CN104404403A - Continuous fiber-reinforced titanium-based composite material and preparation method thereof - Google Patents
Continuous fiber-reinforced titanium-based composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a continuous fiber-reinforced titanium-based composite material and a preparation method thereof. The preparation method of the composite material comprises the following steps: taking aluminum or aluminum alloy, and titanium or titanium alloy as target materials, taking continuous SiC fibers as a reinforcement body, performing magnetron sputtering to manufacture titanium-titanium aluminum composite hybrid precursor fibers depositing titanium aluminum mixing coatings and titanium or titanium alloy coatings on the continuous SiC fibers; winding and paving the precursor fibers, and placing the precursor fibers in a titanium alloy matrix structure, performing the hot pressing or the hot isostatic pressure compositing to obtain the continuous fiber-reinforced titanium-based composite material. The invention also provides the continuous fiber-reinforced titanium-based composite material prepared by the preparation method provided by the invention. The continuous fiber-reinforced titanium-based composite material based on the titanium-titanium aluminum composite hybrid precursor fibers can integrate the advantages of titanium alloy and a titanium aluminum intermetallic compound, and has higher specific strength and specific stiffness, higher high temperature resistance, creepage resistance, oxidation resistance and corrosion resistance, and lower manufacturing cost.
Description
Technical field
The present invention relates to a kind of continuous fiber reinforcing titanium matrix composite and preparation method thereof, belong to metal composite technical field.
Background technology
Along with improving constantly of aircraft engine thrust-weight ratio, more and more higher requirement is proposed to the structured material of engine, the particularly thrust-weight ratio aircraft engine that is greater than 12, require that its structured material has higher specific tenacity, specific rigidity, more excellent high-temperature behavior (hot strength, creep resistance), higher anti-oxidant, corrosion resistance.Existing nickel base superalloy is close to its ultimate-use temperature, and density is too high, more and more can not meet the requirement of high thrust-weight ratio engine to structured material.Continuous SiC fiber strengthens titanium matrix composite and has higher specific tenacity and specific rigidity, higher high temperature resistant and creep resistance, oxidation resistant ability, while loss of weight, greatly can improve the overall performance of engine, therefore become the candidate material of high thrust-weight ratio aircraft engine most with prospects.
At present, the preparation method that continuous SiC fiber strengthens titanium matrix composite has a lot, mainly comprises paper tinsel-fiber-paper tinsel method, powder cloth method, pressure casting method, plasma spraying method, basal body coating layer method etc.
Basal body coating layer method makes the evaporation of metal such as titanium aluminum alloy and be deposited on fiber to form prefabricated precursor wire by the method (method such as magnetron sputtering, electron beam) of physical heating, vapour deposition, then the fiber of band coating is wound around by certain way or arranges and form prefabricated reinforcement and insert the metallic matrix inside such as titanium alloy, through hot pressing or hip moulding.Its advantage of the method be Fiber Distribution evenly, volume fraction is easy to control, and can control the surface reaction of fiber and matrix, can near-net-shape, be easy to the component preparing complicated shape; High microsteping percentage ratio, high performance matrix material can be prepared, but the cost of the method is high, efficiency is low, material use efficiency low (even lower than 1%), need special depositing device, therefore, be generally applicable to the key structure part preparing high-performance, high cost.
As the vitals of aviation field, be all generally adopt basal body coating layer method to strengthen titanium matrix composite to prepare continuous SiC fiber.In basal body coating layer method, compared with electro beam physics vapour deposition (EB-PVD) method, magnetron sputtering physical vapor deposition (MS-PVD) is although method efficiency is lower than electro beam physics vapour deposition, but the material chemical composition and the matrix target consistence that are deposited on SiC fiber surface are good, and coating uniform, be more suitable for preparing the key parts such as engine rotor part.Therefore, the High Performance Aeroengine rotor part of SiC fiber reinforced titanium matrix composite all have employed the preparation method based on magnetron sputtering, but SiC precursor wire is wherein all titanium alloy or the Intermatallic Ti-Al compound of single coating.
The continuous SiC fiber prepared by the SiC precursor wire of single titanium alloy coating strengthens the continuous SiC fiber enhancing titanium matrix composite that titanium composite material is prepared relative to the SiC precursor wire by single Intermatallic Ti-Al compound coating, it is high temperature resistant and creep resisting ability has obvious deficiency, but in resistance to crack extension ability etc., have deficiency because the intrinsic fragility of Intermatallic Ti-Al compound makes again the continuous SiC fiber prepared by the SiC precursor wire of single Intermatallic Ti-Al compound coating strengthen titanium matrix composite, and its preparation temperature is also high.
Summary of the invention
In view of the defect that above-mentioned prior art exists, the object of the invention is to propose a kind of continuous fiber reinforcing titanium matrix composite, precursor wire is mixed based on titanium-titanium aluminium compound, can the advantage of comprehensively titanium alloy and Intermatallic Ti-Al compound, there is higher specific tenacity and specific rigidity, higher high temperature resistant, creep resistance, anti-oxidant and corrosion resistant ability.
The present invention also aims to the preparation method that above-mentioned continuous fiber reinforcing titanium matrix composite is provided.
Object of the present invention is achieved by the following technical programs:
A kind of preparation method of continuous fiber reinforcing titanium matrix composite, it comprises with aluminum or aluminum alloy, titanium or titanium alloy for target, continuous SiC fiber is reinforcement, titanium-titanium aluminium compound that magnetron sputtering is made into titanium deposition aluminium mixed coating and titanium or titanium alloy coating on continuous SiC fiber mixes precursor wire, then this precursor wire be wound around or arrange and insert in titanium alloy substrate structure, obtaining the step of continuous fiber reinforcing titanium matrix composite through hot pressing or hot isostatic pressing compound.
In the preparation method of above-mentioned continuous fiber reinforcing titanium matrix composite, the alloy of aluminium alloy or titanium alloy is the metal of the various trades mark that magnetron sputtering can sputter.
In the preparation method of above-mentioned continuous fiber reinforcing titanium matrix composite, preferably, the method comprises the steps:
Titanium-titanium aluminium compound mixes the preparation of precursor wire:
The titanium of cleaning or titanium alloy target and aluminum or aluminum alloy target are installed, obtaining two planar targets to symmetry, is a pair titanium target or titanium alloy target, pair of aluminum target or aluminium alloy target respectively;
By the SiC Filament-wound Machine of cleaning on the special mouse cage frame of magnetron sputtering equipment, and insert in magnetron sputtering working spaces;
Adopt titanium target or titanium alloy target, aluminium target or aluminium alloy target, sputtering is opened than simultaneously according to setting power, SiC fiber realizes the mixing splash coating of titanium deposition or titanium alloy, aluminum or aluminum alloy, and then deposit one deck titanium or titanium alloy coating, obtain titanium-titanium aluminium compound and mix precursor wire;
The preparation of continuous fiber reinforcing titanium matrix composite:
Titanium-titanium aluminium compound is mixed precursor wire to prepare in the mode of solid matter stacking and become prefabricated reinforcement, be then placed in metal thin-wall jacket, through vacuum stripping and vacuum seal, then carry out hot isostatic pressing and obtain continuous fiber reinforcing titanium matrix composite.
In the preparation method of above-mentioned continuous fiber reinforcing titanium matrix composite, mixing splash coating refers to: when adopting titanium target and aluminium target, opens sputtering, the mixed coating of titanium deposition and aluminium on SiC fiber; When adopting titanium alloy target and aluminium alloy target, open sputtering, the mixed coating of deposited titanium alloys and aluminium alloy on SiC fiber; Same, also can be the mixed coating of titanium and aluminium alloy or the mixed coating of titanium alloy and aluminium.
In the preparation method of above-mentioned continuous fiber reinforcing titanium matrix composite, titanium-titanium aluminium compound mixes precursor wire and prepares in the mode of solid matter stacking and become prefabricated reinforcement, insert in metal thin-wall jacket, reaction in－situ is there is under hot isostatic pressing (also can be hot pressing), and make aluminium wherein be reacted approach exhaustion formation Intermatallic Ti-Al compound, and retained part titanium or titanium alloy, thus prepare the titanium matrix composite that there is built-in titanium-Intermatallic Ti-Al compound and mix prefabricated reinforcement, make it have continuous SiC fiber and strengthen the comprehensive advantage that single titanium matrix composite and continuous SiC fiber strengthen single Intermatallic Ti-Al compound based composites, and overcome owing to adopting titanium aluminium target directly to sputter, some problems that diffusion consolidation produces.
In the preparation method of above-mentioned continuous fiber reinforcing titanium matrix composite, special mouse cage frame refers to the special mouse cage frame in magnetron sputtering equipment, also can with other equipment replacements.
In the preparation method of above-mentioned continuous fiber reinforcing titanium matrix composite, the temperature of described hot isostatic pressing is 900 DEG C-1000 DEG C, and pressure is 100MPa-170MPa, and the time is 1h-4h.
According to specific embodiments, the temperature of described hot isostatic pressing is 950 DEG C, and pressure is 170MPa, and the time is 3h.
In the preparation method of above-mentioned continuous fiber reinforcing titanium matrix composite, preferably, the acceleration voltage of described sputtering is 200-400V, and operating air pressure is 0.1-2Pa, and current density is 3-9mA/cm
2, power density is 0.6-3.6W/cm
2, argon flow amount is 25-75sccm.
In the preparation method of above-mentioned continuous fiber reinforcing titanium matrix composite, preferably, described setting power is than being titanium target or titanium alloy target: aluminium target or aluminium alloy target=1: (0.35-1).
In the preparation method of above-mentioned continuous fiber reinforcing titanium matrix composite, preferably, SiC fiber is obtained by acetone cleaning and washes of absolute alcohol by the SiC fiber of described cleaning successively.
In the preparation method of above-mentioned continuous fiber reinforcing titanium matrix composite, preferably, the titanium target of described cleaning or titanium alloy target and aluminium target or aluminium alloy target are prepared by following method:
Titanium target or titanium alloy target are carried out pickling, aluminium target or aluminium alloy target are carried out alkali cleaning, obtain titanium target or titanium alloy target, aluminium target or the aluminium alloy target of surperficial impurity elimination;
The titanium target of surperficial impurity elimination or titanium alloy target, aluminium target or aluminium alloy target are carried out ultrasonic cleaning respectively successively in acetone, dehydrated alcohol, obtains clean titanium target or titanium alloy target, aluminium target or aluminium alloy target.
In the preparation method of above-mentioned continuous fiber reinforcing titanium matrix composite, namely described titanium alloy-based body structure is metal thin-wall jacket; Preferably, described metal thin-wall jacket comprises titanium alloy jacket, but is not limited thereto.
In the preparation method of above-mentioned continuous fiber reinforcing titanium matrix composite, preferably, the method also comprises and carries out pickling, acetone cleaning and the step of washes of absolute alcohol successively to metal thin-wall jacket.
In the preparation method of above-mentioned continuous fiber reinforcing titanium matrix composite, pickling or alkali cleaning can remove surface impurity, and acetone can wipe oil etc., and dehydrated alcohol can remove acetone residue.
According to specific embodiments, the acid that pickling adopts is HF and HNO
3mixing solutions, alkali cleaning alkali used is NaOH solution.
The continuous fiber reinforcing titanium matrix composite (namely continuous SiC fiber strengthens titanium-Intermatallic Ti-Al compound based composites) that the present invention also provides the preparation method of above-mentioned continuous fiber reinforcing titanium matrix composite to prepare.
The present invention is directed to the deficiency that continuous SiC fiber prepared by the SiC precursor wire that formed by the titanium alloy of single coating or Intermatallic Ti-Al compound strengthens titanium matrix composite to improve, prepare a kind of continuous fiber reinforcing titanium matrix composite mixing precursor wire based on titanium-titanium aluminium compound.This matrix material improves the high temperature strength, creep resisting ability etc. of material by Intermatallic Ti-Al compound, the toughening effect to Intermatallic Ti-Al compound is realized mutually again by the titanium toughness of titanium alloy, improve its intrinsic fragility to improve the performances such as resistance to crack extension ability, realize the mutual supplement with each other's advantages of two kinds of materials.
Because SiC fiber precursor wire composition is determined, be difficult to need to adjust Matrix Composition according to design, simultaneously, because titanium alloy is different with Intermatallic Ti-Al compound diffusion consolidation temperature, if according to the diffusion temperature of titanium alloy, bonding interface can be caused to occur the problems such as defect, if according to Intermatallic Ti-Al compound diffusion temperature, the transformation temperature exceeding titanium alloy can be caused to make it organize change and affect the performance of matrix material.So method of the present invention changes the method for the direct diffusion consolidation in existing technique, formed the mixed deposit of Intermatallic Ti-Al compound and titanium by the method for reaction in－situ.
In addition, Intermatallic Ti-Al compound target is high compared with aluminium alloy target cost, and the titanium alloy that the present invention uses and aluminium alloy preparation of target materials Intermatallic Ti-Al compound can effectively reduce costs.
Outstanding effect of the present invention is:
The continuous fiber reinforcing titanium matrix composite mixing precursor wire based on titanium-titanium aluminium compound of the present invention, can the advantage of comprehensively titanium alloy and Intermatallic Ti-Al compound, there is higher specific tenacity and specific rigidity, higher high temperature resistant, creep resistance, anti-oxidant and corrosion resistant ability, and manufacturing cost is lower.
Accompanying drawing explanation
Fig. 1 a is the microstructure morphology figure (macrostructure) in the transverse section of the continuous fiber reinforcing titanium matrix composite of embodiment gained;
Fig. 1 b is the microstructure morphology figure (mirco structure) in the transverse section of the continuous fiber reinforcing titanium matrix composite of embodiment gained;
Fig. 2 is the continuous fiber reinforcing titanium matrix composite position A of embodiment gained and the XRD figure of position B;
Fig. 3 a is the energy spectrum analysis figure of the continuous fiber reinforcing titanium matrix composite position A of embodiment gained;
Fig. 3 b is the energy spectrum analysis figure of the continuous fiber reinforcing titanium matrix composite position B of embodiment gained;
Fig. 4 is continuous fiber reinforcing titanium matrix composite position A and the position B titanium aluminum binary phasor of embodiment gained.
Embodiment
Below by specific embodiment, method of the present invention is described, be easier to make technical solution of the present invention understand, grasp, but the present invention is not limited thereto.Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment
The present embodiment provides a kind of continuous fiber reinforcing titanium matrix composite, and it is prepared by following method:
Titanium-titanium aluminium compound mixes the preparation of precursor wire:
Titanium alloy target is placed in acid solution (with volume basis, HF:HNO
3: H
2o=5:30:65) pickling 30min in, aluminium alloy target is placed in the NaOH solution alkali cleaning 30min that concentration is 10%, removes surface impurity.Then, by the target after pickling and SiC fiber, be first placed in acetone ultrasonic cleaning 30min, wipe oil, then be placed in dehydrated alcohol ultrasonic cleaning 30min, remove acetone, obtain clean SiC fiber, titanium alloy target and aluminium alloy target.
The titanium alloy target of cleaning and aluminium alloy target are installed, obtaining two planar targets to symmetry, is a pair titanium alloy target, pair of aluminum alloy target material respectively;
By the SiC Filament-wound Machine of cleaning on the special mouse cage frame of magnetron sputtering equipment, and insert in magnetron sputtering working spaces;
Open magnetron sputtering with setting power than simultaneously, the mixing splash coating of deposited titanium alloys and aluminium alloy on SiC fiber, then continue to deposit one deck titanium alloy coating on mixing splash coating, obtain titanium-titanium aluminium compound and mix precursor wire; Wherein, the parameter setting of setting power when magnetron sputtering is as shown in table 1;
The preparation of continuous fiber reinforcing titanium matrix composite:
Titanium alloy jacket is placed in acid solution (with volume basis, HF:HNO
3: H
2o=5:30:65) pickling 2h in, remove surface impurity, be then placed in acetone, ultrasonic cleaning 30min, removes grease, then is placed in dehydrated alcohol, and ultrasonic cleaning 30min, removes acetone, obtains clean titanium alloy jacket.
Titanium-titanium aluminium compound is mixed precursor wire to prepare in the mode of solid matter stacking and become prefabricated reinforcement, be then placed in clean titanium alloy jacket, vacuumize, reach vacuum tightness≤10
-3pa, carries out soldering and sealing, then titanium alloy jacket good for soldering and sealing is placed in hot isostatic pressing stove, 950 DEG C, under the condition of 170MPa, hot isostatic pressing 3h, obtains continuous fiber reinforcing titanium matrix composite.
Table 1
By the continuous fiber reinforcing titanium matrix composite obtained, turnery processing, measures.The transverse section obtaining continuous fiber reinforcing titanium matrix composite is observed, its microstructure morphology as shown in Figure 1 a, 1 b, the mode that its SiC fiber is arranged with six sides is uniformly distributed, volume fraction reaches 64%, fiber is combined well with basal body interface and body material, there is not the defect such as cavity, crackle.Simultaneously, the microstructure of matrix presents two kinds of different patterns, by to the energy spectrum analysis of position A, B and XRD analysis (XRD figure spectrum as shown in Figure 2, energy spectrum analysis as shown in Figure 3 a, 3 b), and bonding titanium aluminum binary phasor (as shown in Figure 4), obtain coordinating of position A and be divided into Ti
3al, position B are TiAl.
The room temperature strength that SiC fiber reinforcement titanium-titanium aluminium that the present embodiment obtains mixes matrix composite reaches 1400MPa, the intensity of 600 DEG C reaches 800MPa, 17.2% is improve compared with the room temperature unit elongation of conventional titanium aluminum matrix material, improve 8.1% compared with conventional Titanium base material at high temperature specific tenacity, improve 100 DEG C than the heat resisting temperature of conventional titanium alloy substrate material.
As can be seen here, the present invention adds the preparation method of heat and other static pressuring processes by mixing magnetron sputtering, utilize titanium aluminium reaction in－situ can prepare the continuous fiber reinforcing titanium-titanium aluminium mixing precursor wire based on titanium-titanium aluminium compound and mix matrix composite, there is higher specific tenacity and specific rigidity, higher high temperature resistant, creep resistance, anti-oxidant and corrosion resistant ability.
Claims (10)
1. the preparation method of a continuous fiber reinforcing titanium matrix composite, it comprises with aluminum or aluminum alloy, titanium or titanium alloy for target, continuous SiC fiber is reinforcement, titanium-titanium aluminium the compound adopting magnetron sputtering to be made into titanium deposition aluminium mixed coating and titanium or titanium alloy coating on continuous SiC fiber mixes precursor wire, then this precursor wire be wound around or arrange and insert in titanium alloy substrate structure, obtaining the step of continuous fiber reinforcing titanium matrix composite through hot pressing or hot isostatic pressing compound.
2. the preparation method of continuous fiber reinforcing titanium matrix composite according to claim 1, is characterized in that: the method comprises the steps:
Titanium-titanium aluminium compound mixes the preparation of precursor wire:
The titanium of cleaning or titanium alloy target and aluminum or aluminum alloy target are installed, obtaining two planar targets to symmetry, is a pair titanium target or titanium alloy target, pair of aluminum target or aluminium alloy target respectively;
By the SiC Filament-wound Machine of cleaning on the special mouse cage frame of magnetron sputtering equipment, and insert in magnetron sputtering working spaces;
Adopt titanium target or titanium alloy target, aluminium target or aluminium alloy target, sputtering is opened than simultaneously according to setting power, SiC fiber realizes the mixing splash coating of titanium deposition or titanium alloy, aluminum or aluminum alloy, and then deposit one deck titanium or titanium alloy coating, obtain titanium-titanium aluminium compound and mix precursor wire;
The preparation of continuous fiber reinforcing titanium matrix composite:
Titanium-titanium aluminium compound is mixed precursor wire to prepare in the mode of solid matter stacking and become prefabricated reinforcement, be then placed in metal thin-wall jacket, through vacuum stripping and vacuum seal, then carry out hot isostatic pressing and obtain continuous fiber reinforcing titanium matrix composite.
3. the preparation method of continuous fiber reinforcing titanium matrix composite according to claim 2, is characterized in that: the temperature of described hot isostatic pressing is 900 DEG C-1000 DEG C, and pressure is 100MPa-170MPa, and the time is 1h-4h.
4. the preparation method of continuous fiber reinforcing titanium matrix composite according to claim 2, is characterized in that: the acceleration voltage of described sputtering is 200-400V, and operating air pressure is 0.1-2Pa, and current density is 3-9mA/cm
2, power density is 0.6-3.6W/cm
2, argon flow amount is 25-75sccm.
5. the preparation method of continuous fiber reinforcing titanium matrix composite according to claim 2, is characterized in that: described setting power is than being titanium target or titanium alloy target: aluminium target or aluminium alloy target=1: (0.35-1).
6. the preparation method of continuous fiber reinforcing titanium matrix composite according to claim 2, is characterized in that: SiC fiber is obtained by acetone cleaning and washes of absolute alcohol by the SiC fiber of described cleaning successively.
7. the preparation method of continuous fiber reinforcing titanium matrix composite according to claim 2, is characterized in that: the titanium target of described cleaning or titanium alloy target and aluminium target or aluminium alloy target are prepared by following method:
Titanium target or titanium alloy target are carried out pickling, aluminium target or aluminium alloy target are carried out alkali cleaning, obtain titanium target or titanium alloy target, aluminium target or the aluminium alloy target of surperficial impurity elimination;
The titanium target of surperficial impurity elimination or titanium alloy target, aluminium target or aluminium alloy target are carried out ultrasonic cleaning respectively successively in acetone, dehydrated alcohol, obtains clean titanium target or titanium alloy target, aluminium target or aluminium alloy target.
8. the preparation method of continuous fiber reinforcing titanium matrix composite according to claim 2, is characterized in that: described metal thin-wall jacket comprises titanium alloy jacket.
9. the preparation method of continuous fiber reinforcing titanium matrix composite according to claim 2, is characterized in that: the method also comprises carries out pickling, acetone cleaning and the step of washes of absolute alcohol successively to metal thin-wall jacket.
10. the continuous fiber reinforcing titanium matrix composite that the preparation method of the continuous fiber reinforcing titanium matrix composite described in any one of claim 1-9 prepares.
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| CN106521369A (en) * | 2016-11-29 | 2017-03-22 | 中国科学院金属研究所 | Dense precursor belt of SiC fiber-reinforced titanium-based composite and preparation method of dense precursor belt |
| CN107815625A (en) * | 2017-11-02 | 2018-03-20 | 中南大学 | The preparation method and product of SiC continuous fiber reinforcing titanium matrix composites |
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| CN115074686B (en) * | 2022-06-29 | 2024-01-12 | 中国航发北京航空材料研究院 | Preparation method of TiAl-based composite material with cracking resistance |
| CN115142008A (en) * | 2022-07-11 | 2022-10-04 | 吉林大学 | Continuous carbon nanotube fiber reinforced copper-based composite material and preparation method and application thereof |
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Application publication date: 20150311 |