CN105861872A - Carbon nanotube reinforced copper-based composite material and preparation method thereof - Google Patents

Carbon nanotube reinforced copper-based composite material and preparation method thereof Download PDF

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CN105861872A
CN105861872A CN201610437393.1A CN201610437393A CN105861872A CN 105861872 A CN105861872 A CN 105861872A CN 201610437393 A CN201610437393 A CN 201610437393A CN 105861872 A CN105861872 A CN 105861872A
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cnt
copper
composite
powder
gallic acid
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邵甄胰
蒋佳芯
宋庭丰
张归航
李峰
蒋小松
朱德贵
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Chengdu Technological University CDTU
Chengdu Univeristy of Technology
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/04Making alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/10Alloys containing non-metals
    • C22C1/1005Pretreatment of the non-metallic additives
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides whether added as such or formed in situ
    • C22C32/0047Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides whether added as such or formed in situ
    • C22C32/0084Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C26/00Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C22C2026/002Carbon nanotubes

Abstract

The invention discloses a carbon nanotube reinforced copper-based composite material. The carbon nanotube reinforced copper-based composite material is prepared from, by weight, 0.5%-5% of surface-modified carbon nanotubes, 2%-5% of graphite, 6%-15% of Ti3SiC2, 2%-5% of boron nitride (BN), 0.01%-0.5% of rare earth element La and the balance copper. The surface-modified carbon nanotubes are carbon nanotubes of which the surfaces are grafted with gallic acid. According to the copper-based composite material, the surface-modified carbon nanotubes are used, the carbon nanotubes are good in dispersity, the bonding area with a copper matrix is large, the reinforcement effect is good, a better stress transfer effect can be achieved, stress concentration is reduced, and defects are reduced. In addition, the carbon nanotubes, graphite powder, Ti3SiC2 powder and BN powder exert the synergistic reinforcement effect in the copper matrix, the mechanical property and friction-resistant and wear-resistant properties of the copper-based composite material are significantly improved, and meanwhile the copper-based composite material has excellent strength and impact resistance. The invention further discloses a preparation method of the copper-based composite material. The method is simple in process, production is easy, and the method has a wide application prospect.

Description

A kind of carbon nanotube reinforced copper-base composite material and preparation method thereof
Technical field
The invention belongs to field of compound material, relate to a kind of Cu-base composites, strengthen particularly to a kind of CNT Cu-base composites and preparation method thereof.
Background technology
CNT since the scientist Iijima by NEC Corporation of Japan in 1991 finds, just one-dimensional with its uniqueness The performances such as structure and unique electricity, optics are paid close attention to by numerous scholars deeply.CNT has high mechanical strength, ideal Elasticity, low thermal coefficient of expansion, size be little etc., and excellent characteristic makes that it has become most potential reinforcement material.
CNT achieves development quickly in terms of strengthening polymer composite, but is strengthening metal-based compound material Material aspect there is also many difficulties.Main difficulty among these is that CNT is the same with its nano material and has the biggest length , there is the biggest Van der Waals force, easily assemble entanglement in footpath ratio, specific surface area and specific surface energy, is difficult in metallic matrix uniformly Dispersion.On the other hand, the surface activity of CNT is relatively low, poor with the wettability of metallic matrix, which results in itself and Metal Substrate Interface cohesion between body is poor.These factors can have a strong impact on the density of metal-base composites, and mechanics, electricity, rubs The performances, especially friction and wear behavior such as scouring damage.In metallic composite field, Cu-base composites is widely used as electricity Sub-element material, sliding material, contact material, heat exchange material etc..Therefore, CNT is in terms of strengthening Cu-base composites Of greatest concern.
For solving problem above, some researchs at present are devoted to first to be modified CNT copper facing or nickel plating, so After use powder metallurgic method to prepare carbon nanotube reinforced copper-base composite material again.But CNT is modified copper facing or plating Nickel, complex process, energy consumption is big.Also some researchs are had to be devoted to use strong acid or nitration mixture that CNT is carried out pretreatment, The surface of CNT forms active group, improves its affinity for metal material, but carbon is received by this processing mode The structure of mitron has certain destruction, it will usually be extremely short CNT by cutting carbon nanotube, destroys its major diameter Ratio, and often need higher temperature and long period, energy consumption is relatively big, and processing procedure is easy to produce the gas of contaminative, band simultaneously Carry out problem of environmental pollution.
Chinese invention patent CN 101619426 A discloses employing mechanical ball milling and is fragmented into by CNT required Carbon nano-crystal palpus, and CNT is carried out pickling, drying, then to mix homogeneously with copper powder, preparation bulk carbon nano-crystal must increase Strong carbon/carbon-copper composite material.But in this enhancing carbon/carbon-copper composite material, the draw ratio of CNT is destroyed, and CNT is bigger Draw ratio is one of key factor strengthening substrate performance;Preprocessing process creates spent acid, for environmental effect relatively simultaneously Greatly, waste water intractability is the highest.
Chinese invention patent CN 103803523 A discloses a kind of surface modification of carbon nanotube and process for dispersing, first adopts With the mixed solution of highly basic and hydrogen peroxide, the surface of CNT is carried out pretreatment, the most again with tannic acid to pretreated CNT is modified processing, and obtains finely disseminated CNT.But, the tannic acid (C of grafting76H52O46) due to knot Structure is complex and molecular weight is bigger so that carbon nano tube surface introduces more C, H, O impurity element, the quality of CNT Receive large effect.Meanwhile, this technical process needs first to use highly basic and hydrogen peroxide to carry out pretreatment, and technique is loaded down with trivial details, and by force All there is certain potential safety hazard in the use of alkali and strong oxidizer.
Summary of the invention
It is an object of the invention to overcome carbon nano-tube material application difficult in Cu-base composites in prior art, The hydraulic performance decline of carbon nano-tube material or the deficiency of environmental pollution it is usually present, it is provided that a kind of CNT strengthens during use Cu-base composites.The good dispersion of CNT in this Cu-base composites, impurity content are low, and maintain complete carbon and receive Nanotube structures, form and specific surface, in composite, the performance of each component produces the effect strengthened altogether, significantly improves cuprio The wear resistance of composite and intensity and impact resistance, reduce the density of Cu-base composites.
It is a further object of the present invention to provide the preparation method of described Cu-base composites.
In order to realize foregoing invention purpose, the invention provides techniques below scheme:
A kind of carbon nanotube reinforced copper-base composite material, comprises following component by weight percentage: surface-modified carbon Nanotube 0.4~5%, graphite 2~6%, Ti3SiC26~15%, boron nitride (BN) 2~5%, rare-earth elements La 0.01~ 0.5%, surplus is copper.
Described surface-modified CNT is the CNT of surface grafting gallic acid.
Gallic acid, also known as gallic acid, gallic acid, its chemical entitled Gallic Acid, chemical formula is C6H2 (OH)3COOH, chemical structural formula shown in formula I, belongs to polyphenols, also belongs to organic acid.
On the one hand, gallic acid can be combined with carbon nano tube surface defect sites by self phenolic hydroxyl group, thus CNT is carried out surface modification, improves its dispersive property, simultaneously because the existence of the functional group such as carboxyl and hydroxyl, also can be Surface grafting more polyfunctional group and biological function macromole.On the other hand, gallic acid can also be by non-chemically acting on absorption In carbon nano tube surface.Two ways plays a role simultaneously and is more conducive to guarantee that enough gallic acids are grafted to CNT Surface, improves the dispersibility of CNT, and physical damnification or chemistry will be caused to damage CNT generation shear action Wound.Whereas if directly untreated CNT and copper powders are made Cu-base composites, matrix there will be because carbon is received The hole that mitron is reunited and formed, causes the combination property of material to reduce, does not reaches good reinforced effects.
Applicant finds, when the weight percent content of component each in Cu-base composites is: through table through substantial amounts of test The modified CNT 0.4-5% in face, powdered graphite 2~6%, Ti3SiC26~15%, BN 2~5%, rare-earth elements La 0.01~0.5%, surplus is when being copper powders, the performance of each component can produce the effect of common enhancing, and CNT and Copper substrate Between form preferable interface cohesion, and then strengthen the wear resistance of Cu-base composites and intensity and impact resistance Property.Wherein, graphite has protection Copper substrate, the effect of anti-melting welding, although graphite is nonwetting with Copper substrate, but the addition of graphite The Wear Mechanism of copper can be changed, the adhesive wear of fine copper transfer the abrasive wear of composite, and graphite linings lamellar knot to Structure, has self lubricity, can form carbon film, thus play the effect of anti-attrition between friction pair.Ti3SiC2With Copper substrate moistening Property good, lamellar structure improve composite friction and wear behavior on play the biggest effect.Rare-earth elements La is only because of it Special outer electronic structure and there is extremely strong chemism, valence state is variable and the characteristic such as thick atom size, becomes high added value Important microalloy element in metal material.The addition of La can improve the compacting consistency of Cu-base composites.BN (boron nitride) Being the non-oxide ceramic material of a kind of synthetic, it and C2 are isoelectronic specieses, therefore have similar crystal with carbon simple substance Structure, common BN has the hexagonal structure (h-BN) being similar to graphite and cubic (c-BN) two class being similar to diamond.BN Have high temperature resistant, heat resistanceheat resistant is shaken, antioxidation, high heat conductance, high resistivity, high dielectric property, self-lubricating, low-density, good adding Physics that work, resistance to chemical attack and various metals not infiltration etc. are excellent and chemical characteristic.BN is introduced in composite permissible Give full play to the advantage of BN, at thermally protective materials, high temperature wave-transparent material, high performance turbine friction material, ORC material It is with a wide range of applications in field, is one of the focus of composite research in recent years.
Further, described carbon nanotube reinforced copper-base composite material, comprise following component by weight percentage: through surface Modified CNT 0.4~5%, graphite 2~5%, Ti3SiC29~15%, boron nitride (BN) 2~5%, rare earth element La0.01~0.2%, surplus is copper.CNT has extraordinary mechanical property, is formed between CNT and Copper substrate Preferably interface cohesion, during extraneous loading force, stress can be transferred to CNT by interface, thus reach the work of enhancing body With.Preferably, Cu-base composites includes following component by weight percentage: surface-modified CNT 0.4~5%, Powdered graphite 2~5%, Ti3SiC2Powder 9~12%, BN powder 2~4%, rare-earth elements La powder 0.01~0.2%, surplus For copper powders.
Optimal the most preferably, Cu-base composites includes following component by weight percentage: surface-modified CNT 0.4-0.6%, powdered graphite 2-4%, Ti3SiC2Powder 9-12%, BN powder 3-4%, rare-earth elements La powder 0.8-0.2%. The raw material of particularly following ratio is processed preparing: surface-modified CNT 0.5%, powdered graphite 3%, Ti3SiC2Powder 10%, BN powder 3.5%, rare-earth elements La powder 0.1%, surplus are copper powders.
Further, CNT is used gallic acid aqueous solution modification to obtain by surface-modified CNT CNT.Preferably, described surface-modified CNT is made through following methods: CNT is joined Galla Turcica (Galla Helepensis) In aqueous acid, it is uniformly dispersed, stands, filter, take filtering residue and be vacuum dried, obtain the CNT of surface modification.Not yet Gallate-based can be attached to the surface of CNT by surface adsorption effect and realize corresponding modification, now, Galla Turcica (Galla Helepensis) Acid and the frame mode of CNT belong to and are non-chemically bonded, and both character can obtain maximized reservation, modified effect The best, and course of reaction is substantially without waste liquid generation.
Preferably, it is formulated that described gallic acid aqueous solution is dissolved in deionized water by gallic acid, and gallic acid is water-soluble In liquid, the concentration of gallic acid is 3~18 μ g/mL.Gallic acid, is on the one hand lacked with carbon nano tube surface by self phenolic hydroxyl group Fall into site combine, grafted functional group thus CNT is carried out surface modification;On the other hand, it is to utilize it the most pi-conjugated Structure and CNT generation pi-pi accumulation effect, thus CNT is modified, improve the dispersibility of CNT.Shen Asking someone to find through test of many times, when the concentration of gallic acid aqueous solution is less than 3 μ g/mL, carbon nano tube surface can be owing to not connecing More functional group on branch, thus affect the raising of its dispersibility.Along with the increase of gallic acid concentration of aqueous solution, CNT The amount of the gallic acid of surface adsorption can increase, when the concentration of gallic acid aqueous solution is more than 18 μ g/mL, on the contrary to Galla Turcica (Galla Helepensis) π-π adsorption between acid and CNT produces very adverse influence, makes the gallic acid of carbon nano tube surface occur , there is the phenomenon that modification amount reduces in desorption, it is impossible to play the effect improving CNT dispersibility.Preferably, described Galla Turcica (Galla Helepensis) The concentration of aqueous acid is 5~15 μ g/mL, and the most preferably, the concentration of described gallic acid aqueous solution is 10 μ g/mL.
Preferably, the ratio of the weight of described CNT and the volume of gallic acid aqueous solution be 0.05~0.5g:20~ 60mL;More preferably 0.05~0.2g:30~50mL;Optimal preferably 0.1g:40mL.
Further, described CNT is single-layer carbon nano-tube, few layer CNT or multilayer carbon nanotube.Described lacks Layer CNT generally refers to the CNT that the number of plies is 1-10 layer, the CNT of particularly 1-5 layer.Described multilamellar carbon is received Mitron is then the concept relative to single-layer carbon nano-tube, generally refers to the CNT of non-monolayer, and multilayer carbon nanotube can wrap Containing few layer CNT, above-mentioned few layer CNT, multilayer carbon nanotube are mainly the title of raw material, can be according to their name Buying is claimed to obtain corresponding raw material.Certainly, described CNT can also is that single-layer carbon nano-tube, few layer CNT and many The mixture of layer CNT.
Preferably, the time of described standing is 12~30h.For gallic acid stronger acids, character is the gentleest, works as standing Time is less than 12h, and the response time is too short, is unfavorable for the abundant combination of gallic acid and CNT;It is longer than between upon standing 30h, its modification is not further added by.More preferably 20~25h, the response time in this range when, gallic acid Optimal with the configuration state of CNT, and response time reaction efficiency is optimal.The optimal preferably response time is 24h.
Preferably, described vacuum drying temperature is 60 DEG C~80 DEG C;When vacuum drying temperature is less than 60 DEG C, it is dried effect Rate is low;When baking temperature is higher than 80 DEG C, non-ization between damage and gallic acid and the CNT of grafted functional group can be caused Weakening of effect;More preferably 60~70 DEG C, optimal preferably 60 DEG C.
Preferably, the described vacuum drying time is 1~3h.When vacuum is less than 1h drying time, and CNT is dried not Completely, affect the performance of CNT and it is characterized;Be longer than 3h between when drying, can cause grafted functional group damage and Non-chemically act between gallic acid and CNT weakens.More preferably 1~2h, the most preferably 2h.
By above to gallic acid concentration of aqueous solution, weight and the gallic acid aqueous solution of CNT volume it Ratio, quiescent time, vacuum drying temperature and time preferred, the dispersion of surface-modified CNT can be improved further Property, reduce the impurity content of CNT simultaneously, and then significantly improve the wear resistance of Cu-base composites and strong Degree and resistance to impact, reduce its density.
The present invention provides a kind of method preparing above-mentioned Cu-base composites.
The preparation method of a kind of Cu-base composites, comprises the steps:
(1) CNT is joined in gallic acid aqueous solution, be uniformly dispersed, stand, filter, take filtering residue and carry out vacuum It is dried, obtains the CNT of surface modification.
(2) by the CNT of surface modification and copper powders, powdered graphite, Ti3SiC2Powder, BN powder, La powder enter Row ball milling mixes powder, obtains composite powder.
(3) composite powder is carried out hot pressed sintering, cooling, then high temperature insostatic pressing (HIP) (Hot Isostatic Pressing, abbreviation HIP) carbon nanotube reinforced copper-base composite material is processed to obtain.
Preferably, described step (2) uses in mechanical milling process agate ball and Achates spherical tank, rotational speed of ball-mill be 150~ 300r/min, Ball-milling Time is 40~60min.Spheroidal graphite rotating speed is less than 150r/min, and Ball-milling Time is less than 40min, can cause multiple Close powder mixing inequality, during follow-up hot pressed sintering can be made, " segregation " phenomenon occurs;Spheroidal graphite rotating speed is higher than 300r/min, Ball-milling Time is higher than 60min, and CNT has obvious shear action.It is further preferred that rotational speed of ball-mill is 200r/ Min, Ball-milling Time is 50min.
Preferably, the temperature of described step (3) hot pressed sintering is 900~1000 DEG C;When sintering temperature can be led less than 900 DEG C Cause sintering imperfect, the sintering neck being firmly combined with between copper granule, can not be formed, do not reach the purpose of densification;Sintering temperature is higher than 1000 DEG C, have Ti3SiC2Thermal decomposition phenomenon, has crisp phase TiC and generates, affect the quality of Cu-base composites.Further, excellent The temperature selecting hot pressed sintering is 930-940 DEG C, preferably 950 DEG C.
Preferably, in described step (3), the pressure of hot pressed sintering is 25~40MPa;Sintering pressure is less than 25Mpa, compound In material compaction process, the adhesion between copper granule is weak, and defect easily occurs in material;Sintering pressure is higher than 40Mpa, in material Stress is big, is easily caused material cracks.It is further preferred that the pressure of hot pressed sintering is 25~30MPa, most preferably it is preferably 28MPa。
Preferably, in described step (3), the time of hot pressed sintering is 1~4h;Sintering time is shorter than 1h, can cause sintering not Completely, good combination can not be formed between each phase, not have the effect of enhancing;Sintering time is longer than 4h, can there is copper granule The phenomenon of abnormal growth, Copper substrate, in large stretch of block, strengthen the faying face mutually and between Copper substrate and reduces, and reinforced effects is paid no attention to Think.More preferably 1~3h;Optimal preferably 2h.
Compared with prior art, beneficial effects of the present invention:
1), Cu-base composites of the present invention employs the CNT of surface modification, with the most modified carbon Nanotube is compared, and the dispersibility of CNT is more preferable, and many with Copper substrate bonded area, reinforced effects is good;And impurity content is low, Reduce impurity and be avoided that some impurity element causes the phenomenon of matrix grain abnormal growth.
2), the Cu-base composites prepared of the present invention maintain the integrity of CNT, overcome tradition strong acid, highly basic After activation processing, the surface of CNT is destroyed serious defect.CNT bigger serface is that its bridging effect is formed Key, especially when material is by extraneous stress, bigger combination interface can play more preferable Stress Transfer effect, and reducing should Power is concentrated, and reduces the appearance of defect.
3), Cu-base composites of the present invention is by the CNT of surface modification, powdered graphite, Ti3SiC2Powder and copper powder End composition, the percentage by weight of each component regulates in optimum range, and each component can work in coordination with the effect strengthened altogether that produces, significantly Improve the wear resistance of Cu-base composites and intensity and resistance to impact, reduce its density.
4), the method for the Cu-base composites described in preparation that the present invention provides does not produces the pollutant such as waste water, spent acid, together Time technique simple, it is easy to produce, be advantageous to popularization and application.
Accompanying drawing illustrates:
Fig. 1 is the CNT Fourier transform infrared spectroscopy figure after variable concentrations gallic acid aqueous solution processes.
Fig. 2 is CNT TEM result figure before and after gallic acid processes.
SEM figure after the composite batch mixing that Fig. 3 embodiment 5~7 content of carbon nanotubes after ball mill mixing is different.
Fig. 4 embodiment 6 is composite powder EDS figure after ball mill mixing.
Detailed description of the invention
Below in conjunction with test example and detailed description of the invention, the present invention is described in further detail.But this should not understood Scope for the above-mentioned theme of the present invention is only limitted to below example, and all technology realized based on present invention belong to this The scope of invention.In the present invention, the percentage ratio for special instruction is weight percentage.
(multilamellar carbon is received for the SWCN (single-layer carbon nano-tube) related in the embodiment of the present invention and multi-walled carbon nano-tubes Mitron) it is purchased from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences.
Embodiment 1
The CNT that preparation is modified
Multi-walled carbon nano-tubes is joined in the gallic acid aqueous solution of 10 μ g/mL, is uniformly dispersed, stand 24h, filter, Collect filtering residue at 60 DEG C, be vacuum dried 2h, obtain the CNT of surface modification.The wherein weight of CNT and no food The ratio of the volume of sub-aqueous acid is 0.5g:60mL.
The CNT 0.1g of the surface modification prepared by the present embodiment 1 is dispersed in 100mL deionized water, quiet After putting 5 days, precipitate under gravity and gradually increase, but between CNT, remain in that dispersity, do not reunite; Contrast with the most modified CNT simultaneously, precipitation i.e. occurs after standing 1 day, and occurs between CNT to reunite now As, show that the CNT of surface modification prepared by embodiment 1 has the dispersibility of excellence.
Embodiment 2
The CNT that preparation is modified
Multi-walled carbon nano-tubes is joined in the gallic acid aqueous solution of 3 μ g/mL, be uniformly dispersed, wherein CNT Weight is 0.5g:60mL with the ratio of the volume of gallic acid aqueous solution;Stand 12h, filter, take filtering residue and be vacuum dried at 70 DEG C 1h, obtains the CNT of surface modification.
The CNT 0.1g of the surface modification prepared by the present embodiment is dispersed in 100mL deionized water, quiet After putting 3 days, precipitate under gravity and gradually increase, but between CNT, remain in that dispersity, do not reunite. Show that the CNT of surface modification prepared by embodiment 2 has the dispersibility of excellence.
Embodiment 3
The CNT that preparation is modified
Multi-walled carbon nano-tubes is joined in the gallic acid aqueous solution of 18 μ g/mL, be uniformly dispersed, wherein CNT Weight is 0.05g:20mL with the ratio of the volume of gallic acid aqueous solution;Stand 30h, filter, take filtering residue vacuum at 80 DEG C and do Dry 3h, obtains the CNT of surface modification.
The CNT 0.1g of the surface modification prepared by the present embodiment is dispersed in 100mL deionized water, quiet After putting 2 days, precipitate under gravity and gradually increase, but between CNT, remain in that dispersity, do not reunite. Show that the CNT of surface modification prepared by embodiment 2 has the dispersibility of excellence.
From embodiment 1~3, the CNT of the surface modification of embodiment 1 preparation stand 5 days after just at gravity Increasingly generate under effect and between precipitation, and CNT, the most well keep dispersity, do not reunite, and embodiment The CNT of the surface modification of 2 and 3 preparations generated precipitation, therefore embodiment after 2~3 days the most under gravity Method described in 1 is substantially better than the method described in embodiment 2 and 3.
Embodiment 4
The CNT that preparation is modified
The impact of the concentration of carbon nanotube dispersibility of gallic acid aqueous solution is discussed on the basis of embodiment 1.
The concentration changing gallic acid aqueous solution is 5 μ g/mL, 20 μ g/mL, and remaining all with embodiment 1, respectively obtains through table The CNT that face is modified.
CNT (the 5 μ g/mL) 0.1g of the surface modification prepared by the present embodiment is dispersed in 100mL deionization In water, after standing 3 days, precipitate under gravity and gradually increase, but between CNT, remain in that dispersity, do not send out Raw reunion.
CNT (the 20 μ g/mL) 0.1g of surface modification prepared by the present embodiment be dispersed in 100ml go from In sub-water, after standing 1 day, precipitating under gravity and gradually increase, gradually there is slight agglomeration in CNT.Show When the concentration of gallic acid aqueous solution is 20 μ g/mL, the modification of CNT is substantially reduced by it.
Fig. 1 is the CNT FTIR spectrum figure after variable concentrations gallic acid aqueous solution processes.Adopt simultaneously Contrast with the CNT (pure CNFs) processed without gallic acid aqueous solution.It will be seen from figure 1 that without Galla Turcica (Galla Helepensis) sour water The Fourier transform infrared spectroscopy figure peak shape of the CNT that solution processes is wider and peak value is more weak;And it is water-soluble through gallic acid CNT after liquid (5 μ g/mL, 10 μ g/mL) process is at 3430cm-1And 1640cm-1Neighbouring there is stronger absworption peak, point Not belonging to stretching vibration absworption peak and the bending vibration absworption peak of-O-H, wherein the peak value of 10 μ g/mL is the strongest.Carbon is received as can be seen here The more functional group of nanotube surface grafting or gallic acid are adsorbed in carbon nano tube surface by non-chemically effect, thus Improve the dispersibility of CNT.And continue to increase the concentration of gallic acid aqueous solution to 20 μ g/mL, 3430cm-1With 1640cm-1Neighbouring absworption peak is substantially with the CNT processed without gallic acid aqueous solution, and this is owing to high concentration does not has Gallate-based aqueous solution produces very adverse influence to the π-π adsorption between gallic acid and CNT, makes carbon nanometer The gallic acid of tube-surface is desorbed, and the phenomenon that modification amount reduces occurs, and then affects the dispersibility of CNT.
According to embodiment 4, through the CNT that 10 μ g/mL gallic acid aqueous solutions process, just exist after standing five days Increasingly generate under the effect of gravity and between precipitation, and CNT, remain in that good dispersity, do not reunite, and CNT after 5 μ g/mL gallic acid aqueous solutions process generates precipitation, the most under gravity through 20 μ After CNT after the process of g/mL gallic acid aqueous solution stands 1 day, precipitate under gravity and gradually increase, CNT Gradually there is slight agglomeration.Simultaneously according to FTIR spectrum figure, at 10 μ g/mL gallic acid aqueous solutions Carbon nano tube surface after reason has more functional group, thus further increases the dispersibility of CNT.To sum up, 20 μ G/mL and 5 μ g/mL and 10 μ g/mL compares, obvious difference, achieves unforeseeable effect, and therefore 10 μ g/mL are that the present invention does not has The optium concentration of gallate-based aqueous solution.
Embodiment 5
The CNT of the surface modification that Example 1 prepares.By weight, by the carbon of 0.5 part of surface modification Nanotube, 3 parts of powdered graphites, 10 parts of Ti3SiC2Powder, 3.5 parts of BN powder, 0.1 part of La powder, 82.9 parts of copper powders mixing, adopt Carrying out ball milling with agate ball and Achates spherical tank and mix powder, rotating speed is 200 turns/min, and Ball-milling Time is 50min, makes powder mixing all Even, obtain composite powder.Composite powder is carried out hot pressed sintering 2h, and the temperature of hot pressed sintering is 950 DEG C, pressure is 28MPa, with stove Cooling, obtains cuprio composite block material, and by this block materials high temperature insostatic pressing (HIP) 2h, HIP sintering temperature is 900 DEG C, pressure For 100MPa, rapid cooling, obtain carbon nanotube reinforced copper-base composite material.
Embodiment 6
The CNT of the surface modification that Example 2 prepares.By weight, by 1 part of CNT, 5 parts of graphite Powder, 15 parts of Ti3SiC2Powder, 6 parts of BN powder, 0.5 part of La powder, 72.5 parts of copper powders mixing, then carry out ball milling and mix powder, Rotating speed is 150 turns/min, and Ball-milling Time is 60min, makes powder mix homogeneously, obtains composite powder.Composite powder is carried out hot pressing Sintering 3h, the temperature of hot pressed sintering is 900 DEG C, pressure is 40MPa, furnace cooling, obtains cuprio composite block material.To obtain Block materials carry out high temperature insostatic pressing (HIP) 2h, HIP sintering temperature is 900 DEG C, pressure is 100MPa, rapid cooling, obtains CNT Strengthen Cu-base composites.
Embodiment 7
The CNT of the surface modification that Example 1 prepares.By weight, by 1.5 parts of CNTs, 2 parts of stones Powdered ink end, 6 parts of Ti3SiC2Powder, 4 parts of BN powder, 0.2 part of La powder, 86.3 parts of copper powders mixing, use agate ball and Achates Spherical tank carries out ball milling and mixes powder, and rotating speed is 200 turns/min, and Ball-milling Time is 50min, makes powder mix homogeneously, obtains composite powder.Will Composite powder carries out hot pressed sintering 2h, and the temperature of hot pressed sintering is 950 DEG C, pressure is 28MPa, furnace cooling, obtains cuprio multiple Close block materials.The block materials obtained is carried out high temperature insostatic pressing (HIP) 2h, and HIP sintering temperature is 900 DEG C, pressure is 100MPa, rapid cooling, obtain carbon nanotube reinforced copper-base composite material.
Fig. 2 (a) is that in embodiment 5, after ball mill mixing, 10000 times of SEM of composite powder scheme, and the left side is due to ball milling high pressure Etc. mechanism generation cold welding and the copper particle cluster of diffusion, be attached on copper particle cluster for tubulose CNT. Fig. 2 (b) is that in embodiment 6, after ball mill mixing, 50000 times of SEM of composite powder scheme, and can be clearly observed single carbon and receive Mitron is attached on copper granule, and the carbon nanotube portion of transparence embeds in copper particulate polymers.Fig. 2 (c) is ball in embodiment 6 The SEM figure of 33000 times of composite powder after mill batch mixing, tiny curling is evenly distributed on copper particle surface transparent sheet-like thing and is carbon Nanotube, CNT is uniformly dispersed as can be seen from FIG., illustrates that the process for dispersing that this patent uses is the most effective.And Fig. 2 (d) For 50000 times of SEM figure of composite powder after ball mill mixing in embodiment 7, it has been found that single CNT, and CNT It is attached to copper particle surface.Ball milling can change the shape of powder particle, and copper granule is the most mellow and the fullest, illustrates that ball milling cold welding effect is the poorest, In embodiment 5~7, between copper granule, cold welding phenomenon is obvious, it can be seen that SWCN is attached on copper granule, illustrates mixed Material effect is overall good, and the architectural feature of integral material is not impacted by the interpolation of CNT simultaneously.
Fig. 3 is the EDS figure of Fig. 2 (b).The unit detected have C, Cu, Ti, Si, B, N, O.Wherein detect O be probably because of There is partial oxidation for copper, prepare that powder in powder detection specimen is inevitable and air contact.
Use Archimedes method measures above-described embodiment and prepared by comparative example the density of Cu-base composites, consistency, And measure its Brinell hardness, tensile strength and comprcssive strength, its result is as shown in table 1.
The experimental result of table 1 embodiment 5~7.
Group Density (g/cm3) Consistency (%) Vickers hardness (HV) Tensile strength (MPa) Comprcssive strength (MPa)
Embodiment 5 6.99 98.00 91.95 78.54 191.32
Embodiment 6 6.74 93.62 73.64 43.98 170.17
Embodiment 7 6.33 99.68 72.68 44.12 160.08
As seen from the results in Table 1, the Cu-base composites that the Cu-base composites of embodiment 5 preparation is prepared with embodiment 6 and 7 Comparing, its micro-vickers hardness has been respectively increased 18.31HV, 19.27HV;Tensile strength be respectively increased 34.56MPa, 34.42MPa;Comprcssive strength has been respectively increased 21.15MPa, 31.24MPa.Therefore, the Cu-base composites phase of embodiment 5 preparation The Cu-base composites prepared for embodiment 6 and embodiment 7, has more excellent hardness and resistance to impact, and embodiment 5 is The preferred forms of Cu-base composites of the present invention, it is possible to the best technique effect reached desired by the present invention.
Test example
The fine copper (comparative example) that the Cu-base composites of testing example 5~7 preparation and same sintering process prepare, Rub resistance under different content of carbon nanotubes (wt%), different loads (F), rotating speed (r/min) three factor (I), polishing machine, Its result is as shown in table 2.
The rub resistance of Cu-base composites of table 2 embodiment 5 preparation, polishing machine
As shown in Table 2, implement 5 preparation Cu-base composites under conditions of load 450N, velocity of rotation 150r/min, Wear extent is only 0.0300g, rubs and examines coefficient and be only 0.250;Under conditions of load 650, sliding speed 50r/min, wear extent Also only have 0.0380g, rub and examine coefficient and be only 0.198.It follows that Cu-base composites of the present invention not only has very well Intensity and resistance to impact, have simultaneously excellence rub resistance, polishing machine.
Embodiment 8-12
Cu-base composites is prepared, wherein the applicable cases of raw material such as following table according to preparation scheme same as in Example 5 Shown in.
The preparation of table 3 Cu-base composites and sign
Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13
CNT 0.4 0.5 0.6 0.5 0.6
Graphite 6 3 2 4 5
Ti3SiC2Powder 11 9 12 8 10
BN powder 2 4 3 5 3
Rare Earth Lanthanum 0.15 0.01 0.08 0.1 0.12
Copper Surplus Surplus Surplus Surplus Surplus
* CNT is the CNT of the surface modification that embodiment 1 prepares.
The data recorded from embodiment form 1-3, when the composition of Cu-base composites is carbon by weight percentage Nanotube 0.4~5%, powdered graphite 2~6%, Ti3SiC2Powder 6~15%, BN powder 2~5%, rare-earth elements La powder 0.01~0.5%, surplus is when being copper powders, the Cu-base composites of preparation has preferable performance.When Cu-base composites Preparing raw material by after further preferably, concrete ratio is: surface-modified CNT 0.4~5%, graphite 2~ 5%, Ti3SiC29~12%, boron nitride (BN) 2~4%, rare-earth elements La 0.01~0.2%, copper surplus, cuprio now Composite has preferably performance.

Claims (10)

1. a carbon nanotube reinforced copper-base composite material, comprises following component: surface-modified carbon is received by weight percentage Mitron 0.4 ~ 5%, graphite 2 ~ 6%, Ti3SiC26 ~ 15%, boron nitride 2 ~ 5%, rare-earth elements La 0.01 ~ 0.5%, surplus is copper;
Described surface-modified CNT is the CNT of surface grafting gallic acid.
Carbon nanotube reinforced copper-base composite material the most according to claim 1, it is characterised in that described CNT increases Strong Cu-base composites, comprises following component by weight percentage: surface-modified CNT 0.4 ~ 5%, graphite 2 ~ 5%, Ti3SiC29 ~ 15%, boron nitride 2 ~ 5%, rare-earth elements La 0.01 ~ 0.2%, surplus is copper.
Carbon nanotube reinforced copper-base composite material the most according to claim 2, it is characterised in that described cuprio composite wood Material includes following component by weight percentage: surface-modified CNT 0.4 ~ 5%, powdered graphite 2 ~ 5%, Ti3SiC2Powder 9 ~ 12%, boron nitride 2 ~ 4%, rare-earth elements La powder 0.01 ~ 0.2%, surplus is copper powders.
Carbon nanotube reinforced copper-base composite material the most according to claim 1, it is characterised in that surface-modified carbon is received Mitron is the CNT that CNT uses gallic acid aqueous solution modification obtain.
Carbon nanotube reinforced copper-base composite material the most according to claim 4, it is characterised in that described surface-modified CNT is made through following methods: is joined by CNT in gallic acid aqueous solution, is uniformly dispersed, and stands, and filters, takes Filtering residue is vacuum dried, and obtains the CNT of surface modification.
6. according to the carbon nanotube reinforced copper-base composite material described in claim 4 or 5, it is characterised in that described gallic acid It is formulated that aqueous solution is dissolved in deionized water by gallic acid, and in gallic acid aqueous solution, the concentration of gallic acid is 3 ~ 18 μ g/ mL。
Carbon nanotube reinforced copper-base composite material the most according to claim 4, it is characterised in that the weight of described CNT Measuring the ratio with the volume of gallic acid aqueous solution is 0.05 ~ 0.5g:20 ~ 60mL.
Carbon nanotube reinforced copper-base composite material the most according to claim 4, it is characterised in that the time of described standing is 12~30h。
9. a preparation method for Cu-base composites, comprises the steps:
(1) CNT is joined in gallic acid aqueous solution, is uniformly dispersed, stand, filter, take filtering residue carry out vacuum do Dry, obtain the CNT of surface modification;
(2) by the CNT of surface modification and copper powders, powdered graphite, Ti3SiC2Powder, BN powder, La powder carry out ball The mixed powder of mill, obtains composite powder;
(3) composite powder is carried out hot pressed sintering, cool down, then hip treatment obtains carbon nanotube reinforced copper-base composite wood Material.
The preparation method of Cu-base composites the most according to claim 9, it is characterised in that described step (3) hot pressing is burnt The temperature of knot is 900 ~ 1000 DEG C.
CN201610437393.1A 2016-06-16 2016-06-16 Carbon nanotube reinforced copper-based composite material and preparation method thereof Pending CN105861872A (en)

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