CN110331314B - Nano TiC modified graphene reinforced titanium-based composite material and preparation method and application thereof - Google Patents
Nano TiC modified graphene reinforced titanium-based composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nano TiC modified graphene reinforced titanium-based composite material as well as a preparation method and application thereof. According to the invention, a three-dimensional mechanical mixing method is adopted, firstly, a layer of nano TiC is coated on the surface of titanium matrix particles, then, a layer of graphene is coated, and the core part of the titanium matrix particles, the middle layer of the nano TiC and the surface layer of the graphene are in a core-shell structure. The method solves the problem that graphene is difficult to uniformly coat the surface of titanium particles in the traditional wet ball milling process. The existence of the nano TiC reduces the interface reaction of the graphene and the titanium matrix in the preparation process to a certain extent, and the nano TiC modified graphene reinforced titanium matrix composite material is obtained through sintering and molding. The composite material has high strength, strong plasticity and good forming and processing performance, and can be applied to the manufacturing industry of aerospace and ships and warships.
Description
Technical Field
The invention relates to a nano TiC modified graphene reinforced titanium-based composite material and a preparation method and application thereof, and belongs to the technical field of metal-based composite materials.
Background
The titanium and the titanium alloy have the characteristics of high specific strength and specific modulus and extreme condition environment resistance, and can be widely applied to the fields of aerospace, automobile industry and the like. The method has considerable application potential in reducing energy consumption and improving the thrust-weight ratio of the engine. Therefore, the development of titanium-based composite materials (TiMCs) has important significance for further improving the performance of the titanium alloy and expanding the application prospect of the titanium alloy. The best reinforcing phase of the (DRTMCs) of the non-continuous titanium-based composite material prepared by the powder metallurgy technology at present is ceramic material TiC particles or TiB whiskers. But the modulus of elasticity and breaking strength of the ceramic material reinforcing phase are far inferior to nanocarbon reinforcements such as carbon nanotubes, nanodiamonds or graphene. This means that the mechanical properties of the titanium-based composite material can be further improved by the nanocarbon reinforcement.
Graphene is a new nano-material with great development potential following carbon nanotubes, and atoms of graphene pass through sp2Hybridization forms a two-dimensional hexagonal honeycomb structure, which makes it easier to disperse than carbon nanotubes. The graphene has excellent electrical, thermal and mechanical properties, so that the graphene has an important application prospect in the aspects of materials, energy, biology and the like, and is a revolutionary material in the future. At present, only a few researchers in reports of graphene reinforced titanium-based composite materials exist on the surface of grapheneModification of Nickel Metal particles (Carbon 137(2018)146-&Engineering A687 (2017) 164-; composites Part A123 (2019) 86-96; journal of Alloys and Compounds 765(2018)1111-1118, and patent CN201810801698.5 of the inventor of the present application in the past. The graphene directly reinforced titanium-based composite material faces two major problems, namely, the wettability of the graphene and a titanium matrix is poor, and the controllable distribution of the graphene in the titanium matrix is difficult to realize; secondly, in the preparation process, the graphene is easy to react with the titanium matrix to generate TiC. The graphene reinforced titanium-based composite material reported in the paper is mostly prepared by adopting an ultrasonic oscillation-wet ball milling mode. For example, in the patent of Zhanghongmei et al, "a titanium-based composite material enhanced by low-content few-layer graphene and preparation method" (CN201610228318.4), graphene powder and absolute ethyl alcohol are mixed and stirred, then titanium powder is added to form mixed slurry, and then the mixed slurry is ball-milled and dried. However, the graphene with a high specific surface area cannot be effectively and uniformly dispersed on the surface of the titanium substrate by wet ball milling, mainly because the graphene and the titanium substrate are not tightly combined and have a low density, and the graphene is easy to fall off from the titanium substrate and suspend on the surface of slurry after ball milling and standing.
Graphene is easy to generate an interfacial reaction with a titanium substrate to generate TiC in a sintering process, and most of current research reports adopt a spark plasma sintering system (SPS) to retain a graphene part under the conditions of low temperature and high pressure (Materials Science)&Engineering a 725(2018) 541-548). However, the composite material sintered at low temperature and high pressure by SPS is often not compact enough, the mechanical property can not meet the requirement, and the high-pressure SPS sintering can only sinter small-sized samples, and can not meet the industrial production. The most ideal measure for reducing the reaction of graphene with the titanium matrix should be to perform surface modification on graphene. Dengchun et al' a polydopamine modified graphene and Ti fixed on the surface4+The synthesis method and the application of the nano material (CN201310077269.5) modify the surface of graphene with polydopamine, so that the material has good biocompatibility and environmental stability. Zhang Chunhua et al patent' method for modifying graphene by nano silver"(CN 201410360213.5) modifies nano silver on the surface of graphene through silver ammonia solution. Therefore, at present, the graphene is modified and mostly applied to the fields of biomedicine and electrochemistry, and the titanium-based composite material in the fields of aerospace and the like is rarely applied.
Disclosure of Invention
The purpose of the invention is as follows: in view of the above technical problems, an object of the present invention is to provide a nano TiC modified graphene reinforced titanium-based composite material. The surface of the graphene is modified with a layer of nano TiC and then serves as a reinforcement body which can be uniformly dispersed in the titanium matrix, and the interface reaction between the graphene and the titanium matrix is reduced to a certain extent. The retention of the graphene can transfer the load of the matrix and improve the bearing capacity of the matrix on one hand, and can generate an Olympic (Orowan) ring to prevent the movement of dislocation on the other hand. Therefore, the nano TiC modified graphene reinforced titanium-based composite material has comprehensive mechanical properties of high strength and high plasticity.
Another object of the present invention is to provide a method for preparing a nano TiC modified graphene reinforced titanium-based composite material. The method comprises the steps of firstly coating a layer of nano TiC on the surface of titanium particles by a three-dimensional mixing method, and then coating a layer of graphene to obtain a core-shell structure with a core part of titanium particles, a middle layer of nano TiC and a surface layer of graphene, so that the effect of modifying the nano TiC on the surface of the graphene is realized. Finally, sintering and forming to obtain the network-shaped titanium-based composite material.
The final purpose of the invention is to provide the application of the nano TiC modified graphene reinforced titanium-based composite material as an aerospace component material.
The technical scheme is as follows: in order to achieve the purpose, the technical scheme of the invention is as follows:
a nano TiC modified graphene reinforced titanium-based composite material is mainly characterized in that titanium or titanium alloy is used as a titanium matrix, graphene with nano TiC modified on the surface is used as a reinforcing phase, and in the microstructure of the composite material, the graphene with nano TiC modified on the surface is uniformly distributed around titanium matrix particles to form a three-dimensional network structure.
The grain size of the nano TiC is 1-100nm, the graphene is sheet graphene, the thickness of each sheet is 1-50nm, the diameter of each sheet is 0.1-50 mu m, the powder particles of the titanium matrix are spherical particles or irregular particles, and the particle size is 1-500 mu m.
The titanium matrix is pure titanium or an alloy consisting of titanium and other alloying elements such as aluminum, vanadium, molybdenum, niobium, tantalum, zirconium, iron, silicon and the like.
The preparation method of the nano TiC modified graphene reinforced titanium-based composite material comprises the following steps:
(1) coating nano TiC on the surface: taking pure titanium or titanium alloy powder, adding nano TiC powder, and mixing for 10-20h in a high-purity argon or air atmosphere;
(2) wrapping graphene on the surface: adding graphene powder into the product obtained in the step (1), and continuously mixing for 10-20 h;
(3) sintering and forming: and (3) carrying out discharge plasma sintering or hot-pressing sintering on the product obtained in the step (2) to obtain the nano TiC modified graphene reinforced titanium-based composite material.
Preferably, the mixing in the steps (1) and (2) is dry mixing by a three-dimensional mixing method, the ball-material ratio is 1:1-5:1, and the rotating speed is 30-150 r/min. Namely, stainless steel or zirconia or alumina grinding balls are added and mixed in a three-dimensional mixer.
Preferably, the preparation method comprises the following steps:
(1) coating nano TiC on the surface: adding nano TiC powder into spherical or irregular pure titanium or titanium alloy powder, adding stainless steel or zirconia grinding balls with the size of 5-20mm, and mixing for 10-20h in a three-dimensional mixer in the atmosphere of high-purity argon or air to ensure that the nano TiC is coated on the surfaces of titanium particles.
(2) Wrapping graphene on the surface: and (2) adding graphene powder into the product obtained in the step (1), and mixing in a three-dimensional mixer for 10-20 hours to coat the graphene on the surface of the titanium particles for modifying the nano TiC.
(3) Sintering and forming: and (3) taking the product obtained in the step (2) according to the size parameter of the required product, and performing discharge plasma sintering or hot-pressing sintering under the vacuum or argon condition to obtain the graphene reinforced titanium-based composite material with the surface modified with titanium carbide.
In the method, the adding proportion of the nano TiC is 0.01-0.1%, preferably 0.03-0.05% of the mass of the titanium matrix, and the adding proportion of the graphene is 0.01-0.5%, preferably 0.2-0.5% of the mass of the titanium matrix.
The discharge plasma sintering conditions are as follows: the pressure is 10-80MPa, the temperature is 900-; the hot-pressing sintering conditions are as follows: under the protection of vacuum or inert atmosphere, the pressure is 10-80MPa, the temperature is 1000-1400 ℃, the heating rate is 10-100 ℃/min, and the heat preservation time at the highest sintering temperature is 10-180 min.
A further preferred preparation method comprises the following steps:
(1) calculating and weighing the original powder: weighing titanium powder, graphene powder and nano TiC powder according to the mass fractions of the graphene powder and the nano TiC powder, wherein the mass fraction of the graphene powder relative to the titanium matrix is 0.01-0.5 wt.%, and the mass fraction of the nano TiC powder relative to the titanium matrix is 0.01-0.1 wt.%.
(2) Mixing by a three-dimensional mixing technology: putting the titanium powder with the corresponding mass fraction in the step (1) into a plastic tank, adding 0.01-0.1 wt.% of nano TiC powder, and adding 5-20mm stainless steel or zirconia or alumina grinding balls, wherein the ball-to-material ratio is 1:1-5:1, and mixing for 10-20h by using a three-dimensional mixer at the rotating speed of 30-150r/min (rpm). And after the end, adding 0.01-0.5 wt.% of graphene powder, and continuously mixing for 10-20 h.
(3) The mixed powder is sieved by a sieve with 100 meshes and 400 meshes.
(4) Sintering and forming: determining the size parameters of the sintered product, weighing a certain mass of the product obtained in the step (3) after calculation, and sintering by the following method:
a. the discharge plasma sintering forming method comprises the following steps: and (3) pouring the powder in the step (3) into a graphite mold, assembling an upper pressure head and a lower pressure head, placing the graphite mold into a discharge plasma sintering furnace for sintering and molding, under the protection of vacuum or high-purity argon, at the pressure of 10-80MPa and the temperature of 900 plus materials of 1200 ℃, measuring the temperature by a thermocouple or infrared temperature, wherein the heating speed is 20-150 ℃/min, and the heat preservation time at the highest sintering temperature is 1-60 min. Naturally furnace cooling, and demoulding to obtain the product.
Alternatively, a hot press sintering method may be employed:
b. the hot-pressing sintering forming method comprises the following steps: and (3) pouring the powder in the step (3) into a graphite mold, assembling an upper pressure head and a lower pressure head, placing the graphite mold into a hot-pressing sintering furnace for sintering and molding, wherein the pressure is 10-80MPa, the temperature is 1000-1400 ℃, the heating speed is 10-100 ℃/min, and the heat preservation time is 10-180min at the highest sintering temperature under the protection of vacuum or inert atmosphere. Naturally furnace cooling, and demoulding to obtain the product.
The nano TiC modified graphene reinforced titanium-based composite material is applied as an aerospace component material. The aerospace or ship vessel part material comprises main structural materials of airplanes and spacecrafts, shell materials of carrier rockets, satellite structure part materials, ship vessel corrosion-resistant structural materials and the like.
According to the nano TiC modified graphene reinforced titanium-based composite material, a layer of nano TiC is modified on the surface of graphene by using a three-dimensional mixing technology, so that the graphene can be uniformly coated on the surface of titanium particles. In the subsequent sintering heat treatment process, due to the protection effect of the nano TiC layer, the graphene is retained to a certain extent, and the titanium-based composite material reinforced by the graphene and the nano TiC in a synergy mode is formed. The existing mixing and dispersing technology is mainly wet ball milling, graphene cannot be effectively and uniformly dispersed on the surface of a titanium matrix by the method, and the graphene is easy to fall off from the titanium matrix and suspend on the surface of slurry after ball milling and standing. The method of the three-dimensional mixing technology is adopted, the powder particles are bonded, cold welded and coated by utilizing the long-time collision and impact of the graphene and the titanium matrix in the mixer, and the excellent dispersion coating effect is obtained without damaging the original structural appearances of the matrix particles and the reinforcement. The three-dimensional mechanical dry mixing method solves the problem that graphene is difficult to uniformly coat the surface of titanium particles in the traditional wet ball milling method. The existence of the nano TiC reduces the interface reaction of the graphene and the titanium matrix in the preparation process to a certain extent, and the nano TiC modified graphene reinforced titanium matrix composite material block is obtained through sintering and molding.
According to the nano TiC modified graphene reinforced titanium-based composite material, the surface of graphene is modified with a layer of nano TiC to serve as a reinforcement, the nano TiC can be uniformly dispersed in a titanium matrix, and the reaction of the graphene and the titanium matrix is reduced to a certain extent. The retention of the graphene can transfer the load of the matrix and improve the bearing capacity of the matrix on one hand, and can generate an Olympic (Orowan) ring to prevent the movement of dislocation on the other hand. Therefore, the nano TiC modified graphene reinforced titanium-based composite material has comprehensive mechanical properties of high strength and high plasticity and good forming and processing properties, and widens the application of titanium alloy in the fields of aerospace and ships and naval vessels.
The technical effects are as follows: compared with the existing ball-milling powder mixing technology, the method provided by the invention enables the surface of the graphene to be modified with a layer of nano TiC by using a three-dimensional material mixing technology, and the nano TiC plays a role in protecting the graphene in the sintering process. In addition, the three-dimensional mixing technology enables graphene to be well coated on the surface of matrix particles, the problem that the graphene is easy to fall off in the wet ball milling process is solved, and the nano TiC modified graphene reinforced titanium-based composite material is obtained through sintering and molding. The composite material has high strength, high plasticity and excellent comprehensive mechanical property.
Drawings
FIG. 1 is a scanning electron micrograph and an EDS detection result of graphene coated spherical titanium powder;
FIG. 2 is an X-ray diffractometer atlas of nano TiC modified graphene reinforced titanium-based composite material of different graphene contents;
fig. 3 is a microhardness trend graph of nano TiC modified graphene reinforced titanium-based composite materials with different graphene contents.
Fig. 4 is a graph of the compressive strength trends of nano TiC modified graphene reinforced titanium-based composites with different graphene contents and Ti6Al 4V;
FIG. 5 is a metallographic microscope picture (A) and a scanning electron microscope morphology picture (B) of the nano TiC-modified graphene-reinforced titanium-based composite material;
FIG. 6 shows a macroscopic morphology (A) and a macroscopic morphology (B) of a scanning electron microscope of a compressed cross section of a product of the nano TiC-modified graphene-reinforced titanium-based composite material;
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1
The nano TiC modified graphene reinforced titanium-based composite material is produced by sintering through a discharge plasma technology, nano TiC powder, graphene powder and spherical Ti-6Al-4V (TC4) powder are used as raw materials, wherein the grain diameter of the nano TiC powder is 40nm, the thickness of a graphene sheet is 1-5nm, the diameter of the graphene sheet is 0.1-6 mu m, the grain size of the titanium powder is 50 mu m (300 meshes), and a cylindrical composite material sintered body with the diameter of 20mm and the height of 10mm is manufactured.
The method comprises the following specific steps:
(1) weighing 20g of TC4 powder, placing in a plastic tank, adding nano TiC powder with a mass fraction of 0.05 wt.% (mass fraction relative to the titanium matrix), adding a certain amount of stainless steel grinding balls, and mixing the ball materials in a ratio of 1: 1. the mixture was continuously mixed on a blender at a speed of 60r/min for 16 h.
(2) The graphene powder was further added in a mass fraction of 0.2 wt.% (mass fraction relative to the titanium matrix) to the above-mentioned plastic tank and continuously mixed on the mixer at a rotational speed of 30r/min for 16 h.
(3) Sieving the mixed powder with 80 mesh sieve.
(4) Determining the size parameters of the sintered product: phi is 20mm, h is 10 mm. The mass of the powder required was calculated to be 13.898g according to the mass density formula.
Pouring the powder of (3) into a graphite mold, assembling an upper pressure head and a lower pressure head, and placing the graphite mold into a spark plasma sintering furnace, wherein SPS sintering parameters are as follows: and measuring the temperature in Ar atmosphere and infrared, wherein the heating speed is 50 ℃/min, the pressure is 60MPa, the temperature is preserved and sintered for 5min, the material is formed compactly, and then the furnace is cooled to the room temperature. The relative density of the sintered product is measured by an Archimedes method, and the calculated density is as high as 99.9%.
Performance testing and organizational structure analysis: respectively carrying out phase analysis on a sample by using an X-ray diffractometer, measuring microhardness by using a microhardness meter, carrying out a compression test by using a microcomputer control electronic universal test, finally analyzing the microstructure of the composite material by using a transmission electron microscope, and observing and analyzing the appearance of a fracture by using a scanning electron microscope.
Example 2
The nano TiC modified graphene reinforced titanium-based composite material is produced by sintering through a discharge plasma technology, nano TiC powder, graphene powder and spherical pure Ti powder are used as raw materials, wherein the particle size of the nano TiC powder is 40nm, the thickness of a graphene sheet is 1-5nm, the diameter of the graphene sheet is 0.1-6 mu m, the particle size of the titanium powder is 80 mu m (200 meshes), and a cylindrical composite material sintered body with the diameter of 20mm and the height of 8mm is manufactured.
The method comprises the following specific steps:
(1) 20g of pure Ti powder (purity 99.5%) are weighed into a plastic jar, nano TiC powder is added in a mass fraction of 0.05 wt.% (mass fraction relative to the titanium matrix), a certain amount of stainless steel grinding balls is added, the ball-to-material ratio is 2: 1. continuously mixing for 20h on a mixer at the rotating speed of 60 r/min.
(2) The graphene powder was continuously added to the plastic tank at a mass fraction of 0.4 wt.% (mass fraction relative to the titanium matrix) and continuously mixed on the mixer at a speed of 60r/min for 20 h.
(3) Sieving the mixed powder with 80 mesh sieve.
(4) Determining the size parameters of the sintered product: phi is 20mm, h is 8 mm. The mass of the powder required was calculated to be 11.118g according to the mass density formula.
Pouring the powder of (3) into a graphite mold, assembling an upper pressure head and a lower pressure head, and placing the graphite mold into a spark plasma sintering furnace, wherein SPS sintering parameters are as follows: measuring temperature in vacuum atmosphere and infrared, heating at 100 deg.C/min and 50MPa, sintering for 5min to compact the material, and cooling to room temperature. The relative density of the sintered product is measured by an Archimedes method, and the calculated density is as high as 99.7%.
Performance testing and organizational structure analysis: respectively carrying out phase analysis on a sample by using an X-ray diffractometer, measuring microhardness by using a microhardness meter, carrying out a compression test by using a microcomputer control electronic universal test, finally analyzing the microstructure of the composite material by using a transmission electron microscope, and observing and analyzing the appearance of a fracture by using a scanning electron microscope.
Example 3
The method is characterized in that nano TiC modified graphene reinforced titanium-based composite material is produced by hot-pressing sintering, nano TiC powder, graphene powder and spherical Ti-12Nb-12Zr powder are used as raw materials, wherein the grain size of the nano TiC powder is 40nm, the thickness of a graphene sheet is 1-5nm, the diameter of the graphene sheet is 0.1-6 mu m, the grain size of the titanium powder is 80 mu m (200 meshes), and a cylindrical composite material sintered body with the diameter of 20mm and the height of 10mm is manufactured.
The method comprises the following specific steps:
(1) weighing 20g of Ti-12Nb-12Zr powder, placing the powder in a plastic tank, adding 0.05 wt% (relative to the mass fraction of the titanium matrix) of nano TiC powder, adding a certain amount of stainless steel grinding balls, and mixing the powder in a ball-to-material ratio of 5: 1. continuously mixing for 10h on a mixer at the rotating speed of 60 r/min.
(2) The graphene powder was further added to the plastic tank in a mass fraction of 0.4 wt.% (mass fraction relative to the titanium matrix) and continuously mixed on the mixer at a rotation speed of 150r/min for 10 h.
(3) Sieving the mixed powder with 80 mesh sieve.
(4) Determining the size parameters of the sintered product: phi is 20mm, h is 10 mm. The mass of the powder required was calculated to be 13.898g according to the mass density formula.
Pouring the powder of (3) into a graphite mold, assembling an upper pressure head and a lower pressure head, and placing the graphite mold into a hot-pressing sintering furnace, wherein the sintering parameters are as follows: sintering for 60min under the conditions of vacuum atmosphere, pressure of 30MPa, temperature of 1300 ℃ and temperature measurement mode of infrared temperature measurement. Wherein the temperature rise speed is 20 ℃/min. Measuring relative density of the sintered product by an Archimedes method, and calculating to obtain the density of 99.34%
Performance testing and organizational structure analysis: respectively carrying out phase analysis on a sample by using an X-ray diffractometer, measuring microhardness by using a microhardness meter, carrying out a compression test by using a microcomputer control electronic universal test, finally analyzing the microstructure of the composite material by using a transmission electron microscope, and observing and analyzing the appearance of a fracture by using a scanning electron microscope.
Example 4
The method is the same as example 2, except that:
the thickness of the graphene sheet is 20-30nm, the substrate with the diameter of 0.1-10 μm is TA15(Ti-6.5Al-2Zr-1Mo-1V) titanium alloy powder, the particle size of the powder is 20 μm, the addition proportion of the nano TiC is 0.03 percent of the titanium substrate, and the addition proportion of the graphene is 0.5 percent of the mass of the substrate titanium.
The relative density of the sintered product is measured by an Archimedes method, and the calculated density is as high as 99.7%.
Performance testing and organizational structure analysis: respectively carrying out phase analysis on a sample by using an X-ray diffractometer, measuring microhardness by using a microhardness meter, carrying out a compression test by using a microcomputer control electronic universal test, finally analyzing the microstructure of the composite material by using a transmission electron microscope, and observing and analyzing the appearance of a fracture by using a scanning electron microscope.
Example 5
The method is the same as example 3, except that:
the graphene sheet has a thickness of 30-50nm and a diameter of 0.1-10 μm. The matrix titanium is TC11(Ti-6.5Al-3.5Mo-1.5Zr-0.3Si) titanium alloy powder, the particle size of the powder is 500 mu m, the addition proportion of the nano TiC is 0.03 percent of the mass of the matrix titanium, and the addition proportion of the graphene is 0.3 percent of the mass of the matrix titanium.
The relative density of the sintered product is measured by an Archimedes method, and the calculated density is as high as 99.9%.
Performance testing and organizational structure analysis: respectively carrying out phase analysis on a sample by using an X-ray diffractometer, measuring microhardness by using a microhardness meter, carrying out a compression test by using a microcomputer control electronic universal test, finally analyzing the microstructure of the composite material by using a transmission electron microscope, and observing and analyzing the appearance of a fracture by using a scanning electron microscope.
Results of performance testing
Fig. 1 shows scanning electron micrographs of titanium spheres coated with graphene and EDS detection results, which show that graphene is partially coated on the surface of the titanium spheres, and the content of C element in the EDS spectrum is as high as 94%.
Fig. 2 is an XRD spectrum of the nano TiC modified graphene reinforced titanium-based composite material with different amounts of added graphene, and a weak diffraction peak of graphene is generated near 26.6 °, indicating that graphene exists in the sintered composite material.
Fig. 3 is a graph of microhardness of nano TiC modified titanium matrix composite, and it can be found that the microhardness of the composite gradually increases with the increase of the content of the reinforcing phase and exceeds the hardness of the titanium matrix when the content of graphene is 0.2%.
Fig. 4 is a stress-strain diagram of a compression test of the nano TiC modified graphene reinforced titanium-based composite material with different amounts of added graphene, and it can be seen that the yield strength and the compressive strength of the material are both significantly increased after a small amount of graphene is added. The compressive strength is maximized at a graphene content of 0.2 wt.%. The yield strength reaches a maximum at a graphene content of 0.4 wt.%. The graphene with different contents can be regulated and controlled according to the mechanical strength requirements of materials with different purposes so as to prepare the titanium-based composite materials with different strong plasticity.
Fig. 5 is a metallographic microscope and a scanning electron microscope photograph of the nano TiC modified titanium-based composite material added with 0.4 wt.% of graphene, it can be observed that the reinforcement is uniformly distributed around the matrix particles to form a discontinuous network structure, and the titanium carbide particles in a dispersed distribution can be found under the scanning electron microscope.
Fig. 6 is a microscopic morphology of a scanning electron microscope of a compression fracture of the nano TiC modified titanium-based composite material with 0.4 wt.% graphene added, and it can be seen that the fracture form is a combination of cleavage fracture and micropore polymerization fracture, and a matrix around titanium carbide particles is torn to generate a dimple, so that the material shows better plasticity while strength is improved. From the high magnification, it can be found that a little graphene exists in the crack gap of the composite material.
Claims (5)
1. The nanometer TiC modified graphene reinforced titanium-based composite material is characterized in that titanium or titanium alloy is used as a titanium matrix, nanometer TiC is arranged in the middle layer, graphene is arranged on the surface layer, the graphene with the nanometer TiC modified on the surface is used as a reinforcing phase and is uniformly distributed around titanium matrix particles to form a network structure, the particle size of the nanometer TiC is 1-100nm, the graphene is sheet graphene, the sheet thickness is 1-50nm, the diameter is 0.1-50 mu m, the powder particles of the titanium matrix are spherical particles or irregular particles, and the particle size is 1-500 mu m; the preparation method of the nano TiC modified graphene reinforced titanium-based composite material comprises the following steps:
(1) coating nano TiC on the surface: adding nano TiC powder into pure titanium or titanium alloy powder, and mixing the pure titanium or titanium alloy powder for 10-20h in a high-purity argon or air atmosphere by a three-dimensional mixing method at a ball-to-material ratio of 2:1-5:1 and a rotating speed of 30-150 r/min;
(2) wrapping graphene on the surface: adding graphene powder into the product obtained in the step (1), and performing dry mixing in a high-purity argon or air atmosphere by adopting a three-dimensional mixing method, wherein the ball-material ratio is 2:1-5:1, the rotating speed is 30-150r/min, and the mixing time is 10-20 h;
(3) sintering and forming: and (3) carrying out discharge plasma sintering or hot-pressing sintering on the product obtained in the step (2) to obtain the nano TiC modified graphene reinforced titanium-based composite material.
2. The nano TiC-modified graphene-reinforced titanium-based composite material of claim 1, wherein the titanium matrix is pure titanium or an alloy of titanium and one or more of aluminum, vanadium, molybdenum, niobium, tantalum, zirconium, iron and silicon.
3. The nano TiC-modified graphene-reinforced titanium-based composite material of claim 1, wherein the nano TiC is added in a proportion of 0.01-0.1% by mass of the titanium matrix, and the graphene is added in a proportion of 0.01-0.5% by mass of the titanium matrix.
4. The nano TiC modified graphene reinforced titanium-based composite material according to claim 1, wherein the conditions of the spark plasma sintering are as follows: the pressure is 10-80MPa, the temperature is 900-; the hot-pressing sintering conditions are as follows: under the protection of vacuum or inert atmosphere, the pressure is 10-80MPa, the temperature is 1000-1400 ℃, the heating rate is 10-100 ℃/min, and the heat preservation time at the highest sintering temperature is 10-180 min.
5. The use of the nano TiC modified graphene reinforced titanium-based composite material of claim 1 as an aerospace component material.
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