CN111270101B - Microalloying cooperative strengthening graphene titanium-based composite material and preparation method thereof - Google Patents
Microalloying cooperative strengthening graphene titanium-based composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- B22F1/0003—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The invention discloses a microalloying synergistically reinforced graphene titanium-based composite material, which takes titanium or a titanium alloy as a matrix, wherein metal for microalloying is uniformly coated on the surface of the titanium or titanium alloy matrix in a quasi-continuous manner in a physical combination mode, and graphene is dispersed on the outer surface of the titanium or titanium alloy matrix coated with the metal for microalloying and forms a quasi-continuous network structure together with in-situ autogenous TiC nano particles and intermetallic compound particles; the invention also discloses a preparation method of the microalloying synergistic strengthening graphene titanium-based composite material, which comprises the steps of ball-milling raw material powder, uniformly stirring the ball-milled raw material powder and the graphene nanosheet suspension solution, drying, and then carrying out hot-pressing sintering. According to the invention, the metal for micro-alloying is adopted for coating, so that the direct contact of graphene and a matrix is avoided, the distribution uniformity and structural integrity of the graphene are improved, and the metal for micro-alloying have a synergistic strengthening effect with TiC nano particles and intermetallic compound particles; the method of the invention has strong operability and is suitable for industrialized production.
Description
Technical Field
The invention belongs to the technical field of metal matrix composite preparation, and particularly relates to a microalloying synergistically reinforced graphene titanium matrix composite and a preparation method thereof.
Background
The titanium-based composite material has low density, high specific strength and excellent high temperature resistance, and has wide development prospect in the fields of aerospace, automobile manufacturing and the like. By introducing the reinforcement with high modulus, high hardness and good high-temperature performance into titanium and titanium alloy, the interaction of the toughness and ductility of a titanium matrix and the high strength and high modulus characteristics of the reinforcement is fully exerted, and the titanium-based composite material with better mechanical property than the titanium alloy is obtained. Therefore, the titanium-based composite material, which is a relatively ideal metal-based structural composite material, shows a plurality of excellent mechanical properties (such as high temperature, fatigue and corrosion resistance) and has important use value. In recent decades, the titanium-based composite material has a rapid development trend in the world, and part of research work of the titanium-based composite material has made breakthrough progress, and the titanium-based composite material starts to be industrialized and scaled, so that the service requirements of the structural material in extreme service environments such as high temperature and high pressure in modern high-technology development are met.
Graphene (Graphene) as a material consisting of carbon atoms in sp2The two-dimensional carbon nanomaterial consisting of the hybrid track has ultrahigh specific strength and excellent electric and heat conduction characteristics, is an ideal reinforcement of a titanium-based composite material, and can remarkably improve the mechanical property and the heat conduction capability of the composite material; meanwhile, the high specific surface area of the graphene-based composite material ensures that a compact composite interface is formed between the graphene and the metal matrix, and the stress load effect is realized, so that the toughness of the composite material is improved. However, the dispersion problem and the serious interface reaction problem of the graphene in the compounding process of the graphene and the titanium matrix lead to the aggregation of a large amount of in-situ synthesized TiC nano particles and no graphene retention, and the service life and the application range of the titanium matrix composite are seriously influenced, so that the original purpose and the application of the design of the graphene reinforced titanium matrix composite are violated. Therefore, designing and developing a graphene titanium-based composite material with a novel structure has important industrial application background and great industry upgrading requirements.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a microalloyed synergistically strengthened graphene titanium-based composite material, aiming at the defects of the prior art. The graphene titanium-based composite material adopts the microalloying metal to be coated on the surface of a titanium or titanium alloy matrix in a quasi-continuous manner, so that the graphene dispersed on the outer surface of the microalloying metal is prevented from directly contacting with the titanium or titanium alloy matrix, the completeness of a two-dimensional nanostructure of the graphene is ensured to a greater extent, and the distribution uniformity of the graphene is improved, so that the dispersion problem and the serious interface reaction problem of the graphene in the compounding process of the graphene and the titanium matrix are avoided, and meanwhile, the in-situ autogenous TiC nano particles and intermetallic compound particles are combined to carry out synergistic strengthening, so that the strength of the graphene titanium-based composite material is obviously improved, and the graphene titanium-based composite material has good extension plasticity.
In order to solve the technical problems, the invention adopts the technical scheme that: the microalloying synergistically reinforced graphene titanium-based composite material is characterized in that titanium or titanium alloy is used as a matrix, metal for microalloying uniformly coats the surface of the titanium or titanium alloy matrix in a quasi-continuous state in a physical combination mode, and graphene is dispersed on the outer surface of the titanium or titanium alloy matrix coated with the metal for microalloying and forms a quasi-continuous network structure together with in-situ self-generated TiC nano particles and intermetallic compound particles; the micro-alloying metal and the graphene do not generate a carbonization reaction, the hardness of the micro-alloying metal is less than that of the titanium or titanium alloy matrix, and the ductility of the micro-alloying metal is greater than that of the titanium or titanium alloy matrix; the yield strength and tensile strength of the microalloyed and synergistically strengthened graphene titanium-based composite material are improved by more than 140MPa compared with the titanium-based composite material prepared from the titanium-based powder with the same components, and the elongation after fracture is more than 10%.
In the microalloyed synergistically reinforced graphene titanium-based composite material, because the microalloying metal is uniformly coated on the surface of the titanium or titanium alloy matrix in a quasi-continuous manner in a physical combination mode, and the graphene is dispersed on the outer surface of the titanium or titanium alloy matrix coated with the microalloying metal to form a quasi-continuous net-shaped structure, the graphene is not directly contacted with the titanium or titanium alloy matrix but directly dispersed on the microalloying metal coated with the titanium or titanium alloy matrix, and because the microalloying metal and the graphene do not generate a carbonization reaction, a tightly combined composite interface cannot be formed between the microalloying metal and the graphene, the integrity of a two-dimensional nanostructure of the graphene is ensured to a greater extent, the distribution of the graphene on the microalloying metal is more uniform, so that the distribution of the graphene on the titanium or titanium alloy matrix is more uniform, and the dispersion problem and serious interface reaction of the graphene in the process of compounding the graphene and the titanium matrix are avoided Problems and the like, and ensures the reinforcement function of the graphene. In the tissues of the microalloyed synergistically reinforced graphene titanium-based composite material, graphene reinforcements are distributed in original beta grain boundaries of a matrix to form a quasi-continuous network structure, a small amount of TiC nano particles are generated in the matrix in situ, microalloyed elements are partially dissolved in the beta grain boundaries around the graphene reinforcements in a solid solution mode, part of the microalloyed elements and the matrix in a local area form an intermetallic compound particle phase through a eutectoid reaction, the TiC nano particles and the intermetallic compound particle phase are both distributed at the original grain boundaries of the titanium matrix in a discontinuous mode, and the quasi-continuous network structure is formed in cooperation with the graphene reinforcements.
In conclusion, the titanium-based composite material disclosed by the invention has the advantages that the graphene structure of the nano structure is retained to the greatest extent, so that the enhancement effect of the graphene is ensured, and the strength performance of the titanium-based composite material is remarkably improved by combining the composite enhancement characteristics of solid solution enhancement of intermetallic compound particle phases, fine crystal enhancement of TiC nano particle enhancement phases, high-density dislocation enhancement and the like; meanwhile, the connection effect between the discontinuous matrixes of the quasi-continuous reticular structure and the shearing-retardation effect of the graphene ensure that the titanium-based composite material has good extension plasticity. Therefore, the titanium-based composite material overcomes the defects of low graphene content and uneven distribution in the traditional graphene titanium-based composite material, effectively exerts the strengthening effect of the graphene reinforcement, improves the yield strength and tensile strength by more than 150MPa compared with the titanium-based composite material corresponding to titanium-based powder with the same component, and has the elongation percentage after fracture of more than 10 percent.
The graphene titanium-based composite material subjected to microalloying cooperative reinforcement is characterized in that the metal for microalloying is copper, nickel or silver. The preferred microalloying metal has high stretch forming and low hardness, good coating properties on titanium-based powder, and is relatively easy to obtain.
In addition, the invention also provides a method for preparing the microalloyed synergistically reinforced graphene titanium-based composite material, which is characterized by comprising the following steps of:
step one, selecting powder: selecting spherical titanium or titanium alloy powder as matrix powder, and selecting metal powder for micro-alloying;
step two, preparing composite powder: adding the base powder selected in the step one and metal powder for microalloying into a ball mill, then sequentially carrying out high-energy ball milling treatment at a high rotating speed and a low rotating speed, and then screening to obtain titanium-based composite powder; the technological parameters of the high-speed high-energy ball milling treatment are as follows: the rotating speed is 450r/min, the ball milling time is 30-50 min, the ball-material ratio is (2-3): 1, and the technological parameters of the low-rotating-speed high-energy ball milling treatment are as follows: the rotating speed is 350r/min, the ball milling time is 2-3 h, and the ball-material ratio is (2-3): 1; the sphericity of the titanium-based composite powder is not less than 0.6, and the surface roughness Ra is more than 2 mu m;
step three, graphene dispersion treatment: ultrasonically dispersing graphene nano sheets in a solvent to obtain a graphene nano sheet suspension solution;
step four, preparing mixed slurry: adding the titanium-based composite powder obtained in the step two into the graphene nanosheet suspension solution obtained in the step three, and mechanically stirring until the mixture is uniform to obtain pasty mixed slurry;
step five, preparing mixed powder: placing the pasty mixed slurry obtained in the fourth step into a vacuum drying oven for drying treatment, and then screening to obtain mixed powder with the surface coated with graphene;
step six, sintering and forming: and D, placing the mixed powder with the surface coated with the graphene obtained in the fifth step into a discharge plasma sintering machine for hot-pressing sintering to obtain the microalloyed synergistically strengthened graphene titanium-based composite material.
The method comprises the steps of firstly utilizing high energy generated by high-energy ball milling treatment, sequentially adopting high-energy ball milling treatment at high rotating speed and low rotating speed, tightly coating microalloying metal on the surface of spherical titanium-based powder through violent impact, enabling the microalloying metal to be uniformly coated on the surface of a titanium or titanium alloy matrix in a quasi-continuous manner in a physical combination mode, then uniformly dispersing graphene on the surface of titanium-based composite powder by adopting a wet mechanical stirring method, drying, then carrying out discharge plasma hot-pressing sintering (SPS), and forming to obtain the microalloying co-reinforced graphene titanium-based composite material. In the discharge plasma hot-pressing sintering process, as the graphene does not have any carbonization reaction with the directly contacted microalloy metal, the two-dimensional structure of the nanoscale graphene is completely protected, the load transfer effect of the graphene reinforcement on the material is exerted to the greatest extent, and the graphene titanium-based composite material is effectively strengthened; meanwhile, a small amount of in-situ self-generated TiC nano particles are generated by the graphene and the matrix in the discharge plasma hot-pressing sintering process, and intermetallic compound particles generated by the high-temperature eutectoid reaction of the local titanium matrix and the microalloying elements act synergistically, so that the strengthening effect on the graphene titanium-based composite material is enhanced jointly.
The method described above, wherein the sphericity of the base powder in the first step is not less than 0.8; the mass purity of the matrix powder and the mass purity of the metal powder for micro-alloying are not less than 99.9 percent. The base powder with sphericity further ensures the uniform coating of the microalloyed metal on the surface of the base powder, and is beneficial to the formation of a quasi-continuous structure; the optimized high-quality-purity matrix powder and the microalloying metal powder avoid the pollution of other impurity elements, and ensure the bonding strength between the powders in the sintering and forming process, thereby obtaining the high-density graphene titanium-based composite material.
The method is characterized in that in the step one, the metal powder for micro-alloying is copper powder, nickel powder or silver powder, and the mass ratio of the metal powder for micro-alloying to the matrix powder is not more than 1: 40. The optimized type and the added amount of the microalloyed metal powder are beneficial to realizing quasi-continuous uniform coating of the matrix powder, inhibiting serious interface reaction between graphene and the matrix powder, strengthening the titanium matrix and avoiding the intermetallic transformation between the matrix and the microalloyed elements caused by excessive microalloyed elementsFormation of Compound phase (Ti)2Cu、Ti2Ni、Ti2Ag) and reducing the extension plasticity of the graphene titanium-based composite material subjected to micro-alloying synergistic strengthening.
The method is characterized in that the mass of the graphene in the third step is not more than 0.5% of the total mass of the graphene and the titanium-based composite powder in the second step. The thickness of the adopted graphene nano sheet is preferably 1 nm-5 nm, and the sheet diameter is preferably 1 μm-3 μm. The preferable addition amount of the graphene is beneficial to uniform dispersion of the graphene, so that the strengthening effect of the graphene is more effectively exerted, and the mechanical property of the microalloyed and synergistically strengthened graphene titanium-based composite material is ensured.
The method is characterized in that the solvent in the third step is a mixed solution composed of tetrahydrofuran, ethylene glycol butyl ether and ethanol, wherein the volume ratio of the tetrahydrofuran to the ethylene glycol butyl ether to the ethanol is 3:3: 6. The mixed solution with the composition is used as a solvent, so that the graphene nanosheets can be sufficiently ultrasonically dispersed, and the graphene nanosheets can be conveniently removed by vacuum drying in the later period; the preferred ultrasonic dispersion period is 5s of ultrasound, the intermittent time is 2s, and the ultrasonic dispersion time is 30-50 min, so that the uniform dispersion of the graphene nanosheets in the solvent is promoted.
The method is characterized in that the technological parameters of the hot-pressing sintering in the sixth step are as follows: the sintering temperature is 900-1000 ℃, the sintering time is 5-8 min, and the sintering pressure is not less than 45 MPa. The selective sintering process parameters are favorable for completely protecting the two-dimensional structure of the nano-scale graphene, the strengthening effect of the graphene reinforcement is favorably exerted, and meanwhile, the preparation of the high-density graphene titanium-based composite material is further realized.
In addition, in the fourth step of the invention, the ratio of the mass of the titanium-based composite powder to the volume of the graphene nanosheet suspension solution is preferably 1: (1-2), the unit of mass is g, the unit of volume is mL, and the preferred mechanical stirring process parameters are as follows: the rotating speed is 300 r/min-450 r/min, the stirring time is 2 h-4 h, the heating temperature is 60 ℃, and the preferable conditions are favorable for realizing the uniform distribution of the graphene on the surface of the titanium-based composite powder and avoiding the agglomeration phenomenon of the graphene.
Compared with the prior art, the invention has the following advantages:
1. according to the graphene titanium-based composite material, the microalloying metal is uniformly coated on the surface of the titanium or titanium alloy matrix in a quasi-continuous manner, and the graphene is dispersed on the outer surface of the microalloying metal to form a quasi-continuous net structure, so that the graphene is prevented from being directly contacted with the titanium or titanium alloy matrix, the integrity of a two-dimensional nano structure of the graphene is ensured to a great extent, the distribution uniformity of the graphene is improved, the dispersion problem and the serious interface reaction problem of the graphene in the process of compounding the graphene and the titanium matrix are avoided, and the reinforcement effect of the graphene is ensured.
2. A small amount of TiC nano particles and intermetallic compound particles contained in the graphene titanium-based composite material are discontinuously distributed at the original crystal boundary of a titanium matrix and form a quasi-continuous network structure in cooperation with a graphene reinforcement body, so that the reinforcing effect of the graphene is combined with the composite reinforcing characteristics of solid solution reinforcement of the intermetallic compound particles, fine crystal reinforcement of the TiC nano particle reinforcement phase, high-density dislocation reinforcement and the like, and the strength performance of the graphene titanium-based composite material is remarkably improved.
3. In the graphene titanium-based composite material, the reinforcement graphene is distributed in an original crystal boundary beta phase of a titanium-based microstructure in a quasi-continuous network structure, and the good extension plasticity of the graphene titanium-based composite material is ensured by the communication effect between discontinuous matrixes and the shearing-retardation effect of the graphene.
4. The graphene titanium-based composite material overcomes the defects of low graphene content and uneven distribution in the traditional graphene titanium-based composite material, the yield strength and the tensile strength of the graphene titanium-based composite material are improved by more than 150MPa compared with the titanium-based composite material corresponding to titanium-based powder with the same component, and the elongation after fracture is more than 10%.
5. The invention adopts the high-energy ball milling treatment of the physical method to ensure that the microalloyed metal is discontinuously and uniformly coated on the surface of the titanium-based powder, avoids the chemical treatment processes of cleaning, sensitizing, activating, depositing and the like in the conventional graphene surface metal chemical coating method, has simple process and strong operability, reduces pollution and production cost, and is suitable for large-scale industrial production
6. According to the graphene titanium-based composite material, due to the shielding effect of the microalloyed metal in the SPS high-temperature forming process, the direct contact of graphene and a titanium matrix is inhibited, so that the serious interface reaction between the graphene and the titanium matrix is avoided, the two-dimensional nanostructure of the graphene is retained to the maximum extent, and the comprehensive mechanical property of the graphene titanium-based composite material is improved.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a scanning electron micrograph of a titanium-based composite powder prepared in example 1 of the present invention.
FIG. 2a is a distribution diagram of Ti element in the region A in FIG. 1.
FIG. 2b is a distribution diagram of Ni element in the region A of FIG. 1.
Fig. 3 is a scanning electron microscope image of the mixed powder of surface-coated graphene prepared in example 1 of the present invention.
Fig. 4 is a metallographic microstructure of a microalloyed co-reinforced graphene titanium-based composite material prepared in example 1 of the invention.
Fig. 5 is a metallographic microstructure of a microalloyed co-reinforced graphene titanium-based composite material prepared in example 2 of the invention.
Detailed Description
Example 1
The microalloyed synergistically strengthened graphene titanium-based composite material of the embodiment takes a CT20 titanium alloy as a matrix, metal nickel for microalloying is uniformly coated on the surface of a CT20 titanium alloy matrix in a quasi-continuous manner in a physical combination mode, and graphene is dispersed on the outer surface of the CT20 titanium alloy coated with the metal nickel for microalloying, and TiC nanoparticles and Ti nanoparticles are uniformly mixed with the titanium alloy2The Ni nano-particles form a quasi-continuous network structure together; the average grain size in the network was 150 μm.
The preparation method of the microalloyed synergistically reinforced graphene titanium-based composite material comprises the following steps:
step one, selecting powder: 200g of spherical CT20 titanium alloy powder with the grain diameter of 80-120 meshes and the sphericity of 0.8 is selected as matrix powder, and 4g of flaky nickel powder with the grain diameter of 200-300 meshes is selected as microalloyed metal powder; the mass purities of the spherical CT20 titanium alloy powder and the flaky nickel powder are both 99.99%;
step two, preparing composite powder: adding the spherical CT20 titanium alloy powder and the flaky nickel powder selected in the step one into a ball mill, then sequentially carrying out high-energy ball milling treatment at high and low rotating speeds, and screening to obtain titanium-based composite powder; the technological parameters of the high-speed high-energy ball milling treatment are as follows: the rotating speed is 450r/min, the ball milling time is 35min, and the ball-material ratio is 3: 1; the technological parameters of the low-rotating-speed high-energy ball milling treatment are as follows: the rotating speed is 350r/min, the ball milling time is 3h, and the ball-material ratio is 3: 1; the sphericity of the titanium-based composite powder is 0.6, and the surface roughness Ra is 2.5 mu m;
step three, graphene dispersion treatment: ultrasonically dispersing 0.6g of graphene nanosheet in 300mL of mixed solution consisting of tetrahydrofuran, ethylene glycol monobutyl ether and ethanol according to the volume ratio of 3:3:6 to obtain graphene nanosheet suspension solution; the thickness of the graphene nano sheet is 1 nm-5 nm, and the sheet diameter is 1 μm-3 μm; the period of ultrasonic dispersion is 5s, the intermission is 2s, and the time of ultrasonic dispersion is 50 min;
step four, preparing mixed slurry: adding the titanium-based composite powder obtained in the step two into the graphene nanosheet suspension solution obtained in the step three, and mechanically stirring until the mixture is uniform to obtain pasty mixed slurry; the mechanical stirring process parameters are as follows: the rotating speed is 350r/min, the stirring time is 2.5h, and the heating temperature is 60 ℃;
step five, preparing mixed powder: placing the pasty mixed slurry obtained in the fourth step in a vacuum drying oven, drying for 15h at the temperature of 80 ℃, and then screening to obtain mixed powder with the surface coated with graphene;
step six, sintering and forming: placing the mixed powder with the surface coated with the graphene obtained in the fifth step into a discharge plasma sintering machine for hot-pressing sintering to obtain a cylindrical microalloyed synergistically strengthened graphene titanium-based composite material with the diameter of 60mm and the height of 14.5 mm; the technological parameters of the hot-pressing sintering are as follows: the sintering temperature is 1000 ℃, the sintering time is 5min, and the sintering pressure is 60 MPa.
Fig. 1 is a scanning electron microscope image of the titanium-based composite powder prepared in this example, and it can be seen from fig. 1 that the microalloyed nickel element is tightly coated on the surface of the titanium-based composite powder in a discontinuous manner, and the surface roughness is high, but the titanium-based composite powder keeps good sphericity.
FIG. 2a is a distribution diagram of Ti element in area A of FIG. 1. from FIG. 2a, it can be seen that the surface of the Ti-based composite powder is not completely coated with the micro-alloying element Ni, thereby ensuring the communication effect between the discontinuous Ti-based matrix of the quasi-network structure and providing the graphene Ti-based composite material of the invention with good ductility.
Fig. 2b is a distribution diagram of the Ni element in the area a in fig. 1, and it can be seen from fig. 2b that a partial area of the surface of the titanium-based composite powder is coated with the micro-alloying element nickel, so that the two-dimensional nanostructure of the graphene is largely retained, and the strengthening effect of the graphene is ensured.
Fig. 3 is a scanning electron microscope image of the titanium-based composite powder coated with graphene prepared in this example, and it can be seen from fig. 3 that a local area of the surface of the titanium-based composite powder is coated with a thinner graphene layer, but most of the surface of the titanium-based powder is not coated, so that the protective effect of the microalloyed metal element nickel on the surface of the graphene in the SPS thermoforming process is ensured.
Fig. 4 shows the metallographic microstructure of the microalloyed co-reinforced graphene titanium-based composite material prepared in this example, and it can be seen from fig. 4 that in the microalloyed co-reinforced graphene titanium-based composite material prepared in this example, the reinforcement graphene and Ti2Ni and a small amount of TiC are mainly distributed at the original beta grain boundary of the CT20 titanium alloy matrix in a discontinuous manner to form a microstructure with a quasi-network structure; and the matrix structure of the CT20 titanium alloy is a Widmannstatten structure typical in the titanium alloy and consists of a coarse lath-shaped alpha phase and an intercrystalline beta transformation structure.
Comparative example 1
The titanium-based material of this comparative example consisted of a CT20 titanium alloy matrix.
The specific process of the preparation method of the titanium-based material of the comparative example is as follows: 200g of spherical CT20 titanium alloy powder with the grain diameter of 80-120 meshes and the sphericity of 0.8 is selected to be placed in a discharge plasma sintering machine for hot-pressing sintering to obtain a cylindrical titanium-based material with the diameter of 60mm and the height of 14.3 mm; the mass purity of the CT20 titanium alloy powder is 99.99%; the technological parameters of the hot-pressing sintering are as follows: the sintering temperature is 1000 ℃, the sintering time is 5min, and the sintering pressure is 60 MPa.
Example 2
The microalloyed synergistically strengthened graphene titanium-based composite material of the embodiment takes a CT20 titanium alloy as a matrix, metal silver for microalloying is uniformly coated on the surface of a CT20 titanium alloy matrix in a quasi-continuous manner in a physical combination mode, and graphene is dispersed on the outer surface of the CT20 titanium alloy matrix coated with the metal silver for microalloying, and TiC nanoparticles and Ti nanoparticles are uniformly mixed with the outer surface of the CT20 titanium alloy matrix2The Ag nano particles form a quasi-continuous net structure together; the average grain size in the network was 100 μm.
The preparation method of the microalloyed synergistically reinforced graphene titanium-based composite material comprises the following steps:
step one, selecting powder: 200g of spherical CT20 titanium alloy powder with the grain diameter of 80-120 meshes and the sphericity of 0.85 is selected as matrix powder, and 5g of flaky silver powder with the grain diameter of 200-300 meshes is selected as microalloyed metal powder; the mass purities of the spherical CT20 titanium alloy powder and the flake silver powder are both 99.99%;
step two, preparing composite powder: adding the spherical CT20 titanium alloy powder and the flake silver powder selected in the step one into a ball mill, then sequentially carrying out high-energy ball milling treatment at high and low rotating speeds, and screening to obtain titanium-based composite powder; the technological parameters of the high-speed high-energy ball milling treatment are as follows: the rotating speed is 400r/min, the ball milling time is 50min, and the ball-material ratio is 2: 1; the technological parameters of the low-rotating-speed high-energy ball milling treatment are as follows: the rotating speed is 350r/min, the ball milling time is 2 hours, and the ball-material ratio is 2: 1; the sphericity of the titanium-based composite powder is 0.65, and the surface roughness Ra is 3 mu m;
step three, graphene dispersion treatment: ultrasonically dispersing 0.6g of graphene nanosheet in 200mL of mixed solution consisting of tetrahydrofuran, butyl cellosolve and ethanol according to the volume ratio of 3:3:6 to obtain graphene nanosheet suspension solution; the thickness of the graphene nano sheet is 1 nm-5 nm, and the sheet diameter is 1 μm-3 μm; the period of ultrasonic dispersion is 5s, the intermission is 2s, and the time of ultrasonic dispersion is 50 min;
step four, preparing mixed slurry: adding the titanium-based composite powder obtained in the step two into the graphene nanosheet suspension solution obtained in the step three, and mechanically stirring until the mixture is uniform to obtain pasty mixed slurry; the mechanical stirring process parameters are as follows: the rotating speed is 300r/min, the stirring time is 4h, and the heating temperature is 60 ℃;
step five, preparing mixed powder: placing the pasty mixed slurry obtained in the fourth step in a vacuum drying oven, drying for 15h at the temperature of 80 ℃, and then screening to obtain mixed powder with the surface coated with graphene;
step six, sintering and forming: placing the mixed powder with the surface coated with the graphene obtained in the fifth step into a discharge plasma sintering machine for hot-pressing sintering to obtain a cylindrical microalloyed synergistically strengthened graphene titanium-based composite material with the diameter of 60mm and the height of 14.5 mm; the technological parameters of the hot-pressing sintering are as follows: the sintering temperature is 950 ℃, the sintering time is 6min, and the sintering pressure is 45 MPa.
FIG. 5 is a metallographic microstructure of the microalloyed co-reinforced graphene titanium-based composite material prepared in this example, and it can be seen from FIG. 5 that in the microalloyed co-reinforced graphene titanium-based composite material prepared in this example, the reinforcement graphene and Ti2Ag and a small amount of TiC are mainly distributed at the original beta grain boundary of the CT20 titanium alloy matrix in a discontinuous manner to form a microscopic structure with a quasi-net structure; and the matrix structure of the CT20 titanium alloy is a Widmannstatten structure typical in the titanium alloy and consists of a coarse lath-shaped alpha phase and an intercrystalline beta transformation structure.
Comparative example 2
The titanium-based material of this comparative example consisted of a CT20 titanium alloy matrix.
The specific process of the preparation method of the titanium-based material of the comparative example is as follows: 200g of spherical CT20 titanium alloy powder with the grain diameter of 120-180 meshes and the sphericity of 0.8 is selected to be placed in a discharge plasma sintering machine for hot-pressing sintering to obtain a cylindrical titanium-based material with the diameter of 60mm and the height of 14.3 mm; the mass purity of the CT20 titanium alloy powder is 99.99%; the technological parameters of the hot-pressing sintering are as follows: the sintering temperature is 950 ℃, the sintering time is 6min, and the sintering pressure is 45 MPa.
Example 3
The microalloyed synergistically strengthened graphene titanium-based composite material of the embodiment takes a CT20 titanium alloy as a matrix, metal silver for microalloying is uniformly coated on the surface of a CT20 titanium alloy matrix in a quasi-continuous manner in a physical combination mode, and graphene is dispersed on the outer surface of the CT20 titanium alloy matrix coated with the metal silver for microalloying, and TiC nanoparticles and Ti nanoparticles are uniformly mixed with the outer surface of the CT20 titanium alloy matrix2The Ag nano particles form a quasi-continuous net structure together; the average grain size in the network was 120 μm.
The preparation method of the microalloyed synergistically reinforced graphene titanium-based composite material comprises the following steps:
step one, selecting powder: 200g of spherical CT20 titanium alloy powder with the grain diameter of 100-150 meshes and the sphericity of 0.85 is selected as matrix powder, and 2g of flaky silver powder with the grain diameter of 200-300 meshes is selected as microalloyed metal powder; the mass purities of the spherical CT20 titanium alloy powder and the flake silver powder are both 99.999%;
step two, preparing composite powder: adding the spherical CT20 titanium alloy powder and the flake silver powder selected in the step one into a ball mill, then sequentially carrying out high-energy ball milling treatment at high and low rotating speeds, and screening to obtain titanium-based composite powder; the technological parameters of the high-speed high-energy ball milling treatment are as follows: the rotating speed is 450r/min, the ball milling time is 30min, and the ball-material ratio is 2.5: 1; the technological parameters of the low-rotating-speed high-energy ball milling treatment are as follows: the rotating speed is 350r/min, the ball milling time is 2.5h, and the ball-to-material ratio is 2.5: 1; the sphericity of the titanium-based composite powder is 0.62, and the surface roughness Ra is 2.8 mu m;
step three, graphene dispersion treatment: ultrasonically dispersing 0.2g of graphene nanosheet in 200mL of mixed solution consisting of tetrahydrofuran, ethylene glycol monobutyl ether and ethanol according to the volume ratio of 3:3:6 to obtain graphene nanosheet suspension solution; the thickness of the graphene nano sheet is 1 nm-5 nm, and the sheet diameter is 1 μm-3 μm; the period of ultrasonic dispersion is 5s, the intermission is 2s, and the time of ultrasonic dispersion is 50 min;
step four, preparing mixed slurry: adding the titanium-based composite powder obtained in the step two into the graphene nanosheet suspension solution obtained in the step three, and mechanically stirring until the mixture is uniform to obtain pasty mixed slurry; the mechanical stirring process parameters are as follows: the rotating speed is 450r/min, the stirring time is 2h, and the heating temperature is 60 ℃;
step five, preparing mixed powder: placing the pasty mixed slurry obtained in the fourth step in a vacuum drying oven, drying for 15h at the temperature of 80 ℃, and then screening to obtain mixed powder with the surface coated with graphene;
step six, sintering and forming: placing the mixed powder with the surface coated with the graphene obtained in the fifth step into a discharge plasma sintering machine for hot-pressing sintering to obtain a cylindrical microalloyed synergistically strengthened graphene titanium-based composite material with the diameter of 60mm and the height of 14.5 mm; the technological parameters of the hot-pressing sintering are as follows: the sintering temperature is 900 ℃, the sintering time is 8min, and the sintering pressure is 50 MPa.
Comparative example 3
The titanium-based material of this comparative example consisted of a CT20 titanium alloy matrix.
The specific process of the preparation method of the titanium-based material of the comparative example is as follows: 200g of spherical CT20 titanium alloy powder with the grain diameter of 100-150 meshes and the sphericity of 0.8 is selected to be placed in a discharge plasma sintering machine for hot-pressing sintering to obtain a cylindrical titanium-based material with the diameter of 60mm and the height of 14.4 mm; the technological parameters of the hot-pressing sintering are as follows: the sintering temperature is 900 ℃, the sintering time is 8min, and the sintering pressure is 50 MPa.
Example 4
The microalloyed synergistically strengthened graphene titanium-based composite material of the embodiment takes the TC4 titanium alloy as a matrix, and the metallic copper for microalloying is uniformly coated on the TC4 titanium alloy in a quasi-continuous manner in a physical combination mannerThe graphene is dispersed on the surface of the gold matrix, and is coated on the outer surface of the TC4 titanium alloy matrix coated by the metallic copper for micro-alloying, and TiC nano particles and Ti2The Cu nano particles form a quasi-continuous network structure together; the average grain size in the network was 150 μm.
The preparation method of the microalloyed synergistically reinforced graphene titanium-based composite material comprises the following steps:
step one, selecting powder: selecting 100g of spherical TC4 titanium alloy powder with the grain diameter of 100 meshes to 150 meshes and the sphericity of 0.8 as matrix powder, and selecting 5g of flaky copper powder with the grain diameter of 200 meshes to 250 meshes as microalloyed metal powder; the mass purity of the spherical TC4 titanium alloy powder and the flake copper powder is 99.999 percent;
step two, preparing composite powder: adding the spherical TC4 titanium alloy powder and the flake copper powder selected in the step one into a ball mill, then sequentially carrying out high-energy ball milling treatment at high and low rotating speeds, and screening to obtain titanium-based composite powder; the technological parameters of the high-speed high-energy ball milling treatment are as follows: the rotating speed is 450r/min, the ball milling time is 30min, and the ball-material ratio is 2.5: 1; the technological parameters of the low-rotating-speed high-energy ball milling treatment are as follows: the rotating speed is 350r/min, the ball milling time is 2.5h, and the ball-to-material ratio is 2.5: 1; the sphericity of the titanium-based composite powder is 0.7, and the surface roughness Ra is 3 mu m;
step three, graphene dispersion treatment: ultrasonically dispersing 0.5g of graphene nanosheet in 100mL of mixed solution consisting of tetrahydrofuran, butyl cellosolve and ethanol according to the volume ratio of 3:3:6 to obtain graphene nanosheet suspension solution; the thickness of the graphene nano sheet is 1 nm-5 nm, and the sheet diameter is 1 μm-3 μm; the period of ultrasonic dispersion is 5s, the intermission is 2s, and the time of ultrasonic dispersion is 50 min;
step four, preparing mixed slurry: adding the titanium-based composite powder obtained in the step two into the graphene nanosheet suspension solution obtained in the step three, and mechanically stirring until the mixture is uniform to obtain pasty mixed slurry; the mechanical stirring process parameters are as follows: the rotating speed is 450r/min, the stirring time is 2h, and the heating temperature is 60 ℃;
step five, preparing mixed powder: placing the pasty mixed slurry obtained in the fourth step in a vacuum drying oven, drying for 8 hours at the temperature of 80 ℃, and then screening to obtain mixed powder with the surface coated with graphene;
step six, sintering and forming: placing the mixed powder with the surface coated with the graphene obtained in the fifth step into a discharge plasma sintering machine for hot-pressing sintering to obtain a cylindrical microalloyed synergistically strengthened graphene titanium-based composite material with the diameter of 60mm and the height of 9.5 mm; the technological parameters of the hot-pressing sintering are as follows: the sintering temperature is 900 ℃, the sintering time is 8min, and the sintering pressure is 60 MPa.
Comparative example 4
The titanium-based material of this comparative example consisted of a TC4 titanium alloy matrix.
The specific process of the preparation method of the titanium-based material of the comparative example is as follows: 100g of spherical TC4 titanium alloy powder with the grain diameter of 100-150 meshes and the sphericity of 0.8 is selected to be placed in a spark plasma sintering machine for hot-pressing sintering to obtain a cylindrical titanium-based material with the diameter of 60mm and the height of 9 mm; the mass purity of the spherical TC4 titanium alloy powder is 99.99%; the technological parameters of the hot-pressing sintering are as follows: the sintering temperature is 900 ℃, the sintering time is 8min, and the sintering pressure is 60 MPa.
Room temperature mechanical property test: the microalloyed co-strengthened graphene titanium-based composite materials prepared in examples 1 to 4 of the present invention and the titanium-based materials prepared in comparative examples 1 to 4 were subjected to uniaxial tensile test (with extensometer) using a universal material testing machine of the Instron model number 598X, and a tensile rate of 1X 10 was set-3s-1The results are shown in table 1 below.
TABLE 1
As can be seen from table 1, the yield strength and tensile strength of the titanium-based microalloyed coated graphene composite materials prepared in examples 1 to 4 of the invention are improved by more than 140MPa compared with the yield strength and tensile strength of the titanium-based materials prepared in comparative examples 1 to 4, and the elongation after fracture is still maintained at more than 10%. The invention shows that the high-energy ball milling process with different rotating speed combinations is adopted for treating the microalloyed metal powder and the titanium-based powder to realize the quasi-continuous close coating of the microalloyed metal on the surface of the spherical titanium-based powder, and then the characteristic of higher roughness of the surface of the obtained composite powder is utilized and the heating mechanical stirring technology is combined to complete the uniform dispersion of graphene on the surface of the composite powder, so that the graphene titanium-based composite material with the quasi-network structure is obtained; in addition, the microalloyed coated graphene titanium-based composite material disclosed by the invention greatly retains a two-dimensional graphene nanostructure, ensures the reinforcing effect of graphene, and remarkably improves the strength performance of the titanium-based composite material by combining the composite reinforcing characteristics of solid solution reinforcement of intermetallic compound particle phase, fine crystal reinforcement of TiC nano particle reinforcing phase, high-density dislocation reinforcement and the like; in addition, the good extension plasticity of the titanium-based composite material is ensured by the communication effect between the discontinuous matrixes of the quasi-net structure and the shear-retardation effect of the graphene.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (8)
1. The microalloying synergistically reinforced graphene titanium-based composite material is characterized in that titanium or titanium alloy is used as a matrix, metal for microalloying uniformly coats the surface of the titanium or titanium alloy matrix in a quasi-continuous state in a physical combination mode, and graphene is dispersed on the outer surface of the titanium or titanium alloy matrix coated with the metal for microalloying and forms a quasi-continuous network structure together with in-situ self-generated TiC nano particles and intermetallic compound particles; the micro-alloying metal and the graphene do not generate a carbonization reaction, the hardness of the micro-alloying metal is less than that of the titanium or titanium alloy matrix, and the ductility of the micro-alloying metal is greater than that of the titanium or titanium alloy matrix; the yield strength and tensile strength of the microalloyed and synergistically strengthened graphene titanium-based composite material are improved by more than 140MPa compared with the titanium-based composite material prepared from the titanium-based powder with the same components, and the elongation after fracture is more than 10%.
2. The microalloyed co-strengthened graphene titanium-based composite material according to claim 1, wherein the microalloying metal is copper, nickel or silver.
3. A method of preparing the microalloyed co-strengthened graphene titanium-based composite material according to claim 1 or 2, wherein the method comprises the following steps:
step one, selecting powder: selecting spherical titanium or titanium alloy powder as matrix powder, and selecting metal powder for micro-alloying;
step two, preparing composite powder: adding the base powder selected in the step one and metal powder for micro-alloying into a ball mill, then sequentially carrying out high-energy ball milling treatment at high and low rotating speeds, and screening to obtain titanium-based composite powder; the technological parameters of the high-speed high-energy ball milling treatment are as follows: the rotating speed is 450r/min, the ball milling time is 30-50 min, the ball-material ratio is (2-3): 1, and the technological parameters of the low-rotating-speed high-energy ball milling treatment are as follows: the rotating speed is 350r/min, the ball milling time is 2-3 h, and the ball-material ratio is (2-3): 1; the sphericity of the titanium-based composite powder is not less than 0.6, and the surface roughness Ra is more than 2 mu m;
step three, graphene dispersion treatment: ultrasonically dispersing graphene nano sheets in a solvent to obtain a graphene nano sheet suspension solution;
step four, preparing mixed slurry: adding the titanium-based composite powder obtained in the step two into the graphene nanosheet suspension solution obtained in the step three, and mechanically stirring until the mixture is uniform to obtain pasty mixed slurry; the mechanical stirring process parameters are as follows: the rotating speed is 300r/min to 450r/min, the stirring time is 2h to 4h, and the heating temperature is 60 ℃;
step five, preparing mixed powder: placing the pasty mixed slurry obtained in the fourth step into a vacuum drying oven for drying treatment, and then screening to obtain mixed powder with the surface coated with graphene;
step six, sintering and forming: and D, placing the mixed powder with the surface coated with the graphene obtained in the fifth step into a discharge plasma sintering machine for hot-pressing sintering to obtain the microalloyed synergistically strengthened graphene titanium-based composite material.
4. The method according to claim 3, wherein the sphericity of the base powder in the first step is not less than 0.8; the mass purity of the matrix powder and the mass purity of the metal powder for micro-alloying are not less than 99.9 percent.
5. The method according to claim 3, wherein the micro-alloying metal powder in the first step is copper powder, nickel powder or silver powder, and the mass ratio of the micro-alloying metal powder to the base powder is not more than 1: 40.
6. The method of claim 3, wherein the mass of the graphene in step three is not greater than 0.5% of the total mass of the graphene and the titanium-based composite powder in step two.
7. The method according to claim 3, wherein the solvent in step three is a mixed solution of tetrahydrofuran, ethylene glycol butyl ether and ethanol, wherein the volume ratio of the tetrahydrofuran, the ethylene glycol butyl ether and the ethanol is 3:3: 6.
8. The method according to claim 3, wherein the process parameters of the hot pressing sintering in the sixth step are as follows: the sintering temperature is 900-1000 ℃, the sintering time is 5-8 min, and the sintering pressure is not less than 45 MPa.
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