CN103757569A - Ordered carbon nano-tube reinforced aluminum matrix composite material and preparation method thereof - Google Patents
Ordered carbon nano-tube reinforced aluminum matrix composite material and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses an ordered carbon nano-tube reinforced aluminum matrix composite material and a preparation method thereof. The composite material comprises aluminum or an alloy thereof adopted as a matrix material and carbon nano-tubes orderedly dispersed in the matrix material. The method comprises: carrying out cross-lamination on plural ordered carbon nano-tube thin film layers and plural aluminum layers or aluminum alloy layers, and carrying out hot rolling to form the ordered carbon nano-tube reinforced aluminum matrix composite material, wherein the ordered carbon nano-tube thin film layer is formed by the plural orderly-dispersed carbon nano-tubes. According to the present invention, the ordered carbon nano-tube thin film such as the superaligned nano-tube thin film and the like is adopted to carry out lamination and hot rolling with the aluminum foil to prepare the composite material so as to achieve orientation distribution of the carbon nano-tubes in the aluminum matrix, completely provide excellent mechanical property and functional characteristics of the carbon nano-tubes, achieve mechanical enhancement and function modification on the aluminum matrix composite material, combine with the hot rolling molding, and provide important practical application prospects.
Description
Technical field
The present invention relates to a kind of preparation technology of aluminum matrix composite, specially refer to a kind of ordered carbon nanotube reinforced aluminum matrix composites and preparation method thereof.
Background technology
Structure lightweight is that aerospace, communications and transportation, electric power transport and great demand and the development trend of industrial equipment, is energy-saving and emission-reduction, improves efficiency, increases voyage load, reduces the key issue of working cost.Wherein lightweight structure material is key core technology, for hard-core technology and Important Project provide critical support material.As Novel light metal-base composites, carbon nanotube enhanced aluminium-based composite material is with its lightweight, high-strength, high rigidity, a series of excellent specific properties such as wear-resistant, corrosion-resistant, show the performance advantage that comprehensively surmounts conventional particles reinforced aluminum matrix composites, its industrial applications prospect represents gradually, receives very big concern.Research shows, the carbon nanotube of 2-5wt% adds, and its reinforced effects can reach the reinforced effects of the SiC ceramic particle of 10-20wt%, and its unit elongation still can remain on more than 4%, and now SiC reinforced particulate system has not almost had plasticity workability.Current Beyer Co., Ltd has released its business-like carbon nanotube and has strengthened 5083 Al alloy composites (registered trademark Zentallium), its tensile strength can reach 700 MPa, Young's modulus 80 GPa, intensity can be compared with carbon steel, density but only have its 1/3rd.Therefore, carbon nanotube enhanced aluminium-based composite material is the superior aluminum matrix composite of tough over-all properties, is subject to the extensive concern of industry member.
Although theoretical investigation shows single-root carbon nano-tube and have superpower mechanical property, Single Walled Carbon Nanotube tensile strength can be up to 200 GPa, Young's modulus 1 TPa, and the performance of carbon nano tube compound material but reaches far away people and expects.Determine that carbon nanotube key factor of mechanical property performance in body material comprises: the compound and interface combination of carbon nanotube dispersed, orientation, high-content.Since being found, carbon nanotube has been considered as outstanding mechanics reinforcement, disperseing, compound and interface carried out large quantity research in conjunction with field, various dispersion complex methods have been developed, but realize the orientation of carbon nanotube in matrix material and arrange that difficulty is very large always, although can make carbon nanotube acquisition wherein partially oriented by plastic processing deformation in polymer matrix composites, in metal-base composites, this technique cannot be competent at.
Carbon nanotube enhanced aluminium-based composite material preparation method has powder metallurgic method, spraying method, hot rolling/hot extrusion, super large viscous deformation processing method, agitating friction welding method, in situ synthesis etc. at present, no matter adopt which kind of method, take carbon nanotube dust raw material as starting point, must be through Ball milling, alloying mixing and follow-up sintering or plastic working moulding, carbon nanotube structure is destroyed seriously, greatly reduce the performance of carbon nanotube mechanical property.The more important thing is, almost could not relate to carbon nanotube distribution of orientations problem, more cannot design matrix material from internal networking structure.CN102787283A discloses a kind of method that carbon nanotube reinforced copper-base composite material is prepared in powder in tube rolling, carries out the standby target product that obtains of hot rolling after carbon nanotube is mixed with copper powder after inclosure copper pipe.CN102424920A discloses a kind of in-situ preparation method of micro-nano lamination metal base composite material, at flake aluminum surface in situ carbon nano-tube, then by lamination hot rolling, prepares target product.Same, in the technology providing in aforementioned two patents of invention, carbon nanotube is to be still randomly dispersed within body material.In addition, current all reports and publication are all without how realizing the ordered arrangement of carbon nanotube in aluminum substrate and the method for network structure design, realize the distribution of orientations of carbon nanotube in matrix metal, be the research work with significant challenge always, still have many Science and Technology problems urgently to be resolved hurrily.
Summary of the invention
The object of the invention is to for deficiency of the prior art, a kind of ordered carbon nanotube reinforced aluminum matrix composites and preparation method thereof is provided, it passes through carbon nanotube ordered distribution in aluminum substrate, can realize manual control assembling and form ordered network structure, give full play to the superpower mechanical property of carbon nanotube one-dimentional structure, realization strengthens aluminum matrix composite mechanical property, give function modified feature simultaneously and realize carbon nanotube network regulation and control Properties of Aluminum Matrix Composites, development has the structure-function integration matrix material of anisotropy functional performance.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of ordered carbon nanotube reinforced aluminum matrix composites, comprises as aluminium or its alloy of body material and is scattered in order the carbon nanotube in described body material.
Further, described matrix material comprises 0.01-10wt% carbon nanotube, and wherein carbon nanotube distributes along setting ordered orientation at least partly.
Further say, described matrix material comprises 0.01-10wt% carbon nanotube, at least partly carbon nanotube with set angle, intersect to form regular network structure.
Further say, described carbon nanotube is all along single direction ordered distribution.
Further say, described ordered carbon nanotube reinforced aluminum matrix composites is by plural ordered carbon nanotube thin film layer and plural aluminium or the cross layered rear hot rolling of its alloy layer are formed.
As one of comparatively preferred embodiment, wherein at least two-layer adjacent ordered carbon nanotube thin film layer is to be bent to form by least one continuous ordered carbon nanotube film.
As one of comparatively preferred embodiment, described ordered carbon nanotube film comprises: classifying raw material as by spinning carbon nano-pipe array, and the super suitable carbon nano-tube film of preparing by array membrane technology.
Wherein at least one ordered carbon nanotube thin film layer, the orientation of carbon nanotube is all different from the orientation of carbon nanotube in another ordered carbon nanotube thin film layer at least.
A preparation method for ordered carbon nanotube reinforced aluminum matrix composites, comprising: plural ordered carbon nanotube thin film layer and plural aluminium or the cross layered rear hot rolling of its alloy layer are formed to described ordered carbon nanotube reinforced aluminum matrix composites; Described ordered carbon nanotube thin film layer is formed by the plural carbon nanotube of ordered distribution.
Further, described ordered carbon nanotube thin film layer is by forming along the plural carbon nanotube of setting distribution of orientations, or described ordered carbon nanotube thin film layer comprises the regular network structure being intersected to form with set angle by plural carbon nanotube.
Further, the method comprise the steps: by plural ordered carbon nanotube thin film layer and plural aluminium or its alloy layer cross layered after, Vacuum Package in sheath material, then in 350-600 ℃ through the above hot-roll forming of two passages.
Compared with prior art, advantage of the present invention is at least:
(1) by by carbon nanotube ordered arrangement in aluminum substrate, be conducive to give full play to the performance advantage of carbon nanotube one-dimentional structure, obtain significant mechanics and strengthen, overcome the deficiency of disordered carbon nanotube, develop its anisotropy calorifics and electric property application;
(2) by hot rolling technology, ordered carbon nanotube film and the hot rolling of aluminium foil lamination are prepared into matrix material, high-temperature residence time is short, there is efficient, the continuous feature of technique, can effectively control aluminum substrate and react with carbon nanotube high-temperature interface, and avoid the violent destruction to carbon nanotube structure in powder metallurgic method mechanical milling process; Meanwhile, based on lamination hot rolling technology, prepare carbon nanotube enhanced aluminium-based composite material and there is important mass-producing exploitation and using value.
(3) by by orderly carbon nanocapsule thin film multi-angle crossing stack, can prepare the aluminum matrix composite that ordered network structure strengthens, realize the effective modulation to anisotropic properties.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of ordered carbon nanotube reinforced aluminum matrix composites in embodiment 1;
Fig. 2 is the mechanical property figure that 1-4 of embodiment obtains ordered carbon nanotube reinforced aluminum matrix composites;
Fig. 3 is the mechanical property figure that embodiment 1,5-7 obtain ordered carbon nanotube reinforced aluminum matrix composites;
Fig. 4 is the mechanical property figure that embodiment 1,8-10 obtain ordered carbon nanotube reinforced aluminum matrix composites.
Embodiment
In view of many defects of prior art, one aspect of the present invention aims to provide a kind of ordered carbon nanotube reinforced aluminum matrix composites, this material consists of carbon nanotube and aluminium or its alloy, wherein aluminium or its alloy are body material, carbon nanotube is in order or rule is arranged is scattered in body material, and carbon nanotube weight percent is 0.01-10%.
Further say, aforementioned carbon nanotube distribution in body material can be along single direction ordered distribution and present any one that arbitrarily angled regular crossover network distributes.
Another aspect of the present invention aims to provide a kind of preparation method of ordered carbon nanotube reinforced aluminum matrix composites, comprising: plural ordered carbon nanotube thin film layer and plural aluminium or the cross layered rear hot rolling of its alloy layer are formed to described ordered carbon nanotube reinforced aluminum matrix composites.
As a kind of scheme that can implement wherein, the method can comprise: adopt the chemical vapour deposition technique preparation can spinning carbon nano pipe array, directly by the super suitable carbon nano-tube film of array membrane technology preparation; Be laid on subsequently aluminium foil surface, through lamination repeatedly, vacuum-sealing is in sheath material; Finally, be preheating to certain temperature, by multiple tracks hot rolling, prepare fine and close blank, machining is subsequently removed sheath material and is obtained target material.
Aforementioned can spinning carbon nano pipe array preparation method can realization by any one in following manner:
(1) by physical deposition techniques at smooth substrate surface deposition catalyst Fe, Co or Fe/Co, substrate can be any one of monocrystalline silicon piece, polysilicon chip, silica glass, pottery; Under 500-900 ℃ of high temperature, by chemical vapour deposition technique, growing subsequently can spinning carbon nano pipe array, and its carbon source adopting can be any one or arbitrary combination of the organic steams such as the organic gass such as methane, ethene, acetylene, Sweet natural gas or ethanol, benzene, toluene;
(2) by directly catalyzer being passed into together with carbon source atmosphere in 500-900 ℃ of high temperature CVD stove, can spinning carbon nano pipe array at substrate surface in-situ deposition, its catalyzer adopting can be organic molysite and the inorganic molysites such as ferrocene, iron trichloride, iron nitrate, and its carbon source adopting can be any one or arbitrary combination of the organic steams such as the organic gass such as methane, ethene, acetylene, Sweet natural gas or ethanol, benzene, toluene.
Certainly, the ordered carbon nanotube film in the present invention also can adopt other known technology preparation of those skilled in the art.
Aforementioned carbon nanotube can be any one of multi-walled carbon nano-tubes, few-wall carbon nanotube and Single Walled Carbon Nanotube.
0.1 micron-1000 microns of aforementioned aluminium and alloy aluminum foil thickness thereof, can be any one or arbitrary combination in the series alloys such as fine aluminium, Al-Si system, Al-Mg system, Al-Cu system, Al-Zn system, Al-Mg system, Al-Mn system, and be not limited to this.
As one of comparatively preferred embodiment, the lamination of aforementioned ordered carbon nanotube film and aluminium foil can be from three layers to any number of plies, and can be with arbitrarily angled crossing stack, and formation carbon nanotube has sequence network.
As one of comparatively preferred embodiment, preceding method specifically can comprise: sample vacuum-sealing in copper pipe or aluminum pipe after, through hot-roll forming repeatedly, hot-rolled temperature 350-600 ℃.
Aforementioned sheath material, except adopting aforementioned copper pipe or aluminum pipe, also can adopt other metal or non-metallic material, and this is those skilled in the art's concrete adjustment according to the demand of practical application.
As a kind of typical embodiment wherein, preceding method can comprise: adopt electron beam evaporation at silicon wafer-based bottom sediments aluminum oxide transition layer, deposit subsequently Fe, Co or Fe/Co composite membrane as carbon nano pipe array growth catalyst, in tube furnace, adopt subsequently the CVD method growth can spinning carbon nano pipe array; Then by array membrane technology, prepare the super suitable carbon nano-tube film with different carbon nanotube structures, be laid on aluminium foil surface, because carbon nanotube has huge surface-area, can adsorbed close at aluminium foil surface, multilayer intersect stacking, by sample vacuum-sealing in aluminum pipe or copper pipe; Then be preheating to certain temperature (350-600 ℃), standby by multi-pass hot rolling, machining obtains fine and close aluminum matrix composite after removing jacket.
In aforementioned preparation method, for obtaining fine and close aluminum matrix composite, in hot rolling technology, preferably control relative reduction more than 50%.
Below in conjunction with accompanying drawing and some embodiment, technical scheme of the present invention is further described.
embodiment 1referring to Fig. 1, this carbon nanotube enhanced aluminium-based composite material is preparation method be achieved in that
Step 1: adopt electron beam evaporation at silicon wafer-based bottom sediments aluminum oxide transition layer, deposit subsequently Fe, Co or Fe/Co composite membrane as carbon nano pipe array growth catalyst, adopt subsequently the chemical Vapor deposition process preparation can spinning carbon nano pipe array in tube furnace; Then by solid phase drawing-die technology, obtain super in-line arrangement carbon nano-tube film;
Step 2: it is that pure aluminum foil 2 surfaces of 0.03mm are repeatedly stacking that super in-line arrangement carbon nano-tube film 1 is laid on to thickness, is cut into the sample that is of a size of 15mm × 20mm;
Step 3: in the copper pipe that is 30mm in external diameter 25mm, wall thickness 0.5mm, length by sample vacuum-sealing, carbon nano-tube film and aluminium foil crossing stack are 7 layers, when relative reduction is 50%, roll rotational speed is that the duo mill of 40rpm is at 500 ℃ of hot-roll formings, machined excision sheath material subsequently, finally obtains ordered carbon nanotube film reinforced aluminum matrix composites.
embodiment 2the difference of the present embodiment and embodiment 1 is, the thick 0.1mm of aluminium foil in step 2.
embodiment 3the difference of the present embodiment and embodiment 1 is, the thick 0.05mm of aluminium foil in step 2.
embodiment 4the difference of the present embodiment and embodiment 1 is, the thick 0.01mm of aluminium foil in step 2.
embodiment 5the difference of the present embodiment and embodiment 1 is, in step 3, crossing stack is 3 layers.
embodiment 6the difference of the present embodiment and embodiment 1 is, in step 3, crossing stack is 5 layers.
embodiment 7the difference of the present embodiment and embodiment 1 is, in step 3, crossing stack is 9 layers.
embodiment 8the difference of the present embodiment and embodiment 1 is, in step 3, rolling temperature is 400 ℃.
embodiment 9the difference of the present embodiment and embodiment 1 is, in step 3, rolling temperature is 450 ℃.
embodiment 10the difference of the present embodiment and embodiment 1 is, in step 3, rolling temperature is 550 ℃.
By the mechanical property of the obtained carbon nanotube enhanced aluminium-based composite material of embodiment 1-10 technique, hardness data etc., refer to Fig. 2-4.If adopt the ordered carbon nanotube film of different carbon nanotube structures to substitute the ordered carbon nanotube film of aforesaid carbon nanotube structure, also can obtain close result.
More than explanation, and the embodiment shown on drawing, can not resolve the design philosophy surely of the present invention that is limited.In technical field of the present invention, holding the identical the knowledgeable of knowing can change technical thought of the present invention with various form improvement, such improvement and change are interpreted as belonging in protection scope of the present invention.
Claims (12)
1. an ordered carbon nanotube reinforced aluminum matrix composites, comprises aluminium or its alloy as body material, it is characterized in that, it also comprises the carbon nanotube being scattered in order in described body material.
2. ordered carbon nanotube reinforced aluminum matrix composites according to claim 1, is characterized in that, it comprises 0.01-10wt% carbon nanotube, and wherein carbon nanotube distributes along setting ordered orientation at least partly.
3. ordered carbon nanotube reinforced aluminum matrix composites according to claim 1, is characterized in that, it comprises 0.01-10wt% carbon nanotube, and wherein carbon nanotube intersects to form regular network structure with set angle at least partly.
4. ordered carbon nanotube reinforced aluminum matrix composites according to claim 1, is characterized in that, it is by plural ordered carbon nanotube thin film layer and plural aluminium or the cross layered rear hot rolling of its alloy layer are formed.
5. ordered carbon nanotube reinforced aluminum matrix composites according to claim 4, is characterized in that, wherein at least two-layer adjacent ordered carbon nanotube thin film layer is to be bent to form by least one continuous ordered carbon nanotube film.
6. according to the ordered carbon nanotube reinforced aluminum matrix composites described in claim 4 or 5, it is characterized in that, described ordered carbon nanotube film comprises: classifying raw material as by spinning carbon nano-pipe array, and the super suitable carbon nano-tube film of preparing by array membrane technology.
7. according to the ordered carbon nanotube reinforced aluminum matrix composites described in claim 4 or 5, it is characterized in that, wherein at least one ordered carbon nanotube thin film layer, the orientation of carbon nanotube is all different from the orientation of carbon nanotube in another ordered carbon nanotube thin film layer at least.
8. ordered carbon nanotube reinforced aluminum matrix composites according to claim 4, is characterized in that, described aluminium or its alloy layer comprise that thickness is aluminium foil or the alloy foil of 0.1 micron-1000 microns.
9. a preparation method for ordered carbon nanotube reinforced aluminum matrix composites, is characterized in that, comprising: plural ordered carbon nanotube thin film layer and plural aluminium or the cross layered rear hot rolling of its alloy layer are formed to described ordered carbon nanotube reinforced aluminum matrix composites;
Described ordered carbon nanotube thin film layer is formed by the plural carbon nanotube of ordered distribution.
10. the preparation method of ordered carbon nanotube reinforced aluminum matrix composites according to claim 9, it is characterized in that, described ordered carbon nanotube film comprises: classifying raw material as by spinning carbon nano-pipe array, and the super suitable carbon nano-tube film of preparing by array membrane technology.
11. preparation methods of ordered carbon nanotube reinforced aluminum matrix composites according to claim 9, it is characterized in that, the method comprise the steps: by plural ordered carbon nanotube thin film layer and plural aluminium or its alloy layer cross layered after, Vacuum Package in sheath material, then in 350-600 ℃ through the above hot-roll forming of two passages.
12. according to the preparation method of ordered carbon nanotube reinforced aluminum matrix composites described in claim 9 or 11, it is characterized in that, described aluminium or its alloy layer comprise that thickness is aluminium and the alloy aluminium foil thereof of 0.1 micron-1000 microns, and described aluminium or its alloy comprise that fine aluminium, Al-Si system, Al-Mg system, Al-Cu system, Al-Zn system, Al-Mg system and Al-Mn are associated any one or the two or more combinations in gold.
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| CN104805432A (en) * | 2015-04-01 | 2015-07-29 | 苏州第一元素纳米技术有限公司 | Preparation method of metal/nanocarbon composite |
| CN105648249A (en) * | 2016-03-02 | 2016-06-08 | 昆明理工大学 | Preparation method for carbon nano tube strengthened aluminum-based multilayer composite material |
| CN105734459A (en) * | 2014-12-12 | 2016-07-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of carbon nanotube reinforced aluminum base composite material |
| CN106048324A (en) * | 2016-07-13 | 2016-10-26 | 安徽祈艾特电子科技股份有限公司 | Carbon nano tube reinforced aluminum-magnesium composite alloy material for automobile electronic packaging and preparation method of alloy material |
| CN107377618A (en) * | 2017-06-21 | 2017-11-24 | 昆明理工大学 | A kind of preparation method of multilayer carbon nanotube/copper composite strip |
| JP2018188732A (en) * | 2017-05-08 | 2018-11-29 | ツィンファ ユニバーシティ | Three-dimensional porous composite material |
| CN110322987A (en) * | 2019-07-09 | 2019-10-11 | 山东大学 | A kind of carbon nanotube enhancing Multi-layer Al-based composite material and preparation method and application |
| US20200102227A1 (en) * | 2018-09-29 | 2020-04-02 | Tsinghua University | Nanoporous copper supported copper oxide nanosheet array composites and method thereof |
| CN112030044A (en) * | 2020-08-21 | 2020-12-04 | 武汉轻工大学 | Carbon nano tube reinforced aluminum matrix composite material and preparation method thereof |
| TWI754783B (en) * | 2018-11-22 | 2022-02-11 | 鴻海精密工業股份有限公司 | Aluminum matrix composite and mehtod thereof |
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| CN105734459A (en) * | 2014-12-12 | 2016-07-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of carbon nanotube reinforced aluminum base composite material |
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| CN105648249A (en) * | 2016-03-02 | 2016-06-08 | 昆明理工大学 | Preparation method for carbon nano tube strengthened aluminum-based multilayer composite material |
| CN106048324A (en) * | 2016-07-13 | 2016-10-26 | 安徽祈艾特电子科技股份有限公司 | Carbon nano tube reinforced aluminum-magnesium composite alloy material for automobile electronic packaging and preparation method of alloy material |
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| TWI754783B (en) * | 2018-11-22 | 2022-02-11 | 鴻海精密工業股份有限公司 | Aluminum matrix composite and mehtod thereof |
| US11312105B2 (en) | 2018-11-22 | 2022-04-26 | Tsinghua University | Aluminum matrix composites and method thereof |
| CN110322987A (en) * | 2019-07-09 | 2019-10-11 | 山东大学 | A kind of carbon nanotube enhancing Multi-layer Al-based composite material and preparation method and application |
| CN110322987B (en) * | 2019-07-09 | 2020-08-18 | 山东大学 | Carbon nanotube reinforced multilayer aluminum matrix composite material and preparation method and application thereof |
| CN112030044A (en) * | 2020-08-21 | 2020-12-04 | 武汉轻工大学 | Carbon nano tube reinforced aluminum matrix composite material and preparation method thereof |
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