CN112695262A - Titanium alloy-based composite material with micro-structure and preparation method thereof - Google Patents
Titanium alloy-based composite material with micro-structure and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 128
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 46
- 238000000498 ball milling Methods 0.000 claims abstract description 43
- 239000010936 titanium Substances 0.000 claims abstract description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 36
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011812 mixed powder Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 238000009826 distribution Methods 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 25
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 239000008188 pellet Substances 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 6
- 230000001788 irregular Effects 0.000 claims description 3
- 230000009977 dual effect Effects 0.000 claims 2
- 238000000280 densification Methods 0.000 abstract description 4
- 238000003825 pressing Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 description 29
- 229910045601 alloy Inorganic materials 0.000 description 15
- 239000000956 alloy Substances 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 239000011268 mixed slurry Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- 240000000591 Strychnos spinosa Species 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- 238000005275 alloying Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 230000002787 reinforcement Effects 0.000 description 5
- 238000005728 strengthening Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000004663 powder metallurgy Methods 0.000 description 4
- 238000009827 uniform distribution Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 229910000756 V alloy Inorganic materials 0.000 description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009828 non-uniform distribution Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910004688 Ti-V Inorganic materials 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- 229910010968 Ti—V Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
- C22C49/10—Refractory metals
- C22C49/11—Titanium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
-
- 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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Abstract
The invention discloses a titanium alloy-based composite material with a micro-structure and a preparation method thereof, wherein the titanium alloy-based composite material comprises the following components in percentage by mass: 90-93 wt% of TiB-Ti-based composite powder, 6 wt% of aluminum powder and 1-4 wt% of vanadium powder, wherein the sum of the mass percentages of the components is 100%; the preparation method comprises the following steps: step 1, performing low-energy ball milling on TiB-Ti-based composite powder, aluminum powder and vanadium powder to obtain mixed powder. And 2, pre-pressing the mixed powder obtained in the step 1 in a graphite mold for molding, and performing sintering densification treatment at 1100-1300 ℃ by adopting spark plasma sintering to obtain the titanium alloy-based composite material with the microstructure. The obtained titanium alloy-based composite material with the microstructure can greatly improve the elongation of the material, inhibit coarsening of TiB whiskers and obtain the titanium alloy-based composite material with good strong plasticity matching.
Description
Technical Field
The invention belongs to the field of metal matrix composite materials, and particularly relates to a titanium alloy matrix composite material with a micro-structure, and a preparation method of the composite material.
Background
The titanium alloy has the excellent characteristics of low density, high specific strength, good biocompatibility and the like, and is widely applied to the fields of automobile instruments, marine equipment, medical instruments, aerospace, military and the like. Among them, the Ti6Al4V alloy belonging to the α + β type is the most typical, most studied and mature titanium alloy at present because of its outstanding performance and commercial utility rate of more than 50%. However, as the application requirements are continuously raised, the wear resistance, heat resistance and strength of the alloy are further improved due to the limit of the self-structure. In recent years, by introducing a TiB reinforcing phase having good compatibility with a matrix into a titanium alloy matrix, a discontinuous reinforced titanium-based composite material (DRTMCs) obtained exhibits more excellent strength, modulus, corrosion resistance, wear resistance and high-temperature mechanical properties than the titanium alloy, and thus is receiving attention. However, it is worth noting that the conventional DRTMCs are usually prepared by using an existing commercial titanium alloy as a matrix, and since the content and the type of alloying elements in the titanium alloy matrix are determined, the added reinforcement is very likely to be incompatible with an alloy system, and an in-situ reaction occurs under certain conditions to destroy the balance of the composition and the structure of the matrix alloy in a micro-area, thereby causing the difficulty in regulating and controlling the structure and performance of the DRTMCs system, and the plasticity/toughness is significantly reduced while the strength is improved, so that the material performance is difficult to meet the application requirements.
In the conventional preparation process of DRTMCs, most researchers often pursue uniform distribution of the reinforcing phase in the matrix to achieve a strong toughness match. However, more and more studies show that the DRTMCs with uniformly distributed reinforcing phases only show limited strengthening effect and poor plastic toughness level (El ≈ 1%), and particularly the DRTMCs prepared by powder metallurgy show great room temperature brittleness. In recent years, related researches show that the problem of poor plasticity and toughness of the DRTMCs prepared by the powder metallurgy method can be effectively solved by changing the uniform distribution state of the reinforcing phase. For example, (Chinese patent TiBw/Ti alloy matrix composite preparation method (application No. 200810136852.8, publication No. 10133607), and Chinese patent high-temperature oxidation-resistant TiCp/Ti alloy matrix composite preparation method (application No. 200910071986.0, publication No. 101550496), both of which are based on H-S theory and grain boundary strengthening theory, design a composite configuration DRTMCs with reinforcing phases in quasi-continuous network distribution, which shows more excellent comprehensive performance than the conventional titanium alloy matrix composite with uniformly distributed reinforcing phases.
Disclosure of Invention
The invention aims to provide a titanium alloy-based composite material with a micro-structure, which can effectively improve the plasticity and toughness of a TiB reinforced titanium alloy-based composite material, greatly improve the elongation under the same tensile strength and obtain the titanium alloy-based composite material with good matching of the strength and the plasticity.
The second purpose of the invention is to provide a preparation method of a titanium alloy-based composite material with a micro-structure, which can ensure that TiB reinforcements are distributed in a microsphere shape in a matrix, and can realize effective regulation and control of the size, the pellet size and the quantity of single TiB whiskers, and on the basis, a matrix structure of a single alpha phase can be converted into a two-phase structure with an alpha + beta type, so that the titanium alloy-based composite material with the micro-structure is obtained.
The first technical scheme adopted by the invention is as follows: a titanium alloy based composite material with a micro-structure comprises the following components in percentage by mass: 90-93 wt% of TiB-Ti-based composite powder, 6 wt% of aluminum powder and 1-4 wt% of vanadium powder, wherein the sum of the mass percentages of the components is 100%;
the content of TiB in the composite powder is 1-10 vol.%.
The first technical solution adopted by the present invention is further characterized in that,
the vanadium powder is irregular in shape, and the particle size distribution range of the powder is 5-20 mu m.
The titanium alloy based composite material has a micro-structure, the phase composition of the micro-structure is alpha + beta type double-phase titanium alloy and TiB whiskers, wherein the TiB whiskers are uniformly distributed in a pellet-shaped structure, and the phase composition of the outer layer structure of the pellet is the alpha + beta type double-phase titanium alloy.
The second technical scheme adopted by the invention is as follows: a preparation method of a titanium alloy-based composite material with a micro-structure specifically comprises the following steps:
step 1, respectively weighing 90 wt.% to 93 wt.% of TiB-Ti-based composite powder, 6 wt.% of aluminum powder and 1 wt.% to 4 wt.% of vanadium powder according to the mass percent, wherein the sum of the mass percent of the TiB-Ti-based composite powder, the aluminum powder and the vanadium powder is 100%, carrying out low-energy ball milling on the TiB-Ti-based composite powder, the aluminum powder and the vanadium powder to obtain mixed powder, wherein a ball-milling auxiliary agent is absolute ethyl alcohol or isopropanol, and the ball-to-material ratio is 2-10: 1; the ball milling speed is 200 r/min-250 r/min; the ball milling time is 2-4 h, and the milling ball is zirconia;
and 2, prepressing and molding the mixed powder obtained in the step 1 in a graphite mold, and sintering and densifying by adopting spark plasma sintering to obtain the titanium alloy-based composite material with the microstructure.
The second technical solution adopted by the present invention is further characterized in that,
in the step 2, the sintering pressure of the discharge plasma is 30MPa, and the sintering process is sintering by a three-step heat preservation method: firstly, heating to 600 ℃, and preserving heat for 30 min; secondly, heating to 750 ℃, and preserving heat for 20 min; and finally, heating to 1100-1300 ℃, and preserving the heat for 5-60 min.
The invention has the beneficial characteristics that: the invention provides a new concept of traceability design for alloying a titanium matrix-reinforced phase composite system, which aims at solving the key problems of micro-area tissues, easily damaged chemical component balance, difficult regulation and control of reinforced phase dimension characteristics and the like existing in alloy matrix compositing in the research of in-situ autogenous non-continuous reinforced titanium matrix composites (DRTMCs), and provides a TiB non-uniform distribution mode with a spherical micro-configuration by adopting a powder metallurgy method, taking TiB-Ti-based composite powder as a raw material, adding alloy elements Al and V in the composite system and utilizing the influence of the alloy elements on the matrix tissues and the TiB distribution mode. The mechanical property and the wear resistance of the composite material are improved by utilizing the structure that TiB is distributed in a pellet form, and meanwhile, the matrix structure is converted into an alpha + beta type dual-phase structure with high ductility and toughness by a composite system alloying mode, so that the material can effectively prevent cracks in the pellets from expanding outwards under the loaded condition, the ductility and toughness of the titanium-based composite material are improved, and the titanium alloy-based composite material with good strong ductility and matching is obtained.
Drawings
FIG. 1 is a metallographic photograph of a titanium alloy-based composite material having a microstructure prepared according to the present invention;
FIG. 2 is a schematic three-dimensional view of a titanium alloy-based composite material having a micro-configuration made in accordance with the present invention;
FIG. 3 is a high magnification (500X) metallographic photograph of a titanium alloy-based composite material having a microstructure prepared in example 1 of the present invention and a titanium-based composite material having a single alpha structure prepared in comparative example 2;
fig. 4 is a stress-strain curve of a titanium alloy-based composite material having a micro-configuration prepared in example 1 of the present invention, a titanium alloy-based composite material in which TiB prepared in comparative example 1 is uniformly distributed, and a titanium alloy-based composite material in which TiB prepared in comparative example 2 is non-uniformly distributed by adding 6 wt.% Al element.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The invention relates to a titanium alloy-based composite material with a micro-structure and a preparation method thereof, which are specifically implemented according to the following steps:
step 1, adding TiB-Ti-based composite powder, aluminum powder and vanadium powder into a low-energy ball mill for low-energy ball milling for 2-4 hours, wherein a ball milling auxiliary agent is absolute ethyl alcohol or isopropanol, the ball milling rotating speed is 200-250 r/min, a grinding ball is zirconium oxide, the ball-material ratio is 2-10: 1, and after the ball milling is finished, placing the powder in a vacuum drying oven for drying for 2-4 hours to obtain mixed powder.
TiB-Ti-based composite powder (application number: 201910528485.4, publication number: 110218907) designed and prepared in the earlier stage by the inventor is used as a raw material, the TiB-Ti-based composite powder is spherical powder prepared by an air atomization method, the particle size range is 15-200 mu m, and the TiB content in the composite powder is 1-10 vol.%. The aluminum powder is atomized spherical powder, the particle size distribution range is 20-30 mu m, the purity is 99.5%, the vanadium powder is irregular, the particle size distribution range of the powder is 5-20 mu m, and the purity is 99.9%.
And 2, pre-pressing the mixed powder obtained in the step 1 in a graphite die for forming, and performing sintering densification treatment by adopting Spark Plasma Sintering (SPS) to obtain the titanium alloy-based composite material with the microstructure.
The sintering pressure of the discharge plasma is 30MPa, and the sintering process adopts a three-step heat preservation method for sintering: firstly, heating to 600 ℃, and preserving heat for 30 min; secondly, heating to 750 ℃, and preserving heat for 20 min; and finally, heating to 1100-1300 ℃, and preserving the heat for 5-60 min.
Comparative example 1
As a comparative example 1 of the invention, the titanium alloy-based composite material with uniformly distributed TiB is prepared by spark plasma sintering, and the preparation method is implemented according to the following steps:
step 1, spherical pure titanium powder, aluminum powder, irregular-shaped vanadium powder and TiB2The powder is weighed according to the mass ratio of 44:3:2:1, and is ball-milled and mixed by a low-energy ball mill, wherein the preparation process of the mixed powder comprises the following steps: the ball-material ratio is 5:1, the ball-milling rotating speed is 250r/min, the ball-milling time is 4h, the ball-milling auxiliary agent is absolute ethyl alcohol, and the grinding ball is zirconia. And (3) carrying out vacuum drying on the mixed slurry obtained by the low-energy ball milling at 60 ℃ for 4h to obtain mixed powder.
Step 2, pre-pressing and molding the mixed powder obtained in the step 1 in a graphite mold, sintering densification treatment is carried out by adopting spark plasma sintering, and a three-step heat preservation method is adopted in the sintering process: firstly, heating to 600 ℃, and preserving heat for 30 min; secondly, heating to 750 ℃, and preserving heat for 20 min; and finally, heating to 1100-1300 ℃, and preserving the heat for 20 min. The sintering temperature of the discharge plasma is 1300 ℃, the sintering pressure is 30MPa, and the sintering time is 1.5h, thus finally obtaining the alpha + beta dual-phase structure titanium alloy matrix composite material with uniformly distributed TiB.
Comparative example 2
As a comparative example 2 of the invention, the titanium-based composite material with non-uniform TiB distribution is prepared by spark plasma sintering, and the preparation method is implemented according to the following steps:
step 1, weighing TiB-Ti-based composite powder and aluminum powder according to the mass ratio of 47:3, and ball-milling and mixing by using a low-energy ball mill, wherein the preparation process of the mixed powder comprises the following steps: the ball-material ratio is 5:1, the ball-milling rotating speed is 250r/min, the ball-milling time is 4h, the ball-milling auxiliary agent is absolute ethyl alcohol, and the grinding ball is zirconia. And (3) carrying out vacuum drying on the mixed slurry obtained by the low-energy ball milling at 60 ℃ for 4h to obtain mixed powder.
Step 2, pre-pressing and molding the mixed powder obtained in the step 1 in a graphite mold, sintering densification treatment is carried out by adopting spark plasma sintering, and a three-step heat preservation method is adopted in the sintering process: firstly, heating to 600 ℃, and preserving heat for 30 min; secondly, heating to 750 ℃, and preserving heat for 20 min; and finally, heating to 1100-1300 ℃, and preserving the heat for 20 min. The sintering temperature of the discharge plasma is 1300 ℃, the sintering pressure is 30MPa, and the sintering time is 1.5 h. Finally obtaining the titanium-based composite material with non-uniform TiB distribution.
Example 1
A titanium alloy based composite material with a micro-structure and a preparation method thereof are specifically implemented according to the following steps:
step 1, weighing TiB-Ti-based composite powder, aluminum powder and vanadium powder according to the mass ratio of 45:3:2, wherein the particle size distribution range of the TiB-Ti-based composite powder is as follows: 15-45 mu m, wherein the TiB content is 3.4 vol.%, the particle size distribution range of the aluminum powder is 20-30 mu m, and the particle size distribution range of the vanadium powder is 5-20 mu m. Ball milling and mixing by adopting a low-energy ball mill, wherein the preparation process of the mixed powder comprises the following steps: adding 0.5ml of absolute ethyl alcohol as a ball milling auxiliary agent according to the ball-material ratio of 5:1, and performing ball milling at the ball milling rotation speed of 250r/min for 4h, wherein the grinding balls are zirconium oxide. And after the ball milling is finished, putting the obtained mixed slurry into a vacuum drying oven for drying for 4 hours at the temperature of 60 ℃ to obtain mixed powder.
And 2, filling the mixed powder obtained in the step 1 into a graphite mold, and sintering and forming by adopting discharge plasma, wherein the sintering process adopts a three-step heat preservation method: firstly, heating to 600 ℃, and preserving heat for 30 min; secondly, heating to 750 ℃, and preserving heat for 20 min; finally, the temperature is increased to 1300 ℃ and the temperature is kept for 20 min. The sintering temperature of the discharge plasma is 1300 ℃, the sintering pressure is 30MPa, and the sintering time is 1.5h, thus finally obtaining the titanium alloy-based composite material with the micro-structure.
Example 2
A titanium alloy based composite material with a micro-structure and a preparation method thereof are specifically implemented according to the following steps:
step 1, weighing TiB-Ti-based composite powder, aluminum powder and vanadium powder according to the mass ratio of 45.5:3:1.5, wherein the particle size range of the TiB-Ti-based composite powder is as follows: 45-125 μm, wherein the TiB content is 3.4 vol.%. The particle size distribution range of the aluminum powder is 20-30 mu m, and the particle size distribution range of the vanadium powder is 5-20 mu m. Ball milling and mixing by adopting a low-energy ball mill, wherein the preparation process of the mixed powder comprises the following steps: adding 1ml of absolute ethyl alcohol as a ball milling assistant according to the ball-material ratio of 2:1, setting the rotating speed of a ball mill to be 250r/min, setting the ball milling time to be 4h, setting the milling ball to be zirconia, putting the mixed slurry into a vacuum drying oven, and carrying out vacuum drying for 2h at 65 ℃ to obtain mixed powder.
And 2, filling the mixed powder obtained in the step 1 into a graphite die, and sintering and forming by adopting discharge plasma. The sintering process adopts a three-step heat preservation method: firstly, heating to 600 ℃, and preserving heat for 30 min; secondly, heating to 750 ℃, and preserving heat for 20 min; finally, the temperature is increased to 1300 ℃ and the temperature is kept for 40 min. The sintering temperature of the discharge plasma is 1300 ℃, the sintering pressure is 30MPa, and the sintering time is 2h, so that the titanium alloy-based composite material with the micro-structure is finally obtained.
Example 3
A titanium alloy based composite material with a micro-structure and a preparation method thereof are specifically implemented according to the following steps:
step 1, weighing TiB-Ti-based composite powder, aluminum powder and vanadium powder according to the mass ratio of 46:3:1, wherein the particle size distribution range of the TiB-Ti-based composite powder is as follows: 125-200 μm, wherein the TiB content is 3.4 vol.%. The particle size distribution range of the aluminum powder is 20-30 mu m, and the particle size distribution range of the vanadium powder is 5-20 mu m. Ball milling and mixing by adopting a low-energy ball mill, wherein the preparation process of the mixed powder comprises the following steps: adding isopropanol as a ball milling aid into the mixture at a ball material ratio of 10:1, wherein the rotating speed of a ball mill is 200r/min, the ball milling time is 2 hours, the milling ball is zirconia, putting the mixed slurry into a vacuum drying oven, and carrying out vacuum drying at 60 ℃ for 4 hours to obtain mixed powder.
And 2, filling the mixed powder obtained in the step 1 into a graphite die, and sintering and forming by adopting discharge plasma. The sintering process adopts a three-step heat preservation method: firstly, heating to 600 ℃, and preserving heat for 30 min; secondly, heating to 750 ℃, and preserving heat for 20 min; finally, the temperature is increased to 1300 ℃ and the temperature is kept for 60 min. The sintering temperature of the discharge plasma is 1300 ℃, the sintering pressure is 30MPa, and the sintering time is 2 h. Finally obtaining the titanium alloy-based composite material with the micro-configuration.
Example 4
A titanium alloy based composite material with a micro-structure and a preparation method thereof are specifically implemented according to the following steps:
step 1, weighing TiB-Ti-based composite powder, aluminum powder and vanadium powder according to the mass ratio of 46.5:3:0.5, wherein the particle size distribution range of the TiB-Ti-based composite powder is as follows: 75-125 μm, wherein the TiB content is 1 vol.%. The particle size distribution range of the aluminum powder is 20-30 mu m, and the particle size distribution range of the vanadium powder is 5-20 mu m. Ball milling and mixing by adopting a low-energy ball mill, wherein the preparation process of the mixed powder comprises the following steps: adding 5ml of absolute ethyl alcohol into the mixture according to the mass ratio of 10:1, wherein the rotating speed of the ball mill is 200r/min, the ball milling time is 4h, and the grinding ball is zirconium oxide. And (3) putting the mixed slurry into a vacuum drying oven, and performing vacuum drying for 4 hours at 70 ℃ to obtain mixed powder.
And 2, filling the mixed powder obtained in the step 1 into a graphite die, and sintering and forming by adopting discharge plasma. The sintering process adopts a three-step heat preservation method: firstly, heating to 600 ℃, and preserving heat for 30 min; secondly, heating to 750 ℃, and preserving heat for 20 min; finally, the temperature is increased to 1200 ℃, and the temperature is kept for 20 min. The sintering temperature of the discharge plasma is 1200 ℃, the sintering pressure is 30MPa, and the sintering time is 1.5 h. Finally obtaining the titanium alloy-based composite material with the micro-configuration.
Example 5
A titanium alloy based composite material with a micro-structure and a preparation method thereof are specifically implemented according to the following steps:
step 1, weighing TiB-Ti-based composite powder, aluminum powder and vanadium powder according to the mass ratio of 45:3:2, wherein the particle size distribution range of the TiB-Ti-based composite powder is as follows: 75-150 μm, wherein the TiB content is 10 vol.%. The particle size distribution range of the aluminum powder is 20-30 mu m, and the particle size distribution range of the vanadium powder is 5-20 mu m. Ball milling and mixing by adopting a low-energy ball mill, wherein the preparation process of the mixed powder comprises the following steps: the ball material ratio is 7: 1; adding isopropanol serving as a ball milling auxiliary agent, wherein the ball milling speed is 250 r/min; the ball milling time is 3h, and the milling ball is zirconia. And (3) putting the mixed slurry into a vacuum drying oven, and performing vacuum drying for 3h at 65 ℃ to obtain mixed powder.
And 2, filling the mixed powder obtained in the step 1 into a graphite die, and sintering and forming by adopting discharge plasma. The sintering process comprises the following steps: sintering by a three-step heat preservation method, namely firstly raising the temperature to 600 ℃ at the heating rate of 50 ℃/min, and preserving the temperature for 30 min; secondly, raising the temperature to 750 ℃ at the heating rate of 30 ℃/min, and preserving the heat for 20 min; finally, the temperature is raised to 1100 ℃ at the heating rate of 20 ℃/min, and the temperature is kept for 15 min. The pressure during sintering was 30 MPa. Finally obtaining the titanium alloy-based composite material with the micro-configuration.
Example 6
A titanium alloy based composite material with a micro-structure and a preparation method thereof are specifically implemented according to the following steps:
step 1, weighing TiB-Ti-based composite powder, aluminum powder and vanadium powder according to the mass ratio of 45:3:2, wherein the particle size distribution range of the TiB-Ti-based composite powder is as follows: 75-150 μm, wherein the TiB content is 10 vol.%. The particle size distribution range of the aluminum powder is 20-30 mu m, and the particle size distribution range of the vanadium powder is 5-20 mu m. Ball milling and mixing by adopting a low-energy ball mill, wherein the preparation process of the mixed powder comprises the following steps: the mass ratio of the ball materials is 5: 1; adding isopropanol serving as a ball milling auxiliary agent, wherein the ball milling speed is 250 r/min; the ball milling time is 4h, and the milling ball is zirconia. And (3) putting the mixed slurry into a vacuum drying oven, and carrying out vacuum drying for 3h at 70 ℃ to obtain mixed powder.
And 2, filling the mixed powder obtained in the step 1 into a graphite die, and sintering and forming by adopting discharge plasma. The sintering process comprises the following steps: sintering by a three-step heat preservation method, namely firstly raising the temperature to 600 ℃ at the heating rate of 50 ℃/min, and preserving the temperature for 30 min; secondly, raising the temperature to 750 ℃ at the heating rate of 30 ℃/min, and preserving the heat for 20 min; finally, the temperature is raised to 1100 ℃ at the heating rate of 20 ℃/min, and the temperature is kept for 15 min. The pressure during sintering was 30 MPa. Finally obtaining the titanium alloy-based composite material with the micro-configuration.
The titanium alloy-based composite material with the micro-structure prepared by the invention is subjected to microstructure morphology analysis and mechanical property test. The prepared tissue and properties of the invention are as follows:
(1) the micro-structure of the titanium alloy-based composite material consists of whisker-shaped TiB and an alpha + beta type dual-phase titanium alloy matrix. Fig. 1 is a metallographic micrograph of the TiB reinforced titanium alloy based composite prepared in example 1. As can be seen from figure 1, the TiB whiskers are distributed in a pellet shape, the diameter of the pellets is distributed between 15 mu m and 200 mu m, the diameter of the pellets is equivalent to the particle diameter of the original TiB-Ti-based composite powder, the spacing between the pellets is 40 mu m to 60 mu m, and the substrate structure can be obviously seen to have a typical alpha + beta type dual-phase structure shape, so that the alloying process of a composite system can be effectively realized by adding aluminum elements and vanadium elements in the TiB-Ti composite powder in a powder metallurgy mode, the TiB whiskers are favorably distributed in the pellet shape, and the formation of the structure provides effective guarantee for the improvement of the mechanical property of the material.
(2) The titanium alloy-based composite material having the micro-configuration has isotropy. Fig. 2 is a schematic three-dimensional view formed by a macroscopic metallographic micrograph of the titanium alloy-based composite material of the present invention, and it can be seen from fig. 2 that TiB whiskers are uniformly distributed in a titanium alloy matrix in the form of micro-pellets to form a titanium alloy-based composite material having a micro-configuration.
(3) Fig. 3(a) is a metallographic micrograph of a single TiB pellet in the titanium alloy-based composite material with a microstructure prepared by the present invention, and it is measured that most of the TiB whiskers have aspect ratios ranging from 4 to 6, and fig. 3(b) is a metallographic micrograph of the TiB whiskers in the composite material prepared by the comparative example 2, wherein the aspect ratios of the TiB whiskers range from 9 to 12. As is apparent from comparing fig. 3(a) and (b), the addition of vanadium, which is an alloying element, in the present invention significantly affects the size of the TiB reinforcement and suppresses the coarsening behavior of the TiB whiskers at higher sintering temperatures, as compared to the single addition of Al element in comparative example 2.
(4) The titanium alloy-based composite material with the micro-structure has excellent mechanical property and greatly improved elongation. Fig. 3 shows stress-strain curves of the composite materials prepared in example 1, comparative example 1 and comparative example 2. As can be seen by comparison, the titanium alloy-based composite material having the microstructure had a maximum tensile strength of 1070MPa, a yield strength of 1026MPa, and an elongation of 11.9%. The titanium-based composite material (single alpha phase) with TiB in non-uniform distribution formed by adding the aluminum element has the maximum tensile strength of 980MPa, the yield strength of 927MPa and the elongation of 6.2 percent. The maximum tensile strength of the TiB reinforced titanium alloy-based composite material with uniform distribution is 961MPa, the yield strength is 950MPa, and the elongation is only 3.6%. Therefore, compared with the traditional titanium alloy-based composite material with TiB uniformly distributed, the titanium alloy-based composite material with the micro-structure has the advantages that the strength is improved, the elongation is greatly improved, and the titanium alloy-based composite material with good strong plasticity matching is obtained. The addition of the Al element effectively promotes the TiB whiskers to be distributed in a pellet shape, and the formation of the structure can play a role in improving the mechanical property, hardness, wear resistance and the like of the composite material; the addition of the vanadium alloy element promotes the matrix structure to be converted from a single alpha phase to an alpha + beta phase to form an alpha + beta type dual-phase titanium alloy matrix with high ductility and toughness, so that the material can effectively hinder the expansion of cracks in the pellets to the matrix under the loaded condition, and the purpose of improving the ductility and toughness of the composite material is realized. On the basis, compared with the method of adding Al element alone, the vanadium can affect the size distribution of the TiB whisker, inhibit the phenomenon that the TiB whisker is obviously coarsened at high temperature, and effectively exert the strengthening effect.
Compared with the TiB enhanced TMCs with the novel three-dimensional pellet composite configuration and the preparation method (application number: 2020112394480), the single alpha-phase matrix structure is converted into an alpha + beta double-phase structure by adding alpha-phase and beta-phase stable alloy elements into a composite system, and the obtained materials are obviously different in mechanism, structure and performance. The invention can play the following roles by adding alloy elements of aluminum and vanadium into a spherical TiB-Ti composite powder system:
(1) adding an alloy element vanadium: as a beta stable element, vanadium is added into a TiB-Ti composite powder system, alpha phase and beta phase with different proportions can be obtained in a matrix structure, which is beneficial to forming alpha + beta type dual-phase structure by the matrix, titanium alloy combining the advantages of single-phase alpha alloy (good weldability) and two-phase alloy (heat treatment strengthening and good plasticity and toughness) is obtained, and the characteristics of no eutectoid reaction and intermetallic compound generation in the Ti-V system are utilized, so that the plastic deformation capability of the composite material is greatly improved, and the exertion of the plasticity and toughness of the material is guaranteed. In addition, compared with the independent addition of aluminum element, the addition of vanadium alloy element can influence the size distribution of the TiB reinforcement, so that the coarsening phenomenon of the TiB whisker under the high-temperature sintering condition is effectively inhibited, the strengthening effect of the TiB reinforcement is fully exerted, and the improvement of the mechanical property of the titanium alloy matrix is guaranteed. This is an effect that is not achieved by the composite material of application No. 2020112394480.
(2) Adding an alloy element of aluminum: by utilizing the characteristic of low melting point (660 ℃) of aluminum and combining with higher sintering temperature (more than 1000 ℃) in the spark plasma sintering process of titanium and titanium alloy, the alloy element aluminum fills up gaps of the spherical TiB-Ti-based composite powder in the form of molten aluminum liquid in the sintering process, and by utilizing mutual diffusion between the alloy element aluminum and the spherical TiB-Ti-based composite powder, a titanium-aluminum intermetallic compound layer with a core-shell structure is formed on the surface of the spherical composite powder, so that TiB whiskers in the composite powder can be inhibited from diffusing and growing outwards, and the formation of a micro-configuration is ensured. At high temperature, the titanium-aluminum intermetallic compound layer is decomposed, and the aluminum element is completely dissolved in the matrix to form the titanium alloy matrix composite material with the micro-configuration.
The titanium alloy-based composite material with the micro-structure prepared by the invention can realize effective regulation and control of the structure, the size and the matrix structure of the micro-structure only by regulating the content of the added alloy elements and the particle size of the composite powder in a composite system. Compared with the DRTMCs with uniform distribution under the same TiB content, the titanium alloy-based composite material with the microstructure designed and prepared by the invention has greatly improved elongation while improving the material strength.
Claims (5)
1. The titanium alloy-based composite material with the micro-structure is characterized by comprising the following components in percentage by mass: 90-93 wt% of TiB-Ti-based composite powder, 6 wt% of aluminum powder and 1-4 wt% of vanadium powder, wherein the sum of the mass percentages of the components is 100%;
the composite powder has a TiB content of 1-10 vol.%.
2. The titanium alloy-based composite material with the micro-structure as recited in claim 1, wherein the vanadium powder is irregular in shape, and the particle size distribution range of the powder is 5 to 20 μm.
3. The titanium alloy-based composite material with the micro-structure as claimed in claim 1, wherein the titanium alloy-based composite material has a micro-structure, and the phase composition of the micro-structure comprises α + β type dual phase titanium alloy and TiB whiskers, wherein the TiB whiskers are uniformly distributed in a pellet-like structure, and the phase composition of the pellet outer layer structure comprises α + β type dual phase titanium alloy.
4. A preparation method of a titanium alloy-based composite material with a micro-structure is characterized by comprising the following steps:
step 1, respectively weighing 90 wt.% to 93 wt.% of TiB-Ti-based composite powder, 6 wt.% of aluminum powder and 1 wt.% to 4 wt.% of vanadium powder according to the mass percent, wherein the sum of the mass percent of the TiB-Ti-based composite powder, the aluminum powder and the vanadium powder is 100%, carrying out low-energy ball milling on the TiB-Ti-based composite powder, the aluminum powder and the vanadium powder to obtain mixed powder, wherein a ball-milling auxiliary agent is absolute ethyl alcohol or isopropanol, and the ball-to-material ratio is 2-10: 1; the ball milling speed is 200 r/min-250 r/min; the ball milling time is 2-4 h, and the milling ball is zirconia;
and 2, prepressing and molding the mixed powder obtained in the step 1 in a graphite mold, and sintering and densifying by adopting spark plasma sintering to obtain the titanium alloy-based composite material with the microstructure.
5. The method for preparing a titanium alloy-based composite material with a micro-structure according to claim 4, wherein the spark plasma sintering pressure in the step 2 is 30MPa, and the sintering process is sintering by a three-step heat preservation method: firstly, heating to 600 ℃, and preserving heat for 30 min; secondly, heating to 750 ℃, and preserving heat for 20 min; and finally, heating to 1100-1300 ℃, and preserving the heat for 5-60 min.
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| CN115747568A (en) * | 2022-11-01 | 2023-03-07 | 西安理工大学 | Three-dimensional pellet micro-configuration TiC reinforced titanium-based composite material and preparation method thereof |
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