CN109652679B - Carbon nanotube and endogenous nano TiC particle mixed reinforced aluminum-based composite material and preparation method thereof - Google Patents

Carbon nanotube and endogenous nano TiC particle mixed reinforced aluminum-based composite material and preparation method thereof Download PDF

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CN109652679B
CN109652679B CN201811609884.5A CN201811609884A CN109652679B CN 109652679 B CN109652679 B CN 109652679B CN 201811609884 A CN201811609884 A CN 201811609884A CN 109652679 B CN109652679 B CN 109652679B
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CN109652679A (en
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杨宏宇
刘林
邱丰
舒世立
陈靓瑜
邵勇
黄忠富
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Hangzhou Jiyan Nano Technology Co ltd
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Jiangsu University of Science and Technology
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C21/00—Alloys based on aluminium
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    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C22C2026/002—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract

The invention discloses a carbon nanotube and nano TiC particle mixed reinforced aluminum-based composite material and a preparation method thereof, wherein the composite material comprises the following components in percentage by mass: carbon nanotubes: 0.5-5%, TiC: 18-38%, Al: 60 to 80 percent. The preparation method comprises the following steps: (1) ultrasonically dispersing the carbon nanotubes; (2) preparing precursor powder CNTs-Ti-Al; (3) compacting, sintering and densifying are integrated. The process takes part of CNTs in a CNTs-Ti-Al system as a carbon source to react with alloy powder Ti to introduce in-situ endogenetic nano ceramic particles, and the residual CNTs after the reaction are taken as a reinforcing phase. The generation of TiC can improve the problems of poor wettability and low interface bonding strength between CNTs and an Al matrix, realize the coupling interaction and synergistic strengthening of the matrix between double reinforced phases (CNTs + TiC) with different dimensions in the Al-based composite material, greatly improve the comprehensive performance of the composite material and have important application value.

Description

Carbon nanotube and endogenous nano TiC particle mixed reinforced aluminum-based composite material and preparation method thereof
Technical Field
The invention relates to an aluminum-based composite material, in particular to a carbon nanotube and endogenous nano TiC particle hybrid reinforced aluminum-based composite material and a preparation method thereof.
Background
The aluminum-based composite material has great application value and wide application potential in the fields of military, aviation, aerospace and civil use, and is one of the most important lightweight high-performance materials in the fields of equipment manufacturing, high-speed trains, military and military industry, aerospace, nuclear power materials and the like. However, with the rapid development of scientific technology, the industrial and military technical requirements are continuously increased, and the requirements for high-performance light structural materials are higher and higher, so that the materials are required to have excellent structural performance and multifunctional response characteristics. Therefore, there is a need to improve the comprehensive performance of aluminum matrix composites.
Carbon Nanotubes (CNTs) have a one-dimensional tubular structure and excellent mechanical, physical and chemical properties, such as high tensile strength (50-200GPa, about 100 times of steel) and low density (1.2-2.1 g/cm)31/6-1/7 for steel), extremely high modulus of elasticity (comparable to diamond), remarkably high thermal conductivity (over 3000W/m · K) and low coefficient of thermal expansion (1.0 × 10)-6K) And the unique structure and excellent comprehensive performance make the carbon nanotube have great application foreground in reinforced metal-base composite material and are considered as the optimal reinforcing phase. But the carbon nanotubes have poor wettability with an Al matrix, are easy to generate harmful reaction at an interface and have poor interface bonding property; in addition, carbon tubes are not easy to disperse in a matrix and are easy to agglomerate and wind because of high specific surface energy and van der waals force. The current research shows that the performance of the metal matrix composite material prepared by taking CNTs as the only reinforcing phase is far from the theoretical value.
The nano carbide ceramic particles are used as an isotropic nano hard reinforcing phase, and have the advantages of high strength, high hardness, high wear resistance, high thermal stability and the like, and the in-situ endogenetic process enables the ceramic particles to be easily and uniformly distributed in a matrix, the interface between the ceramic particles and the matrix is clean, the bonding strength is high, but the comprehensive performance of the ceramic particles is inferior to CNTs, the metal is reinforced by single nano ceramic particles in the field of metal-based composite materials, the performance improvement degree of the metal reaches the bottleneck, and the metal is difficult to break through greatly.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a carbon nanotube and endogenous nanometer TiC particle hybrid reinforced aluminum-based composite material and a preparation method thereof, wherein the composite material is a CNTs-TiC/Al composite material which is reinforced by one-dimensional and three-dimensional biphase; the preparation method comprises the steps of preparing a CNTs-TiC/Al composite material with one-dimensional and three-dimensional double reinforced phases mixed by reacting, hot-pressing and sintering mixed powder of CNTs, Ti and Al, and regulating and controlling the percentage content of CNTs and TiC to realize the CNTs-TiC mixed distribution of double reinforced phases with different dimensions in the Al-based composite material.
The technical scheme is as follows: the Carbon Nanotubes (CNTs) and endogenous nano TiC particles mixed reinforced aluminum matrix composite material comprises 0.5-5% of carbon nanotubes, 18-38% of TiC and 60-80% of Al by mass percent, preferably 1.82-4.61% of carbon nanotubes, 18.18-36.37% of TiC and 60-80% of Al by mass percent.
The preparation method of the Carbon Nanotubes (CNTs) and endogenous nano TiC particles mixed reinforced aluminum matrix composite material comprises the following steps:
(1) putting the mixed powder of the carbon nano-tube, Ti and Al into a graphite die for pressing to obtain a compact;
(2) preserving the temperature of the compact obtained in the step (1) for 5-50min in a vacuum system at the temperature of 500-; and then continuously heating until the pressure is suddenly increased, rapidly pressurizing to 40-100MPa, stopping heating and cooling to room temperature to finish hot-pressing sintering and densification of the powder mixture, thereby obtaining the composite material. The composite material comprises 20-40% of CNTs and TiC ceramic particles by mass.
The preparation of the carbon nanotube, Ti and Al mixed powder in the step (1) comprises the following steps:
(1-1) weighing Al powder and Ti powder, adding the Al powder and the Ti powder into the carbon nanotube ethanol suspension, and performing electromagnetic stirring and ultrasonic oscillation to obtain a mixture ethanol solution;
wherein the electromagnetic stirring time is 0.5-5 hours, and the rotating speed is 100-3000 r/min; the ultrasonic oscillation time is 1-4 hours, and the frequency is 20-60 KHz.
And (1-2) drying the ethanol solution of the mixture obtained in the step (1-1) by using a rotary evaporator, and removing the alcohol solvent to obtain a powder mixture.
Wherein, the evaporation flask is placed in a constant temperature water bath kettle at 40-80 ℃ for 1-4 hours, the rotating speed of the flask is 50-200r/min, and the negative pressure of the solution in the flask is 200-800 mm Hg.
And (1-3) putting the powder mixture obtained in the step (1-2) into a zirconium dioxide ball milling tank, sealing the ball milling tank, then installing the ball milling tank on a horizontal mixer, and mixing for 12-72 hours by using zirconium dioxide grinding balls to obtain the mixed powder of the carbon nanotubes, Ti and Al.
Wherein the rotating speed of the horizontal mixer is set to be 20-120 r/min; ZrO (ZrO)2The mass ratio of the grinding balls to the mixed powder is 8-13:1, and the total volume of the powder and the zirconia grinding balls is not more than 80% of the capacity of the ball milling tank.
In the step (1-1), the preparation of the carbon nanotube ethanol suspension comprises the step of adding the carbon nanotubes into ethanol, and performing ultrasonic stirring at room temperature until carbon nanotube groups are dispersed into a linear suspension.
Wherein the ultrasonic frequency is 20-60KHz, and the stirring time is 1-4 hours.
In the step (1), the mass percentages of the carbon nanotubes, Ti and Al in the mixed powder are respectively 5.45-10.90%, 14.55-29.10% and 60-80%; the molar ratio of CNTs to Ti is 1.5-2.5:1, and the mass ratio of CNTs to Ti is 1: 2.67-1.6.
The carbon nanotube is of a multi-wall structure, the outer diameter is 5-30nm, the length is 5-60 mu m, and the purity is more than 95.0%; the granularity of the Al powder is 200-2000 meshes, and the purity is more than 99.95 percent; the granularity of the Ti powder is 500-3000 meshes, and the purity is more than 99.95 percent.
The green compact is hydraulically pressed. The pressed blank comprises the following specific steps: putting mixed powder of CNTs, Ti and Al into a graphite mold, putting the graphite mold filled with the powder mixture into a vacuum hot-pressing sintering furnace, setting pre-pressure to be 0.1-0.5 ton, closing a furnace door, starting a vacuumizing system, observing the indication number of a vacuum degree display window, and when the vacuum degree display furnace is lower than 0.8 multiplied by 10, the pressure in the furnace is lower than- 3After Pa, turning on a heating power supply, heating to 100-40K/min at a heating rate of 300 ℃, and preserving heat for 30-60min to remove moisture and degas; after the heat preservation state lasts for 15min, starting a hydraulic system, gradually pressurizing with 0.2-1 ton of force until the pressure value reaches 15-60MPa, and maintaining the pressure for 5-10 min; and then gradually reducing the pressure by 0.5-1 ton, and keeping the pre-pressure by 0.1-0.5 ton to finish the compaction of the powder mixture.
Before the mixed powder of the multi-wall carbon nano tube, Ti and Al is filled into a graphite mould, the method also comprises the step of smearing the hexagonal boron nitride ethanol solution on the part which can be contacted by the mixed powder in the graphite mould. The method comprises the following specific steps: preparing the hexagonal boron nitride powder into a dilute hexagonal boron nitride ethanol solution, then coating the hexagonal boron nitride solution on the inner wall of a sleeve, a gasket, a pressure head and other parts of the graphite mold which can be in contact with the powder, waiting for more than 2min, volatilizing the ethanol, and then filling the powder mixture into the graphite mold. Wherein the particle size of the hexagonal boron nitride powder is 0.5-5 μm.
The graphite mold is a hot isostatic pressing high-strength graphite mold, the outer sleeve is circular, the outer surface of the outer sleeve is matched with the outer surface of the inner sleeve in a conical surface mode, and the conical angle is 3-8 degrees; the inner sleeve can be in an integral or split type, the thickness is larger than 10mm, the cross section of the sleeve can be in a round shape or a square shape with a fillet, the inner diameter of the round shape is 20-80mm, the length and the width of the square shape are 20-100mm, the radius of the chamfer is 3-10mm, the height of the sleeve is 100 plus 220mm, the thickness of the graphite gasket is 3-8mm, the cross section shape and the height of the pressure lever are consistent with the cross section shape and the height of the sleeve, the pressure lever is in clearance fit with the inner surface of the sleeve, and the value of the clearance at two sides.
In the step (2), the mixture is heated to 500-600 ℃ at a heating rate of 10-60K/min.
In the step (2), after heat preservation is carried out for 5-50min, heating is continuously carried out at the heating rate of 40-100K/min until the pressure is suddenly increased.
In summary, the preparation method of the Carbon Nanotubes (CNTs) and endogenous TiC nanoparticles hybrid reinforced aluminum matrix composite specifically comprises the following steps:
step 1: adding carbon nanotubes into ethanol, stirring for 1-4 hours in ultrasonic wave of 20-60KHz at room temperature, and dispersing carbon nanotube groups into linear suspension.
Wherein, the concentration of the carbon nano-tube is 3-5g/L, preferably 3.5-4.8g/L, the carbon nano-tube is of a multi-wall structure, and the outer diameter is as follows: 5-30nm, length: 5-60 μm, purity > 95.0%.
Step 2: al powder with the granularity of 200-2000 meshes and the purity of more than 99.95 percent and Ti powder with the granularity of 500-3000 meshes and the purity of more than 99.95 percent are added into the carbon nano-tube ethanol suspension. Electromagnetically stirring the mixture ethanol solution for 0.5-5 hours at room temperature, wherein the rotating speed of the electromagnetic stirring is 100-3000 r/min; then, the ultrasonic oscillation is carried out for 1 to 4 hours, and the frequency of the ultrasonic oscillation is 20 to 60 KHz. Drying the mixture ethanol solution by using a rotary evaporator, placing the evaporation flask in a constant-temperature water bath kettle at the temperature of 40-80 ℃ for 1-4 hours, wherein the rotation speed of the flask is 50-200r/min, and the negative pressure of the solution in the flask is 200-800 mmHg. Removing the alcohol solvent and taking out the powder mixture.
Wherein the concentration of the Al powder and the Ti powder in the ethanol suspension is 15-50g/L, 8-12.5g/L, preferably 16.6-50g/L and 8.3-12g/L respectively.
And step 3: weighing 50g of the powder mixture, putting the powder mixture into a zirconium dioxide ball milling tank, and putting ZrO in the tank in advance2400g-650g of grinding balls, the diameter of the grinding balls is 5-22mm, and the number of the grinding balls is 6, the diameter of the grinding balls is 5mm, 7mm, 11mm, 15mm, 20mm and 22mm, and each grinding ball is 5-9; the ball milling pot is installed on a horizontal mixer after being sealed, the rotating speed of the mixer is set to be 20-120r/min, and the time for uniform mixing is 12-72 h.
Wherein, ZrO2The mass ratio of the grinding balls to the mixed powder is 8-13:1, and the total volume of the powder and the zirconia grinding balls is not more than 80% of the capacity of the ball milling tank.
Wherein, the molar ratio of CNTs to Ti in the powder mixture is 1.5-2.5:1, and the mass ratio of CNTs to Ti is 1: 2.67-1.6; the CNTs powder has the mass content of 5.45-10.90 wt.%, the Ti powder content of 14.55-29.10 wt.%, and the Al powder content of 60-80 wt.%.
And 4, step 4: weighing 2-5g of hexagonal boron nitride powder with the particle size of 0.5-5 mu m, filling the hexagonal boron nitride powder into a 50-250ml beaker, adding 5-30ml of alcohol into the beaker, and preparing the hexagonal boron nitride powder into a dilute hexagonal boron nitride solution; and (3) coating the hexagonal boron nitride solution on the inner wall of a sleeve, a gasket, a pressure head and other parts of the graphite mold, which can be in contact with the powder, waiting for more than 2min, volatilizing alcohol, and then filling the powder mixture into the graphite mold.
And 5: putting the graphite mould filled with the powder mixture into a vacuum hot-pressing sintering furnace, and setting the pre-pressure to be 0.1-0.5 ton; closing the furnace door, starting the vacuum-pumping system, observing the indication number of the vacuum degree display window, and waiting for the vacuum degree to display that the pressure in the furnace is lower than 0.8 multiplied by 10-3After Pa, turning on a heating power supply, heating to 100-300 ℃ at a heating rate of 10-40K/min, and preserving heat for 30-60 min;
step 6: after the heat preservation state lasts for 15min, starting a hydraulic system, gradually pressurizing with 0.2-1 ton of force until the pressure value reaches 15-60MPa, and maintaining the pressure for 5-10 min; and then gradually reducing the pressure by 0.5-1 ton, and keeping the pre-pressure by 0.1-0.5 ton to finish the compaction of the powder mixture.
And 7: continuously heating to 600 ℃ at the heating rate of 10-60K/min, and keeping the temperature for 5-50min to make the target temperature consistent with the actual temperature and the internal and external temperatures of the hearth and the billet; and then, continuously heating at the temperature rising rate of 40-100K/min, rapidly pressurizing to 40-100MPa when the pressure indication in the vacuum degree display window is suddenly increased, simultaneously immediately closing a heating power supply, and cooling to the room temperature along with the furnace to finish the hot-pressing sintering and densification of the powder mixture.
Preferably, in the step 4 or 5, the graphite mold is a hot isostatic pressing high-strength graphite mold, the outer sleeve is circular, the outer surfaces of the outer sleeve and the inner sleeve are in conical surface fit, and the taper angle is 3-8 degrees; the inner sleeve can be in an integral or split type, the thickness is larger than 10mm, the cross section of the sleeve can be in a round shape or a square shape with a fillet, the inner diameter of the round shape is 20-80mm, the length and the width of the square shape are 20-100mm, the radius of the chamfer is 3-10mm, the height of the sleeve is 100 plus 220mm, the thickness of the graphite gasket is 3-8mm, the cross section shape and the height of the pressure lever are consistent with the cross section shape and the height of the sleeve, the pressure lever is in clearance fit with the inner surface of the sleeve, and the value of the clearance at two sides.
The preparation method is characterized in that a part of CNTs are used as a reinforcing phase, a part of CNTs are used as a carbon source for in-situ reaction of carbide ceramic, and the in-situ hot-pressing reaction, hot-pressing sintering and densification are integrated to prepare the compact aluminum-based composite material reinforced by blending carbon nanotubes and endogenetic nano-carbide ceramic particles. The generation of ceramic particles can instantly increase the temperature of the system, and is beneficial to improving the wettability between CNTs and an Al matrix; furthermore, the wettability of the endogenous ceramic particles and Al is better than that of CNTs and Al, and the ceramic particles generated on the surfaces of the CNTs can improve the bonding strength of the interface of the enhanced phase and the Al matrix; meanwhile, the generated ceramic particles are used as a second reinforcing phase to perform the coupling action with CNTs, so that the interface structure of the CNTs and Al can be improved; in addition, the formation of ceramic particles can absorb the amorphous carbon attached to the surface of the CNTs, and the reaction is firstly carried out at the structural defects of the surface of the CNTs, so that the interface can be purified. Finally, the carbon tube can be pinned by the nano dot-shaped particle reinforced phase which is uniformly distributed in the matrix, and the two reinforced phases are cooperated to reinforce the aluminum alloy matrix, so that the high-performance aluminum matrix composite material which has excellent comprehensive performance and can be applied to structural and functional applications can be prepared. Therefore, the invention has important application value.
Has the advantages that: 1. according to the two-phase reinforced aluminum-based composite material with different dimensions, the CNTs-TiC/Al composite material with one-dimensional and three-dimensional two-phase synergistic reinforcement is prepared through in-situ endogenesis, the percentage content of the CNTs and TiC is regulated and controlled, the one-dimensional nano-tubular reinforcing phase and the three-dimensional nano-particle reinforcing phase stably exist in an Al matrix, the interface is good, the distribution is uniform, and the CNTs-TiC hybrid distribution and the synergistic reinforcement of the two-reinforcing phases with different dimensions in the Al-based composite material are realized;
2. the invention provides a preparation method of a two-phase reinforced aluminum-based composite material with different dimensions, which is characterized in that CNTs, Ti and Al are mixed to obtain mixed powder, and the mixed powder is subjected to reaction hot-pressing sintering to prepare a CNTs-TiC/Al composite material with one-dimensional and two-dimensional reinforced phases, part of CNTs in a CNTs-Ti-Al system is used as a carbon source to react with alloy powder Ti to be introduced into in-situ nano ceramic particles, and the residual CNTs after the reaction are used as reinforced phases. The generation of TiC can improve the problems of poor wettability and low interface bonding strength between CNTs and an Al matrix, and meanwhile, the nano dot-shaped particle reinforced phases uniformly distributed in the matrix are beneficial to pinning the carbon tubes, so that the coupling interaction synergistic strengthening of the matrix between double reinforced phases (CNTs + TiC) with different dimensionalities in the Al-based composite material is realized, the comprehensive performance of the composite material is greatly improved, and the composite material has important application value.
Drawings
FIG. 1 is an X-ray diffraction analysis chart of the composite material obtained in example 1 of the present invention.
FIG. 2 is a Raman spectrum of the composite material obtained in example 1 of the present invention.
FIG. 3 is an X-ray diffraction analysis chart of the composite material obtained in example 2 of the present invention.
FIG. 4 is a Raman spectrum of the composite material obtained in example 2 of the present invention.
FIG. 5 is an X-ray diffraction analysis chart of the composite material obtained in example 3 of the present invention.
FIG. 6 is a Raman spectrum of the composite material obtained in example 3 of the present invention.
FIG. 7 is an X-ray diffraction analysis chart of the composite material obtained in example 4 of the present invention.
FIG. 8 is a Raman spectrum of the composite material obtained in example 4 of the present invention.
FIG. 9 is an X-ray diffraction analysis chart of the composite material obtained in comparative example 1 of the present invention.
FIG. 10 is an X-ray diffraction analysis chart of the composite material obtained in comparative example 2 of the present invention.
Detailed Description
Example 1
A carbon nanotube and endogenous nanometer TiC granule mix the aluminium base composite material of reinforcement and its preparation method, including the following steps:
firstly, ultrasonic dispersion of carbon nanotubes:
step 1.1: 2.72g of carbon nanotubes are added into 600ml of ethanol, and then stirred for 1 hour in 30KHz ultrasonic waves at room temperature, so that carbon nanotube clusters are dispersed into linear suspension. Wherein, the carbon nanotube is the multi-walled structure, and the external diameter: 5-30nm, length: 5-60 μm, purity > 95.0%.
(II) preparing precursor powder CNTs-Ti-Al:
step 2.1: wet mixing and drying of precursor powder: 40g of Al powder with the granularity of 1200 meshes and the purity of more than 99.95 percent and 7.28g of Ti powder with the granularity of 1500 meshes and the purity of more than 99.95 percent are added into the carbon nanotube ethanol suspension. Electromagnetically stirring the mixture ethanol solution for 2 hours at room temperature, wherein the rotating speed of the electromagnetic stirring is 400 r/min; then, the mixture was subjected to ultrasonic vibration at a frequency of 30KHz for 1 hour. The ethanol solution of the mixture was dried using a rotary evaporator, and the evaporation flask was placed in a water bath at a constant temperature of 50 ℃ for 2 hours while rotating the flask at 80r/min and keeping the negative pressure of the solution in the flask at 500 mm Hg. Removing the alcohol solvent and taking out the powder mixture.
Step 2.2: ball milling of precursor powder: 50g of the powder mixture is put into a zirconium dioxide ball milling tank, and ZrO is placed in the tank in advance2480g of grinding balls, wherein the diameters of the grinding balls are 5-22mm, 6 grinding balls are used, and the diameters of the grinding balls are 5mm, 7mm, 11mm, 15mm, 20mm and 22mm respectively, and 6 grinding balls are used; the ball milling pot is installed on a horizontal mixer after being sealed, the rotating speed of the mixer is set to be 90r/min, and the time for uniform mixing is 50 hours; wherein the mass ratio of the ZrO2 grinding balls to the mixed powder is 9.6:1, and the total volume of the powder and the zirconia grinding balls is not more than 80 percent of the capacity of the ball-milling tank.
The molar ratio of CNTs to Ti in the powder mixture is 1.5:1, and the mass ratio of CNTs to Ti is 1: 2.67; the content of CNTs powder is 5.45 wt.%, the content of Ti powder is 14.55 wt.%, and the content of Al powder is 80 wt.%. The mass fraction of the produced nano TiC ceramic particles after the reaction is 18.18 wt.%, and the mass fraction of the residual CNTs is 1.82 wt.%.
(III) compacting, sintering and densifying:
step 3.1: coating a release agent: weighing 2g of 0.5 mu m hexagonal boron nitride powder, filling the powder into a 50ml beaker, adding 10ml of alcohol into the beaker, and preparing the solution into a thin hexagonal boron nitride solution; and (3) coating the hexagonal boron nitride solution on the inner wall of a sleeve, a gasket, a pressure head and other parts of the graphite mold, which can be in contact with the powder, waiting for more than 2min, volatilizing alcohol, and then filling the powder mixture into the graphite mold.
Step 3.2: dehumidification and degassing: putting the graphite mould filled with the powder mixture into a vacuum hot-pressing sintering furnace, and setting the pre-pressure to be 0.2 ton; closing the furnace door, starting the vacuum-pumping system, observing the indication number of the vacuum degree display window, and waiting for the vacuum degree to display that the pressure in the furnace is lower than 0.8 multiplied by 10-3After Pa, turning on a heating power supply, heating to 100 ℃ at a heating rate of 10K/min, and keeping the temperature for 30 min;
step 3.3: pressing: after the heat preservation state lasts for 15min, starting a hydraulic system, gradually pressurizing with 0.8 ton force until the pressure value reaches 20MPa, and maintaining the pressure for 5 min; then, the pressure was gradually reduced by 1 ton, and the pre-pressure was maintained at 0.2 ton, thereby completing the green compact of the powder mixture.
Step 3.4: sintering and densification: continuously heating to 500 ℃ at the heating rate of 10K/min, and keeping the temperature for 30min to ensure that the target temperature is consistent with the actual temperature and the internal and external temperatures of the hearth and the billet; and then, continuing heating at the heating rate of 100K/min, rapidly pressurizing to 80MPa when the pressure indication in the vacuum degree display window is suddenly increased, simultaneously immediately closing a heating power supply, and cooling to room temperature along with the furnace to finish the hot-pressing sintering and densification of the powder mixture.
Wherein, the graphite mould in the steps 3.1 and 3.2 is a hot isostatic pressing high-strength graphite mould, the outer sleeve is circular, the outer surface of the outer sleeve is matched with the outer surface of the inner sleeve by adopting a conical surface, and the cone angle is 5 degrees; the inner sleeve is of an integral type, the thickness of the inner sleeve is larger than 10mm, the cross section of the sleeve is circular, the inner diameter of the circular sleeve is 20mm, the height of the sleeve is 100mm, the thickness of the graphite gasket is 5mm, the cross section shape and the height of the compression bar are consistent with the cross section shape and the height keeping degree of the sleeve, the compression bar is in clearance fit with the inner surface of the sleeve, and the value of the clearance of two sides is smaller than 0..
The two-phase hybrid reinforced (CNTs-TiC)/Al-based composite prepared by in-situ in the CNTs-Ti-Al system and containing 18.18 wt.% nano TiC ceramic particles and 1.82 wt.% CNTs, fig. 1 is an X-ray diffraction analysis of the aluminum-based composite prepared in example 1, and it can be seen from fig. 1 that the (CNTs-TiC)/Al-based composite is made of Al, TiC, CNTs, Al4C3And a small amount of Al3Ti phase composition. FIG. 2 is a Raman spectrum of the aluminum-based composite prepared in example 1, and it can be seen from FIG. 2 that CNTs characteristic peak exists in the (CNTs-TiC)/Al-based composite.
Example 2
A carbon nanotube and endogenous nanometer TiC granule mix the aluminium base composite material of reinforcement and its preparation method, including the following steps:
firstly, ultrasonic dispersion of carbon nanotubes:
step 1.1: 5.45g of carbon nanotubes are added into 1500ml of ethanol, and then stirred for 4 hours in 60KHz ultrasonic waves at room temperature, so that carbon nanotube clusters are dispersed into linear suspension. Wherein, the carbon nanotube is the multi-walled structure, and the external diameter: 5-30nm, length: 5-60 μm, purity > 95.0%.
(II) preparing precursor powder CNTs-Ti-Al:
step 2.1: wet mixing and drying of precursor powder: 30g of Al powder with the granularity of 2000 meshes and the purity of more than 99.95 percent and 14.55g of Ti powder with the granularity of 3000 meshes and the purity of more than 99.95 percent are added into the carbon nanotube ethanol suspension. Electromagnetically stirring the mixture ethanol solution for 5 hours at room temperature, wherein the rotating speed of the electromagnetic stirring is 1500 r/min; then, the mixture was subjected to ultrasonic oscillation at a frequency of 60KHz for 4 hours. The ethanol solution of the mixture was dried using a rotary evaporator, and the evaporation flask was placed in a water bath at 80 ℃ for 4 hours at a constant temperature with a rotation speed of 180r/min and a negative pressure of 800 mm Hg. Removing the alcohol solvent and taking out the powder mixture.
Step 2.2: ball milling of precursor powder: weighing 50g of the powder mixture, putting the powder mixture into a zirconium dioxide ball milling tank, and putting ZrO in the tank in advance2640g of grinding balls, the diameters of the grinding balls are 5-22mm, the total number of the grinding balls is 6, the diameters of the grinding balls are respectively 5mm, 7mm, 11mm, 15mm, 20mm and 22mm, and 8 grinding balls are respectively arranged; the ball milling pot is installed on a horizontal mixer after being sealed, the rotating speed of the mixer is set to be 120r/min, and the time for uniform mixing is 72 hours; wherein ZrO2The mass ratio of the grinding balls to the mixed powder is 12.8:1, and the total volume of the powder and the zirconia grinding balls is not more than 80% of the capacity of the ball milling tank.
The molar ratio of CNTs to Ti in the powder mixture is 1.5:1, and the mass ratio of CNTs to Ti is 1: 2.67; the content of CNTs powder is 10.90 wt.%, the content of Ti powder is 29.10 wt.%, and the content of Al powder is 60 wt.%. The mass fraction of the produced nano TiC ceramic particles after the reaction is 36.37 wt.%, and the mass fraction of the residual CNTs is 3.63 wt.%.
(III) compacting, sintering and densifying:
step 3.1: coating a release agent: weighing 5g of hexagonal boron nitride powder with the particle size of 3 mu m, filling the hexagonal boron nitride powder into a 200ml beaker, adding 30ml of alcohol into the beaker, and preparing the hexagonal boron nitride powder into a thin hexagonal boron nitride solution; and (3) coating the hexagonal boron nitride solution on the inner wall of a sleeve, a gasket, a pressure head and other parts of the graphite mold, which can be in contact with the powder, waiting for more than 2min, volatilizing alcohol, and then filling the powder mixture into the graphite mold.
Step 3.2: dehumidification and degassing: putting the graphite mould filled with the powder mixture into a vacuum hot-pressing sintering furnace, and setting the pre-pressure to be 0.5 ton; closing the furnace door, starting the vacuum-pumping system, observing the indication number of the vacuum degree display window, and waiting for the vacuum degree to display that the pressure in the furnace is lower than 0.8 multiplied by 10-3After Pa, turning on a heating power supply, heating to 300 ℃ at a heating rate of 20K/min, and keeping the temperature for 60 min;
step 3.3: pressing: after the heat preservation state lasts for 15min, starting a hydraulic system, gradually pressurizing with 0.2 ton force until the pressure value reaches 50MPa, and maintaining the pressure for 10 min; then, the pressure was gradually reduced by 0.5 ton, and the pre-pressure was maintained by 0.5 ton, thereby completing the green compact of the powder mixture.
Step 3.4: sintering and densification: continuously heating to 600 ℃ at the heating rate of 20K/min, and keeping the temperature for 45min to ensure that the target temperature is consistent with the actual temperature and the internal and external temperatures of the hearth and the billet; and then, continuing heating at the heating rate of 70K/min, rapidly pressurizing to 100MPa when the pressure indication in the vacuum degree display window is suddenly increased, simultaneously immediately closing a heating power supply, and cooling to room temperature along with the furnace to finish the hot-pressing sintering and densification of the powder mixture.
Wherein, the graphite mould in the steps 3.1 and 3.2 is a hot isostatic pressing high-strength graphite mould, the outer sleeve is circular, the outer surface of the outer sleeve is matched with the outer surface of the inner sleeve by adopting a conical surface, and the taper angle is 8 degrees; the inner sleeve is divided into two sections, the thickness is more than 10mm, the cross section of the sleeve is circular, the inner diameter of the circular section is 25mm, the height of the sleeve is 120mm, the thickness of the graphite gasket is 5mm, the cross section shape and the height of the pressure lever are consistent with the cross section shape and the height of the sleeve, the pressure lever is in clearance fit with the inner surface of the sleeve, and the value of the clearance of two sides is less than 0.1mm
A two-phase hybrid enhanced (CNTs-TiC)/Al-based composite prepared by in-situ in situ reactions of CNTs-Ti-Al system and containing 36.37 wt.% nano TiC ceramic particles and 3.63 wt.% CNTs, fig. 3 is an X-ray diffraction analysis of the aluminum-based composite prepared in example 2, and it can be seen from fig. 3 that the (CNTs-TiC)/Al-based composite is composed of Al, TiC, CNTs, Al4C3And a small amount of Al3Ti phase composition. FIG. 4 is a Raman spectrum of the aluminum matrix composite prepared in example 2, and it can be seen from FIG. 4 that (CNTs-TiC)) CNTs characteristic peak exists in the/Al-based composite.
Example 3
A carbon nanotube and endogenous nanometer TiC granule mix the aluminium base composite material of reinforcement and its preparation method, including the following steps:
firstly, ultrasonic dispersion of carbon nanotubes:
step 1.1: 5g of carbon nanotubes are added into 1200ml of ethanol, and then stirred for 3 hours in 50KHz ultrasonic waves at room temperature, so that carbon nanotube groups are dispersed into linear suspension. Wherein, the carbon nanotube is the multi-walled structure, and the external diameter: 5-30nm, length: 5-60 μm, purity > 95.0%.
(II) preparing precursor powder CNTs-Ti-Al:
step 2.1: wet mixing and drying of precursor powder: 35g of Al powder with the granularity of 1800 meshes and the purity of more than 99.95 percent and 10g of Ti powder with the granularity of 2500 meshes and the purity of more than 99.95 percent are added into the carbon nanotube ethanol suspension. Electromagnetically stirring the mixture ethanol solution for 4 hours at room temperature, wherein the rotating speed of the electromagnetic stirring is 1200 r/min; then, the mixture was subjected to ultrasonic vibration at a frequency of 50KHz for 3 hours. The ethanol solution of the mixture was dried using a rotary evaporator, and the evaporation flask was placed in a water bath at a constant temperature of 70 ℃ for 3 hours while rotating the flask at 150r/min and keeping the negative pressure of the solution in the flask at 700 mmHg. Removing the alcohol solvent and taking out the powder mixture.
Step 2.2: ball milling of precursor powder: weighing 50g of the powder mixture, putting the powder mixture into a zirconium dioxide ball milling tank, and putting 560g of ZrO2 grinding balls with the diameter of 5-22mm in advance in the tank, wherein the diameters of 6 grinding balls are respectively 5mm, 7mm, 11mm, 15mm, 20mm and 22mm, and 7 grinding balls are respectively arranged in the tank; the ball milling pot is installed on a horizontal mixer after being sealed, the rotating speed of the mixer is set to be 110r/min, and the time for uniform mixing is 66 hours; wherein ZrO2The mass ratio of the grinding balls to the mixed powder is 11.2:1, and the total volume of the powder and the zirconia grinding balls is not more than 80% of the capacity of the ball milling tank.
The molar ratio of CNTs to Ti in the powder mixture is 2:1, and the mass ratio of CNTs to Ti is 1: 2; the content of CNTs powder is 10 wt.%, the content of Ti powder is 20 wt.%, and the content of Al powder is 70 wt.%. The mass fraction of the produced nano TiC ceramic particles after the reaction is 25 wt.%, and the mass fraction of the residual CNTs is 5 wt.%.
(III) compacting, sintering and densifying:
step 3.1: coating a release agent: weighing 4g of 2-micron hexagonal boron nitride powder, filling the powder into a 150ml beaker, adding 25ml of alcohol into the beaker, and preparing the solution into a thin hexagonal boron nitride solution; and (3) coating the hexagonal boron nitride solution on the inner wall of a sleeve, a gasket, a pressure head and other parts of the graphite mold, which can be in contact with the powder, waiting for more than 2min, volatilizing alcohol, and then filling the powder mixture into the graphite mold.
Step 3.2: dehumidification and degassing: putting the graphite mould filled with the powder mixture into a vacuum hot-pressing sintering furnace, and setting the pre-pressure to be 0.4 ton; closing the furnace door, starting the vacuum-pumping system, observing the indication number of the vacuum degree display window, and waiting for the vacuum degree to display that the pressure in the furnace is lower than 0.8 multiplied by 10-3After Pa, turning on a heating power supply, heating to 200 ℃ at a heating rate of 15K/min, and keeping the temperature for 50 min;
step 3.3: pressing: after the heat preservation state lasts for 15min, starting a hydraulic system, gradually pressurizing with 0.5 ton force until the pressure value reaches 40MPa, and maintaining the pressure for 8 min; then, the pressure was gradually reduced by 0.6 ton, and the pre-pressure was maintained at 0.4 ton, thereby completing the green compact of the powder mixture.
Step 3.4: sintering and densification: continuously heating to 550 ℃ at the heating rate of 15K/min, and preserving heat for 40min to ensure that the target temperature is consistent with the actual temperature and the internal and external temperatures of the hearth and the billet; and then, continuing heating at the heating rate of 80K/min, rapidly pressurizing to 90MPa when the pressure indication in the vacuum degree display window is suddenly increased, simultaneously immediately closing a heating power supply, and cooling to room temperature along with the furnace to finish the hot-pressing sintering and densification of the powder mixture.
Wherein, the graphite mould in the steps 3.1 and 3.2 is a hot isostatic pressing high-strength graphite mould, the outer sleeve is circular, the outer surface of the outer sleeve is matched with the outer surface of the inner sleeve by adopting a conical surface, and the taper angle is 6 degrees; the inner sleeve adopts the integral type, and thickness is greater than 10mm, and sleeve cross section shape is the square of taking the radius angle, and square length and width are 25mm and 20mm respectively, chamfer radius 3mm, sleeve height 120mm, graphite gasket thickness 8mm, and depression bar cross section shape and height are unanimous with sleeve cross section shape and height maintenance degree, depression bar and sleeve internal surface clearance fit, and bilateral clearance value is less than 0.1 mm.
The two-phase hybrid reinforced (CNTs-TiC)/Al-based composite prepared by in situ in the CNTs-Ti-Al system and containing 25 wt.% nano TiC ceramic particles and 5 wt.% CNTs, fig. 5 is an X-ray diffraction analysis of the aluminum-based composite prepared in example 3, and it can be seen from fig. 5 that the (CNTs-TiC)/Al-based composite is made of Al, TiC, CNTs, Al4C3And a minor amount of Al3Ti phase. FIG. 6 is a Raman spectrum of the aluminum-based composite prepared in example 3, and it can be seen from FIG. 6 that CNTs characteristic peak exists in the (CNTs-TiC)/Al-based composite.
Example 4
A carbon nanotube and endogenous nanometer TiC granule mix the aluminium base composite material of reinforcement and its preparation method, including the following steps:
firstly, ultrasonic dispersion of carbon nanotubes:
step 1.1: 3.84g of carbon nanotubes are added into 800ml of ethanol, and then stirred for 2 hours in 40KHz ultrasonic waves at room temperature, so that carbon nanotube groups are dispersed into linear suspension. Wherein, the carbon nanotube is the multi-walled structure, and the external diameter: 5-30nm, length: 5-60 μm, purity > 95.0%.
(II) preparing precursor powder CNTs-Ti-Al:
step 2.1: wet mixing and drying of precursor powder: 40g of Al powder with the granularity of 1500 meshes and the purity of more than 99.95 percent and 6.16g of Ti powder with the granularity of 2000 meshes and the purity of more than 99.95 percent are added into the carbon nanotube ethanol suspension. Electromagnetically stirring the mixture ethanol solution for 3 hours at room temperature, wherein the rotating speed of the electromagnetic stirring is 800 r/min; then, the mixture was subjected to ultrasonic oscillation at a frequency of 40KHz for 2 hours. The ethanol solution of the mixture was dried using a rotary evaporator, and the evaporation flask was placed in a water bath at a constant temperature of 60 ℃ for 2 hours while rotating the flask at 100r/min and keeping the negative pressure of the solution in the flask at 600 mmHg. Removing the alcohol solvent and taking out the powder mixture.
Step 2.2: ball milling of precursor powder: weighing 50g of the powder mixture, and putting the powder mixture into a zirconium dioxide ball milling tankZrO is placed in the inner and outer tanks in advance2480g of grinding balls, wherein the diameters of the grinding balls are 5-22mm, 6 grinding balls are used, and the diameters of the grinding balls are 5mm, 7mm, 11mm, 15mm, 20mm and 22mm respectively, and 6 grinding balls are used; the ball milling pot is installed on a horizontal mixer after being sealed, the rotating speed of the mixer is set to be 100r/min, and the time for uniform mixing is 58 hours; wherein ZrO2The mass ratio of the grinding balls to the mixed powder is 9.6:1, and the total volume of the powder and the zirconia grinding balls is not more than 80% of the capacity of the ball milling tank.
The molar ratio of CNTs to Ti in the powder mixture is 2.5:1, and the mass ratio of CNTs to Ti is 1: 1.6; the content of CNTs powder is 7.68 wt.%, the content of Ti powder is 12.32 wt.%, and the content of Al powder is 80 wt.%. The mass fraction of the produced nano TiC ceramic particles after the reaction is 15.39 wt.%, and the mass fraction of the residual CNTs is 4.61 wt.%.
(III) compacting, sintering and densifying:
step 3.1: coating a release agent: weighing 3g of 1-micron hexagonal boron nitride powder, filling the powder into a 100ml beaker, adding 20ml of alcohol into the beaker, and preparing the solution into a thin hexagonal boron nitride solution; and (3) coating the hexagonal boron nitride solution on the inner wall of a sleeve, a gasket, a pressure head and other parts of the graphite mold, which can be in contact with the powder, waiting for more than 2min, volatilizing alcohol, and then filling the powder mixture into the graphite mold.
Step 3.2: dehumidification and degassing: putting the graphite mould filled with the powder mixture into a vacuum hot-pressing sintering furnace, and setting the pre-pressure to be 0.3 ton; closing the furnace door, starting a vacuumizing system, observing the readings of a vacuum degree display window, starting a heating power supply after the vacuum degree display furnace pressure is lower than 0.8 multiplied by 10 < -3 > Pa, heating to 100 ℃ at a heating rate of 10K/min, and preserving heat for 40 min;
step 3.3: pressing: after the heat preservation state lasts for 15min, starting a hydraulic system, gradually pressurizing with 0.6 ton force until the pressure value reaches 30MPa, and maintaining the pressure for 6 min; then, the pressure was gradually reduced by 0.8 ton, and the pre-pressure was maintained at 0.3 ton, thereby completing the green compact of the powder mixture.
Step 3.4: sintering and densification: continuously heating to 500 ℃ at the heating rate of 10K/min, and keeping the temperature for 30min to ensure that the target temperature is consistent with the actual temperature and the internal and external temperatures of the hearth and the billet; and then, continuously heating at the heating rate of 90K/min, rapidly pressurizing to 80MPa when the pressure indication in the vacuum degree display window is suddenly increased, simultaneously immediately closing a heating power supply, and cooling to room temperature along with the furnace to finish the hot-pressing sintering and densification of the powder mixture.
Wherein, the graphite mould in the steps 3.1 and 3.2 is a hot isostatic pressing high-strength graphite mould, the outer sleeve is circular, the outer surface of the outer sleeve is matched with the outer surface of the inner sleeve by adopting a conical surface, and the taper angle is 4 degrees; the inner skleeve adopts and divides two lamella formulas, and thickness is greater than 10mm, and sleeve cross sectional shape can be for taking the square of fillet, and square length and width are 30mm and 20mm respectively, chamfer radius 5mm, sleeve height 100mm, graphite gasket thickness 8mm, and depression bar cross sectional shape and height are unanimous with sleeve cross sectional shape and height maintenance degree, depression bar and sleeve internal surface clearance fit, and bilateral clearance value is less than 0.1 mm.
A two-phase hybrid enhanced (CNTs-TiC)/Al-based composite prepared by in situ in the CNTs-Ti-Al system and containing 15.39 wt.% nano TiC ceramic particles and 4.61 wt.% CNTs, fig. 7 is an X-ray diffraction analysis of the aluminum-based composite prepared in example 4, and it can be seen from fig. 7 that the (CNTs-TiC)/Al-based composite is Al, TiC, CNTs, Al4C3And a small amount of Al3Ti phase composition. FIG. 8 is a Raman spectrum of the aluminum-based composite prepared in example 4, and it can be seen from FIG. 8 that CNTs characteristic peak exists in the (CNTs-TiC)/Al-based composite.
Comparative example 1
The preparation method of this comparative example comprises the following steps:
firstly, ultrasonic dispersion of carbon nanotubes:
step 1.1: 1.92g of carbon nanotubes are added into 500ml of ethanol, and then stirred for 2 hours in 40KHz ultrasonic waves at room temperature, so that carbon nanotube groups are dispersed into linear suspension. Wherein, the carbon nanotube is the multi-walled structure, and the external diameter: 5-30nm, length: 5-60 μm, purity > 95.0%.
(II) preparing precursor powder CNTs-Ti-Al:
step 2.1: wet mixing and drying of precursor powder: 45g of Al powder with the granularity of 1500 meshes and the purity of more than 99.95 percent and 3.08g of Ti powder with the granularity of 2000 meshes and the purity of more than 99.95 percent are added into the carbon nanotube ethanol suspension. Electromagnetically stirring the mixture ethanol solution for 3 hours at room temperature, wherein the rotating speed of the electromagnetic stirring is 800 r/min; then, the mixture was subjected to ultrasonic oscillation at a frequency of 40KHz for 2 hours. The ethanol solution of the mixture was dried using a rotary evaporator, and the evaporation flask was placed in a water bath at a constant temperature of 60 ℃ for 2 hours while rotating the flask at 100r/min and keeping the negative pressure of the solution in the flask at 600 mmHg. Removing the alcohol solvent and taking out the powder mixture.
Step 2.2: ball milling of precursor powder: weighing 50g of the powder mixture, putting the powder mixture into a zirconium dioxide ball milling tank, and putting 480g of ZrO2 grinding balls with the diameter of 5-22mm in advance in the tank, wherein the diameters of the grinding balls are respectively 5mm, 7mm, 11mm, 15mm, 20mm and 22mm, and 6 grinding balls are respectively arranged in the tank; the ball milling pot is installed on a horizontal mixer after being sealed, the rotating speed of the mixer is set to be 100r/min, and the time for uniform mixing is 58 hours; wherein ZrO2The mass ratio of the grinding balls to the mixed powder is 9.6:1, and the total volume of the powder and the zirconia grinding balls is not more than 80% of the capacity of the ball milling tank.
The molar ratio of CNTs to Ti in the powder mixture is 2.5:1, and the mass ratio of CNTs to Ti is 1: 1.6; the content of CNTs powder is 3.84 wt.%, the content of Ti powder is 6.16 wt.%, and the content of Al powder is 90 wt.%. The mass fraction of the produced nano TiC ceramic particles after the reaction is 7.69 wt.%.
(III) compacting, sintering and densifying:
step 3.1: coating a release agent: weighing 3g of 1-micron hexagonal boron nitride powder, filling the powder into a 100ml beaker, adding 20ml of alcohol into the beaker, and preparing the solution into a thin hexagonal boron nitride solution; and (3) coating the hexagonal boron nitride solution on the inner wall of a sleeve, a gasket, a pressure head and other parts of the graphite mold, which can be in contact with the powder, waiting for more than 2min, volatilizing alcohol, and then filling the powder mixture into the graphite mold.
Step 3.2: dehumidification and degassing: putting the graphite mould filled with the powder mixture into a vacuum hot-pressing sintering furnace, and setting the pre-pressure to be 0.3 ton; closing the furnace door, starting the vacuum-pumping system, observing the indication number of the vacuum degree display window, and waiting for the vacuum degree to display that the pressure in the furnace is lower than 0.8 multiplied by 10-3After Pa, turn on and addA thermal power supply, which is heated to 100 ℃ at the heating rate of 10K/min and is kept for 40 min;
step 3.3: pressing: after the heat preservation state lasts for 15min, starting a hydraulic system, gradually pressurizing with 0.6 ton force until the pressure value reaches 30MPa, and maintaining the pressure for 6 min; then, the pressure was gradually reduced by 0.8 ton, and the pre-pressure was maintained at 0.3 ton, thereby completing the green compact of the powder mixture.
Step 3.4: sintering and densification: continuously heating to 500 ℃ at the heating rate of 10K/min, and keeping the temperature for 30min to ensure that the target temperature is consistent with the actual temperature and the internal and external temperatures of the hearth and the billet; and then, continuously heating at the heating rate of 90K/min, rapidly pressurizing to 80MPa when the pressure indication in the vacuum degree display window is suddenly increased, simultaneously immediately closing a heating power supply, and cooling to room temperature along with the furnace to finish the hot-pressing sintering and densification of the powder mixture.
Wherein, the graphite mould in the steps 3.1 and 3.2 is a hot isostatic pressing high-strength graphite mould, the outer sleeve is circular, the outer surface of the outer sleeve is matched with the outer surface of the inner sleeve by adopting a conical surface, and the taper angle is 4 degrees; the inner skleeve adopts and divides two lamella formulas, and thickness is greater than 10mm, and sleeve cross sectional shape can be for taking the square of fillet, and square length and width are 30mm and 20mm respectively, chamfer radius 5mm, sleeve height 100mm, graphite gasket thickness 8mm, and depression bar cross sectional shape and height are unanimous with sleeve cross sectional shape and height maintenance degree, depression bar and sleeve internal surface clearance fit, and bilateral clearance value is less than 0.1 mm.
The biphase hybrid enhanced (CNTs-TiC)/Al-based composite is prepared by the in-situ endogenous reaction of the CNTs-Ti-Al system, FIG. 9 is the X-ray diffraction analysis of the aluminum-based composite prepared in the comparative example 1, and it can be known from FIG. 9 that the (CNTs-TiC)/Al-based composite is Al, TiC and Al4C3Phase composition. This comparative example shows that when the Al content is 90%, a two-phase hybrid-reinforced (CNTs-TiC)/Al-based composite cannot be formed.
Comparative example 2
The preparation method of this comparative example comprises the following steps:
firstly, ultrasonic dispersion of carbon nanotubes:
step 1.1: adding 3g of carbon nanotubes into 600ml of ethanol, stirring for 3 hours in 50KHz ultrasonic waves at room temperature, and dispersing carbon nanotube groups into linear suspension. Wherein, the carbon nanotube is the multi-walled structure, and the external diameter: 5-30nm, length: 5-60 μm, purity > 95.0%.
(II) preparing precursor powder CNTs-Ti-Al:
step 2.1: wet mixing and drying of precursor powder: 35g of Al powder with the granularity of 1800 meshes and the purity of more than 99.95 percent and 12g of Ti powder with the granularity of 2500 meshes and the purity of more than 99.95 percent are added into the carbon nanotube ethanol suspension. Electromagnetically stirring the mixture ethanol solution for 4 hours at room temperature, wherein the rotating speed of the electromagnetic stirring is 1200 r/min; then, the mixture was subjected to ultrasonic vibration at a frequency of 50KHz for 3 hours. The ethanol solution of the mixture was dried using a rotary evaporator, and the evaporation flask was placed in a water bath at a constant temperature of 70 ℃ for 3 hours while rotating the flask at 150r/min and keeping the negative pressure of the solution in the flask at 700 mmHg. Removing the alcohol solvent and taking out the powder mixture.
Step 2.2: ball milling of precursor powder: weighing 50g of the powder mixture, putting the powder mixture into a zirconium dioxide ball milling tank, and putting ZrO in the tank in advance2560g of grinding balls, the diameters of the grinding balls are 5-22mm, 6 types of grinding balls are used, the diameters of the grinding balls are 5mm, 7mm, 11mm, 15mm, 20mm and 22mm, and 7 grinding balls are used; the ball milling pot is installed on a horizontal mixer after being sealed, the rotating speed of the mixer is set to be 110r/min, and the time for uniform mixing is 66 hours; wherein ZrO2The mass ratio of the grinding balls to the mixed powder is 11.2:1, and the total volume of the powder and the zirconia grinding balls is not more than 80% of the capacity of the ball milling tank.
The molar ratio of CNTs to Ti in the powder mixture is 1:1, and the mass ratio of CNTs to Ti is 1: 4; the content of CNTs powder is 6 wt.%, the content of Ti powder is 24 wt.%, and the content of Al powder is 70 wt.%. The mass fraction of the produced nano TiC ceramic particles after the reaction is 30 wt.%, and the mass fraction of the residual CNTs is 0 wt.%.
(III) compacting, sintering and densifying:
step 3.1: coating a release agent: weighing 4g of 2-micron hexagonal boron nitride powder, filling the powder into a 150ml beaker, adding 25ml of alcohol into the beaker, and preparing the solution into a thin hexagonal boron nitride solution; and (3) coating the hexagonal boron nitride solution on the inner wall of a sleeve, a gasket, a pressure head and other parts of the graphite mold, which can be in contact with the powder, waiting for more than 2min, volatilizing alcohol, and then filling the powder mixture into the graphite mold.
Step 3.2: dehumidification and degassing: putting the graphite mould filled with the powder mixture into a vacuum hot-pressing sintering furnace, and setting the pre-pressure to be 0.4 ton; closing the furnace door, starting the vacuum-pumping system, observing the indication number of the vacuum degree display window, and waiting for the vacuum degree to display that the pressure in the furnace is lower than 0.8 multiplied by 10-3After Pa, turning on a heating power supply, heating to 200 ℃ at a heating rate of 15K/min, and keeping the temperature for 50 min;
step 3.3: pressing: after the heat preservation state lasts for 15min, starting a hydraulic system, gradually pressurizing with 0.5 ton force until the pressure value reaches 40MPa, and maintaining the pressure for 8 min; then, the pressure was gradually reduced by 0.6 ton, and the pre-pressure was maintained at 0.4 ton, thereby completing the green compact of the powder mixture.
Step 3.4: sintering and densification: continuously heating to 550 ℃ at the heating rate of 15K/min, and preserving heat for 40min to ensure that the target temperature is consistent with the actual temperature and the internal and external temperatures of the hearth and the billet; and then, continuing heating at the heating rate of 80K/min, rapidly pressurizing to 90MPa when the pressure indication in the vacuum degree display window is suddenly increased, simultaneously immediately closing a heating power supply, and cooling to room temperature along with the furnace to finish the hot-pressing sintering and densification of the powder mixture.
Wherein, the graphite die in the step (3.1) is a hot isostatic pressing high-strength graphite die, the outer sleeve is circular, the outer surfaces of the outer sleeve and the inner sleeve are matched by adopting a conical surface, and the cone angle is 6 degrees; the inner sleeve adopts the integral type, and thickness is greater than 10mm, and sleeve cross section shape is the square of taking the radius angle, and square length and width are 25mm and 20mm respectively, chamfer radius 3mm, sleeve height 120mm, graphite gasket thickness 8mm, and depression bar cross section shape and height are unanimous with sleeve cross section shape and height maintenance degree, depression bar and sleeve internal surface clearance fit, and bilateral clearance value is less than 0.1 mm.
The biphase hybrid enhanced (CNTs-TiC)/Al-based composite is prepared through the in-situ endogenous reaction of the CNTs-Ti-Al system, FIG. 10 is the X-ray diffraction analysis of the aluminum-based composite prepared in the comparative example 2, and it can be known from FIG. 10 that the Al-based composite consists of Al and TiC phases. This comparative example illustrates that when the molar ratio of CNTs to Ti is 1:1 and the mass ratio of CNTs to Ti is 1:4, a two-phase hybrid-reinforced (CNTs-TiC)/Al-based composite cannot be formed.
TABLE 1 example and comparative example CNTs-Ti-Al system proportion and content of each component of composite material after reaction
Figure BDA0001924468530000161
As can be seen from Table 1: when the molar ratio of MWCNTs to Ti is 1.5-2.5:1 and the addition amount of Al powder is 60-80 wt.%, a (CNTs-TiC)/Al-based composite material consisting of Al, TiC and CNTs phases can be prepared, wherein the mass percentage is TiC: 8.18-36.37 wt.%; CNTs: 1.82-4.61 wt.%. When the Al powder is added in an amount of 90 wt.% or more or the MWCNTs/Ti molar ratio is 1:1, the two-phase hybrid reinforced (CNTs-TiC)/Al-based composite material cannot be prepared.

Claims (8)

1. A carbon nanotube and endogenous nanometer TiC granule mix the aluminium base composite material of reinforcement, characterized by that: the composite material consists of 0.5 to 5 mass percent of carbon nanotubes, 18 to 38 mass percent of TiC and 60 to 80 mass percent of Al; the preparation method of the composite material comprises the following steps:
(1) putting the mixed powder of the carbon nano-tube, Ti and Al into a graphite die for pressing to obtain a compact; the mass percentages of the carbon nano-tube, the Ti and the Al in the mixed powder are respectively 5.45-10.90%, 14.55-29.10% and 60-80%;
(2) and (2) preserving the temperature of the compact obtained in the step (1) for 5-50min under the conditions of a vacuum system and 600 ℃, then continuously heating until the pressure is suddenly increased, rapidly pressurizing to 40-100MPa, stopping heating and cooling to room temperature to obtain the composite material.
2. The composite material of claim 1, wherein the preparation of the mixed powder of carbon nanotubes, Ti and Al in step (1) comprises the following steps:
(1-1) weighing Al powder and Ti powder, adding the Al powder and the Ti powder into the carbon nanotube ethanol suspension, and performing electromagnetic stirring and ultrasonic oscillation to obtain a mixture ethanol solution;
(1-2) drying the ethanol solution of the mixture obtained in the step (1-1) to obtain a powder mixture;
and (1-3) mixing the powder mixture grinding balls obtained in the step (1-2) for 12-72 hours to obtain the carbon nanotube, Ti and Al mixed powder.
3. The composite material of claim 2, wherein: in the step (1-1), the preparation of the carbon nanotube ethanol suspension comprises the step of adding the carbon nanotubes into ethanol, and performing ultrasonic stirring until carbon nanotube groups are dispersed into linear suspension.
4. The composite material of claim 1, wherein: the carbon nanotube is of a multi-wall structure, the outer diameter is 5-30nm, the length is 5-60 mu m, and the purity is more than 95.0%; the granularity of the Al powder is 200-2000 meshes, and the purity is more than 99.95 percent; the granularity of the Ti powder is 500-3000 meshes, and the purity is more than 99.95 percent.
5. The composite material of claim 1, wherein: the green compact is hydraulically pressed.
6. The composite material of claim 1, wherein: the carbon nanotube is of a multi-walled structure, and before the mixed powder of the multi-walled carbon nanotube, Ti and Al is filled into a graphite mold, the method also comprises the step of smearing a hexagonal boron nitride ethanol solution on the part which can be contacted with the mixed powder in the graphite mold.
7. The composite material of claim 1, wherein: in the step (2), the mixture is heated to 500-600 ℃ at a heating rate of 10-60K/min.
8. The composite material of claim 1, wherein: in the step (2), after heat preservation is carried out for 5-50min, heating is continuously carried out at the heating rate of 40-100K/min until the pressure is suddenly increased.
CN201811609884.5A 2018-12-27 2018-12-27 Carbon nanotube and endogenous nano TiC particle mixed reinforced aluminum-based composite material and preparation method thereof Active CN109652679B (en)

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* Cited by examiner, † Cited by third party
Title
Exploring the reinforcing effect of TiC and CNT in dual-reinforced Al-matrix composites;Farhad Saba等;《Diamond & Related Materials》;20180910;第180-189页 *

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