CN106544537B - A kind of preparation method of carbon nanotube enhanced aluminium-based composite material - Google Patents
A kind of preparation method of carbon nanotube enhanced aluminium-based composite material Download PDFInfo
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- CN106544537B CN106544537B CN201610928860.0A CN201610928860A CN106544537B CN 106544537 B CN106544537 B CN 106544537B CN 201610928860 A CN201610928860 A CN 201610928860A CN 106544537 B CN106544537 B CN 106544537B
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- 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
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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
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- 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
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- 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
Abstract
The invention provides a kind of preparation method of carbon nanotube enhanced aluminium-based composite material, this method obtains the dispersed composite powder of carbon pipe using low temperature ball milling first, then composite blank is made in powder consolidation by dress jacket, degasification and high temperature insostatic pressing (HIP), bar, section bar or forging products are formed through the conventional hot-working method such as extruding, forging and pressing again, are finally heat-treated.This method CNT can be made to be obtained in alloy matrix aluminum good dispersiveness, its reinforcement degree of injury are small, the composite microstructure of formation is uniform, interface cohesion is good.The material has high intensity and plasticity simultaneously, is expected to be applied to the field that Aero-Space, automobile etc. have high-strength light structural material tight demand.
Description
Technical field
The invention provides a kind of preparation method of carbon nanotube enhanced aluminium-based composite material, belong to metal-base composites
Technical field.
Background technology
Aluminum matrix composite has high specific strength, specific modulus, good conductive and heat-conductive and high-temperature behavior, in aviation
Applied and cause increasing concern in the fields such as space flight, automobile and microelectronics.CNT have unique structure and
Excellent physics, chemical property (its Young's modulus up to 1-1.8TPa, tensile strength up to 150GPa, density up to 1.2~
1.8g/cm3, thermal coefficient of expansion is almost nil, while also has good toughness and plastic deformation ability), its combination property is remote
It is a kind of preferable reinforcement of composite better than the particle or fiber that presently, there are.However, carbon pipe specific surface area is big, surface
Can be high, often it is attached together (the Van der Waals combination energy between the CNT to contact with each other with Van der Waals force between them
About 500eV/ μm) form aggregate；In addition, carbon pipe surface inertia is big, lack active group, the solubility in various solvents
All very low, this is just to its in the base scattered and they bring very big difficulty with intermetallic interface cohesion.
In order that carbon pipe is uniformly distributed and obtained in the base high performance aluminum matrix composite, various countries researcher is in mistake
Organic solvent and ultrasonic disperse, high-energy ball milling, fabricated in situ, molecular scale mixing, melt infiltration are employed in the more than ten years gone
The methods of, these technologies of preparing all achieve success to a certain extent.The but performance of CNTs/Al composites and theoretical phase
Than greatest differences still be present, its potentiality is brought into play far away.The CNT for being presently used for aluminum matrix composite preparation is big
Prepared more using CVD, compared with graphite acr method and laser evaporization method, the method has an advantages such as yield is big, cost is low, but by
The carbon pipe of this production often mutually crimps, is intertwined, and this obviously brings bigger obstacle to dispersion process.By carbon nanometer
Pipe in the base it is dispersed can be related to mostly carbon length of tube shorten (either will add matrix after carbon pipe shortization in advance,
Or prescinded during being mixed with matrix), high-energy ball milling with its is simple to operate, can batch processing become at present extensively
One of method used.Obviously, shortization can cause carbon pipe end-blown to increase, and structural intergrity reduces, in addition, in mechanical milling process
Strong collision also structural pipe wall can be caused to damage.Theoretically, CNT be considered as it is bent by graphite-based roll and
Into its reactivity is very low, and (surface free energy is only 0.15J/m2), but due to the generation of various defects, itself and alloy matrix aluminum
Generation carbide (the Al that chemically reacts will occur at high temperature4C3).Carbon is difficult to spontaneous profit with the most metals including Al
Wet, although research shows, interfacial reaction to a certain extent can improve wetability, increase interface bond strength, largely
The generation of reactant undoubtedly weakens the invigoration effect of reinforcement, therefore reduces the degree of injury of reinforcement in composite, essence
The problem of really regulation and control interface structure is equally one extremely important.
The content of the invention
The present invention is in view of the above-mentioned problems of the prior art, provide a kind of carbon nanotube enhanced aluminium-based composite material
Preparation method, the purpose is to realize dispersed, reduction reinforcement degree of injury of the CNT in alloy matrix aluminum, formed
The high-performance aluminum-base composite material that microstructure is uniform, interface cohesion is good.
The purpose of the present invention is achieved through the following technical solutions：
The preparation process of this kind of carbon nanotube enhanced aluminium-based composite material is：The aluminium that average grain diameter is 10~120 μm is closed
Bronze end is fitted into stirring ball mill with CNT, is passed through liquid nitrogen (or liquid argon) and carries out low temperature ball milling.In mechanical milling process, carbon
Nanotube, metal dust and abrading-ball are fully immersed in liquid nitrogen；After ball milling terminates, powder slurries are collected in rustless steel container
And stand.After liquid nitrogen volatilization, dry powder is loaded into aluminium jacket, aluminum matrix composite base is made in deaerated, high temperature insostatic pressing (HIP)
Material, blank is subjected to hot extrusion, hot rolling or forging bar, section bar, sheet material or forging is made, be finally heat-treated.Wherein：
A diameter of 10~80nm of the CNT, length are 2~50 μm, account for the 0.1~5% of composite powder quality；
The technological parameter of ball milling is：Rotational speed of ball-mill is 80~500r/min, and Ball-milling Time is 0.5~10h, ball material mass ratio
For 1:5~50, Material quality of grinding balls is steel or ceramics, a diameter of 3~15mm；
The technological parameter of degasification is：The aluminium jacket for loading composite powder is carried out using resistance furnace and vacuum pump set heating and
Vacuumize, be first evacuated to vacuum at room temperature less than 1 × 10-1Pa, then begin to warm up, and keep vacuumizing, when temperature reaches
At 300 DEG C, 2~5h is incubated, it is finally heated to 440~500 DEG C, and vacuum is evacuated to less than 2 × 10-3Pa, it then will remove gas port
Soldering and sealing；
The technological parameter of high temperature insostatic pressing (HIP) is：To the mixed-powder in jacket carry out consolidate shaping hip temperature be
400~500 DEG C, pressure is 100~130MPa, and the time is 2~5h.
Aluminium jacket is made by pure aluminum or aluminum alloy, with except gas port.Aluminum matrix composite blank is removed by machining car
Obtained after aluminium alloy jacket.
Technical solution of the present invention has compared with existing high-energy ball milling method prepares carbon nanotube enhanced aluminium-based composite material
Advantages below：
(1) Ball-milling Time is short, and carbon pipe is scattered more uniform
The present invention carries out ball milling in liquid nitrogen, and the flexible of carbon pipe reduces under low temperature, is more easy to occur to break under shearing force
Split, so as to carbon pipe, quickly shortization, winding body are disengaged；On the other hand, strong mechanical agitation and liquid-nitrogen boiling make carbon pipe and
Al alloy powder mixes repeatedly, therefore reinforcement being uniformly distributed in the base is able to quickly realize (about several hours), and passes
Ball milling unite typically in 15-48h.In addition, under low temperature, metal dust cold welding weakens, and is easy to develop towards flaking direction, increases
With the contact area of CNT, also dispersiveness is further improved.
(2) powder high purity, process contamination are small
Ball milling in the present invention is carried out in inertia cryogenic media, substantially not with air contact, therefore Powder Oxidation can
Can property very little.Compared with traditional ball milling, it is not required that addition suppresses the process control agent (such as stearic acid) of coldwelding, further
Reduce the pollution of external additive.
(3) carbon tubular construction is complete in composite, is well combined with basal body interface
Due to the processing time is short of low temperature ball milling, while belong to wet ball grinding, mixed process is relatively soft, so as to reduce
Wall defects caused by collision.When carrying out being consolidated into type using high temperature insostatic pressing (HIP) and extruding, without large-sized brittle carbides
Produce, carbon pipe is maintained as the invigoration effect of reinforcement；But the meanwhile nanoscale generated at former carbon defective tube
Al4C3Wetability is improved, adds interface bond strength.
Brief description of the drawings
Fig. 1 is the schematic diagram of stirring ball mill in embodiment
Fig. 2 (a) and the transmission electron microscope photo that (b) is composite in embodiment
Fig. 3 is the Raman scattering collection of illustrative plates of composite in embodiment
Embodiment
Technical solution of the present invention is described in further detail below in conjunction with drawings and examples：
Embodiment
Using 2009 Al alloy powders, its composition is 3.0wt.%Cu, 1.5wt.%Mg, Al surplus, and average grain diameter is 30 μ
m；The nominal diameter of multi-walled carbon nanotube is 40~60nm, and length is 5~15 μm.1kg Al alloy powder and more wall carbon are received
The mixed-powder and 40Kg abrading-balls of mitron are fitted into stirring ball mill, Material quality of grinding balls ZrO2, multi-walled carbon nanotube accounts for mixing
The 1.0% of powder quality, ball radius are respectively 3mm, 5mm, 8mm, and corresponding mass ratio is 2:1:1, accompanying drawing 1 is stirring-type ball
Grinding machine schematic diagram.
Liquid nitrogen is passed through into ball grinder, after abrading-ball and mixed-powder are totally immersed into liquid nitrogen, starts ball milling, its rotating speed is
180r/min, Ball-milling Time 2h.Observation amount of liquid nitrogen is paid attention in mechanical milling process, it is flooded abrading-ball and mixed powder all the time
End, otherwise, first suspend ball milling and supplement liquid nitrogen.After ball milling terminates, powder slurries are collected in rustless steel container, stand 3h,
After liquid nitrogen volatilization, dry composite powder is obtained.
Dry composite powder is fitted into 80 × 180mm of Ф aluminium jacket, it is small that jacket is evacuated into vacuum at room temperature
In 1 × 10-1Pa, then begin to warm up, and keep vacuumizing, when temperature reaches 300 DEG C, be incubated 2h, be then heated to 480
DEG C, degasification to vacuum is less than 2 × 10-3Pa, finally sealed.
Jacket is subjected to high temperature insostatic pressing (HIP), temperature is 465 DEG C, pressure 120MPa, time 3h.
Aluminium jacket is removed by machining, obtains carbon nanotube enhanced aluminium-based composite material blank.Extruded in 1000t bedrooms
Blank is hot extruded into bar on machine, extrusion temperature is 460 DEG C, extruding rate 2mm/s, extrusion ratio 18：1, extruded barses are straight
Footpath is Ф 15mm.
By extruded barses at 498 DEG C solution treatment 4h, in room temperature water of then quenching, finally carry out natrual ageing.
Table 1 gives the room temperature tensile properties of high-performance carbon nanotube reinforced aluminum matrix composites prepared by the present invention, with
Aluminum matrix alloy is compared, and tension and yield strength significantly improve and (25% and 24% be respectively increased), and still have good plasticity
(elongation percentage 10.2%), compared with having been reported (Liu etc., 2012), either tensile strength, yield strength be also in the present invention
It is that elongation percentage is all significantly higher than the latter.Fig. 2 is the microstructure photo of composite, it is seen that its crystal grain is tiny, while tubulose knot
The CNT of structure is uniformly distributed in the base.Fig. 3 gives the Raman spectrum of composite and original state CNT, with reference to
Microscopic appearance, it further demonstrate that the structure of carbon pipe in material preparation process keeps preferable, and ID/IGValue increase mainly due to
Caused by the change of carbon length of tube.
The mechanical property of the CNT/2009 aluminum matrix composites of table 1
[1]Z.Y.Liu,B.L.Xiao,W.G.Wang,et al.Carbon 50(5)(2012)1843-1852。
Claims (2)
- A kind of 1. preparation method of carbon nanotube enhanced aluminium-based composite material, it is characterised in that：It it is 10~120 μm by average grain diameter Al alloy powder and CNT is fitted into stirring ball mill, liquid nitrogen or liquid argon progress low temperature ball milling are passed through, after ball milling Powder slurries load aluminium jacket after drying, and aluminum matrix composite blank is made in deaerated, high temperature insostatic pressing (HIP), and blank is carried out into hot extrusion Bar, section bar, sheet material or forging is made in pressure, hot rolling or forging, is finally heat-treated, in：A diameter of 10~80nm of the CNT, length are 2~50 μm, account for the 0.1~5% of mixed-powder quality；The technological parameter of ball milling is：Rotational speed of ball-mill is 80~500r/min, and Ball-milling Time is 0.5~10h, and ball material mass ratio is 1: 5~50, Material quality of grinding balls is steel or ceramics, a diameter of 3~15mm；The technological parameter of degasification is：The aluminium jacket for loading composite powder is heated and taken out very using resistance furnace and vacuum pump set Sky, vacuum is first evacuated at room temperature less than 1 × 10-1Pa, then begin to warm up, and keep vacuumizing, when temperature reaches 300 DEG C When, 2~5h is incubated, it is finally heated to 440~500 DEG C, and vacuum is evacuated to less than 2 × 10-3Pa；The technological parameter of high temperature insostatic pressing (HIP) is：Mixed-powder in jacket consolidate the hip temperature of shaping for 400~ 500 DEG C, pressure is 100~130MPa, and the time is 2~5h.
- 2. the preparation method of carbon nanotube enhanced aluminium-based composite material according to claim 1, it is characterised in that：Carbon nanometer Pipe uses after pretreatment, pre-processes as surface functionalization, graphitization or nickel plating, copper.
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| CN107099687A (en) * | 2017-04-14 | 2017-08-29 | 武汉理工大学 | A kind of boron carbide particles strengthen the preparation method of nanometer/Ultra-fine Grained aluminum matrix composite |
| CN112111700B (en) * | 2020-09-02 | 2022-03-04 | 上海交通大学 | Online quenching heat treatment method for nano-carbon reinforced aluminum alloy composite extruded section |
| CN112024896B (en) * | 2020-10-16 | 2023-03-28 | 湘潭大学 | Preparation method of CNTs-ZA27 zinc-aluminum-based composite bar with high C content |
| CN113373341A (en) * | 2021-06-18 | 2021-09-10 | 苏州第一元素纳米技术有限公司 | Manufacturing process of carbon nano tube reinforced aluminum electric power fitting |
| CN113684391B (en) * | 2021-08-20 | 2022-05-27 | 中国兵器科学研究院宁波分院 | Preparation method of high-performance aluminum alloy and composite material thereof |
| CN114950649B (en) * | 2022-04-29 | 2024-04-09 | 中国人民解放军总医院第三医学中心 | Constant low-temperature grinding device and method for preparing micron-sized biological hard tissue material |
| CN115261689A (en) * | 2022-07-29 | 2022-11-01 | 苏州第一元素纳米技术有限公司 | Light aluminum alloy composite material and preparation method and application thereof |
| CN116497250B (en) * | 2023-06-27 | 2023-10-27 | 有研工程技术研究院有限公司 | High-modulus aluminum-based composite foil and preparation method thereof |
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