CN112410601A - Preparation method of graphene-boron heterostructure titanium-based composite material - Google Patents
Preparation method of graphene-boron heterostructure titanium-based composite material Download PDFInfo
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 239000010936 titanium Substances 0.000 title claims abstract description 195
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 194
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 137
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 96
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 50
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 38
- 238000000498 ball milling Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 22
- 239000011812 mixed powder Substances 0.000 claims description 19
- 238000000465 moulding Methods 0.000 claims description 12
- 238000002490 spark plasma sintering Methods 0.000 claims description 10
- 239000011258 core-shell material Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 7
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- 239000013078 crystal Substances 0.000 abstract description 5
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- 239000000463 material Substances 0.000 description 31
- 230000003014 reinforcing effect Effects 0.000 description 8
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- 101000686227 Homo sapiens Ras-related protein R-Ras2 Proteins 0.000 description 6
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
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- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
- C22C14/00—Alloys based on titanium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
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- 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
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
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- 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 preparation method of a graphene-boron heterostructure titanium-based composite material, which comprises the steps of coating graphene on the surface of large-particle-size titanium-based powder to obtain graphene-coated titanium-based powder, coating boron powder on the surface of small-particle-size titanium-based powder to obtain boron-coated titanium-based powder, mixing the graphene-coated titanium-based powder and the boron-coated titanium-based powder, and sintering to obtain the graphene-boron heterostructure titanium-based composite material. According to the invention, TiB whisker hooks formed by sintering the graphene-coated titanium-based powder and the boron-coated titanium-based powder in situ are hooked in TiC and unreacted residual graphene around the TiC, so that the interface bonding between titanium bases in the titanium-based composite material is reinforced, meanwhile, TiB and TiC play a role in dispersion strengthening at a crystal boundary, the TiB whisker and the residual graphene play a role in load transfer, and the TiB, the graphene and the TiC are synergistically strengthened, so that the mechanical property of the graphene-boron heterostructure titanium-based composite material is improved.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a preparation method of a graphene-boron heterostructure titanium-based composite material.
Background
Titanium (Ti) and titanium alloys are widely used in the industries of aviation, oceans, chemical engineering and the like due to high specific strength, high specific modulus, good oxidation resistance and corrosion resistance, and are already in service in space shuttles, engine blades, automobile parts and the like. However, the defects of poor wear resistance, low hardness and the like of titanium and titanium alloys limit the application thereof. Therefore, new materials must be developed in addition to the conventional titanium alloys. Titanium-based composites can overcome these disadvantages and are therefore a focus of research. How to improve the comprehensive performance of the titanium-based composite material is also important. The shape state, size and content of the reinforcing phase have great influence on the performance of the composite material, and the performance of the matrix material and the bonding strength of the interface also have great influence on the comprehensive performance of the composite material. The choice of matrix and reinforcement phase materials is of great importance. For the metal matrix composite material, the metal matrix has high toughness, so a ceramic phase is usually added as a reinforcing phase, and the toughness of the metal and the high strength and high hardness of the ceramic can be combined, so that the overall performance of the composite material is improved. At present, carbide, boride or other reinforced phases with high hardness and high melting point are used as the main materials of choice for the metal matrix composite.
Most commonly selected as the reinforcing phase for titanium-based composites are TiB and TiC. The density and thermal expansion coefficient of the two materials are close to those of titanium, and the elastic modulus and tensile strength of the two materials are far higher than those of titanium, so that the two materials become the best choice for reinforcing phase materials. More importantly, the wettability of TiC and titanium is good. Graphene is a two-dimensional carbon material with carbon atoms in an sp2 hybridized form, and has excellent electric and thermal conductivity and good mechanical properties. Compared with the traditional material, the graphene has higher strength, elongation and larger specific surface area, and the in-situ synthesized TiC of the graphene and the titanium matrix can well match the strength and ductility of the prepared composite material, so that the graphene is an ideal material for reinforcing the titanium matrix composite material.
In the past, the titanium-based composite material is prepared by adopting a powder metallurgy mode, and powder with uniform particle size is selected as a raw material for selecting a titanium matrix. The research reported at present mainly adopts a method of coating graphene and boron powder in a mixed manner by a ball milling method or coating graphene and boron powder step by step, researches the mixed enhancement effect of graphene and boron in a metal-based composite material, and reports the synergistic effect of the graphene and the boron. Studies on heterostructures have been reported.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a graphene-boron heterostructure titanium-based composite material, aiming at the defects of the prior art. According to the method, graphene and boron powder are correspondingly coated on the surface of large-particle-size titanium-based powder and the surface of small-particle-size titanium-based powder respectively and then mixed and sintered, TiB whiskers with a hook net structure formed by in-situ self-generation are hooked in TiC and unreacted residual graphene around the TiC, so that interface bonding between titanium matrixes in the titanium-based composite material is reinforced, meanwhile, the TiB and the TiC play a role in dispersion strengthening at a crystal boundary, the TiB whiskers and the residual graphene play a role in load transfer, the TiB, the graphene and the TiC are strengthened in a synergistic mode, and the mechanical property of the graphene-boron heterostructure titanium-based composite material is improved.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a graphene-boron heterostructure titanium-based composite material is characterized in that the method selects the same large-particle-size titanium-based powder and small-particle-size titanium-based powder as raw materials, graphene is coated on the surface of the large-particle-size titanium-based powder to obtain graphene-coated titanium-based powder, boron powder is coated on the surface of the small-particle-size titanium-based powder to obtain boron-coated titanium-based powder, then the graphene-boron heterostructure titanium-based powder and the boron-coated titanium-based powder are mixed to form graphene-boron heterostructure titanium-based mixed powder, and then sintering is carried out to obtain the graphene-boron heterostructure titanium-based composite material; the titanium-based powder with the large particle size and the titanium-based powder with the small particle size are both titanium powder or titanium alloy powder, and the particle diameter ratio of the titanium-based powder with the large particle size to the titanium-based powder with the small particle size is (2-5): 1.
preparing a metal-based composite material by adopting an in-situ synthesis method, selecting boron powder and graphene as original reinforcing phases, correspondingly coating the graphene and the boron powder on the surface of large-particle-size titanium-based powder and the surface of small-particle-size titanium-based powder respectively, then mixing to obtain uniform graphene-boron heterostructure titanium-based mixed powder, and sintering to form a quasi-continuous core-shell structure of small-sphere-large-sphere surrounding the graphene-coated titanium-based powder, so as to obtain the graphene-boron heterostructure titanium-based composite material; in the sintering process, boron powder and the surface of the small-particle-size titanium-based powder coated by the boron powder form TiB whiskers in situ, graphene and the surface of the large-particle-size titanium-based powder coated by the graphene form TiC in situ, and the TiB whiskers with a hook net structure are hooked in the TiC and unreacted residual graphene around the TiC, so that the interface combination between titanium matrixes in the titanium-based composite material is reinforced, the growth of crystal grains is effectively hindered, and the titanium matrixes are refined; meanwhile, TiB and TiC play a role in dispersion strengthening at the crystal boundary, and TiB whiskers and residual graphene play a role in load transfer; the multiple strengthening effects realize the synergistic strengthening of the TiB, the graphene and the TiC, effectively improve the mechanical property of the graphene-boron heterostructure titanium-based composite material and improve the mechanical property of the graphene-boron heterostructure titanium-based composite material.
The preparation method of the graphene-boron heterostructure titanium-based composite material is characterized by comprising the following steps of:
step one, carrying out low-energy ball milling treatment on graphene and large-particle-size titanium-based powder to obtain graphene-coated titanium-based powder;
secondly, performing low-energy ball milling treatment on the boron powder and the small-particle-size titanium-based powder to obtain boron-coated titanium-based powder;
step three, mixing the graphene-coated titanium-based powder obtained in the step one and the boron-coated titanium-based powder obtained in the step two, and performing low-energy ball milling treatment to obtain graphene-boron heterostructure titanium-based mixed powder;
and step four, sintering and molding the graphene-boron heterostructure titanium-based mixed powder obtained in the step three to obtain the graphene-boron heterostructure titanium-based composite material.
According to the invention, graphene with a lamellar structure is uniformly coated on the surface of titanium-based powder with a large particle size by adopting a low-energy ball milling method to obtain graphene coated titanium-based powder, boron powder is uniformly coated on the surface of titanium-based powder with a small particle size by adopting a low-energy ball milling method to obtain boron coated titanium-based powder, then the two kinds of powder are uniformly mixed by adopting the low-energy ball milling method, the structural damage of the graphene and the boron powder is avoided, TiB whiskers and TiC are fully generated after sintering, and a large amount of TiB whiskers are fully hooked in the TiC and the residual graphene because the boron coated titanium-based powder is coated around the graphene coated titanium-based powder, so that the interface bonding force between titanium substrates is further improved, the synergistic strengthening effect of the TiB, the graphene and the TiC is enhanced, and the mechanical property of the graphene-boron heterostructure titanium-based composite material is improved.
The preparation method of the graphene-boron heterostructure titanium-based composite material is characterized in that the particle size of the large-particle-size titanium-based powder in the first step is more than 100 microns. The titanium-based powder with the optimal particle size coats the graphene with the lamellar structure, so that a better graphene dispersing effect is obtained.
The preparation method of the graphene-boron heterostructure titanium-based composite material is characterized in that the sheet diameter size of graphene in the first step is 0.5-5 microns. The graphene with the optimal size has a better coating area, and is beneficial to obtaining a better coating effect.
The preparation method of the graphene-boron heterostructure titanium-based composite material is characterized in that in the step one, graphene is coated on the surface of titanium-based powder to form a discontinuous core-shell structure in the graphene-coated titanium-based powder.
The preparation method of the graphene-boron heterostructure titanium-based composite material is characterized in that the particle size of the small-particle-size titanium-based powder in the second step is less than 60 mu m.
The preparation method of the graphene-boron heterostructure titanium-based composite material is characterized in that the particle size of the boron powder in the second step is 1-3 mu m. The boron powder with the optimized particle size has fine particles and better uniform dispersion effect.
The preparation method of the graphene-boron heterostructure titanium-based composite material is characterized in that the rotation speed of the low-energy ball milling treatment in the first step and the second step is 200r/min, and the time is 4 h; and in the third step, the rotating speed of the low-energy ball milling treatment is 100r/min, and the time is 10 min.
The preparation method of the graphene-boron heterostructure titanium-based composite material is characterized in that the mass ratio of the graphene-coated titanium-based powder to the boron-coated titanium-based powder in the third step is 7: 3.
The preparation method of the graphene-boron heterostructure titanium-based composite material is characterized in that the sintering molding in the fourth step adopts discharge plasma sintering, the temperature rise rate of the discharge plasma sintering is 100 ℃/min, the temperature is 900-1100 ℃, the time is 6min, and the pressure is 40-60 MPa. The optimized discharge plasma sintering process parameters are beneficial to the in-situ self-generation of TiC on the surface of the graphene and the large-particle-size titanium-based powder coated by the graphene, and simultaneously, enough residual graphene is kept, and the in-situ self-generation of TiB whiskers with a needle-punched structure on the surface of the boron powder and the small-particle-size titanium-based powder coated by the boron powder effectively guarantees the reinforcing effect of TiB whisker hooks on a matrix interface in the residual graphene, and realizes the synergistic reinforcing effect of TiB, graphene and TiC.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, graphene and boron powder are correspondingly coated on the surface of large-particle-size titanium-based powder and the surface of small-particle-size titanium-based powder respectively and then mixed and sintered, TiB whiskers with a hook net structure formed by in-situ self-generation are hooked in TiC and unreacted residual graphene around the TiC, so that the interface combination between titanium matrixes in the titanium-based composite material is reinforced, meanwhile, TiB and TiC play a role in dispersion strengthening at a crystal boundary, the TiB whiskers and the residual graphene play a role in load transfer, and the TiB, the graphene and the TiC are strengthened in a synergistic manner, so that the mechanical property of the titanium-based composite material with the graphene-boron heterostructure is improved.
2. According to the invention, the graphene and boron powder are correspondingly coated on the surface of the titanium-based powder with larger particle size difference to obtain the graphene-coated titanium-based powder and the boron-coated titanium-based powder, and the particle size difference of the two powders is larger, so that the gap between the particles is smaller, the structure of the graphene-boron heterostructure titanium-based composite material obtained after sintering is more compact, and the mechanical property of the graphene-boron heterostructure titanium-based composite material is further improved.
3. The method has the advantages of simple process, strong operability and lower production cost, and is beneficial to large-scale industrial production.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
Fig. 1 is an SEM image of a graphene-boron heterostructure titanium-based composite material prepared in example 1 of the present invention.
Fig. 2 is a morphology diagram of a heterostructure in the graphene-boron heterostructure titanium-based composite material prepared in example 1 of the present invention.
FIG. 3 is a tensile curve of the graphene-boron heterostructure titanium-based composite material prepared in examples 1-2 of the present invention and the heterostructure alloy material prepared in comparative examples 1-2.
Detailed Description
Example 1
The embodiment comprises the following steps:
putting 0.3g of graphene and 70g of TC4 titanium alloy spherical powder into a planetary ball mill, and carrying out low-energy ball milling treatment for 4 hours at the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain TC4 titanium alloy spherical powder coated with graphene; the sheet diameter of the graphene is 0.5-5 mu m, the thickness of the graphene is 1-3 nm, and the particle diameter of the TC4 titanium alloy spherical powder is 150-250 mu m; in the graphene-coated TC4 titanium alloy spherical powder, graphene is coated on the surface of titanium-based powder to form a discontinuous core-shell structure;
secondly, putting 0.2g of boron powder and 30g of TC4 titanium alloy spherical powder into a planetary ball mill, and carrying out low-energy ball milling treatment for 4 hours under the conditions of the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain boron-coated TC4 titanium alloy spherical powder; the particle size of the TC4 titanium alloy spherical powder is 15-53 mu m, and the particle size of the boron powder is 1-3 mu m;
step three, carrying out low-energy ball milling treatment on the graphene-coated TC4 titanium alloy spherical powder obtained in the step one and the boron-coated TC4 titanium alloy spherical powder obtained in the step two for 10min under the conditions of the rotating speed of 100r/min and the ball-to-material ratio of 5:1 to obtain graphene-boron heterostructure titanium-based mixed powder;
step four, performing discharge plasma sintering molding on the graphene-boron heterostructure titanium-based mixed powder obtained in the step three to obtain a graphene-boron heterostructure titanium-based composite material; the temperature rise rate of the spark plasma sintering is 100 ℃/min, the temperature is 1000 ℃, the time is 6min, and the pressure is 40 MPa.
Fig. 1 is an SEM image of the graphene-boron heterostructure titanium-based composite material prepared in this example, and it can be seen from fig. 1 that the small-sized TC4 titanium alloy spherical powder particles in the graphene-boron heterostructure titanium-based composite material surround the large-sized TC4 titanium alloy spherical powder particles to form a structure of "small sphere-in-large sphere".
Fig. 2 is a morphology diagram of a heterostructure in the graphene-boron heterostructure titanium-based composite material prepared in this embodiment, and it can be seen from fig. 2 that TiB whiskers in the graphene-boron heterostructure titanium-based composite material cross TiC and residual Graphene (GNPs) and are well embedded at a grain boundary to form a hooking effect.
Comparative example 1
This comparative example comprises the following steps: carrying out low-energy ball milling treatment on 70g of TC4 titanium alloy spherical powder with the particle size of 150-250 microns and 30g of TC4 titanium alloy spherical powder with the particle size of 15-53 microns for 20min under the conditions of the rotation speed of 200r/min and the ball-to-material ratio of 5:1, and then carrying out discharge plasma sintering molding to obtain a TC4 alloy material with a heterostructure; the temperature rise rate of the spark plasma sintering is 100 ℃/min, the temperature is 1000 ℃, the time is 6min, and the pressure is 40 MPa.
Example 2
The embodiment comprises the following steps:
putting 0.3g of graphene and 70g of TA1 titanium spherical powder into a planetary ball mill, and carrying out low-energy ball milling treatment for 4 hours at the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain graphene-coated TA1 titanium spherical powder; the sheet diameter of the graphene is 0.5-5 mu m, the thickness of the graphene is 1-3 nm, and the particle diameter of the TA1 titanium spherical powder is 100-180 mu m;
secondly, placing 0.2g of boron powder and 30g of TA1 titanium spherical powder into a planetary ball mill, and carrying out low-energy ball milling treatment for 4 hours under the conditions of the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain boron-coated TA1 titanium spherical powder; the particle size of the TA1 titanium spherical powder is 15-53 mu m, and the particle size of the boron powder is 1-3 mu m;
step three, carrying out low-energy ball milling treatment on the graphene-coated TA1 titanium spherical powder obtained in the step one and the boron-coated TA1 titanium spherical powder obtained in the step two for 20min under the conditions of the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain graphene-boron heterostructure titanium-based mixed powder;
step four, performing discharge plasma sintering molding on the graphene-boron heterostructure titanium-based mixed powder obtained in the step three to obtain a graphene-boron heterostructure titanium-based composite material; the temperature rise rate of the spark plasma sintering is 100 ℃/min, the temperature is 900 ℃, the time is 6min, and the pressure is 45 MPa.
Comparative example 2
This comparative example comprises the following steps: carrying out low-energy ball milling treatment on 70g of TA1 titanium spherical powder with the particle size of 100-180 microns and 30g of TA1 titanium spherical powder with the particle size of 15-53 microns for 20min under the conditions of the rotation speed of 200r/min and the ball-to-material ratio of 5:1, and then carrying out discharge plasma sintering molding to obtain a TA1 titanium material with a heterostructure; the temperature rise rate of the spark plasma sintering is 100 ℃/min, the temperature is 900 ℃, the time is 6min, and the pressure is 45 MPa.
Fig. 3 is a tensile curve diagram of the graphene-boron heterostructure titanium-based composite material prepared in examples 1-2 of the present invention and the heterostructure alloy material prepared in comparative examples 1-2 of the present invention, and it can be seen from fig. 3 that the mechanical properties of the graphene-boron heterostructure titanium-based composite material prepared by the method of the present invention are improved compared with the corresponding heterostructure alloy material.
Example 3
The embodiment comprises the following steps:
putting 0.3g of graphene and 70g of TC4 titanium alloy spherical powder into a planetary ball mill, and carrying out low-energy ball milling treatment for 4 hours at the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain TC4 titanium alloy spherical powder coated with graphene; the sheet diameter of the graphene is 0.5-5 mu m, the thickness of the graphene is 1-3 nm, and the particle diameter of the TC4 titanium alloy spherical powder is 150-250 mu m;
secondly, putting 0.2g of boron powder and 30g of TC4 titanium alloy spherical powder into a planetary ball mill, and carrying out low-energy ball milling treatment for 4 hours under the conditions of the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain boron-coated TC4 titanium alloy spherical powder; the particle size of the TC4 titanium alloy spherical powder is 15-53 mu m, and the particle size of the boron powder is 500 nm;
step three, carrying out low-energy ball milling treatment on the graphene-coated TC4 titanium alloy spherical powder obtained in the step one and the boron-coated TC4 titanium alloy spherical powder obtained in the step two for 4 hours at the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain graphene-boron heterostructure titanium-based mixed powder;
step four, performing discharge plasma sintering molding on the graphene-boron heterostructure titanium-based mixed powder obtained in the step three to obtain a graphene-boron heterostructure titanium-based composite material; the temperature rise rate of the spark plasma sintering is 100 ℃/min, the temperature is 1100 ℃, the time is 6min, and the pressure is 60 MPa.
Example 4
The embodiment comprises the following steps:
putting 0.3g of graphene and 70g of TC21 titanium alloy spherical powder into a planetary ball mill, and carrying out low-energy ball milling treatment for 4 hours at the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain TC21 titanium alloy spherical powder coated with graphene; the sheet diameter of the graphene is 0.5-5 mu m, the thickness of the graphene is 1-3 nm, and the particle diameter of the TC21 titanium alloy spherical powder is 100-150 mu m;
secondly, putting 0.2g of boron powder and 30g of TC21 titanium alloy spherical powder into a planetary ball mill, and carrying out low-energy ball milling treatment for 4 hours under the conditions of the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain boron-coated TC21 titanium alloy spherical powder; the particle size of the TC21 titanium alloy spherical powder is 15-53 mu m, and the particle size of the boron powder is 1-3 mu m;
step three, carrying out low-energy ball milling treatment on the graphene-coated titanium-based powder obtained in the step one and the boron-coated titanium-based powder obtained in the step two for 4 hours under the conditions of the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain graphene-boron heterostructure titanium-based mixed powder;
step four, performing discharge plasma sintering molding on the graphene-boron heterostructure titanium-based mixed powder obtained in the step three to obtain a graphene-boron heterostructure titanium-based composite material; the temperature rise rate of the spark plasma sintering is 100 ℃/min, the temperature is 1000 ℃, the time is 6min, and the pressure is 40 MPa.
Example 5
The embodiment comprises the following steps:
putting 0.3g of graphene and 50g of TA1 titanium spherical powder into a planetary ball mill, and carrying out low-energy ball milling treatment for 4 hours at the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain graphene-coated TA1 titanium spherical powder; the sheet diameter of the graphene is 0.5-5 mu m, the thickness of the graphene is 1-3 nm, and the particle diameter of the TA1 titanium spherical powder is 100-180 mu m;
secondly, placing 0.2g of boron powder and 50g of TA1 titanium spherical powder into a planetary ball mill, and carrying out low-energy ball milling treatment for 4 hours under the conditions of the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain boron-coated TA1 titanium spherical powder; the particle size of the TA1 titanium spherical powder is 15-53 mu m, and the particle size of the boron powder is 1-3 mu m;
step three, carrying out low-energy ball milling treatment on the graphene-coated titanium-based powder obtained in the step one and the boron-coated titanium-based powder obtained in the step two for 4 hours under the conditions of the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain graphene-boron heterostructure titanium-based mixed powder;
step four, performing discharge plasma sintering molding on the graphene-boron heterostructure titanium-based mixed powder obtained in the step three to obtain a graphene-boron heterostructure titanium-based composite material; the temperature rise rate of the spark plasma sintering is 100 ℃/min, the temperature is 900 ℃, the time is 6min, and the pressure is 45 MPa.
Example 6
The embodiment comprises the following steps:
putting 0.3g of graphene and 50g of TC4 titanium alloy spherical powder into a planetary ball mill, and carrying out low-energy ball milling treatment for 4 hours at the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain TC4 titanium alloy spherical powder coated with graphene; the sheet diameter of the graphene is 0.5-5 mu m, the thickness of the graphene is 1-3 nm, and the particle diameter of the TC4 titanium alloy spherical powder is 100-250 mu m;
secondly, putting 0.2g of boron powder and 30g of TC4 titanium alloy spherical powder into a planetary ball mill, and carrying out low-energy ball milling treatment for 4 hours under the conditions of the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain boron-coated TC4 titanium alloy spherical powder; the particle size of the TC4 titanium alloy spherical powder is 15-53 mu m, and the particle size of the boron powder is 1-3 mu m;
step three, carrying out low-energy ball milling treatment on the graphene-coated titanium-based powder obtained in the step one and the boron-coated titanium-based powder obtained in the step two for 4 hours under the conditions of the rotating speed of 200r/min and the ball-to-material ratio of 5:1 to obtain graphene-boron heterostructure titanium-based mixed powder;
step four, performing discharge plasma sintering molding on the graphene-boron heterostructure titanium-based mixed powder obtained in the step three to obtain a graphene-boron heterostructure titanium-based composite material; the temperature rise rate of the spark plasma sintering is 100 ℃/min, the temperature is 900 ℃, the time is 6min, and the pressure is 45 MPa.
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 (10)
1. A preparation method of a graphene-boron heterostructure titanium-based composite material is characterized in that the method selects the same large-particle-size titanium-based powder and small-particle-size titanium-based powder as raw materials, graphene is coated on the surface of the large-particle-size titanium-based powder to obtain graphene-coated titanium-based powder, boron powder is coated on the surface of the small-particle-size titanium-based powder to obtain boron-coated titanium-based powder, then the graphene-boron heterostructure titanium-based powder and the boron-coated titanium-based powder are mixed to form graphene-boron heterostructure titanium-based mixed powder, and then sintering is carried out to obtain the graphene-boron heterostructure titanium-based composite material; the titanium-based powder with the large particle size and the titanium-based powder with the small particle size are both titanium powder or titanium alloy powder, and the particle diameter ratio of the titanium-based powder with the large particle size to the titanium-based powder with the small particle size is (2-5): 1.
2. the method of preparing a graphene-boron heterostructure titanium-based composite material of claim 1, comprising the steps of:
step one, carrying out low-energy ball milling treatment on graphene and large-particle-size titanium-based powder to obtain graphene-coated titanium-based powder;
secondly, performing low-energy ball milling treatment on the boron powder and the small-particle-size titanium-based powder to obtain boron-coated titanium-based powder;
step three, mixing the graphene-coated titanium-based powder obtained in the step one and the boron-coated titanium-based powder obtained in the step two, and performing low-energy ball milling treatment to obtain graphene-boron heterostructure titanium-based mixed powder;
and step four, sintering and molding the graphene-boron heterostructure titanium-based mixed powder obtained in the step three to obtain the graphene-boron heterostructure titanium-based composite material.
3. The method of claim 2, wherein the titanium-based powder with large particle size in the first step has a particle size of 100 μm or more.
4. The method for preparing a graphene-boron heterostructure titanium-based composite material of claim 2, wherein the graphene in the first step has a sheet diameter size of 0.5 μm to 5 μm.
5. The method for preparing a graphene-boron heterostructure titanium-based composite material of claim 2, wherein in the step one, graphene is coated on the surface of the titanium-based powder to form a discontinuous core-shell structure.
6. The method for preparing a graphene-boron heterostructure titanium-based composite material as claimed in claim 2, wherein the particle size of the small-particle size titanium-based powder in the second step is 60 μm or less.
7. The method for preparing a graphene-boron heterostructure titanium-based composite material of claim 2, wherein the particle size of the boron powder in the second step is 1 μm to 3 μm.
8. The preparation method of the graphene-boron heterostructure titanium-based composite material as claimed in claim 2, wherein the rotation speed of the low-energy ball milling treatment in the first step and the second step is 200r/min, and the time is 4 h; and in the third step, the rotating speed of the low-energy ball milling treatment is 100r/min, and the time is 10 min.
9. The method for preparing the graphene-boron heterostructure titanium-based composite material of claim 2, wherein the mass ratio of the graphene-coated titanium-based powder to the boron-coated titanium-based powder in the step three is 7: 3.
10. The method for preparing the graphene-boron heterostructure titanium-based composite material of claim 2, wherein the sintering molding in the fourth step is spark plasma sintering, the temperature rise rate of the spark plasma sintering is 100 ℃/min, the temperature is 900-1100 ℃, the time is 6min, and the pressure is 40-60 MPa.
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| CN113458388A (en) * | 2021-07-02 | 2021-10-01 | 南京工业大学 | Multi-scale composite material based on mismatching of titanium alloy particle size and graphene layer thickness and preparation method thereof |
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| CN111961902A (en) * | 2020-08-14 | 2020-11-20 | 东南大学 | Titanium-based composite material with heterogeneous structure and preparation method and application thereof |
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| CN111961902A (en) * | 2020-08-14 | 2020-11-20 | 东南大学 | Titanium-based composite material with heterogeneous structure and preparation method and application thereof |
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| CN113070471A (en) * | 2021-03-24 | 2021-07-06 | 东北大学 | Preparation method of titanium-graphene composite material with strong plasticity matching |
| CN113458388A (en) * | 2021-07-02 | 2021-10-01 | 南京工业大学 | Multi-scale composite material based on mismatching of titanium alloy particle size and graphene layer thickness and preparation method thereof |
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