silicon carbide nanowire reinforced titanium matrix composite prepared in this embodiment, and it can be seen from fig. 4 that, in the fracture process of the silicon carbide nanowire reinforced titanium matrix composite prepared in this embodiment, the silicon carbide nanowire is pulled out from the titanium matrix, so that the crack propagation route is prolonged, and the mechanical property of the silicon carbide nanowire reinforced titanium matrix composite is improved.
Comparative example 1
This comparative example comprises the following steps:
step one, drying 100g of titanium powder with the granularity of 15-45 mu m for 8 hours at the temperature of 80 ℃;
step five, putting the dried titanium powder in the step one into a die with the diameter of 30mm, then placing the die into a discharge plasma hot-pressing sintering furnace for discharge plasma hot-pressing sintering, and cooling to obtain the titanium-based composite material; the technological parameters of the spark plasma hot-pressing sintering are as follows: vacuum degree of 1.0X 10-3Pa, temperature 600 ℃, pressure 180MPa, and heat preservation time 5 min.
Fig. 5 is a fracture SEM image (5000 ×) of the titanium-based material prepared in the present comparative example, and it can be seen from fig. 5 that the silicon carbide nanowires were not present in the titanium-based material prepared in the present comparative example.
Comparative example 2
This comparative example comprises the following steps:
step one, mixing absolute ethyl alcohol and ethyl orthosilicate, uniformly stirring, adding distilled water and hydrochloric acid solution with the mass concentration of 37%, and uniformly stirring to obtain silicon dioxide sol; the molar ratio of the absolute ethyl alcohol to the ethyl orthosilicate to the hydrochloric acid in the distilled water to the hydrochloric acid solution is 3: 0.5: 3: 0.1;
step two, adding graphite powder with the granularity of 60-150 meshes into the silica sol obtained in the step one, stirring for 20min, then placing the silica sol into a drying oven, and drying for 12h at the temperature of 100 ℃ to obtain graphite powder coated with the silica sol; the mass ratio of the graphite powder with the granularity of 60 meshes to 150 meshes to the silicon dioxide sol is 1: 5;
step three, placing the graphite powder coated with the silica sol obtained in the step two in a high-temperature tube furnace for carbothermic reduction reaction, and then sequentially carrying out primary ultrasonic cleaning, primary centrifugation, secondary ultrasonic cleaning and secondary centrifugation to remove supernatant of the secondary centrifugation, so as to obtain a precipitate which is a silicon carbide nanowire; the rotating speeds adopted by the primary centrifugation and the secondary centrifugation are both 8000 r/min; the specific process of the carbothermic reduction reaction is as follows: heating to 1400 ℃ at the speed of 5 ℃/min under the condition of argon protective atmosphere, and then preserving heat for 1 h; the diameter of the silicon carbide nanowire is 50 nm;
step four, adding 0.01g of the silicon carbide nanowires obtained in the step three into 100g of absolute ethyl alcohol, performing ultrasonic treatment for 60min, then adding 100g of titanium powder with the granularity of 15-45 microns, mechanically stirring the titanium powder uniformly for 6h under the condition of heat preservation of a water bath kettle at the temperature of 60 ℃, and drying the titanium powder for 8h under the condition of the temperature of 80 ℃ to obtain mixed powder of the silicon carbide nanowires and the titanium powder;
step five, putting the mixed powder of the silicon carbide nanowires and the titanium powder obtained in the step four into a die, then placing the die into a discharge plasma hot-pressing sintering furnace for discharge plasma hot-pressing sintering, and cooling to obtain the silicon carbide nanowire reinforced titanium-based composite material; the diameter of the die is 30 mm; the technological parameters of the spark plasma hot-pressing sintering are as follows: vacuum degree of 1.0X 10-3Pa, 1200 ℃, 40MPa and 5min of heat preservation time.
FIG. 6 is a SEM image (5000X) of a fracture of the SiC nanowire-reinforced Ti-based composite material prepared in the present comparative example, and it can be seen from FIG. 6 that the SiC nanowire in the SiC nanowire-reinforced Ti-based composite material prepared in the present comparative example completely loses the original feature under the high-temperature sintering condition.
Comparing fig. 4, fig. 5 and fig. 6, the titanium-based composite material can be prepared by adopting the silicon carbide nanowire as the reinforcing phase, and the low-temperature high-pressure sintering is carried out by adopting the discharge plasma sintering process, so that the original characteristic morphology of the silicon carbide nanowire is better preserved, and the mechanical property of the titanium-based composite material is better enhanced; and the conventional vacuum hot-pressing sintering process is adopted for high-temperature low-pressure sintering, because the sintering temperature is too high, the activity ratio of titanium in the matrix is higher, the silicon carbide nanowire is easy to react with titanium to generate carbide and silicide, and the inherent structural characteristics of the silicon carbide nanowire are lost, so that the reinforcing effect of the silicon carbide nanowire is weakened.
Example 2
The embodiment comprises the following steps:
step one, mixing absolute ethyl alcohol and ethyl orthosilicate, uniformly stirring, adding distilled water and hydrochloric acid solution with the mass concentration of 37%, and uniformly stirring to obtain silicon dioxide sol; the molar ratio of the absolute ethyl alcohol to the ethyl orthosilicate to the hydrochloric acid in the distilled water to the hydrochloric acid solution is 5: 2: 8: 0.5;
step two, adding graphite powder with the granularity of 60-150 meshes into the silica sol obtained in the step one, stirring for 60min, then placing the silica sol into a drying oven, and drying for 24h at the temperature of 100 ℃ to obtain graphite powder coated with the silica sol; the mass ratio of the graphite powder with the granularity of 60 meshes to 150 meshes to the silicon dioxide sol is 1: 5;
step three, placing the graphite powder coated with the silica sol obtained in the step two in a high-temperature tube furnace for carbothermic reduction reaction, and then sequentially carrying out primary ultrasonic cleaning, primary centrifugation, secondary ultrasonic cleaning and secondary centrifugation to remove supernatant of the secondary centrifugation, so as to obtain a precipitate which is a silicon carbide nanowire; the rotating speeds adopted by the primary centrifugation and the secondary centrifugation are both 10000 r/min; the specific process of the carbothermic reduction reaction is as follows: heating to 1700 ℃ at the speed of 10 ℃/min under the condition of argon protective atmosphere, and then preserving heat for 3 h; the diameter of the silicon carbide nanowire is 200 nm;
step four, adding 10g of the silicon carbide nanowires obtained in the step three into 100g of absolute ethyl alcohol, performing ultrasonic treatment for 120min, then adding 90g of titanium powder with the granularity of 15-45 microns, mechanically stirring the titanium powder uniformly for 12h at the temperature of 80 ℃ in a water bath kettle, and drying the titanium powder for 12h at the temperature of 100 ℃ to obtain mixed powder of the silicon carbide nanowires and the titanium powder;
step five, putting the mixed powder of the silicon carbide nanowires and the titanium powder obtained in the step four into a die, then placing the die into a discharge plasma hot-pressing sintering furnace for discharge plasma hot-pressing sintering, and cooling to obtain the silicon carbide nanowire reinforced titanium-based composite material; the diameter of the die is 60 mm; the technological parameters of the spark plasma hot-pressing sintering are as follows: degree of vacuum of 3.0X 10-3Pa, 900 ℃, 40MPa and 10min of heat preservation time.
Example 3
The embodiment comprises the following steps:
step one, mixing absolute ethyl alcohol and ethyl orthosilicate, uniformly stirring, adding distilled water and hydrochloric acid solution with the mass concentration of 37%, and uniformly stirring to obtain silicon dioxide sol; the molar ratio of the absolute ethyl alcohol to the ethyl orthosilicate to the hydrochloric acid in the distilled water to the hydrochloric acid solution is 4: 1.5: 6: 0.3;
step two, adding graphite powder with the granularity of 60-150 meshes into the silica sol obtained in the step one, stirring for 40min, then placing the silica sol into a drying oven, and drying for 20h at the temperature of 100 ℃ to obtain graphite powder coated with the silica sol; the mass ratio of the graphite powder with the granularity of 60 meshes to 150 meshes to the silicon dioxide sol is 1: 5;
step three, placing the graphite powder coated with the silica sol obtained in the step two in a high-temperature tube furnace for carbothermic reduction reaction, and then sequentially carrying out primary ultrasonic cleaning, primary centrifugation, secondary ultrasonic cleaning and secondary centrifugation to remove supernatant of the secondary centrifugation, so as to obtain a precipitate which is a silicon carbide nanowire; the rotating speeds adopted by the primary centrifugation and the secondary centrifugation are 9000 r/min; the specific process of the carbothermic reduction reaction is as follows: heating to 1500 ℃ at the speed of 9 ℃/min under the condition of argon protective atmosphere, and then preserving heat for 2 h; the diameter of the silicon carbide nanowire is 100 nm;
step four, adding 0.3g of the silicon carbide nanowires obtained in the step three into 100g of absolute ethyl alcohol for ultrasonic treatment for 80min, then adding 100g of titanium powder with the granularity of 15-45 microns, mechanically stirring the titanium powder uniformly for 10h at the temperature of 70 ℃ in a water bath kettle, and drying the titanium powder for 10h at the temperature of 90 ℃ to obtain mixed powder of the silicon carbide nanowires and the titanium powder;
step five, putting the mixed powder of the silicon carbide nanowires and the titanium powder obtained in the step four into a die, then placing the die into a discharge plasma hot-pressing sintering furnace for discharge plasma hot-pressing sintering, and cooling to obtain the silicon carbide nanowire reinforced titanium-based composite material; the diameter of the die is 50 mm; the technological parameters of the spark plasma hot-pressing sintering are as follows: degree of vacuum of 2.0X 10-3Pa, temperature 700 ℃, pressure 60MPa, and heat preservation time 6 min.
The silicon carbide nanowire reinforced titanium-based composite materials prepared in examples 1 to 3 and comparative example 2 of the present invention and the titanium-based material prepared in comparative example 1 were subjected to mechanical property tests, and the results are shown in table 1 below, with compressive yield strength as the test standard.
Table 1 examples 1 to 3, comparative example 2, and the titanium-based material prepared in comparative example 1
As can be seen from Table 1, the compressive yield strength of the silicon carbide nanowire reinforced titanium-based composite materials prepared in examples 1 to 3 of the present invention is higher than that of the titanium-based material prepared in comparative example 1 and that of the silicon carbide nanowire reinforced titanium-based composite material prepared in comparative example 2; under the same preparation process conditions, the compressive yield strength of the silicon carbide nanowire reinforced titanium-based composite material prepared by low-temperature sintering in the embodiment 1 is higher than that of the silicon carbide nanowire reinforced titanium-based composite material prepared by high-temperature sintering in the comparative example 2, which shows that the discharge plasma hot-pressing sintering is carried out under the conditions of low temperature and high pressure, so that the silicon carbide nanowire and titanium are prevented from reacting to generate carbide and silicide in a high-temperature environment in the conventional hot-sintering process, the toughening effect of the silicon carbide nanowire is ensured, and the mechanical property of the silicon carbide nanowire reinforced titanium-based composite material is improved; under the same discharge plasma hot-pressing sintering parameter conditions, the compressive yield strength of the titanium-based composite material prepared by using the silicon carbide nanowires as the reinforcing phase in the embodiment 1 is higher than that of the titanium-based material prepared by not using the silicon carbide nanowires in the comparative example 1, which shows that under the discharge plasma hot-pressing sintering action, the silicon carbide nanowires are tightly combined with the titanium base to form a multi-scale toughening structure, the toughening effect of the silicon carbide nanowires is improved, and the mechanical property of the silicon carbide nanowire reinforced titanium-based composite material is improved.
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 (9)
1. A method for preparing a silicon carbide nanowire reinforced titanium-based composite material at low temperature is characterized by comprising the following steps:
step one, mixing absolute ethyl alcohol and ethyl orthosilicate, uniformly stirring, adding distilled water and a hydrochloric acid solution, and uniformly stirring to obtain a silicon dioxide sol; the molar ratio of the absolute ethyl alcohol to the ethyl orthosilicate to the hydrochloric acid in the distilled water to the hydrochloric acid solution is (3-5): (0.5-2): (3-8): (0.1 to 0.5); the mass concentration of the hydrochloric acid solution is 37%;
step two, adding graphite powder with the granularity of 60-150 meshes into the silica sol obtained in the step one, uniformly stirring, then placing the mixture into a drying oven, and drying the mixture for 12-24 hours at the temperature of 100 ℃ to obtain graphite powder coated with the silica sol;
step three, placing the graphite powder coated with the silicon dioxide sol obtained in the step two in a high-temperature tube furnace for carbothermic reduction reaction, then carrying out ultrasonic cleaning and centrifugation, and removing supernatant fluid to obtain a precipitate which is a silicon carbide nanowire; the specific process of the carbothermic reduction reaction is as follows: heating to 1400-1700 ℃ at the speed of 5-10 ℃/min under the condition of argon protective atmosphere, and then preserving heat for 1-3 h;
step four, adding the silicon carbide nanowires obtained in the step three into absolute ethyl alcohol, performing ultrasonic treatment for 60-120 min, then adding titanium powder, mechanically stirring uniformly under the condition of heat preservation of a water bath kettle at 60-80 ℃, and drying to obtain mixed powder of the silicon carbide nanowires and the titanium powder;
step five, putting the mixed powder of the silicon carbide nanowires and the titanium powder obtained in the step four into a die, then placing the die into a discharge plasma hot-pressing sintering furnace for discharge plasma hot-pressing sintering, and cooling to obtain the silicon carbide nanowire reinforced titanium-based composite material; the technological parameters of the spark plasma hot-pressing sintering are as follows: vacuum degree of 1.0X 10-3Pa～3.0×10-3Pa, the temperature is 600-900 ℃, the pressure is 40-180 MPa, and the heat preservation time is 5-10 min.
2. The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at the low temperature according to claim 1, wherein the mass ratio of the graphite powder with the particle size of 60-150 meshes to the silica sol in the second step is 1:5, and the stirring is carried out for 20-60 min.
3. The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at the low temperature according to claim 1, wherein the ultrasonic cleaning and the centrifuging are performed twice in the third step, and the rotating speed for the centrifuging is 8000r/min to 10000 r/min.
4. The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at the low temperature according to claim 1, wherein the diameter of the silicon carbide nanowire obtained in the step three is 50nm to 200 nm.
5. The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at the low temperature according to claim 1, wherein the titanium powder in the fourth step has a particle size of 15 μm to 45 μm.
6. The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at low temperature according to claim 1, wherein the mechanical stirring is performed for 6-12 h in the fourth step.
7. The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at the low temperature according to claim 1, wherein the drying temperature in the fourth step is 80-100 ℃ and the drying time is 8-12 h.
8. The method for preparing the silicon carbide nanowire reinforced titanium matrix composite material at the low temperature according to claim 1, wherein the diameter of the mold in the fifth step is 30mm to 60 mm.
9. The method for preparing the silicon carbide nanowire reinforced titanium-based composite material at the low temperature as claimed in claim 1, wherein the mass fraction of the silicon carbide nanowires in the silicon carbide nanowire reinforced titanium-based composite material in the fifth step is 0.01-10%.
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