CN102102156A - Multiphase particle enhanced powder metallurgical titanium-based composite material and preparation method thereof - Google Patents
Multiphase particle enhanced powder metallurgical titanium-based composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a multiphase particle enhanced powder metallurgical titanium-based composite material and a preparation method thereof. The material comprises three or more of titanium boride, titanium carbide, titanium silicide and titanium silicon carbide. The method comprises the following steps of: weighing titanium powder, boron carbide powder, silicon carbide powder and alloying element powder with certain granularity according to the weight percent ratio of components; uniformly mixing the powder by a mixing method; pressing into a blank with a certain shape by a compression molding process; putting the blank into a vacuum hot-pressing sintering furnace for sintering; and cooling with the furnace to obtain in-situ synthesized multiphase particle enhanced powder metallurgical titanium-based composite material. The process is simple, the boron carbide powder and the silicon carbide powder in different ratios are added during mixing, and the multiphase particle dispersion enhanced titanium-based composite material which comprises the titanium boride, the titanium carbide, the titanium silicide, the titanium silicon carbide and the like is generated through in-situ reaction. The material meets the requirements of aerospace, an advanced weapon system, an automobile engine and the like on high specific strength, high specific rigidity, wear resistance and corrosion resistance.
Description
Technical field
The present invention relates to a kind of powder metallurgy titanium matrix composite, relate to a kind of heterogeneous particle enhanced powder metallurgy titanium matrix composite specifically, the invention still further relates to this preparation methods.
Background technology
Granule intensified titanium-base compound material has in fields such as aerospace, sophisticated and futuristic weapons system and motor car engines widely and uses because of having high specific tenacity, specific modulus and high wear resisting property.But because the composite material strength height, resistance to deformation is big, makes its processing suffering, thereby has limited the application of granule intensified titanium-base compound material.
Powder metallurgy technology is a kind of nearly forming technique, avoids the tissue, the composition segregation that occur in the fusion casting production process, the problem that crystal grain is thick, and the granularity of particle wild phase and volume fraction can be adjusted in the larger context.But because of active high, the powder surface of titanium is easy to form oxide film, hinder its sintering densification, the development of powder metallurgy granule intensified titanium-base compound material and application are restricted.
The original position synthesis technique is a kind of method that obtains granule intensified titanium-base compound material, and the matrix material of this method preparation has been avoided more helping guaranteeing the performance of material at inner mutually cavity and the crackle of producing of particle.
Find by prior art documents, people such as Yu Lanlan are at " rare metal wall bulletin ", 2006,25 (4): 1-5, write articles " granule intensified titanium-base compound material research new development ", this article has been introduced Japanese Toyota company and has since nineteen ninety-eight been adopted powder metallurgy technology to prepare the TiB particle enhanced titanium matrix composite that in-situ particle generates, and has been applied on motor car engine.But this composite material by adopting is single TiB reinforced particulate, and therefore the composite property that obtains is single, and over-all properties is poor, has limited its application.
Summary of the invention
First technical problem to be solved by this invention provide a kind of strengthen the body kind many, distribute more evenly, strengthen the heterogeneous particle enhanced powder metallurgy titanium matrix composite that body combines with basal body interface better, over-all properties is more excellent.
Second technical problem to be solved by this invention provides a kind of preparation method of above-mentioned matrix material, and it is simple to have technology, and the titanium matrix composite of being produced has higher density, the quality product high comprehensive performance.
In order to solve above-mentioned first technical problem, heterogeneous particle enhanced powder metallurgy titanium matrix composite provided by the invention by component and weight percent is: B
4C 1%～20%, and SiC 1%～20%, alloy element 0%～11%, and all the other generate heterogeneous enhancing body particle for the powdered material of titanium by vacuum heating-press sintering, and described heterogeneous enhancing body particle comprises titanium boride (TiB or TiB
2), titanium carbide (TiC), titanium silicide (Ti
5Si
3), titanium silicon-carbon (Ti
3SiC
2) in more than three kinds or three kinds.
Described B
4C and SiC must add simultaneously, to obtain the heterogeneous reinforced particulate of different ratios.
Described alloy element is one or more of all titanium alloy elements.
Described titanium boride is TiB or TiB
2
In order to solve above-mentioned second technical problem, the method for the heterogeneous particle enhanced of preparation provided by the invention powder metallurgy titanium matrix composite is:
According to according to B
4C 1%～20%, SiC 1%～20%, alloy element 0%～11%, all the other take by weighing titanium valve for the weight percent of titanium, boron carbide powder, carborundum powder, the alloy element powder, adopt V-type machine or ball mill blending means that raw material powder is mixed, under the pressure of 300～600MPa, with the powder that mixes by die press technology for forming be pressed into have definite shape (as cylindrical, shapes such as cuboid, but shape does not have particular requirement) green compact, green compact are put into the vacuum heating-press sintering stove carry out sintering 2～8h at 1250～1650 ℃, vacuum tightness is 1 * 10
-1MPa～1 * 10
-3MPa, the mechanical pressure that is applied is 5～25Mpa, gets titanium boride, titanium carbide, titanium silicide, the heterogeneous particulate powder metallurgy of titanium silicon-carbon titanium matrix composite behind the furnace cooling.
Concrete preparation technology of the present invention comprises the steps:
Step 1: according to B
4C 1%～20%, and SiC 1%～20%, alloy element 0%～11%, and all the other take by weighing titanium valve, boron carbide powder, carborundum powder, alloy element powder for the weight percent of titanium;
Step 2: adopt V-type machine or ball mill that the powder mixes that step 1 takes by weighing is even;
Step 3: under the pressure of 300MPa～500MPa, adopt forming method to be pressed into green compact in the powder that mixes with predetermined profile;
Step 4: is 1 * 10 with prefabricated green compact in vacuum tightness
-1MPa～1 * 10
-3Under the MPa, temperature is sintering in the vacuum heating-press sintering stove that 1250～1650 ℃, sintering time are 2～8h, the mechanical pressure that applied is 5～25MPa, what obtain that disperse distributes contains heterogeneous particle enhanced powder metallurgy titanium matrix composites such as titanium boride, titanium carbide, titanium silicide, titanium silicon-carbon.
Compared with prior art, the present invention uses the vacuum heating-press sintering method under the situation that does not change traditional powder metallurgy preparation technology and equipment, improves the density of sintered titanium based composites, reduces the hole quantity in the sintered titanium based composites.By boron carbide powder and the carborundum powder that adds different ratios simultaneously, heterogeneous particles such as the titanium boride that the disperse that reaction in generation volume fraction is different distributes, titanium carbide, titanium silicide, titanium silicon-carbon, further improve the mechanical property of sintered titanium based composites, thereby obtain the comparatively good powder metallurgy titanium matrix composite of over-all properties.The ultimate compression strength of sintered compact alloy reaches 2100MPa, and density reaches 99.8%.
The advantage of this technology is by boron carbide powder that adds different ratios simultaneously and carborundum powder, and the powder metallurgical technique of employing vacuum heating-press sintering, obtain the heterogeneous particle enhanced of the in-situ authigenic powder metallurgy titanium matrix composite product of high densification and high comprehensive performance, satisfy the requirement of actual industrial production.
Reaction in of the present invention obtains containing titanium boride (TiB or TiB
2), titanium carbide (TiC), titanium silicide (Ti
5Si
3), titanium silicon-carbon (Ti
3SiC
2) wait heterogeneous particle enhanced titanium matrix composite, traditional powder metallurgy process is combined with the reaction in technology, utilize the reaction between titanium valve, norbide, silicon carbide and the alloy element powder, simple and fast, cheaply prepare strengthen body kind many (more than three kinds or three kinds), distribute more evenly, the enhancing composite element that body combines with basal body interface better, over-all properties is more excellent, be applicable to the member that aerospace, sophisticated and futuristic weapons system and automotive industry etc. need, but this method suitability for industrialized production.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is to implement under the prerequisite in following technical solution of the present invention, has provided detailed embodiment and specific operation process.
The comparative example 1:
Prepared composition is Ti-5Al-4Mo-4V (massfraction) a powder metallurgy titanium alloy down together.Raw materials used is-100 order titanium valves ,-300 order aluminium powders ,-200 order molybdenum powders ,-150 order A1-58V master alloyed powders.Take by weighing raw material powder according to alloy proportion, raw material powder powder ball milling on ball mill mixes, and is molded into green compact then under the pressure of 300MPa, green compact is put into vacuum sintering furnace carry out high temperature sintering, and vacuum degree control is 1 * 10
-3MPa, sintering temperature is 1250 ℃, sintering time 6h.The incompressible intensity of the heterogeneous particle enhanced powder metallurgy titanium matrix composite of gained is 1210MPa, and the density that the drainage test obtains sintered compact is 91%.
Provide following examples in conjunction with method of the present invention:
Embodiment 1:
Be prepared into heterogeneous particle enhanced (TiB
2+ TiC+Ti
3SiC
2)/Ti matrix material, starting material adopt titanium valve, boron carbide powder and carborundum powder, according to weight percent Ti: B
4C: SiC=98: take by weighing raw material powder at 1: 1.Raw material powder powder ball milling on ball mill mixes, and is molded into green compact then under the pressure of 300MPa, green compact is put into the vacuum heating-press sintering stove carry out high temperature sintering, and vacuum degree control is 1 * 10
-1MPa, sintering temperature is 1350 ℃, sintering time 8h, institute's applied pressure is 5MPa.The incompressible intensity of the heterogeneous particle enhanced powder metallurgy titanium matrix composite of gained is 1950MPa, and the density that the drainage test obtains sintered compact is 98.5%.
Embodiment 2:
Be prepared into heterogeneous particle enhanced (TiB
2+ TiC+Ti
5Si
3)/Ti matrix material, starting material adopt titanium valve, boron carbide powder and carborundum powder, according to weight percent Ti: B
4C: SiC=89: take by weighing raw material powder at 10: 1.Raw material powder powder ball milling on ball mill mixes, and is molded into green compact then under the pressure of 450MPa, green compact is put into the vacuum heating-press sintering stove carry out high temperature sintering, and vacuum degree control is 1 * 10
-2MPa, sintering temperature is 1450 ℃, sintering time 2h, institute's applied pressure is 15MPa.The incompressible intensity of the heterogeneous particle enhanced powder metallurgy titanium matrix composite of gained is 1820MPa, and the density that the drainage test obtains sintered compact is 99.3%.
Embodiment 3:
Be prepared into heterogeneous particle enhanced (TiB
2+ TiC+Ti
3SiC
2+ Ti
5Si
3)/Ti matrix material, starting material adopt titanium valve, boron carbide powder and carborundum powder, according to weight percent Ti: B
4C: SiC=89: take by weighing raw material powder at 1: 10.Raw material powder powder ball milling on ball mill mixes, and is molded into green compact then under the pressure of 600MPa, green compact is put into the vacuum heating-press sintering stove carry out high temperature sintering, and vacuum degree control is 1 * 10
-3MPa, sintering temperature is 1650, sintering time 8h, institute's applied pressure is 15MPa.The incompressible intensity of the heterogeneous particle enhanced powder metallurgy titanium matrix composite of gained is 2010MPa, and the density that the drainage test obtains sintered compact is 99.7%.
Embodiment 4:
Be prepared into heterogeneous particle enhanced (TiB+TiB
2+ TiC+Ti
3SiC
2+ Ti
5Si
3)/Ti-5Al-4Mo-4V matrix material, starting material adopt titanium valve, aluminium powder, molybdenum powder, aluminum-vanadium alloy powder, boron carbide powder and carborundum powder, according to weight percent (Ti-5Al-4Mo-4V): B
4C: SiC=79: take by weighing raw material powder at 20: 1.Raw material powder powder ball milling on ball mill mixes, and is molded into green compact then under the pressure of 300MPa, green compact is put into the vacuum heating-press sintering stove carry out high temperature sintering, and vacuum degree control is 1 * 10
-1MPa, sintering temperature is 1350, sintering time 4h, institute's applied pressure is 25MPa.The incompressible intensity of the heterogeneous particle enhanced powder metallurgy titanium matrix composite of gained is 2050MPa, and the density that the drainage test obtains sintered compact is 99.6%.
Embodiment 5:
Be prepared into heterogeneous particle enhanced (TiB
2+ TiC+Ti
3SiC
2+ Ti
5Si
3)/Ti-5Al-4Mo-4V-2.5Ta matrix material, starting material adopt titanium valve, aluminium powder, molybdenum powder, aluminum-vanadium alloy powder, tantalum powder, boron carbide powder and carborundum powder, according to weight percent (Ti-5Al-4Mo-4V-5Ta): B
4C: SiC=75: take by weighing raw material powder at 5: 20.The raw material powder powder mixes on the V-type machine, is molded into green compact then under the pressure of 450MPa, green compact is put into the vacuum heating-press sintering stove carry out high temperature sintering, and vacuum degree control is 1 * 10
-3MPa, sintering temperature is 1450, sintering time 4h, institute's applied pressure is 5MPa.The incompressible intensity of the heterogeneous particle enhanced powder metallurgy titanium matrix composite of gained is 1965MPa, and the density that the drainage test obtains sintered compact is 99.2%.
Embodiment 6:
Be prepared into heterogeneous enhancing body particle enhanced (TiB+TiB
2+ TiC+Ti
3SiC
2+ Ti
5Si
3)/Ti-5Al-4Mo-4V-2Nb matrix material, starting material adopt titanium valve, aluminium powder, molybdenum powder, aluminum-vanadium alloy powder, niobium powder, boron carbide powder and carborundum powder, according to weight percent (Ti-5Al-4Mo-4V-2Nb): B
4C: SiC=80: take by weighing raw material powder at 10: 10.The raw material powder powder mixes on the V-type machine, is molded into green compact then under the pressure of 600MPa, green compact is put into the vacuum heating-press sintering stove carry out high temperature sintering, and vacuum degree control is 1 * 10
-3MPa, sintering temperature is 1250 ℃, sintering time 8h, institute's applied pressure is 25MPa.The incompressible intensity of the heterogeneous particle enhanced powder metallurgy titanium matrix composite of gained is 2103MPa, and the density that the drainage test obtains sintered compact is 99.7%.
Embodiment 7:
Be prepared into heterogeneous particle enhanced (TiB+TiB
2+ TiC+Ti
3SiC
2+ Ti
5Si
3)/Ti-5Al-4Mo-4V-5Ag matrix material, starting material adopt titanium valve, aluminium powder, molybdenum powder, aluminum-vanadium alloy powder, niobium powder, boron carbide powder and carborundum powder, according to weight percent (Ti-5Al-4Mo-4V-5Ag): B
4C: SiC=80: take by weighing raw material powder at 10: 10.The raw material powder powder mixes on the V-type machine, is molded into green compact then under the pressure of 600MPa, green compact is put into the vacuum heating-press sintering stove carry out high temperature sintering, and vacuum degree control is 1 * 10
-3MPa, sintering temperature is 1650, sintering time 2h, institute's applied pressure is 25MPa.The incompressible intensity of the heterogeneous particle enhanced powder metallurgy titanium matrix composite of gained is 2015MPa, and the density that the drainage test obtains sintered compact is 99.9%.
Embodiment 8:
Be prepared into heterogeneous particle enhanced (TiB
2+ TiC+Ti
3SiC
2)/Ti-5Al-4V matrix material, starting material adopt titanium valve, aluminium powder, aluminum-vanadium alloy powder, boron carbide powder and carborundum powder, according to weight percent (Ti-5Al-4V): B
4C: SiC=80: take by weighing raw material powder at 10: 10.Raw material powder powder ball milling on ball mill mixes, and is molded into green compact then under the pressure of 300MPa, green compact is put into the vacuum heating-press sintering stove carry out high temperature sintering, and vacuum degree control is 1 * 10
-3MPa, sintering temperature is 1350, sintering time 8h, institute's applied pressure is 25MPa.The incompressible intensity of the heterogeneous particle enhanced powder metallurgy titanium matrix composite of gained is 1916MPa, and the density that the drainage test obtains sintered compact is 99.4%.
Embodiment 9:
Be prepared into heterogeneous particle enhanced (TiB+TiB
2+ TiC+Ti
3SiC
2)/Ti-5Al-4Mo matrix material, starting material adopt titanium valve, aluminium powder, molybdenum powder, boron carbide powder and carborundum powder, according to weight percent (Ti-5Al-4Mo): B
4C: SiC=75: take by weighing raw material powder at 20: 5.Raw material powder powder ball milling on ball mill mixes, and is molded into green compact then under the pressure of 600MPa, green compact is put into the vacuum heating-press sintering stove carry out high temperature sintering, and vacuum degree control is 1 * 10
-3MPa, sintering temperature is 1650, sintering time 8h, institute's applied pressure is 20MPa.The incompressible intensity of the heterogeneous particle enhanced powder metallurgy titanium matrix composite of gained is 2100MPa, and the density that the drainage test obtains sintered compact is 99.3%.
Embodiment 10:
Be prepared into heterogeneous particle enhanced (TiB+TiB
2+ TiC+Ti
3SiC
2)/Ti-15Mo-5Zr-3Al matrix material, starting material adopt titanium valve, aluminium powder, molybdenum powder, zirconium powder, boron carbide powder and carborundum powder, according to weight percent (Ti-15Mo-5Zr-3A1): B
4C: SiC=75: take by weighing raw material powder at 20: 5.Raw material powder powder ball milling on ball mill mixes, and is molded into green compact then under the pressure of 500MPa, green compact is put into the vacuum heating-press sintering stove carry out high temperature sintering, and vacuum degree control is 1 * 10
-3MPa, sintering temperature is 1500 ℃, sintering time 6h, institute's applied pressure is 25MPa.The incompressible intensity of the heterogeneous particle enhanced powder metallurgy titanium matrix composite of gained is 2000MPa, and the density that the drainage test obtains sintered compact is 99.5%.
Embodiment 11:
Be prepared into heterogeneous particle enhanced (TiB
2+ TiC+Ti
3SiC
2)/Ti-7Mo-4Fe matrix material, starting material adopt titanium valve, iron powder, molybdenum powder, boron carbide powder and carborundum powder, according to weight percent (Ti-7Mo-4Fe): B
4C: SiC=80: take by weighing raw material powder at 10: 10.Raw material powder powder ball milling on ball mill mixes, and is molded into green compact then under the pressure of 400MPa, green compact is put into the vacuum heating-press sintering stove carry out high temperature sintering, and vacuum degree control is 1 * 10
-2MPa, sintering temperature is 1450 ℃, sintering time 4h, institute's applied pressure is 15MPa.The incompressible intensity of the heterogeneous particle enhanced powder metallurgy titanium matrix composite of gained is 1874MPa, and the density that the drainage test obtains sintered compact is 99.1%.
Claims (7)
1. heterogeneous particle enhanced powder metallurgy titanium matrix composite by component and weight percent is: B
4C 1%～20%, SiC 1%～20%, alloy element 0%～11%, all the other generate heterogeneous enhancing body particle for the powdered material of titanium by vacuum heating-press sintering, it is characterized in that: described heterogeneous enhancing body particle comprise in titanium boride, titanium carbide, titanium silicide, the titanium silicon-carbon more than three kinds or three kinds.
2. heterogeneous particle enhanced powder metallurgy titanium matrix composite according to claim 1 is characterized in that: described B
4C and SiC must add simultaneously, to obtain the heterogeneous reinforced particulate of different ratios.
3. heterogeneous particle enhanced powder metallurgy titanium matrix composite according to claim 1, it is characterized in that: described alloy element is one or more of all titanium alloy elements.
4. heterogeneous particle enhanced powder metallurgy titanium matrix composite according to claim 1, it is characterized in that: described titanium boride is TiB or TiB
2
5. prepare the method for the described heterogeneous particle enhanced powder metallurgy titanium matrix composite of claim 1, it is characterized in that: comprise the steps:
Step 1: according to B
4C 1%～20%, and SiC 1%～20%, alloy element 0%～11%, and all the other take by weighing titanium valve, boron carbide powder, carborundum powder, alloy element powder for the weight percent of titanium;
Step 2: adopt hybrid system that the powder mixes that step 1 takes by weighing is even;
Step 3: adopt forming method to be pressed into green compact in the powder that mixes in the step 2 with predetermined profile;
Step 4: prefabricated green compact are placed on sintering in the vacuum heating-press sintering stove, and vacuum tightness is 1 * 10
-1MPa～1 * 10
-3MPa, the mechanical pressure that is applied is 5～25Mpa, and sintering temperature is 1250～1650 ℃, and sintering time is 2～8h, must contain the heterogeneous particle enhanced powder metallurgy titanium matrix composite of titanium boride, titanium carbide, titanium silicide, titanium silicon-carbon behind the furnace cooling.
6. the method for the heterogeneous particle enhanced of preparation according to claim 5 powder metallurgy titanium matrix composite is characterized in that: described hybrid system adopts V-type machine or ball mill to mix.
7. the method for the heterogeneous particle enhanced of preparation according to claim 5 powder metallurgy titanium matrix composite, it is characterized in that: the molding pressure of described forming method is 300～600MPa.
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Cited By (9)
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| CN103334045A (en) * | 2013-06-07 | 2013-10-02 | 昆明理工大学 | Laser combustion synthesized TiN-enhanced titanium-based composite material and method thereof |
| WO2017190246A1 (en) * | 2016-05-04 | 2017-11-09 | Lumiant Corporation | Titanium silicide matrix composite with in situ formed titanium carbide reinforcement |
| CN109735743A (en) * | 2019-03-22 | 2019-05-10 | 上海材料研究所 | A kind of titanium alloy composite material and preparation method thereof, laser gain material are manufactured method |
| CN110205520A (en) * | 2019-05-13 | 2019-09-06 | 湖南工业大学 | A kind of high-speed heavy-load trains brake disc ceramics enhancing titanium alloy material |
| CN110923506A (en) * | 2019-12-13 | 2020-03-27 | 陕西易莱德新材料科技有限公司 | High-ductility titanium alloy material and preparation method thereof |
| CN113699426A (en) * | 2021-08-20 | 2021-11-26 | 中国兵器科学研究院宁波分院 | Titanium-based composite material and preparation method thereof |
| CN113843419A (en) * | 2021-09-04 | 2021-12-28 | 安徽中科春谷激光产业技术研究院有限公司 | Selective laser melting preparation in-situ generated TiC + Ti3SiC2Method for reinforcing titanium-based composite material |
| CN115044792A (en) * | 2022-05-09 | 2022-09-13 | 哈尔滨工业大学 | Particle-reinforced titanium-based composite material and preparation method thereof |
| CN115505787A (en) * | 2022-09-30 | 2022-12-23 | 中国航发北京航空材料研究院 | Light high-temperature-resistant titanium-based multi-principal-element composite material |
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| CN103334045A (en) * | 2013-06-07 | 2013-10-02 | 昆明理工大学 | Laser combustion synthesized TiN-enhanced titanium-based composite material and method thereof |
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| CN113843419A (en) * | 2021-09-04 | 2021-12-28 | 安徽中科春谷激光产业技术研究院有限公司 | Selective laser melting preparation in-situ generated TiC + Ti3SiC2Method for reinforcing titanium-based composite material |
| CN115044792A (en) * | 2022-05-09 | 2022-09-13 | 哈尔滨工业大学 | Particle-reinforced titanium-based composite material and preparation method thereof |
| CN115044792B (en) * | 2022-05-09 | 2022-12-20 | 哈尔滨工业大学 | Particle-reinforced titanium-based composite material and preparation method thereof |
| CN115505787A (en) * | 2022-09-30 | 2022-12-23 | 中国航发北京航空材料研究院 | Light high-temperature-resistant titanium-based multi-principal-element composite material |
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