CN109652679A - Carbon nanotubes and Nei Sheng nano-TiC particle hybrid reinforced aluminum-matrix composite material and preparation method thereof - Google Patents

Carbon nanotubes and Nei Sheng nano-TiC particle hybrid reinforced aluminum-matrix composite material and preparation method thereof Download PDF

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CN109652679A
CN109652679A CN201811609884.5A CN201811609884A CN109652679A CN 109652679 A CN109652679 A CN 109652679A CN 201811609884 A CN201811609884 A CN 201811609884A CN 109652679 A CN109652679 A CN 109652679A
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powder
carbon nanotubes
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CN109652679B (en
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杨宏宇
刘林
邱丰
舒世立
陈靓瑜
邵勇
黄忠富
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Hangzhou Jiyan Nano Technology Co ltd
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Jiangsu University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/058—Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C22C2026/002—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C22C2026/006—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes with additional metal compounds being carbides

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Abstract

The invention discloses a kind of carbon nanotubes and nano-TiC particle hybrid reinforced aluminum-matrix composite material and preparation method thereof, composite material includes that mass percent is respectively as follows: carbon nanotubes: 0.5-5%, TiC:18-38%, Al:60-80%.Preparation method includes: (1) carbon nanotubes ultrasonic disperse；(2) preparation of precursor powder CNTs-Ti-Al；(3) green compact, sintering and densification integration.Part CNTs in CNTs-Ti-Al system is reacted as carbon source and alloy powder Ti and introduces the nano-ceramic particle of in-situ endogenic by this technique, and remaining CNTs is as reinforced phase after reaction.The generation of TiC can improve the problem that wetability is poor, interface bond strength is not high between CNTs and Al matrix, it realizes and couples interaction cooperative reinforcing matrix in Al based composites between double reinforced phases (CNTs+TiC) of different dimensions, the comprehensive performance of composite material is greatly improved, there is important application value.

Description

Carbon nanotubes and Nei Sheng nano-TiC particle hybrid reinforced aluminum-matrix composite material and its system Preparation Method
Technical field
The present invention relates to aluminum matrix composite more particularly to a kind of carbon nanotubes and Nei Sheng nano-TiC particle hybrid buildup Aluminum matrix composite and preparation method thereof.
Background technique
Aluminum matrix composite has great application value in military, Aeronautics and Astronautics and civil field and widely answers It is the most important lightweights in fields such as current equipment manufacturing, bullet train, military military project, aerospace, nuclear material with potentiality One of high performance material.But with the rapid development of science and technology, industry and military technology demand are continuously improved, to high performance light Structural material material requires industry higher and higher, does not require nothing more than it with excellent structural behaviour, it is also required to have both multi-functional response Characteristic.Therefore, the comprehensive performance that aluminum matrix composite is continuously improved also is needed.
Carbon nanotubes (Carbon Nanotubes, CNTs) has one-dimensional tubular structure and excellent mechanics, physics, chemistry Characteristic, such as high-tensile (50-200GPa, about the 100 of steel times), lower density (1.2-2.1g/cm3, the 1/6-1/ of steel 7), high elasticity modulus (working as with diamond phase), significant high thermal conductivity coefficient (more than 3000W/mK) and low thermal expansion system Number (1.0 × 10-6K) etc., this unique structure and brilliant comprehensive performance make carbon nanotubes in reinforced metal base composite wood Material field shows huge application prospect, it is considered to be optimal reinforced phase.But carbon nanotubes and Al matrix wetability are not Adverse reaction easily occurs for good, interface, and interfacial bonding property is poor；In addition, because of carbon pipe specific surface energy with higher and Van der Waals Power, causes it to be not easy to disperse in the base, easily occurs reuniting and wrapping phenomena.Current study show that using CNTs as unique The performance of the metal-base composites of reinforced phase preparation reaches far away theoretical value.
And nano-carbide ceramic particle is as isotropic nanometer of hard reinforced phase, except with high intensity, high rigidity, Except the advantages that high-wearing feature and high thermal stability, in-situ endogenic technique also makes ceramic particle easily realize uniform point in the base Cloth, and clean interfaces, bond strength are high between matrix, but the comprehensive performance of ceramic particle is inferior to CNTs, in metal-based compound Material Field enhances metal by single nano-ceramic particle, and performance improves degree and has reached bottleneck, is difficult to have again very big It breaks through.
Summary of the invention
Goal of the invention: the present invention provides a kind of carbon nanotubes and Nei Sheng nano-TiC particle hybrid reinforced aluminum-matrix composite wood Material and preparation method thereof, composite material are the CNTs-TiC/Al composite material of peacekeeping three-dimensional biphase cooperative enhancing；Preparation method The mixed powder of CNTs, Ti and Al are prepared into the CNTs-TiC/ that the three-dimensional double reinforced phases of a peacekeeping mix by reactive hot press sintering Al composite material, and regulate and control the percentage composition of CNTs and TiC, realize double reinforced phases of different dimensions in Al based composites CNTs-TiC mixes distribution.
Technical solution: carbon nanotubes (CNTs) of the invention and interior raw nano-TiC particle hybrid reinforced aluminum-matrix composite material, The Al, preferably 1.82-4.61% of TiC and 60-80% including carbon nanotubes, 18-38% that mass percent is 0.5-5% Carbon nanotubes, 18.18-36.37% TiC and 60-80% Al.
The preparation method of above-mentioned carbon nanotubes (CNTs) and interior raw nano-TiC particle hybrid reinforced aluminum-matrix composite material, packet Include following steps:
(1) mixed powder of carbon nanotubes, Ti and Al are fitted into graphite jig and carry out green compact, obtain briquet；
(2) briquet obtained in step (1) is kept the temperature into 5-50min under the conditions of vacuum system and 500-600 DEG C, makes target Temperature is consistent with actual temperature, burner hearth and briquet internal and external temperature；When then proceeding to be heated to pressure to increase suddenly, it is forced into rapidly 40-100MPa is simultaneously stopped and heats and be cooled to room temperature, completes hot pressed sintering and the densification of powder mixture, obtains described Composite material.The mass percentage of CNTs and TiC ceramic particle is 20-40% in the composite material.
Carbon nanotubes described in step (1), Ti and Al mixed powder preparation the following steps are included:
(1-1) weighs Al powder, Ti powder, is added in carbon nanotubes alcohol suspension and carries out electromagnetic agitation, ultrasonic vibration, Obtain mixture ethanol solution；
Wherein, 0.5-5 hours a length of when the electromagnetic agitation, revolving speed 100-3000r/min；It is a length of when ultrasonic vibration 1-4 hours, frequency 20-60KHz.
(1-2) is dried mixture ethanol solution obtained in step (1-1) using Rotary Evaporators, removes alcohol Powder mixture is obtained after solvent.
Wherein, evaporation flask is placed in 40-80 DEG C of thermostat water bath 1-4 hours, flask rotation speed is 50- 200r/min, solution negative pressure is 200-800 millimetres of mercury in bottle.
Powder mixture obtained in step (1-2) is put into zirconium dioxide ball grinder by (1-3), after ball grinder is sealed It is installed on Horizontal type mixer, using zirconium dioxide abrading-ball mixing 12-72h, obtains the carbon nanotubes, Ti and Al mixed powder Body.
Wherein, the revolving speed of the Horizontal type mixer is set as 20-120r/min；ZrO2The mass ratio of abrading-ball and mixed-powder For 8-13:1, the overall volume of powder and zirconium oxide balls is no more than the 80% of ball milling tankage size.
In step (1-1), the preparation of the carbon nanotubes alcohol suspension includes being added to carbon nanotubes in ethyl alcohol Ultrasonic wave is carried out under room temperature stirs the step of being dispersed into linear suspension to carbon nanotubes group.
Wherein, ultrasonic frequency 20-60KHz, when stirring, are 1-4 hours a length of.
In step (1), the mass percentage of carbon nanotubes, Ti and Al is respectively 5.45- in the mixed powder 10.90%, 14.55-29.10%, 60-80%；The molar ratio of CNTs:Ti is 1.5-2.5:1, and the mass ratio of CNTs:Ti is 1: 2.67-1.6。
The carbon nanotubes is multi wall structure, and outer diameter 5-30nm, length is 5-60 μm, purity > 95.0%；The grain of Al powder Degree is 200-2000 mesh, purity > 99.95%；The granularity of Ti powder is 500-3000 mesh, purity > 99.95%.
The green compact is by the way of hydraulic.Green compact specific steps are as follows: the mixed powder of CNTs, Ti and Al are packed into graphite In mold, the graphite jig equipped with powder mixture is put into vacuum sintering funace, is arranged precompression 0.1-0.5 tons, is closed Closed furnace door starts pumped vacuum systems, and observes vacuum degree display window registration, shows that furnace pressure is lower than 0.8 × 10 to vacuum degree- 3After Pa, heating power supply is opened, with the heating rate of 10-40K/min, 100-300 DEG C is heated to, keeps the temperature 30-60min, with dehumidifying Degasification；After keeping warm mode continues 15min, starts hydraulic system, pressure value is forced into step by step with 0.2-1 tons of power and reaches 15- 60MPa, pressure maintaining 5-10min；Then it is depressurized step by step with 0.5-1 tons of power, retains precompression 0.1-0.5 tons, complete powder mixing The green compact of object.
It further includes by mixed powder in graphite jig that the mixed powder of multi-walled carbon nanotube, Ti and Al, which are fitted into before graphite jig, Smear the step of hexagonal boron nitride ethanol solution in the position that body can contact.Specific steps are as follows: modulate hexagonal boron nitride powder At thin hexagonal boron nitride ethanol solution, then, hexagonal boron nitride solution is applied to sleeve lining, the pad of graphite jig The position that piece, pressure head etc. can be contacted with powder waits 2min or more that powder mixture is packed into graphite mo(u)ld after alcohol volatilization In tool.Wherein, the granularity of hexagonal boron nitride powder is 0.5-5 μm.
The graphite jig is hot isostatic pressing high-strength graphite mold, and outer sleeve is circle, outer sleeve and inner sleeve appearance Face use cone match, 3-8 ° of cone angle；Monoblock type or point two-flap type can be used in inner sleeve, and thickness is greater than 10mm, sleeve cross section Shape can be for circle or with the rectangular of rounded corner, circular inner diameter 20-80mm, rectangular length and width 20-100mm, chamfer radius 3- 10mm, sleeve height 100-220mm, Graphite pad thickness 3-8mm, compression bar transverse shape and height and sleeve transverse shape Consistent with height conservation degree, compression bar and sleeve interior surface clearance fit, bilateral gap width are less than 0.1mm.
In step (2), 500-600 DEG C is heated to the heating rate of 10-60K/min.
In step (2), after keeping the temperature 5-50min, continue to be heated to pressure with the heating rate of 40-100K/min to rise suddenly It is high.
In conclusion the preparation side of carbon nanotubes (CNTs) and interior raw nano-TiC particle hybrid reinforced aluminum-matrix composite material Method, specifically includes the following steps:
Step 1: carbon nanotubes being added in ethyl alcohol, then at room temperature, is stirred in the ultrasonic wave of 20-60KHz It mixes 1-4 hours, carbon nanotubes group is dispersed into linear suspension.
Wherein, the concentration of carbon nanotubes is 3-5g/L, preferably 3.5-4.8g/L, is multi wall structure, outer diameter: 5-30nm, length Degree: 5-60 μm, purity > 95.0%.
Step 2: by granularity be 200-2000 mesh, the Al powder of purity > 99.95% and granularity be 500-3000 mesh, purity > 99.95% Ti powder, is added in carbon nanotubes alcohol suspension.At room temperature, mixture ethanol solution progress electromagnetism is stirred It mixes 0.5-5 hours, the revolving speed of electromagnetic agitation is 100-3000r/min；Then, ultrasonic vibration 1-4 hours, the frequency of ultrasonic vibration For 20-60KHz.Mixture ethanol solution is dried using Rotary Evaporators, evaporation flask is placed in 40-80 DEG C of constant temperature 1-4 hours in water-bath, while flask rotation speed is 50-200r/min, and solution negative pressure is 200-800 millimetres of mercury in bottle. Powder mixture is taken out after removal spirit solvent.
Wherein, the concentration in alcohol suspension of Al powder and Ti powder is respectively 15-50g/L, 8-12.5g/L, preferably 16.6-50g/L、8.3-12g/L。
Step 3: the above powder mixture being weighed into 50g and is put into zirconium dioxide ball grinder, ZrO is pre-placed in tank2Mill Ball 400g-650g, ball radius 5-22mm, totally 6 kinds, diameter is respectively 5mm, 7mm, 11mm, 15mm, 20mm, 22mm, and every kind 5-9；Ball grinder is installed on Horizontal type mixer after being sealed, and the revolving speed of batch mixer is set as 20-120r/min, is uniformly mixed Time be 12-72h.
Wherein, ZrO2The mass ratio of abrading-ball and mixed-powder is 8-13:1, and the overall volume of powder and zirconium oxide balls is not More than the 80% of ball milling tankage size.
Wherein, the molar ratio of CNTs:Ti is 1.5-2.5:1 in above-mentioned powder mixture, and the mass ratio of CNTs:Ti is 1: 2.67-1.6；CNTs powder mass content is 5.45-10.90wt.%, and Ti powder content is 14.55-29.10wt.%, Al powder content For 60-80wt.%.
Step 4: weighing 0.5-5 μm of hexagonal boron nitride powder 2-5g and be fitted into 50-250ml beaker, then into beaker The alcohol of 5-30ml is added, is modulated into thin hexagonal boron nitride solution；Hexagonal boron nitride solution is applied to graphite mo(u)ld The position that sleeve lining, gasket, pressure head of tool etc. can be contacted with powder waits 2min or more to mix powder after alcohol volatilization Object is closed to be fitted into graphite jig.
Step 5: the graphite jig equipped with powder mixture being put into vacuum sintering funace, precompression 0.1- is set 0.5 ton；Fire door is closed, starts pumped vacuum systems, and observe vacuum degree display window registration, shows that furnace pressure is lower than to vacuum degree 0.8×10-3After Pa, heating power supply is opened, with the heating rate of 10-40K/min, 100-300 DEG C is heated to, keeps the temperature 30- 60min；
Step 6: after keeping warm mode continues 15min, starting hydraulic system, pressure is forced into step by step with 0.2-1 tons of power Value reaches 15-60MPa, pressure maintaining 5-10min；Then it is depressurized step by step with 0.5-1 tons of power, retains precompression 0.1-0.5 tons, completed The green compact of powder mixture.
Step 7: continuing to be heated to 500-600 DEG C with the heating rate of 10-60K/min, keep the temperature 5-50min, make target temperature It spends consistent with actual temperature, burner hearth and briquet internal and external temperature；Then, continue to heat with the heating rate of 40-100K/min, surely When pressure registration in reciprocal of duty cycle display window occurs increasing phenomenon suddenly, it is forced into 40-100MPa rapidly, while closing heating immediately Hot pressed sintering and the densification of powder mixture are completed in power supply, furnace cooling to room temperature.
Preferably, in step 4 or 5, graphite jig is hot isostatic pressing high-strength graphite mold, and outer sleeve is circle, outer sleeve With inner sleeve outer surface use cone match, 3-8 ° of cone angle；Monoblock type can be used in inner sleeve or point two-flap type, thickness are greater than 10mm, sleeve transverse shape can be for circles or with the rectangular of rounded corner, circular inner diameter 20-80mm, rectangular length and width 20- 100mm, chamfer radius 3-10mm, sleeve height 100-220mm, Graphite pad thickness 3-8mm, compression bar transverse shape and height Consistent with sleeve transverse shape and height conservation degree, compression bar and sleeve interior surface clearance fit, bilateral gap width are less than 0.1mm。
Carbon source using CNTs a part as reinforced phase, a part as carbide ceramics reaction in-situ, passes through in-situ heat A kind of carbon nanotubes is prepared in pressure reaction+hot pressed sintering+densification integration and Nei Sheng nano-carbide ceramic particle is blended and increases Strong fine and close aluminum matrix composite, preparation process is simple, and sintering, reaction, one step of densification are completed, and more can crucially solve Existing problems when certainly carbon pipe and ceramic particle are respectively as single reinforced phase.The generation of ceramic particle can improve moment The temperature of system is conducive to improve the wetability between CNTs and Al matrix；Moreover, the wetability of interior raw ceramic particle and Al are good It is strong in the combination that the ceramic particle of CNTs Surface Creation can improve reinforced phase and Al basal body interface in the wetability of CNTs and Al Degree；Meanwhile the ceramic particle of generation can improve the boundary of CNTs and Al as the second reinforced phase and CNTs mutual coupling Face structure；In addition, the amorphous carbon of the absorbable surface the CNTs attachment of the formation of ceramic particle, and take the lead in lacking in CNTs surface texture Sunken place reacts, so as to purify interface.Finally, equally distributed nano-dotted particulates reinforcements are conducive to follow closely in matrix Prick carbon pipe, two kinds of reinforced phase cooperative reinforcing alloy matrix aluminums, can prepare high comprehensive performance can be applied to structure, function is answered High-performance aluminum-base composite material.Therefore, the present invention has important application value.
The utility model has the advantages that the two-phase reinforced aluminum matrix composites of 1, different dimensions provided by the invention, pass through in-situ endogenic The CNTs-TiC/Al composite material of peacekeeping three-dimensional biphase cooperative enhancing is prepared, and has regulated and controled the percentage composition of CNTs and TiC, 1-dimention nano tubulose reinforced phase and three-dimensional nanoparticles reinforced phase are stabilized in Al matrix, and interface is good, are evenly distributed, real Double reinforced phase CNTs-TiC of different dimensions mix distribution and cooperative reinforcing in existing Al based composites；
2, the preparation method of the two-phase reinforced aluminum matrix composites of different dimensions provided by the invention, by CNTs, Ti and Al It obtains mixed powder and the CNTs-TiC/Al composite material that the three-dimensional double reinforced phases of one peacekeeping mix is prepared by reactive hot press sintering, It reacts using the part CNTs in CNTs-Ti-Al system as carbon source and alloy powder Ti and introduces the nanometer pottery of in-situ endogenic Porcelain particle, remaining CNTs is as reinforced phase after reaction.The generation of TiC can improve that wetability between CNTs and Al matrix is poor, interface The not high problem of bond strength, meanwhile, equally distributed nano-dotted particulates reinforcements are conducive to pinning carbon pipe in matrix, real Interaction cooperative reinforcing matrix is coupled in existing Al based composites between double reinforced phases (CNTs+TiC) of different dimensions, is greatly mentioned The high comprehensive performance of composite material, has important application value.
Detailed description of the invention
Fig. 1 is the X-ray diffraction analysis figure for the composite material that embodiment 1 obtains in the present invention.
Fig. 2 is the Raman spectrogram for the composite material that embodiment 1 obtains in the present invention.
Fig. 3 is the X-ray diffraction analysis figure for the composite material that embodiment 2 obtains in the present invention.
Fig. 4 is the Raman spectrogram for the composite material that embodiment 2 obtains in the present invention.
Fig. 5 is the X-ray diffraction analysis figure for the composite material that embodiment 3 obtains in the present invention.
Fig. 6 is the Raman spectrogram for the composite material that embodiment 3 obtains in the present invention.
Fig. 7 is the X-ray diffraction analysis figure for the composite material that embodiment 4 obtains in the present invention.
Fig. 8 is the Raman spectrogram for the composite material that embodiment 4 obtains in the present invention.
Fig. 9 is the X-ray diffraction analysis figure for the composite material that comparative example 1 obtains in the present invention.
Figure 10 is the X-ray diffraction analysis figure for the composite material that comparative example 2 obtains in the present invention.
Specific embodiment
Embodiment 1
A kind of carbon nanotubes and Nei Sheng nano-TiC particle hybrid reinforced aluminum-matrix composite material and preparation method, including it is following Step:
(1) carbon nanotubes ultrasonic disperse:
Step 1.1: 2.72g carbon nanotubes being added in 600ml ethyl alcohol, then at room temperature, in the super of 30KHz It is stirred 1 hour in sound wave, carbon nanotubes group is dispersed into linear suspension.Wherein, carbon nanotubes is multi wall structure, outer diameter: 5- 30nm, length: 5-60 μm, purity > 95.0%.
(2) preparation of precursor powder CNTs-Ti-Al:
Step 2.1: precursor powder wet mixing and drying: being 1200 mesh, the Al powder 40g of purity > 99.95% and granularity by granularity For 1500 mesh, the Ti powder 7.28g of purity > 99.95%, it is added in carbon nanotubes alcohol suspension.At room temperature, by mixture Ethanol solution carries out electromagnetic agitation 2 hours, and the revolving speed of electromagnetic agitation is 400r/min；Then, ultrasonic vibration 1 hour, ultrasound shake The frequency swung is 30KHz.Mixture ethanol solution is dried using Rotary Evaporators, evaporation flask is placed in 50 DEG C of perseverance 2 hours in warm water bath, while flask rotation speed is 80r/min, and solution negative pressure is 500 millimetress of mercury in bottle.Remove alcohol Powder mixture is taken out after solvent.
Step 2.2: the ball milling of precursor powder: the above powder mixture 50g is put into zirconium dioxide ball grinder, pre- in tank First place ZrO2Abrading-ball 480g, ball radius 5-22mm, totally 6 kinds, diameter be respectively 5mm, 7mm, 11mm, 15mm, 20mm, 22mm, 6 every kind；Ball grinder is installed on Horizontal type mixer after being sealed, and the revolving speed of batch mixer is set as 90r/min, uniformly The mixed time is 50 hours；Wherein the mass ratio of ZrO2 abrading-ball and mixed-powder is 9.6:1, powder and zirconium oxide balls it is total Body volume is no more than the 80% of ball milling tankage size.
The molar ratio of CNTs:Ti is 1.5:1 in above-mentioned powder mixture, and the mass ratio of CNTs:Ti is 1:2.67；CNTs powder Content is 5.45wt.%, and Ti powder content is 14.55wt.%, and Al powder content is 80wt.%.Nano TiC ceramics are generated after reaction The mass fraction of particle is 18.18wt.%, and the mass fraction of remaining CNTs is 1.82wt.%.
(3) green compact, sintering and densification:
Step 3.1: smearing release agent: weighing 0.5 μm of hexagonal boron nitride powder 2g and be fitted into 50ml beaker, then to burning The alcohol of 10ml is added in cup, is modulated into thin hexagonal boron nitride solution；Hexagonal boron nitride solution is applied to graphite The position that sleeve lining, gasket, pressure head of mold etc. can be contacted with powder waits 2min or more, after alcohol volatilization, by powder Mixture is fitted into graphite jig.
Step 3.2: dehumidifying degasification: the graphite jig equipped with powder mixture is put into vacuum sintering funace, is arranged 0.2 ton of precompression；Fire door is closed, starts pumped vacuum systems, and observe vacuum degree display window registration, shows furnace internal pressure to vacuum degree Power is lower than 0.8 × 10-3After Pa, heating power supply is opened, with the heating rate of 10K/min, 100 DEG C is heated to, keeps the temperature 30min；
Step 3.3: green compact: after keeping warm mode continues 15min, starting hydraulic system, be forced into step by step with 0.8 ton of power Pressure value reaches 20MPa, pressure maintaining 5min；Then it is depressurized step by step with 1 ton of power, retains 0.2 ton of precompression, complete powder mixture Green compact.
Step 3.4: sintering and densification: continuing to be heated to 500 DEG C with the heating rate of 10K/min, keep the temperature 30min, make Target temperature is consistent with actual temperature, burner hearth and briquet internal and external temperature；Then, continue to heat with the heating rate of 100K/min, When the pressure registration in vacuum degree display window occurs increasing phenomenon suddenly, it is forced into 80MPa rapidly, while closing heating immediately Hot pressed sintering and the densification of powder mixture are completed in power supply, furnace cooling to room temperature.
Wherein, the graphite jig in step 3.1 and 3.2 is hot isostatic pressing high-strength graphite mold, and outer sleeve is circle, housing Cylinder with inner sleeve outer surface use cone match, 5 ° of cone angle；Inner sleeve uses monoblock type, and thickness is greater than 10mm, sleeve cross section Shape be circle, circular inner diameter 20mm, sleeve height 100mm, Graphite pad thickness 5mm, compression bar transverse shape and highly with Sleeve transverse shape is consistent with height conservation degree, and compression bar and sleeve interior surface clearance fit, bilateral gap width are less than 0.1mm.
Contain 18.18wt.% nano TiC ceramic particle by what is prepared in the reaction of CNTs-Ti-Al system in-situ endogenic Compound with (CNTs-TiC)/Al base of the two-phase hybrid buildup of 1.82wt.%CNTs, Fig. 1 is aluminum-base composite prepared by example 1 X-ray diffraction analysis, as shown in Figure 1, should (CNTs-TiC)/Al base it is compound by Al, TiC, CNTs, Al4C3With it is a small amount of Al3Ti phase composition.Fig. 2 is the Raman spectrogram of aluminum-base composite prepared by example 1, as shown in Figure 2, (CNTs-TiC)/ There are CNTs characteristic peaks during Al base is compound.
Embodiment 2
A kind of carbon nanotubes and Nei Sheng nano-TiC particle hybrid reinforced aluminum-matrix composite material and preparation method, including it is following Step:
(1) carbon nanotubes ultrasonic disperse:
Step 1.1: 5.45g carbon nanotubes being added in 1500ml ethyl alcohol, then at room temperature, 60KHz's It is stirred 4 hours in ultrasonic wave, carbon nanotubes group is dispersed into linear suspension.Wherein, carbon nanotubes be multi wall structure, outer diameter: 5-30nm, length: 5-60 μm, purity > 95.0%.
(2) preparation of precursor powder CNTs-Ti-Al:
Step 2.1: precursor powder wet mixing and drying: being 2000 mesh, the Al powder 30g of purity > 99.95% and granularity by granularity For 3000 mesh, the Ti powder 14.55g of purity > 99.95%, it is added in carbon nanotubes alcohol suspension.At room temperature, it will mix Object ethanol solution carries out electromagnetic agitation 5 hours, and the revolving speed of electromagnetic agitation is 1500r/min；Then, ultrasonic vibration 4 hours, ultrasound The frequency of concussion is 60KHz.Mixture ethanol solution is dried using Rotary Evaporators, evaporation flask is placed in 80 DEG C 4 hours in thermostat water bath, while flask rotation speed is 180r/min, and solution negative pressure is 800 millimetress of mercury in bottle.Remove wine Powder mixture is taken out after smart solvent.
Step 2.2: the ball milling of precursor powder: weighing 50g for the above powder mixture and be put into zirconium dioxide ball grinder, tank In be pre-placed ZrO2Abrading-ball 640g, ball radius 5-22mm, totally 6 kinds, diameter be respectively 5mm, 7mm, 11mm, 15mm, 20mm, 22mm, 8 every kind；Ball grinder is installed on Horizontal type mixer after being sealed, and the revolving speed of batch mixer is set as 120r/ Min, mixed uniformly time are 72 hours；Wherein ZrO2The mass ratio of abrading-ball and mixed-powder is 12.8:1, powder and oxidation The overall volume of zirconium abrading-ball is no more than the 80% of ball milling tankage size.
The molar ratio of CNTs:Ti is 1.5:1 in above-mentioned powder mixture, and the mass ratio of CNTs:Ti is 1:2.67；CNTs powder Content is 10.90wt.%, and Ti powder content is 29.10wt.%, and Al powder content is 60wt.%.Nano TiC ceramics are generated after reaction The mass fraction of particle is 36.37wt.%, and the mass fraction of remaining CNTs is 3.63wt.%.
(3) green compact, sintering and densification:
Step 3.1: smearing release agent: weighing 3 μm of hexagonal boron nitride powder 5g and be fitted into 200ml beaker, then to burning The alcohol of 30ml is added in cup, is modulated into thin hexagonal boron nitride solution；Hexagonal boron nitride solution is applied to graphite The position that sleeve lining, gasket, pressure head of mold etc. can be contacted with powder waits 2min or more, after alcohol volatilization, by powder Mixture is fitted into graphite jig.
Step 3.2: dehumidifying degasification: the graphite jig equipped with powder mixture is put into vacuum sintering funace, is arranged 0.5 ton of precompression；Fire door is closed, starts pumped vacuum systems, and observe vacuum degree display window registration, shows furnace internal pressure to vacuum degree Power is lower than 0.8 × 10-3After Pa, heating power supply is opened, with the heating rate of 20K/min, 300 DEG C is heated to, keeps the temperature 60min；
Step 3.3: green compact: after keeping warm mode continues 15min, starting hydraulic system, be forced into step by step with 0.2 ton of power Pressure value reaches 50MPa, pressure maintaining 10min；Then it is depressurized step by step with 0.5 ton of power, retains 0.5 ton of precompression, it is mixed to complete powder Close the green compact of object.
Step 3.4: sintering and densification: continuing to be heated to 600 DEG C with the heating rate of 20K/min, keep the temperature 45min, make Target temperature is consistent with actual temperature, burner hearth and briquet internal and external temperature；Then, continue to heat with the heating rate of 70K/min, when When pressure registration in vacuum degree display window occurs increasing phenomenon suddenly, it is forced into 100MPa rapidly, while closing heating immediately Hot pressed sintering and the densification of powder mixture are completed in power supply, furnace cooling to room temperature.
Wherein, the graphite jig in step 3.1 and 3.2 is hot isostatic pressing high-strength graphite mold, and outer sleeve is circle, housing Cylinder with inner sleeve outer surface use cone match, 8 ° of cone angle；Inner sleeve is using two-flap type is divided, and thickness is greater than 10mm, and sleeve is cross-section Face shape is circle, circular inner diameter 25mm, sleeve height 120mm, Graphite pad thickness 5mm, compression bar transverse shape and height Consistent with sleeve transverse shape and height conservation degree, compression bar and sleeve interior surface clearance fit, bilateral gap width are less than 0.1mm
Contain 36.37wt.% nano TiC ceramic particle by what is prepared in the reaction of CNTs-Ti-Al system in-situ endogenic Compound with (CNTs-TiC)/Al base of the two-phase hybrid buildup of 3.63wt.%CNTs, Fig. 3 is aluminum-base composite prepared by example 2 X-ray diffraction analysis, as shown in Figure 3, should (CNTs-TiC)/Al base it is compound by Al, TiC, CNTs, Al4C3With it is a small amount of Al3Ti phase composition.Fig. 4 is the Raman spectrogram of aluminum-base composite prepared by example 2, as shown in Figure 4, (CNTs-TiC)/ There are CNTs characteristic peaks during Al base is compound.
Embodiment 3
A kind of carbon nanotubes and Nei Sheng nano-TiC particle hybrid reinforced aluminum-matrix composite material and preparation method, including it is following Step:
(1) carbon nanotubes ultrasonic disperse:
Step 1.1: 5g carbon nanotubes being added in 1200ml ethyl alcohol, then at room temperature, in the ultrasonic wave of 50KHz Middle stirring 3 hours, is dispersed into linear suspension for carbon nanotubes group.Wherein, carbon nanotubes be multi wall structure, outer diameter: 5-30nm, Length: 5-60 μm, purity > 95.0%.
(2) preparation of precursor powder CNTs-Ti-Al:
Step 2.1: precursor powder wet mixing and drying: being 1800 mesh, the Al powder 35g of purity > 99.95% and granularity by granularity For 2500 mesh, the Ti powder 10g of purity > 99.95%, it is added in carbon nanotubes alcohol suspension.At room temperature, by mixture second Alcoholic solution carries out electromagnetic agitation 4 hours, and the revolving speed of electromagnetic agitation is 1200r/min；Then, ultrasonic vibration 3 hours, ultrasonic vibration Frequency be 50KHz.Mixture ethanol solution is dried using Rotary Evaporators, evaporation flask is placed in 70 DEG C of constant temperature 3 hours in water-bath, while flask rotation speed is 150r/min, and solution negative pressure is 700 millimetress of mercury in bottle.It is molten to remove alcohol Powder mixture is taken out after agent.
Step 2.2: the ball milling of precursor powder: weighing 50g for the above powder mixture and be put into zirconium dioxide ball grinder, tank In be pre-placed ZrO2 abrading-ball 560g, ball radius 5-22mm, totally 6 kinds, diameter be respectively 5mm, 7mm, 11mm, 15mm, 20mm, 22mm, 7 every kind；Ball grinder is installed on Horizontal type mixer after being sealed, and the revolving speed of batch mixer is set as 110r/ Min, mixed uniformly time are 66 hours；Wherein ZrO2The mass ratio of abrading-ball and mixed-powder is 11.2:1, powder and oxidation The overall volume of zirconium abrading-ball is no more than the 80% of ball milling tankage size.
The molar ratio of CNTs:Ti is 2:1 in above-mentioned powder mixture, and the mass ratio of CNTs:Ti is 1:2；CNTs powder content For 10wt.%, Ti powder content is 20wt.%, and Al powder content is 70wt.%.The quality of nano TiC ceramic particle is generated after reaction Score is 25wt.%, and the mass fraction of remaining CNTs is 5wt.%.
(3) green compact, sintering and densification:
Step 3.1: smearing release agent: weighing 2 μm of hexagonal boron nitride powder 4g and be fitted into 150ml beaker, then to burning The alcohol of 25ml is added in cup, is modulated into thin hexagonal boron nitride solution；Hexagonal boron nitride solution is applied to graphite The position that sleeve lining, gasket, pressure head of mold etc. can be contacted with powder waits 2min or more, after alcohol volatilization, by powder Mixture is fitted into graphite jig.
Step 3.2: dehumidifying degasification: the graphite jig equipped with powder mixture is put into vacuum sintering funace, is arranged 0.4 ton of precompression；Fire door is closed, starts pumped vacuum systems, and observe vacuum degree display window registration, shows furnace internal pressure to vacuum degree Power is lower than 0.8 × 10-3After Pa, heating power supply is opened, with the heating rate of 15K/min, 200 DEG C is heated to, keeps the temperature 50min；
Step 3.3: green compact: after keeping warm mode continues 15min, starting hydraulic system, be forced into step by step with 0.5 ton of power Pressure value reaches 40MPa, pressure maintaining 8min；Then it is depressurized step by step with 0.6 ton of power, retains 0.4 ton of precompression, complete powder mixing The green compact of object.
Step 3.4: sintering and densification: continuing to be heated to 550 DEG C with the heating rate of 15K/min, keep the temperature 40min, make Target temperature is consistent with actual temperature, burner hearth and briquet internal and external temperature；Then, continue to heat with the heating rate of 80K/min, when When pressure registration in vacuum degree display window occurs increasing phenomenon suddenly, it is forced into 90MPa rapidly, while closing heating electricity immediately Hot pressed sintering and the densification of powder mixture are completed in source, furnace cooling to room temperature.
Wherein, the graphite jig in step 3.1 and 3.2 is hot isostatic pressing high-strength graphite mold, and outer sleeve is circle, housing Cylinder with inner sleeve outer surface use cone match, 6 ° of cone angle；Inner sleeve uses monoblock type, and thickness is greater than 10mm, sleeve cross section Shape is with the rectangular of rounded corner, rectangular length and wide respectively 25mm and 20mm, chamfer radius 3mm, sleeve height 120mm, stone Black spacer thickness 8mm, compression bar transverse shape and height, compression bar and sleeve consistent with sleeve transverse shape and height conservation degree Internal surface gaps cooperation, bilateral gap width are less than 0.1mm.
By the reaction of CNTs-Ti-Al system in-situ endogenic prepare containing 25wt.% nano TiC ceramic particle and (CNTs-TiC)/Al base of the two-phase hybrid buildup of 5wt.%CNTs is compound, and Fig. 5 is that the X of aluminum-base composite prepared by example 3 is penetrated It is compound by Al, TiC, CNTs, Al to be somebody's turn to do (CNTs-TiC)/Al base as shown in Figure 5 for line diffraction analysis4C3With a small amount of Al3Ti phase group At.Fig. 6 be example 3 prepared by aluminum-base composite Raman spectrogram, as shown in Figure 6, should (CNTs-TiC)/Al base it is compound in There are CNTs characteristic peaks.
Embodiment 4
A kind of carbon nanotubes and Nei Sheng nano-TiC particle hybrid reinforced aluminum-matrix composite material and preparation method, including it is following Step:
(1) carbon nanotubes ultrasonic disperse:
Step 1.1: 3.84g carbon nanotubes being added in 800ml ethyl alcohol, then at room temperature, in the ultrasound of 40KHz It is stirred 2 hours in wave, carbon nanotubes group is dispersed into linear suspension.Wherein, carbon nanotubes is multi wall structure, outer diameter: 5- 30nm, length: 5-60 μm, purity > 95.0%.
(2) preparation of precursor powder CNTs-Ti-Al:
Step 2.1: precursor powder wet mixing and drying: being 1500 mesh, the Al powder 40g of purity > 99.95% and granularity by granularity For 2000 mesh, the Ti powder 6.16g of purity > 99.95%, it is added in carbon nanotubes alcohol suspension.At room temperature, by mixture Ethanol solution carries out electromagnetic agitation 3 hours, and the revolving speed of electromagnetic agitation is 800r/min；Then, ultrasonic vibration 2 hours, ultrasound shake The frequency swung is 40KHz.Mixture ethanol solution is dried using Rotary Evaporators, evaporation flask is placed in 60 DEG C of perseverance 2 hours in warm water bath, while flask rotation speed is 100r/min, and solution negative pressure is 600 millimetress of mercury in bottle.Remove alcohol Powder mixture is taken out after solvent.
Step 2.2: the ball milling of precursor powder: weighing 50g for the above powder mixture and be put into zirconium dioxide ball grinder, tank In be pre-placed ZrO2Abrading-ball 480g, ball radius 5-22mm, totally 6 kinds, diameter be respectively 5mm, 7mm, 11mm, 15mm, 20mm, 22mm, 6 every kind；Ball grinder is installed on Horizontal type mixer after being sealed, and the revolving speed of batch mixer is set as 100r/ Min, mixed uniformly time are 58 hours；Wherein ZrO2The mass ratio of abrading-ball and mixed-powder is 9.6:1, powder and zirconium oxide The overall volume of abrading-ball is no more than the 80% of ball milling tankage size.
The molar ratio of CNTs:Ti is 2.5:1 in above-mentioned powder mixture, and the mass ratio of CNTs:Ti is 1:1.6；CNTs powder Content is 7.68wt.%, and Ti powder content is 12.32wt.%, and Al powder content is 80wt.%.Nano TiC ceramics are generated after reaction The mass fraction of particle is 15.39wt.%, and the mass fraction of remaining CNTs is 4.61wt.%.
(3) green compact, sintering and densification:
Step 3.1: smearing release agent: weighing 1 μm of hexagonal boron nitride powder 3g and be fitted into 100ml beaker, then to burning The alcohol of 20ml is added in cup, is modulated into thin hexagonal boron nitride solution；Hexagonal boron nitride solution is applied to graphite The position that sleeve lining, gasket, pressure head of mold etc. can be contacted with powder waits 2min or more, after alcohol volatilization, by powder Mixture is fitted into graphite jig.
Step 3.2: dehumidifying degasification: the graphite jig equipped with powder mixture is put into vacuum sintering funace, is arranged 0.3 ton of precompression；Fire door is closed, starts pumped vacuum systems, and observe vacuum degree display window registration, shows furnace internal pressure to vacuum degree After power is lower than 0.8 × 10-3Pa, heating power supply is opened, with the heating rate of 10K/min, 100 DEG C is heated to, keeps the temperature 40min；
Step 3.3: green compact: after keeping warm mode continues 15min, starting hydraulic system, be forced into step by step with 0.6 ton of power Pressure value reaches 30MPa, pressure maintaining 6min；Then it is depressurized step by step with 0.8 ton of power, retains 0.3 ton of precompression, complete powder mixing The green compact of object.
Step 3.4: sintering and densification: continuing to be heated to 500 DEG C with the heating rate of 10K/min, keep the temperature 30min, make Target temperature is consistent with actual temperature, burner hearth and briquet internal and external temperature；Then, continue to heat with the heating rate of 90K/min, when When pressure registration in vacuum degree display window occurs increasing phenomenon suddenly, it is forced into 80MPa rapidly, while closing heating electricity immediately Hot pressed sintering and the densification of powder mixture are completed in source, furnace cooling to room temperature.
Wherein, the graphite jig in step 3.1 and 3.2 is hot isostatic pressing high-strength graphite mold, and outer sleeve is circle, housing Cylinder with inner sleeve outer surface use cone match, 4 ° of cone angle；Inner sleeve is using two-flap type is divided, and thickness is greater than 10mm, and sleeve is cross-section Face shape can be for the rectangular of rounded corner, rectangular length and wide respectively 30mm and 20mm, chamfer radius 5mm, sleeve height 100mm, Graphite pad thickness 8mm, compression bar transverse shape and height are consistent with sleeve transverse shape and height conservation degree, pressure Bar and sleeve interior surface clearance fit, bilateral gap width are less than 0.1mm.
Contain 15.39wt.% nano TiC ceramic particle by what is prepared in the reaction of CNTs-Ti-Al system in-situ endogenic Compound with (CNTs-TiC)/Al base of the two-phase hybrid buildup of 4.61wt.%CNTs, Fig. 7 is aluminum-base composite prepared by example 4 X-ray diffraction analysis as shown in Figure 7 should (CNTs-TiC)/Al base compound Al, TiC, CNTs, Al4C3With a small amount of Al3Ti Phase composition.Fig. 8 is the Raman spectrogram of aluminum-base composite prepared by example 4, as shown in Figure 8, it is multiple to be somebody's turn to do (CNTs-TiC)/Al base There are CNTs characteristic peaks in conjunction.
Comparative example 1
The preparation method of this comparative example the following steps are included:
(1) carbon nanotubes ultrasonic disperse:
Step 1.1: 1.92g carbon nanotubes being added in 500ml ethyl alcohol, then at room temperature, in the ultrasound of 40KHz It is stirred 2 hours in wave, carbon nanotubes group is dispersed into linear suspension.Wherein, carbon nanotubes is multi wall structure, outer diameter: 5- 30nm, length: 5-60 μm, purity > 95.0%.
(2) preparation of precursor powder CNTs-Ti-Al:
Step 2.1: precursor powder wet mixing and drying: being 1500 mesh, the Al powder 45g of purity > 99.95% and granularity by granularity For 2000 mesh, the Ti powder 3.08g of purity > 99.95%, it is added in carbon nanotubes alcohol suspension.At room temperature, by mixture Ethanol solution carries out electromagnetic agitation 3 hours, and the revolving speed of electromagnetic agitation is 800r/min；Then, ultrasonic vibration 2 hours, ultrasound shake The frequency swung is 40KHz.Mixture ethanol solution is dried using Rotary Evaporators, evaporation flask is placed in 60 DEG C of perseverance 2 hours in warm water bath, while flask rotation speed is 100r/min, and solution negative pressure is 600 millimetress of mercury in bottle.Remove alcohol Powder mixture is taken out after solvent.
Step 2.2: the ball milling of precursor powder: weighing 50g for the above powder mixture and be put into zirconium dioxide ball grinder, tank In be pre-placed ZrO2 abrading-ball 480g, ball radius 5-22mm, totally 6 kinds, diameter be respectively 5mm, 7mm, 11mm, 15mm, 20mm, 22mm, 6 every kind；Ball grinder is installed on Horizontal type mixer after being sealed, and the revolving speed of batch mixer is set as 100r/ Min, mixed uniformly time are 58 hours；Wherein ZrO2The mass ratio of abrading-ball and mixed-powder is 9.6:1, powder and zirconium oxide The overall volume of abrading-ball is no more than the 80% of ball milling tankage size.
The molar ratio of CNTs:Ti is 2.5:1 in above-mentioned powder mixture, and the mass ratio of CNTs:Ti is 1:1.6；CNTs powder Content is 3.84wt.%, and Ti powder content is 6.16wt.%, and Al powder content is 90wt.%.Nano TiC ceramics are generated after reaction The mass fraction of grain is 7.69wt.%.
(3) green compact, sintering and densification:
Step 3.1: smearing release agent: weighing 1 μm of hexagonal boron nitride powder 3g and be fitted into 100ml beaker, then to burning The alcohol of 20ml is added in cup, is modulated into thin hexagonal boron nitride solution；Hexagonal boron nitride solution is applied to graphite The position that sleeve lining, gasket, pressure head of mold etc. can be contacted with powder waits 2min or more, after alcohol volatilization, by powder Mixture is fitted into graphite jig.
Step 3.2: dehumidifying degasification: the graphite jig equipped with powder mixture is put into vacuum sintering funace, is arranged 0.3 ton of precompression；Fire door is closed, starts pumped vacuum systems, and observe vacuum degree display window registration, shows furnace internal pressure to vacuum degree Power is lower than 0.8 × 10-3After Pa, heating power supply is opened, with the heating rate of 10K/min, 100 DEG C is heated to, keeps the temperature 40min；
Step 3.3: green compact: after keeping warm mode continues 15min, starting hydraulic system, be forced into step by step with 0.6 ton of power Pressure value reaches 30MPa, pressure maintaining 6min；Then it is depressurized step by step with 0.8 ton of power, retains 0.3 ton of precompression, complete powder mixing The green compact of object.
Step 3.4: sintering and densification: continuing to be heated to 500 DEG C with the heating rate of 10K/min, keep the temperature 30min, make Target temperature is consistent with actual temperature, burner hearth and briquet internal and external temperature；Then, continue to heat with the heating rate of 90K/min, when When pressure registration in vacuum degree display window occurs increasing phenomenon suddenly, it is forced into 80MPa rapidly, while closing heating electricity immediately Hot pressed sintering and the densification of powder mixture are completed in source, furnace cooling to room temperature.
Wherein, the graphite jig in step 3.1 and 3.2 is hot isostatic pressing high-strength graphite mold, and outer sleeve is circle, housing Cylinder with inner sleeve outer surface use cone match, 4 ° of cone angle；Inner sleeve is using two-flap type is divided, and thickness is greater than 10mm, and sleeve is cross-section Face shape can be for the rectangular of rounded corner, rectangular length and wide respectively 30mm and 20mm, chamfer radius 5mm, sleeve height 100mm, Graphite pad thickness 8mm, compression bar transverse shape and height are consistent with sleeve transverse shape and height conservation degree, pressure Bar and sleeve interior surface clearance fit, bilateral gap width are less than 0.1mm.
It is multiple by (the CNTs-TiC)/Al base for reacting preparation two-phase hybrid buildup in CNTs-Ti-Al system in-situ endogenic It closes, Fig. 9 is the X-ray diffraction analysis of aluminum-base composite prepared by comparative example 1, as shown in Figure 9, should (CNTs-TiC)/Al base Compound Al, TiC, Al4C3Phase composition.Through comparative example explanation when Al content is 90%, two-phase hybrid buildup can not be generated (CNTs-TiC)/Al base it is compound.
Comparative example 2
The preparation method of this comparative example the following steps are included:
(1) carbon nanotubes ultrasonic disperse:
Step 1.1: 3g carbon nanotubes being added in 600ml ethyl alcohol, then at room temperature, in the ultrasonic wave of 50KHz Middle stirring 3 hours, is dispersed into linear suspension for carbon nanotubes group.Wherein, carbon nanotubes be multi wall structure, outer diameter: 5-30nm, Length: 5-60 μm, purity > 95.0%.
(2) preparation of precursor powder CNTs-Ti-Al:
Step 2.1: precursor powder wet mixing and drying: being 1800 mesh, the Al powder 35g of purity > 99.95% and granularity by granularity For 2500 mesh, the Ti powder 12g of purity > 99.95%, it is added in carbon nanotubes alcohol suspension.At room temperature, by mixture second Alcoholic solution carries out electromagnetic agitation 4 hours, and the revolving speed of electromagnetic agitation is 1200r/min；Then, ultrasonic vibration 3 hours, ultrasonic vibration Frequency be 50KHz.Mixture ethanol solution is dried using Rotary Evaporators, evaporation flask is placed in 70 DEG C of constant temperature 3 hours in water-bath, while flask rotation speed is 150r/min, and solution negative pressure is 700 millimetress of mercury in bottle.It is molten to remove alcohol Powder mixture is taken out after agent.
Step 2.2: the ball milling of precursor powder: weighing 50g for the above powder mixture and be put into zirconium dioxide ball grinder, tank In be pre-placed ZrO2Abrading-ball 560g, ball radius 5-22mm, totally 6 kinds, diameter be respectively 5mm, 7mm, 11mm, 15mm, 20mm, 22mm, 7 every kind；Ball grinder is installed on Horizontal type mixer after being sealed, and the revolving speed of batch mixer is set as 110r/ Min, mixed uniformly time are 66 hours；Wherein ZrO2The mass ratio of abrading-ball and mixed-powder is 11.2:1, powder and oxidation The overall volume of zirconium abrading-ball is no more than the 80% of ball milling tankage size.
The molar ratio of CNTs:Ti is 1:1 in above-mentioned powder mixture, and the mass ratio of CNTs:Ti is 1:4；CNTs powder content For 6wt.%, Ti powder content is 24wt.%, and Al powder content is 70wt.%.The quality of nano TiC ceramic particle is generated after reaction Score is 30wt.%, and the mass fraction of remaining CNTs is 0wt.%.
(3) green compact, sintering and densification:
Step 3.1: smearing release agent: weighing 2 μm of hexagonal boron nitride powder 4g and be fitted into 150ml beaker, then to burning The alcohol of 25ml is added in cup, is modulated into thin hexagonal boron nitride solution；Hexagonal boron nitride solution is applied to graphite The position that sleeve lining, gasket, pressure head of mold etc. can be contacted with powder waits 2min or more, after alcohol volatilization, by powder Mixture is fitted into graphite jig.
Step 3.2: dehumidifying degasification: the graphite jig equipped with powder mixture is put into vacuum sintering funace, is arranged 0.4 ton of precompression；Fire door is closed, starts pumped vacuum systems, and observe vacuum degree display window registration, shows furnace internal pressure to vacuum degree Power is lower than 0.8 × 10-3After Pa, heating power supply is opened, with the heating rate of 15K/min, 200 DEG C is heated to, keeps the temperature 50min；
Step 3.3: green compact: after keeping warm mode continues 15min, starting hydraulic system, be forced into step by step with 0.5 ton of power Pressure value reaches 40MPa, pressure maintaining 8min；Then it is depressurized step by step with 0.6 ton of power, retains 0.4 ton of precompression, complete powder mixing The green compact of object.
Step 3.4: sintering and densification: continuing to be heated to 550 DEG C with the heating rate of 15K/min, keep the temperature 40min, make Target temperature is consistent with actual temperature, burner hearth and briquet internal and external temperature；Then, continue to heat with the heating rate of 80K/min, when When pressure registration in vacuum degree display window occurs increasing phenomenon suddenly, it is forced into 90MPa rapidly, while closing heating electricity immediately Hot pressed sintering and the densification of powder mixture are completed in source, furnace cooling to room temperature.
Wherein, the graphite jig in step (3.1) is hot isostatic pressing high-strength graphite mold, and outer sleeve is circle, outer sleeve With inner sleeve outer surface use cone match, 6 ° of cone angle；Inner sleeve uses monoblock type, and thickness is greater than 10mm, sleeve cross section shape Shape is with the rectangular of rounded corner, rectangular length and wide respectively 25mm and 20mm, chamfer radius 3mm, sleeve height 120mm, graphite Spacer thickness 8mm, compression bar transverse shape and height are consistent with sleeve transverse shape and height conservation degree, in compression bar and sleeve Surface gap cooperation, bilateral gap width are less than 0.1mm.
It is multiple by (the CNTs-TiC)/Al base for reacting preparation two-phase hybrid buildup in CNTs-Ti-Al system in-situ endogenic Close, Figure 10 be comparative example 2 prepared by aluminum-base composite X-ray diffraction analysis, as shown in Figure 10, the Al base it is compound by Al, TiC phase composition.Illustrated when the molar ratio of CNTs:Ti is 1:1, and the mass ratio of CNTs:Ti is 1:4, not by the comparative example (CNTs-TiC)/Al base that two-phase hybrid buildup can be generated is compound.
1 embodiment and comparative example CNTs-Ti-Al system of table is with composite material each component content after when reacting
As shown in Table 1: when MWCNTs:Ti molar ratio is between 1.5-2.5:1, the additional amount of Al powder 60-80wt.% it Between when, (CNTs-TiC)/Al based composites by Al, TiC and CNTs phase composition can be prepared, wherein mass percent is TiC:8.18-36.37wt.%；CNTs:1.82-4.61wt.%.And when Al powder additional amount is equal to greatly 90wt.% or MWCNTs: When Ti molar ratio is 1:1, (CNTs-TiC)/Al based composites of two-phase hybrid buildup can not be prepared.

Claims (10)

1. a kind of carbon nanotubes and Nei Sheng nano-TiC particle hybrid reinforced aluminum-matrix composite material, it is characterised in that: including quality hundred Divide the Al of the TiC and 60-80% than the carbon nanotubes, 18-38% that are 0.5-5%.
2. the preparation method of a kind of carbon nanotubes and Nei Sheng nano-TiC particle hybrid reinforced aluminum-matrix composite material, which is characterized in that The following steps are included:
(1) mixed powder of carbon nanotubes, Ti and Al are fitted into graphite jig and carry out green compact, obtain briquet；
(2) briquet obtained in step (1) is kept the temperature into 5-50min under the conditions of vacuum system and 500-600 DEG C, then proceedes to add When heat to pressure increases suddenly, it is forced into 40-100MPa rapidly, is simultaneously stopped and heats and be cooled to room temperature, obtain described compound Material.
3. preparation method according to claim 2, which is characterized in that carbon nanotubes described in step (1), Ti and Al mixing Powder preparation the following steps are included:
(1-1) weighs Al powder, Ti powder, is added in carbon nanotubes alcohol suspension and carries out electromagnetic agitation, ultrasonic vibration, obtain Mixture ethanol solution；
Mixture ethanol solution obtained in step (1-1) is dried in (1-2), obtains powder mixture.
Powder mixture abrading-ball mixing 12-72h obtained in step (1-2) is obtained the carbon nanotubes, Ti and Al by (1-3) Mixed powder.
4. preparation method according to claim 3, it is characterised in that: in step (1-1), the carbon nanotubes ethyl alcohol suspends The preparation of liquid includes being added to carbon nanotubes in ethyl alcohol to carry out ultrasonic wave and stir to carbon nanotubes group and be dispersed into linear suspension The step of.
5. preparation method according to claim 2, it is characterised in that: in step (1), nano-sized carbon in the mixed powder The mass percentage of pipe, Ti and Al is respectively 5.45-10.90%, 14.55-29.10%, 60-80%.
6. preparation method according to claim 2, it is characterised in that: the carbon nanotubes is multi wall structure, outer diameter 5- 30nm, length are 5-60 μm, purity > 95.0%；The granularity of Al powder is 200-2000 mesh, purity > 99.95%；The granularity of Ti powder For 500-3000 mesh, purity > 99.95%.
7. preparation method according to claim 2, it is characterised in that: the green compact is by the way of hydraulic.
8. preparation method according to claim 2, it is characterised in that: by the mixed powder of multi-walled carbon nanotube, Ti and Al It is fitted into before graphite jig the position for further including can contact mixed powder in graphite jig and smears hexagonal boron nitride ethanol solution The step of.
9. preparation method according to claim 2, it is characterised in that: in step (2), with the heating rate of 10-60K/min It is heated to 500-600 DEG C.
10. preparation method according to claim 2, it is characterised in that: in step (2), after keeping the temperature 550min, with 40- The heating rate of 100K/min continues to be heated to pressure to increase suddenly.
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CN113308630A (en) * 2021-05-28 2021-08-27 昆明理工大学 In-situ CNTs @ Ti hybrid reinforced aluminum matrix composite and preparation method thereof

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CN112941360A (en) * 2021-01-11 2021-06-11 南昌大学 Preparation method of carbon nanotube reinforced aluminum alloy semi-solid slurry
CN112941360B (en) * 2021-01-11 2022-05-20 南昌大学 Preparation method of carbon nano tube reinforced aluminum alloy semi-solid slurry
CN113308630A (en) * 2021-05-28 2021-08-27 昆明理工大学 In-situ CNTs @ Ti hybrid reinforced aluminum matrix composite and preparation method thereof

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